Energy Transport between Hole Gas and Crystal Lattice in Diluted Magnetic Semiconductor
小学上册第十次英语第一单元综合卷
小学上册英语第一单元综合卷英语试题一、综合题(本题有100小题,每小题1分,共100分.每小题不选、错误,均不给分)1.What does a clock measure?A. DistanceB. TimeC. WeightD. Temperature2.advocacy organization) campaigns for change. The ____3.The ancient Romans spoke ______ (拉丁语).4.What is the main ingredient in pizza dough?A. RiceB. FlourC. CornD. OatsB5.My cat likes to watch _______ (蝴蝶) outside.6.What is the number of legs on an insect?A. SixB. EightC. FourD. TenA7.The stars are ______ at night. (shining)8.The badger is known for its digging ______ (能力).9. A ____(collaborative project team) works towards a common goal.10. A ______ helps to protect against predators.11.What do you call a person who studies animals?A. BiologistB. ZoologistC. EcologistD. Naturalist12.What do we call the hard outer covering of an egg?A. ShellB. YolkC. WhiteD. AlbumenA Shell13.What is the name of the famous American actress known for her role in "The Wizard of Oz"?A. Judy GarlandB. Marilyn MonroeC. Audrey HepburnD. Meryl StreepA14.Which shape has three sides?A. CircleB. SquareC. TriangleD. RectangleC Triangle15. A __________ is a reaction that produces heat.16.The grasshopper jumps on the ______.17.Which planet has the most moons?A. EarthB. JupiterC. SaturnD. Neptune18.The Alamo is a famous site in _______ history.19.ts can be grown ______ (室内). Some pla20.The ______ is a part of a plant that holds the leaves.21.My dad is a ________ (农民).22.What is the capital of the Democratic Republic of the Congo?A. KinshasaB. BrazzavilleC. LuandaD. KampalaA Kinshasa23.The clock says it is ________ o'clock.24.Trees provide us with ______.25.She is _______ (smiling) at the camera.26.I love _______ (参加)社区活动。
顺层长钻孔预抽煤层瓦斯防突技术在潘三矿的应用
Modelling and Assimilation of Atmospheric Chemistry - ecmwf建模与大气化学ECMWF同化
Why Atmospheric Chemistry at NWP centres ?
- or in a NWP Training Course?
Environmental concern Air pollution Ozone hole Climate change
ppt 1:1012
Atmospheric Chemistry
Transport
Chemical Reactions
Photolysis
catalytical Cycles
Emissions
Atmospheric Reservoir
Training Data assimilation and Satellite Data – Johannes Flemming Dr. Martin Schultz - Max-Planck-Institut für Meteorologie, Hamburg
Rodwell and Jung Published in Quart. J. Roy. Meteorol. Soc., 134, 1479.1497 (2019)
Training Data assimilation and Satellite Data – Johannes Flemming
An other motivation …
Transport
wet & dry Deposition
Modelling atmospheric composition
Mass balance equation for chemical species ( up to 150 in state-of-the-art
Macromolecules, 2004, 37 (15), pp 5531–5537
Synthesis of Asymmetrically Arranged Dendrimers with a Carbazole Dendron and a Phenylazomethine DendronAtsushi Kimoto,Jun-Sang Cho,Masayoshi Higuchi,and Kimihisa Yamamoto* Department of Chemistry,Faculty of Science and Technology,Keio University,Yokohama223-8522,JapanReceived January5,2004;Revised Manuscript Received May19,2004ABSTRACT:Asymmetrically arranged dendrimers with a carbazole dendron and a phenylazomethine dendron were synthesized by the combination of Ullmann reaction and a dehydration reaction in the presence of titanium tetrachloride.Stepwise complexation in the phenylazomethine dendron unit within these dendrimers and SnCl2suggests a gradient in the electron density associated with the imine groups. The complexation of the dendrimer changes the HOMO/LUMO energy gap of the dendrimer.We show the dendrimers with higher generations have the larger HOMO values.The most electron-rich molecule, Cz3-DPA3,has the highest HOMO value of5.35eV and,accordingly,is expected to have the lowest barrier for the hole injection from the ITO electrode(4.6eV)in OLEDs.However,for the HOMO energy levels of the carbazole dendrimer complex with SnCl2,the energy levels of the carbazoles did not change based on almost the same redox potentials as those of the dendrimers ing Cz3-DPA3as a hole-transport layer(HTL),only complexation with metal ions results in the enhanced maximum luminescence from4041to10640cd/m2by only complexing with SnCl2under the nonoptimized conditions.A complexation leads to a high EL efficiency because of the p-type-doped structure of the dendrimers as a hole-transport layer.IntroductionBranches of the dendrimers1,2with a monodispersed and well-defined structure growing up symmetrically by modular synthesis3have developed with a regular architecture,producing materials of intriguing proper-ties,such as light harvesting,4catalysis,5and so on,with a better amorphous property and high solubility due to the geometry of these molecules without close packing. We should note that dendrimers,especially rigid ones, can possibly be regularly assembled by packing on a plate without deformation of the molecule6and are expected to expand the field of nanomaterials.7,8The synthetic control to obtain designed dendrimers arranged asymmetrically,such as layered,9-11seg-mented,9,12,13or tailored ones,14,15is difficult,requiring stepwise synthetic methodology.Generally,asymmetri-cally substituted dendrimer building blocks are pre-pared by interrupting after the first of two possible reactions using a large excess of monomer.Indeed,when preparing asymmetric soft dendrimers withσbonds,the developing process,which includes many types of reac-tions with a lower reactivity,is easily applied to asym-metric building blocks.However,asymmetric building blocks with rigid branches consisting ofπ-conjugated bonds are difficult to prepare because of a few varieties of growth reactions and reacting substituents with high reactivity.Thus,few examples of preparing and devel-oping asymmetrical dendritic copolymers are reported, compared with those of symmetrically substituted ones, and above all,to the best of our knowledge,few examples of rigid asymmetric dendrimers have been reported.16Organic materials for various electrooptical applica-tions,for example,organic light-emitting diodes(OLE-Ds)17and photocells,18generally consist of rigidπ-con-jugated structures with a narrow HOMO-LUMO gap.Above all,a number of dendrimers have been applied in OLEDs19-21designed by their characteristic synthetic procedure,the convergent method.The advantages of adopting monodispersed and well-defined dendrimers as active components in OLEDs are that they can be easily prepared in high purity and have a better amorphous property and high solubility due to their geometry without close packing,resulting in the easier fabrication of thin films by the spin-coating method,a promising approach for large area display applications as well as polymeric materials.Efforts have been ongoing to develop a novel hole-transport polymer for advanced electronic devices.This is a key material for improving the turn-on voltage, luminescence intensity,operation lifetime,full color display capability,durability,reasonable power ef-ficiency,and so on.Generally,such high-performance devices are obtained by developing sequential HOMO/ LUMO energy gradients in the device by introducing the multilayered structure fabricated by repeatedly making thin films.For example,introducing another layer on the ITO electrode,with a HOMO energy level between that of the hole-transporting layer and of the electrode,that is a hole-injecting layer,lowers the energy barrier for hole injection.This approach involves placing the injecting layer between the ITO and the transport layer,such as copper phthalocyanine (CuPc)22and4,4′,4′′-tris(3-methylphenylphenylamino)-triphenylamine(m-MTDATA),19thus resulting in an enhanced EL efficiency.Another approach to develop the characters of the OLEDs has recently been raised by the insertion of thick doped materials such as doped triarylamine,23,24poly(vinylcarbazole),25polythio-phene,26-29and polyaniline,30,31resulting in the en-hancement of a carrier injection and transport with a lower driving voltage.However,these two approaches require highly layered structures because of their mo-lecular structures and syntheses and the indefinite*Corresponding author:e-mail yamamoto@chem.keio.ac.jp.5531Macromolecules2004,37,5531-553710.1021/ma0499674CCC:$27.50©2004American Chemical SocietyPublished on Web07/01/2004functional separation of the buffer and hole transport in one component.Moreover,the use of polymeric materials is restricted by the fabrication of such more complex structures because of the erosion of the fabri-cated film in advance followed by the method of making thin films,the spin-coating method.We now report the syntheses of asymmetrically ar-ranged dendrimers with a carbazole dendron (hole transporter)and a phenylazomethine dendron (metal collector)with a definite functional chemical structure.Stepwise complexation in the phenylazomethine den-dron unit within these dendrimers and SnCl 2suggests a gradient in the electron density associated with the imine groups,and the complexation of the dendrimer changes the HOMO/LUMO energy gap of the den-drimer.Only complexation with metal ions results in a high EL efficiency because of the p-type-doped structure of the dendrimers as a hole-transport layer.Experimental SectionAll chemicals were purchased from Aldrich,Tokyo Kasei Co.,Ltd.,and Kantoh Kagaku Co.,Inc.(reagent grade),and used without further purification.UV -vis spectra were obtained using a Shimadzu UV-2400PC spectrometer.1H NMR and 13C NMR spectra were measured on a JEOL 400MHz ET-NMR (JMN 400).Cyclic voltammetry experiments were performed with a BAS-100electrochemistry analyzer.All measurements were carried out at room temperature with a conventional three-electrode configuration consisting of a platinum working electrode,an auxiliary platinum electrode,and a nonaqueous Ag/AgNO 3reference electrode.The solvent in all experiments was 1,2-dichloroethane,and the supporting electrolyte was 0.1M tetrabutylammonium hexafluorophosphate.The E 1/2values were determined as 1/2(E pa +E pc ),where E pa and E pc are the anodic and cathodic peak potentials,respectively.All poten-tials reported are referenced to Fc/Fc +external and are not corrected for the junction potential.Conventional OLED devices having the ITO/dendrimer/Alq/CsF/Al structure were fabricated by spin-coating the den-drimer solutions in chlorobenzene on an ITO-coated glass anode.Alq (50nm),CsF (2nm),and Al (100nm)were successively vacuum-deposited on top of the hole-transporting layer.The emitting area was 9mm 2.The current -voltage characteristics were measured using an Advantest R6243current/voltage unit.Luminance was measured with a Minolta LS-100luminance meter under air at room temperature.The dendrimer complex was prepared by the following method.To a solution of the dendrimer in chloroform was added a solution of SnCl 2(1equiv vs the dendrimer)in acetonitrile.The yellow solution changed to light orange based on the complexation and evaporated to dryness to give the dendrimer complex.Cz2Dendron.To a solution of carbazole (8.35g,50.0mmol)in acetic acid (140mL)was added potassium iodide (11g,66.3mmol).With stirring,potassium iodate (16g,74.8mmol)was slowly added to the mixture and refluxed for 10min.The reaction mixture was cooled to room temperature,and then the mixture of iodinated compounds (7.0g)was obtained by filtration.The mixture was dissolved in acetic anhydride (42mL)and added boron trifluoride diethyl etherate (0.15mL)with refluxing for 20min to yield 9-acetyl-3,6-diiodocarbazole (3.94g,39%,two steps)as a residue.A mixture of carbazole (6.38g,38.2mmol),9-acetyl-3,6-diiodocarbazole (8.0g,17.4mmol),and copper(I)oxide (7.45g,52.1mmol)in N ,N -dimethylacetamide (DMAc)(150mL)was heated in an oil bath at 160°C for 36h.The reaction mixture was cooled to room temperature and then filtered through Celite.The filtrate was poured into a large amount of methanol (2L),and the mixture of acetylated Cz2dendron was obtained by filtration.The mixture was dissolved in THF (350mL),DMSO (150mL),H 2O (10mL),and then KOH (9.72g,0.173mol)was added,and the mixture was refluxed for 2h.The reaction mixture was cooled to room temperature,neutralized by HCl,and then poured into water to give the final mixture.Cz2dendron (4.73g,55%,two steps)was isolated by silica gel column chroma-tography using 4:1hexane/ethyl acetate with 2%Et 3N from the mixture.1H NMR (400MHz,CDCl 3,TMS standard,20°C,ppm):δ8.48(s,1H),8.20(d,J )2.0Hz,2H),8.16(d,J )8.0Hz,4H),7.69(d,J )8.8Hz,2H),7.61(dd,J )8.4,2.0Hz,2H),7.42-7.35(m,8H),7.30-7.25(m,4H).13C NMR (100MHz,CDCl 3,TMS standard,20°C,ppm):δ141.68,139.15,129.85,126.14,125.79,124.00,123.03,120.20,119.74,119.58,111.95,109.64.MALDI-TOF-MS:497.2([M]+calcd for C 36H 23N 3:497.19).General Procedure for the Ullmann Reaction.A mix-ture of p -iodoacetanilide and the corresponding carbazole dendron and an excess amount of copper(I)oxide in N ,N -dimethylacetamide (DMAc)was heated in an oil bath at 160°C for 24h under a N 2atmosphere.The reaction mixture was cooled to room temperature and then filtered through Celite to remove excess copper complex.The filtrate was evaporated to dryness.The pure product was isolated by silica gel column chromatography.Cz1-NHAc.The previous procedure was followed using 1.31g (5.00mmol)of p -iodoacetanilide,0.930g (5.56mmol)of carbazole,and 1.07g (7.50mmol)of copper oxide.The product was isolated by silica gel column chromatography using 2:1hexane/ethyl acetate with 2%Et 3N as eluent,yielding 1.15gChart 1.Structures ofDendrimers5532Kimoto et al.Macromolecules,Vol.37,No.15,2004(77%).1H NMR(400MHz,CDCl3,TMS standard,20°C,ppm):δ8.14(d,7.6Hz,2H),7.74(d,J)8.8Hz,2H),7.51(d,J)8.8Hz,2H),7.43-7.35(m,5H),7.28(dd,J)8.8,7.6Hz,2H),2.25(s,3H).13C NMR(100MHz,CDCl3,TMS standard,20°C,ppm):δ168.31,140.83,136.92,133.47,127.70,125.85,123.17,121.01,120.21,119.81,109.60,24.72.MALDI-TOF-MS:299.3([M]+calcd for C20H16N2O:300.13).Anal.Calcdfor C20H16N2O:C,79.98;H,5.37;N,9.33.Found:C,79.96;H,5.52;N,9.23.Cz2-NHAc.The above procedure was followed using0.521g(2.00mmol)of p-iodoacetanilide,1.10g(2.20mmol)of Cz2dendron,and0.429g(3.00mmol)of copper oxide.The productwas isolated by silica gel column chromatography using2:1hexane/ethyl acetate with2%Et3N as eluent,yielding1.24g(99%).1H NMR(400MHz,CDCl3,TMS standard,20°C,ppm):δ8.26(s,2H),8.16(d,J)7.6Hz,4H),7.83(d,J)8.8Hz,2H),7.66(d,J)8.8Hz,2H),7.60(t,J)8.4Hz,4H),7.41-7.37(m,9H),7.29-7.25(m,4H),2.27(s,3H).13C NMR(100MHz,CDCl3,TMS standard,20°C,ppm):δ168.39,141.64,140.66,137.63,132.74,130.23,127.82,126.18,125.80,123.77,123.05,121.23,120.21,119.61,111.15,109.63,24.86.MALDI-TOF-MS:630.6([M]+calcd for C44H30N4O:630.24).General Procedure for the Hydrolysis/Deprotectionof the Amide Bond.To a solution of amide in THF andmethanol were slowly added water and an excess amount ofH2SO4.After refluxing for2h,the reaction mixture was cooledin an ice bath,neutralized by NaOH(aq),and then extractedwith CHCl3.The organic layer was washed with Na2CO3solution,dried over anhydrous Na2SO4,and evaporated todryness.The pure product was isolated by silica gel columnchromatography.Cz1-NH2.The previous procedure was followed using0.303g(1.01mmol)of Cz1-NHAc,0.9mL of water,and1.0mL(20mmol)of H2SO4.The product was isolated by silica gel columnchromatography using2:1hexane/ethyl acetate with2%Et3Nas eluent,yielding0.258g(99%).1H NMR(400MHz,CDCl3,TMS standard,20°C,ppm):δ8.13(d,J)8.0Hz,2H),7.39(t,J)7.6Hz,2H),7.33-7.24(m,6H),6.86(d,J)6.6Hz,2H),3.85(s,2H).13C NMR(100MHz,CDCl3,TMS standard,20°C,ppm):δ145.82,141.38,128.42,128.07,125.63,122.87,120.10,119.33,115.83,109.70.MALDI-TOF-MS:257.2([M]+calcd for C18H14N2:258.12).Anal.Calcd for C18H14N2:C,83.69;H,5.46;N,10.84.Found:C,83.42;H,5.86;N,10.33.Cz2-NH2.The above procedure was followed using0.296g(0.469mmol)of Cz2-NHAc,0.42mL of water,and0.25mL(4.7mmol)of H2SO4.The product was isolated by silica gelcolumn chromatography using1:2hexane/ethyl acetate with2%Et3N as eluent,yielding0.168g(61%).1H NMR(400MHz,CDCl3,TMS standard,20°C,ppm):δ8.24(s,2H),8.15(d,J )8.0Hz,4H),7.56(t,9.6Hz,4H),7.43-7.36(m,10H),7.30-7.23(m,4H),6.90(d,J)8.4Hz,2H),3.89(s,2H).13C NMR(100MHz,CDCl3,TMS standard,20°C,ppm):δ146.47,141.71,141.21,135.64,129.77,128.44,127.23,125.99,125.77,123.42,123.01,120.19,119.53,115.95,111.25,109.67.MALDI-TOF-MS:587.3([M]+calcd for C42H28N4:588.23).Procedure for the Synthesis of Cz3-NH2.The anilinederivative substituted by the Cz3dendron(Cz3-NH2)wasprepared according to the following procedures as well as thereported ones:Cz1-I2-NHAc.To a solution of Cz1-NHAc(0.600g,2.00mmol)in acetic acid(25mL)was added potassium iodide(0.442g,2.66mmol).With stirring,potassium iodate(0.642g,3.00mmol)was slowly added to the mixture and refluxedfor20min.The reaction mixture was cooled to room tem-perature,and then the pure product(0.967g,88%)wasobtained by filtration and washed with NaHCO3(aq)andwater.1H NMR(400MHz,DMSO-d6,TMS standard,20°C,ppm):δ10.26(s,1H),8.71(s,2H),7.87(d,J)8.6Hz,2H),7.71(d,J)8.6Hz,2H),7.51(d,J)7.8Hz,2H),7.17(d,J)7.8Hz,2H),2.12(s,3H).13C NMR(100MHz,DMSO-d6,TMSstandard,20°C,ppm):δ168.41,139.44,139.00,134.67,130.25,129.37,127.03,123.72,120.15,112.09,83.35,24.10.MALDI-TOF-MS:551.0([M]+calcd for C20H14I2N2O:551.92).Anal.Calcd for C20H14I2N2O:C,43.51;H, 2.56;N, 5.07.Found:C,43.57;H,2.82;N,4.67.Cz3-NH2.The previous procedure of Ullmann reaction wasfollowed using0.822g(1.49mmol)of Cz1-I2-NHAc,1.64g(3.30mmol)of Cz2dendron,and0.644g(4.50mmol)of copperoxide.The product was purified by silica gel column chroma-tography using chloroform as eluent.The above procedure ofthe hydrolysis/deprotection was followed using1.4mL of waterand1.6mL(30mmol)of H2SO4.The product was isolated bysilica gel column chromatography using2:2:1hexane/ethylacetate/chloroform with2%Et3N as eluent,yielding0.685g(37%,two steps).1H NMR(400MHz,CDCl3,TMS standard,20°C,ppm):δ8.50-8.27(m,8H),8.16-8.13(m,6H),7.80-7.15(m,34H),7.05-6.78(m,4H),3.97-3.83(m,2H).13C NMR(100MHz,CDCl3,TMS standard,20°C,ppm):δ146.54,141.69,141.50,140.84,140.54,134.84,134.55,130.00,129.29,129.06,128.53,128.33,128.16,126.84,126.46,126.16,125.79,124.80,123.95,123.59,123.02,120.19,119.65,119.57,116.04,115.92,115.80,112.31,111.95,111.37,111.26,109.68.MALDI-TOF-MS:1250.4([M]+calcd for C90H56N8:1248.46).General Procedure for the Synthesis of the Asym-metrically Arranged Dendrimers with a Carbazole Den-dron and a Phenylazomethine Dendron.To a mixture ofCzm-NH2(m)1-3),the corresponding phenylazomethinedendron,DPAn(n)1-3),and DABCO in chlorobenzene wasadded TiCl4dropwise.The addition funnel was rinsed withchlorobenzene.The reaction mixture was heated in an oil bathat125°C for4h.The precipitate was removed by filtration.The filtrate was concentrated,and the pure product wasisolated by silica gel column chromatography.Cz1-DPA1.The previous procedure was followed using0.240g(0.931mmol)of Cz1-NH2,0.254g(1.40mmol)ofbenzophenone(DPA1),0.157g(1.40mmol)of DABCO,and0.132g(6.98mmol)of TiCl4.The product was isolated by silicagel column chromatography using9:1:1hexane/ethyl acetate/chloroform with2%Et3N as eluent,yielding0.245g(62%). 1H NMR(400MHz,CDCl3,TMS standard,20°C,ppm):δ8.11 (d,7.2Hz,2H),7.82(d,J)7.2Hz,2H),7.53-7.20(m,16H),6.93(d,J)8.8Hz,2H).13C NMR(100MHz,CDCl3,TMSstandard,20°C,ppm):δ169.03,150.59,140.98,139.29,135.97,132.51,130.92,129.52,129.36,128.82,128.22,127.97,127.32,125.71,123.08,122.27,120.14,119.59,109.63.MALDI-TOF-Mass:420.6([M]+calcd for C31H22N2:422.2).Anal.Calcdfor C31H22N2:C,88.12;H,5.25;N,6.63.Found:C,87.72;H,5.48;N,6.47.Cz2-DPA2.The previous procedure was followed using0.0993g(0.169mmol)of Cz2-NH2,0.184g(0.340mmol)ofDPA2,0.246g(2.19mmol)of DABCO,and0.104g(0.547mmol)of TiCl4.The product was isolated by silica gel columnchromatography using chloroform with2%Et3N as eluent,yielding0.163g(87%).1H NMR(400MHz,CDCl3,TMSstandard,20°C,ppm):δ8.27(s,2H),8.16(d,J)7.6Hz,4H),7.77(d,J)7.2Hz,2H),7.70(d,J)7.2Hz,21H),7.63-6.94(m,40H),6.78(d,J)8.4Hz,2H),6.68(d,J)8.4Hz,2H).13C NMR(100MHz,CDCl3,TMS standard,20°C,ppm):δ168.93,168.68,168.45,153.85,151.99,151.58,141.67, 139.20,138.90,135.75,134.23,131.41,130.95,130.49,130.35,130.12,130.04,129.38,129.25,128.82,128.67,128.18,128.02,127.69,127.36,126.07,125.80,123.63,123.04,122.88,120.55,120.34,120.19,119.57,111.30,109.64.MALDI-TOF-Mass:1110.4([M]+calcd for C31H22N2:1109.0).Anal.Calcd forC81H54N6:C,87.54;H,4.90;N,7.56.Found:C,87.39;H,5.06;N,7.46.Cz3-DPA3.The previous procedure was followed using0.425g(0.340mmol)of Cz3-NH2,0.427g(0.340mmol)ofDPA3,0.246g(2.19mmol)of DABCO,and0.104g(0.547mmol)of TiCl4.The product was isolated by silica gel columnchromatography using chloroform with2%Et3N as eluent,yielding0.746g(88%).1H NMR(400MHz,CDCl3,TMSstandard,20°C,ppm):δ8.51(s,2H),8.30(s,4H),8.15(d,J )7.2Hz,8H),7.80-6.95(m,88H),6.89(t,J)8.8Hz,4H), 6.76-6.55(m,12H).13C NMR(100MHz,CDCl3,TMS stan-dard,20°C,ppm):δ168.78,168.54,168.41,168.26,168.12,154.37,153.79,153.71,153.37,151.90,151.78,151.30,141.59,141.39,139.10,138.91,138.67,135.55,133.99,133.82,133.60,130.82,130.48,130.36,130.20,129.98,129.27,128.60,128.06,127.91,127.74,127.50,126.37,126.09,125.70,125.34,123.68,Macromolecules,Vol.37,No.15,2004Asymmetrically Arranged Dendrimers5533123.54,122.94,120.83,120.74,120.40,120.10,119.93,119.60,119.49,111.69,111.16,109.55.MALDI-TOF-Mass:2487.0([M]+calcd for C 31H 22N 2:2486.3).Results and DiscussionThe reactivity and generality of the substrate con-structing the phenylazomethine backbone are much higher than those of an arylamine backbone.Although the triarylamine can easily be formed using palladium-catalyzed reactions,various reaction conditions,such as palladium complex,ligands,and so on,are required,resulting in lower generalities.On the other hand,the formation of the phenylazomethine backbone affords great generality by the dehydration reaction of aromatic amines with aromatic ketones in the presence of tita-nium(IV)tetrachloride and 1,4-diazabicyclo[2.2.2]octane (DABCO).For these reasons,we considered the strategy to prepare the asymmetrically substituted dendrimers by first introducing a dendritic carbazole unit and then the dendritic phenylazomethines.As shown in Scheme 1,the Cz2dendron,32that is,the carbazole trimer,was obtained by the combination of the iodination,33acety-lation,and the modified Ullmann condensation 34(Scheme 1).We adopted the acetyl group for the protection of the amines.This is due to the high thermal stability of the amide bond compared with that of the Boc (t -butoxy-carbonyl)group that is a traditional protecting group of amines.The aniline derivatives with a carbazole dendron (Czm-NH 2)were obtained from p -iodoacetanilide usingthe same reactions.35The convergent approach was employed to synthesize the first-generation (G1)and second-generation (G2)dendrimers.The G1and G2substituted aniline derivatives were simply synthesized from p -iodoacetanilide,and carbazole or Cz2dendron,via the Ullmann condensation to yield Cz1-NHAc and Cz2-NHAc ,respectively (Scheme 2),following the hy-drolysis reaction of the amide-protecting unit using sulfuric acid to obtain Cz1-NH 2and Cz2-NH 2,respec-tively.Generally,the hydrolysis of the amide can easily proceed in the presence of a strong base such as NaOH,KOH,and so on.35However,in this case,this hydrolysis reaction cannot proceed when using them.The synthesis of Cz3-NH 2was carried out with a route like a double-stage convergent method as shown in Scheme 3.This is due to the decreased reactivity of the amine site at the Cz3dendron,which can be synthesized by the same procedures as the Cz2dendron.We then adopted the growth procedure stacking the Cz2dendron on the carbazole unit.First,the iodination of Cz1-NHAc was pursued to give Cz1-I 2-NHAc ,and then Cz1-I 2-NHAc was allowed to react with the Cz2den-dron under the Ullmann reaction conditions successfully yielding Cz3-NH 2.36As shown in Scheme 4,a series of dendrimers substituted asymmetrically (Czm-DPAn )were synthe-sized by the dehydration reaction using TiCl 4from the corresponding 4-amino-N -phenylcarbazoles (Czm-NH 2)and phenylazomethine dendron (DPAn ),which were obtained by a previously reported procedure.6,37These dendrimers were characterized by 1H and 13C NMR spectroscopies,elemental analysis,and matrix-assisted laser desorption/ionization time-of-flight mass spectros-copy (MALDI-TOF-MS).The addition of SnCl 2to a chloroform/acetonitrile solution of asymmetrically substituted dendrimers (Czm-DPAn )resulted in a complexation with a stepwise spectral change,similar to that for the previously reported dendrimers.38-41During addition of SnCl 2,the solution color of Cz3-DPA3changed from light to deeper yellow.We observed that the complexation was complete in 10min by the spectral change after the addition of SnCl 2;that is,the complexation equilibrium is reached within at least several ing UV -vis spec-troscopy to profile the complexation until an equimolarScheme 1.Synthesis of Cz2DendronaaReagents and conditions:(i)KI,KIO 3,AcOH,20min;(ii)Ac 2O,BF 3-Et 2O,10min;(iii)carbazole,Cu 2O,DMAc,36h;(iv)KOH,H 2O,THF,DMSO,2h.Scheme 2.Syntheses of Cz1-NH 2and Cz2-NH 2aaReagents and conditions:(i)carbazole,Cu 2O,DMAc,24h;(ii)H 2SO 4,H 2O,THF,MeOH,2h;(iii)CzG2dendron,Cu 2O,DMAc,24h.5534Kimoto et al.Macromolecules,Vol.37,No.15,2004amount of SnCl 2had been added,three changes in the position of the isosbestic points were observed,indicat-ing that the complexation proceeds,not randomly,but stepwise.This result suggests that three different complexes are successively formed upon the SnCl 2addition.The absorption band around 400nm attributed to the complex increases with a decrease in the absorption bands around 320nm,attributed to the phenylazome-thine unit.The spectra of Cz3-DPA3gradually changed,with an isosbestic point at 374nm up to the addition of 1equiv of SnCl 2(Figure 1).The isosbestic point then shifted upon the further addition of SnCl 2and appeared at 372nm between 1and 3equiv,moving to 368nm when adding between 3and 7equiv.Overall,the number of added equivalents of SnCl 2required to induce a shift was in agreement with the number of imine sites present in the different layers of Cz3-DPA3.The titration results suggest that the complexation proceeds in a stepwise fashion from the core imines to the terminal imines of Cz3-DPA3(Scheme 5).42A similar stepwise complexation was also observed with Cz2-DPA2.From the theoretical calculations,the stepwise complexation requires the larger equilibrium constants with at least 10times larger of the inner imine sites than the outer ones.39In other words,the basicity forScheme 3.Synthesis of Cz3-NH 2aaReagents and conditions:(i)KI,KIO 3,AcOH,20min;(ii)Cz2dendron,Cu 2O,DMAc,24h;(iii)H 2SO 4,H 2O,THF,MeOH,2h.Scheme 4.General Synthesis of Czm-DPAn DendrimersaaReagents and conditions:(i)TiCl 4,DABCO,PhCl.Figure 1.UV -vis spectra changes of Cz3-DPA3on stepwise addition of equimolar SnCl 2in CH 3CN/CHCl 3)1/4.(Inset)Enlargements focusing isosbestic points.Table 1.Physical Data of the Dendrimers (Czm-DPAn)and Their Complex with 1SnCl 2oxidation potential/V vs Fc/Fc +acalcd HOMO/eVCz1-DPA10.687,0.882-5.49Cz1-DPA1-SnCl 20.616,0.753-5.42Cz2-DPA20.616,0.753-5.41Cz2-DPA2-SnCl 20.594,0.739-5.39Cz3-DPA30.555,0.735-5.35Cz3-DPA3-SnCl 20.538,0.734-5.34aMeasured in 1,2-dichloroethane.Macromolecules,Vol.37,No.15,2004Asymmetrically Arranged Dendrimers 5535the inner phenylazomethine is higher with increasing the generation number,and the stability of the pheny-lazomethine -SnCl 2complex intensified.In another aspect,the higher coordination constant of inner imines conducts phenylazomethine dendron to the highly elec-tron-donating substituent.The electrochemical properties of the dendrimers were studied by cyclic voltammetry.The HOMO values are determined from the first oxidation potential values with respect to ferrocene (Fc),as shown in Table 1.43All the dendrimers displayed quasi-reversible oxidation waves attributed to the oxidation of triarylamine in the region between 0.2and 1.4V vs Fc/Fc +.We have found that comparing the generation of the asymmetrically arranged dendrimers,the reduced oxidation potential of the Czm unit was observed on the basis of the electron richness and,therefore,the HOMO values with higher generations.Indeed,the most electron-rich mol-ecule,Cz3-DPA3,has the highest HOMO value of -5.35eV and,accordingly,expected to have the lowest barrier to hole injection from the ITO electrode (-4.6eV)in plexing with 1equiv of SnCl 2,redox waves resulted with almost the same potential (-5.34eV)as previously observed in the oxidation wave of the carbazole dendron.However,an additional stable redox wave attributed to the reduction of the azomethine -metal complex unit was not observed within the poten-tial range.A bright green emission was observed for all the cells when a positive dc voltage was applied to the ITO electrode.The electroluminescence spectrum was in accord with the photoluminescence spectrum of Alq.This indicates that the electroluminescence originates from the recombination of holes and electrons injected into Alq.For the two-layer OLEDs,Cz3-DPA3and its complex with the SnCl 2films were then employed as the hole-transporting layer.To a solution of the den-drimer in chloroform was added a solution of SnCl 2(1equiv vs the dendrimer)in acetonitrile.The yellow solution changed to light orange based on the complex-ation and evaporated to dryness to give the dendrimer complex.The films were obtained by the spin-coating method.As shown in Figure 2and Table 2,the low driving voltage and enhanced efficiency were followed by simply assembling the metal ions.The turn-on voltage was reduced from 5.6to 3.0V,and the maxi-mum luminescence was enhanced from 4041to 10640cd/m 2by only complexing with SnCl 2under the nonop-timized conditions.Also,the current performance of the G3-Sn complex was over 10times greater (227.3mA/cm 2)for the same forward driving voltage (9V)com-pared to that of the uncomplexed device (18.4mA/cm 2).The threshold voltages for obtaining a luminance of 100cd/m 2were 9.2and 6.1V for the cells,respectively.For the HOMO energy levels of the carbazole -dendrimer complex,the energy levels of the carbazoles did not change on the basis of the same redox potentials when complexing.When considering the influence of doping on the turn-on voltage and the performance at a lower driving voltage,the reduction in the bulk resistance followed by the p-type doping facilitates efficient hole injection into HTL.40The reduction of space charge layers at the interface of the ITO and the dendrimer complex leads to efficient carrier injection due to tunneling.In summary,we have synthesized asymmetrically arranged dendrimers with a carbazole dendron and a phenylazomethine dendron.Stepwise complexation in the phenylazomethine dendron unit within these den-drimers and SnCl 2suggests a gradient in the electron density associated with the imine groups,and the complexation of the dendrimer changes the HOMO/LUMO energy gap of the dendrimer.Only complexation with metal ions results in a high EL efficiency because of the p-type-doped structure of the dendrimers as a hole-transport layer as our past research.A develop-ment study about the mechanism for the development of hole-transport in OLEDs is now in progress.Acknowledgment.This work was supported by a Kanagawa Academy Science and Technology Research Grant (Project No.23)and Grant-in-Aid for the 21st Century COE program “KEIO Life Conjugate Chemis-Table 2.Electroluminescence Properties for the DevicesHTLturn-on voltage/V max brightness/cd/m 2current density a /mA/cm 2driving voltage b /Vcurrent density b /mA/m 2EL eff b /lm/W quantum eff b /%Cz3-DPA35.6404118.49.27.860.430.42Cz3-DPA3+SnCl 23.010640227.36.17.040.730.46aTaken at 9V.b Taken at 100cd/m 2.Scheme 5.Schematic Representation of StepwiseComplexation of Cz3-DPA3with SnCl 2aaThis complexation thermodynamically proceeds in a step-wise fashion from the core imines to the terminal ones,according to the electron gradients of Cz3-DPA3.Figure 2.Luminance -voltage characteristics of double-layer OLEDs with CsF -Al cathodes using Cz3-DPA3(diamond)and its complex (square)with 1SnCl 2as HTL.5536Kimoto et al.Macromolecules,Vol.37,No.15,2004。
Two-Dimensional Gas of Massless Dirac Fermions in Graphene
Two-Dimensional Gas of Massless Dirac Fermions in Graphene K.S. Novoselov1, A.K. Geim1, S.V. Morozov2, D. Jiang1, M.I. Katsnelson3, I.V. Grigorieva1, S.V. Dubonos2, A.A. Firsov21Manchester Centre for Mesoscience and Nanotechnology, University of Manchester, Manchester, M13 9PL, UK2Institute for Microelectronics Technology, 142432, Chernogolovka, Russia3Institute for Molecules and Materials, Radboud University of Nijmegen, Toernooiveld 1, 6525 ED Nijmegen, the NetherlandsElectronic properties of materials are commonly described by quasiparticles that behave as nonrelativistic electrons with a finite mass and obey the Schrödinger equation. Here we report a condensed matter system where electron transport is essentially governed by the Dirac equation and charge carriers mimic relativistic particles with zero mass and an effective “speed of light” c∗ ≈106m/s. Our studies of graphene – a single atomic layer of carbon – have revealed a variety of unusual phenomena characteristic of two-dimensional (2D) Dirac fermions. In particular, we have observed that a) the integer quantum Hall effect in graphene is anomalous in that it occurs at halfinteger filling factors; b) graphene’s conductivity never falls below a minimum value corresponding to the conductance quantum e2/h, even when carrier concentrations tend to zero; c) the cyclotron mass mc of massless carriers with energy E in graphene is described by equation E =mcc∗2; and d) Shubnikov-de Haas oscillations in graphene exhibit a phase shift of π due to Berry’s phase.Graphene is a monolayer of carbon atoms packed into a dense honeycomb crystal structure that can be viewed as either an individual atomic plane extracted from graphite or unrolled single-wall carbon nanotubes or as a giant flat fullerene molecule. This material was not studied experimentally before and, until recently [1,2], presumed not to exist. To obtain graphene samples, we used the original procedures described in [1], which involve micromechanical cleavage of graphite followed by identification and selection of monolayers using a combination of optical, scanning-electron and atomic-force microscopies. The selected graphene films were further processed into multi-terminal devices such as the one shown in Fig. 1, following standard microfabrication procedures [2]. Despite being only one atom thick and unprotected from the environment, our graphene devices remain stable under ambient conditions and exhibit high mobility of charge carriers. Below we focus on the physics of “ideal” (single-layer) graphene which has a different electronic structure and exhibits properties qualitatively different from those characteristic of either ultra-thin graphite films (which are semimetals and whose material properties were studied recently [2-5]) or even of our other devices consisting of just two layers of graphene (see further). Figure 1 shows the electric field effect [2-4] in graphene. Its conductivity σ increases linearly with increasing gate voltage Vg for both polarities and the Hall effect changes its sign at Vg ≈0. This behaviour shows that substantial concentrations of electrons (holes) are induced by positive (negative) gate voltages. Away from the transition region Vg ≈0, Hall coefficient RH = 1/ne varies as 1/Vg where n is the concentration of electrons or holes and e the electron charge. The linear dependence 1/RH ∝Vg yields n =α·Vg with α ≈7.3·1010cm-2/V, in agreement with the theoretical estimate n/Vg ≈7.2·1010cm-2/V for the surface charge density induced by the field effect (see Fig. 1’s caption). The agreement indicates that all the induced carriers are mobile and there are no trapped charges in graphene. From the linear dependence σ(Vg) we found carrier mobilities µ =σ/ne, whichreached up to 5,000 cm2/Vs for both electrons and holes, were independent of temperature T between 10 and 100K and probably still limited by defects in parent graphite. To characterise graphene further, we studied Shubnikov-de Haas oscillations (SdHO). Figure 2 shows examples of these oscillations for different magnetic fields B, gate voltages and temperatures. Unlike ultra-thin graphite [2], graphene exhibits only one set of SdHO for both electrons and holes. By using standard fan diagrams [2,3], we have determined the fundamental SdHO frequency BF for various Vg. The resulting dependence of BF as a function of n is plotted in Fig. 3a. Both carriers exhibit the same linear dependence BF = β·n with β ≈1.04·10-15 T·m2 (±2%). Theoretically, for any 2D system β is defined only by its degeneracy f so that BF =φ0n/f, where φ0 =4.14·10-15 T·m2 is the flux quantum. Comparison with the experiment yields f =4, in agreement with the double-spin and double-valley degeneracy expected for graphene [6,7] (cf. caption of Fig. 2). Note however an anomalous feature of SdHO in graphene, which is their phase. In contrast to conventional metals, graphene’s longitudinal resistance ρxx(B) exhibits maxima rather than minima at integer values of the Landau filling factor ν (Fig. 2a). Fig. 3b emphasizes this fact by comparing the phase of SdHO in graphene with that in a thin graphite film [2]. The origin of the “odd” phase is explained below. Another unusual feature of 2D transport in graphene clearly reveals itself in the T-dependence of SdHO (Fig. 2b). Indeed, with increasing T the oscillations at high Vg (high n) decay more rapidly. One can see that the last oscillation (Vg ≈100V) becomes practically invisible already at 80K whereas the first one (Vg <10V) clearly survives at 140K and, in fact, remains notable even at room temperature. To quantify this behaviour we measured the T-dependence of SdHO’s amplitude at various gate voltages and magnetic fields. The results could be fitted accurately (Fig. 3c) by the standard expression T/sinh(2π2kBTmc/heB), which yielded mc varying between ≈ 0.02 and 0.07m0 (m0 is the free electron mass). Changes in mc are well described by a square-root dependence mc ∝n1/2 (Fig. 3d). To explain the observed behaviour of mc, we refer to the semiclassical expressions BF = (h/2πe)S(E) and mc =(h2/2π)∂S(E)/∂E where S(E) =πk2 is the area in k-space of the orbits at the Fermi energy E(k) [8]. Combining these expressions with the experimentally-found dependences mc ∝n1/2 and BF =(h/4e)n it is straightforward to show that S must be proportional to E2 which yields E ∝k. Hence, the data in Fig. 3 unambiguously prove the linear dispersion E =hkc∗ for both electrons and holes with a common origin at E =0 [6,7]. Furthermore, the above equations also imply mc =E/c∗2 =(h2n/4πc∗2)1/2 and the best fit to our data yields c∗ ≈1⋅106 m/s, in agreement with band structure calculations [6,7]. The employed semiclassical model is fully justified by a recent theory for graphene [9], which shows that SdHO’s amplitude can indeed be described by the above expression T/sinh(2π2kBTmc/heB) with mc =E/c∗2. Note that, even though the linear spectrum of fermions in graphene (Fig. 3e) implies zero rest mass, their cyclotron mass is not zero. The unusual response of massless fermions to magnetic field is highlighted further by their behaviour in the high-field limit where SdHO evolve into the quantum Hall effect (QHE). Figure 4 shows Hall conductivity σxy of graphene plotted as a function of electron and hole concentrations in a constant field B. Pronounced QHE plateaux are clearly seen but, surprisingly, they do not occur in the expected sequence σxy =(4e2/h)N where N is integer. On the contrary, the plateaux correspond to half-integer ν so that the first plateau occurs at 2e2/h and the sequence is (4e2/h)(N + ½). Note that the transition from the lowest hole (ν =–½) to lowest electron (ν =+½) Landau level (LL) in graphene requires the same number of carriers (∆n =4B/φ0 ≈1.2·1012cm-2) as the transition between other nearest levels (cf. distances between minima in ρxx). This results in a ladder of equidistant steps in σxy which are not interrupted when passing through zero. To emphasize this highly unusual behaviour, Fig. 4 also shows σxy for a graphite film consisting of only two graphene layers where the sequence of plateaux returns to normal and the first plateau is at 4e2/h, as in the conventional QHE. We attribute this qualitative transition between graphene and its two-layer counterpart to the fact that fermions in the latter exhibit a finite mass near n ≈0 (as found experimentally; to be published elsewhere) and can no longer be described as massless Dirac particles. 2The half-integer QHE in graphene has recently been suggested by two theory groups [10,11], stimulated by our work on thin graphite films [2] but unaware of the present experiment. The effect is single-particle and intimately related to subtle properties of massless Dirac fermions, in particular, to the existence of both electron- and hole-like Landau states at exactly zero energy [912]. The latter can be viewed as a direct consequence of the Atiyah-Singer index theorem that plays an important role in quantum field theory and the theory of superstrings [13,14]. For the case of 2D massless Dirac fermions, the theorem guarantees the existence of Landau states at E=0 by relating the difference in the number of such states with opposite chiralities to the total flux through the system (note that magnetic field can also be inhomogeneous). To explain the half-integer QHE qualitatively, we invoke the formal expression [9-12] for the energy of massless relativistic fermions in quantized fields, EN =[2ehc∗2B(N +½ ±½)]1/2. In QED, sign ± describes two spins whereas in the case of graphene it refers to “pseudospins”. The latter have nothing to do with the real spin but are “built in” the Dirac-like spectrum of graphene, and their origin can be traced to the presence of two carbon sublattices. The above formula shows that the lowest LL (N =0) appears at E =0 (in agreement with the index theorem) and accommodates fermions with only one (minus) projection of the pseudospin. All other levels N ≥1 are occupied by fermions with both (±) pseudospins. This implies that for N =0 the degeneracy is half of that for any other N. Alternatively, one can say that all LL have the same “compound” degeneracy but zeroenergy LL is shared equally by electrons and holes. As a result the first Hall plateau occurs at half the normal filling and, oddly, both ν = –½ and +½ correspond to the same LL (N =0). All other levels have normal degeneracy 4B/φ0 and, therefore, remain shifted by the same ½ from the standard sequence. This explains the QHE at ν =N + ½ and, at the same time, the “odd” phase of SdHO (minima in ρxx correspond to plateaux in ρxy and, hence, occur at half-integer ν; see Figs. 2&3), in agreement with theory [9-12]. Note however that from another perspective the phase shift can be viewed as the direct manifestation of Berry’s phase acquired by Dirac fermions moving in magnetic field [15,16]. Finally, we return to zero-field behaviour and discuss another feature related to graphene’s relativistic-like spectrum. The spectrum implies vanishing concentrations of both carriers near the Dirac point E =0 (Fig. 3e), which suggests that low-T resistivity of the zero-gap semiconductor should diverge at Vg ≈0. However, neither of our devices showed such behaviour. On the contrary, in the transition region between holes and electrons graphene’s conductivity never falls below a well-defined value, practically independent of T between 4 and 100K. Fig. 1c plots values of the maximum resistivity ρmax(B =0) found in 15 different devices, which within an experimental error of ≈15% all exhibit ρmax ≈6.5kΩ, independent of their mobility that varies by a factor of 10. Given the quadruple degeneracy f, it is obvious to associate ρmax with h/fe2 =6.45kΩ where h/e2 is the resistance quantum. We emphasize that it is the resistivity (or conductivity) rather than resistance (or conductance), which is quantized in graphene (i.e., resistance R measured experimentally was not quantized but scaled in the usual manner as R =ρL/w with changing length L and width w of our devices). Thus, the effect is completely different from the conductance quantization observed previously in quantum transport experiments. However surprising, the minimum conductivity is an intrinsic property of electronic systems described by the Dirac equation [17-20]. It is due to the fact that, in the presence of disorder, localization effects in such systems are strongly suppressed and emerge only at exponentially large length scales. Assuming the absence of localization, the observed minimum conductivity can be explained qualitatively by invoking Mott’s argument [21] that mean-free-path l of charge carriers in a metal can never be shorter that their wavelength λF. Then, σ =neµ can be re-written as σ = (e2/h)kFl and, hence, σ cannot be smaller than ≈e2/h per each type of carriers. This argument is known to have failed for 2D systems with a parabolic spectrum where disorder leads to localization and eventually to insulating behaviour [17,18]. For the case of 2D Dirac fermions, no localization is expected [17-20] and, accordingly, Mott’s argument can be used. Although there is a broad theoretical consensus [18-23,10,11] that a 2D gas of Dirac fermions should exhibit a minimum 3conductivity of about e2/h, this quantization was not expected to be accurate and most theories suggest a value of ≈e2/πh, in disagreement with the experiment. In conclusion, graphene exhibits electronic properties distinctive for a 2D gas of particles described by the Dirac rather than Schrödinger equation. This 2D system is not only interesting in itself but also allows one to access – in a condensed matter experiment – the subtle and rich physics of quantum electrodynamics [24-27] and provides a bench-top setting for studies of phenomena relevant to cosmology and astrophysics [27,28].1. Novoselov, K.S. et al. PNAS 102, 10451 (2005). 2. Novoselov, K.S. et al. Science 306, 666 (2004); cond-mat/0505319. 3. Zhang, Y., Small, J.P., Amori, M.E.S. & Kim, P. Phys. Rev. Lett. 94, 176803 (2005). 4. Berger, C. et al. J. Phys. Chem. B, 108, 19912 (2004). 5. Bunch, J.S., Yaish, Y., Brink, M., Bolotin, K. & McEuen, P.L. Nanoletters 5, 287 (2005). 6. Dresselhaus, M.S. & Dresselhaus, G. Adv. Phys. 51, 1 (2002). 7. Brandt, N.B., Chudinov, S.M. & Ponomarev, Y.G. Semimetals 1: Graphite and Its Compounds (North-Holland, Amsterdam, 1988). 8. Vonsovsky, S.V. and Katsnelson, M.I. Quantum Solid State Physics (Springer, New York, 1989). 9. Gusynin, V.P. & Sharapov, S.G. Phys. Rev. B 71, 125124 (2005). 10. Gusynin, V.P. & Sharapov, S.G. cond-mat/0506575. 11. Peres, N.M.R., Guinea, F. & Castro Neto, A.H. cond-mat/0506709. 12. Zheng, Y. & Ando, T. Phys. Rev. B 65, 245420 (2002). 13. Kaku, M. Introduction to Superstrings (Springer, New York, 1988). 14. Nakahara, M. Geometry, Topology and Physics (IOP Publishing, Bristol, 1990). 15. Mikitik, G. P. & Sharlai, Yu.V. Phys. Rev. Lett. 82, 2147 (1999). 16. Luk’yanchuk, I.A. & Kopelevich, Y. Phys. Rev. Lett. 93, 166402 (2004). 17. Abrahams, E., Anderson, P.W., Licciardello, D.C. & Ramakrishnan, T.V. Phys. Rev. Lett. 42, 673 (1979). 18. Fradkin, E. Phys. Rev. B 33, 3263 (1986). 19. Lee, P.A. Phys. Rev. Lett. 71, 1887 (1993). 20. Ziegler, K. Phys. Rev. Lett. 80, 3113 (1998). 21. Mott, N.F. & Davis, E.A. Electron Processes in Non-Crystalline Materials (Clarendon Press, Oxford, 1979). 22. Morita, Y. & Hatsugai, Y. Phys. Rev. Lett. 79, 3728 (1997). 23. Nersesyan, A.A., Tsvelik, A.M. & Wenger, F. Phys. Rev. Lett. 72, 2628 (1997). 24. Rose, M.E. Relativistic Electron Theory (John Wiley, New York, 1961). 25. Berestetskii, V.B., Lifshitz, E.M. & Pitaevskii, L.P. Relativistic Quantum Theory (Pergamon Press, Oxford, 1971). 26. Lai, D. Rev. Mod. Phys. 73, 629 (2001). 27. Fradkin, E. Field Theories of Condensed Matter Systems (Westview Press, Oxford, 1997). 28. Volovik, G.E. The Universe in a Helium Droplet (Clarendon Press, Oxford, 2003).Acknowledgements This research was supported by the EPSRC (UK). We are most grateful to L. Glazman, V. Falko, S. Sharapov and A. Castro Netto for helpful discussions. K.S.N. was supported by Leverhulme Trust. S.V.M., S.V.D. and A.A.F. acknowledge support from the Russian Academy of Science and INTAS.43µ (m2/Vs)0.8c4P0.4 22 σ (1/kΩ)10K0 0 1/RH(T/kΩ) 1 2ρmax (h/4e2)1-5010 Vg (V) 50 -10ab 0 -100-500 Vg (V)50100Figure 1. Electric field effect in graphene. a, Scanning electron microscope image of one of our experimental devices (width of the central wire is 0.2µm). False colours are chosen to match real colours as seen in an optical microscope for larger areas of the same materials. Changes in graphene’s conductivity σ (main panel) and Hall coefficient RH (b) as a function of gate voltage Vg. σ and RH were measured in magnetic fields B =0 and 2T, respectively. The induced carrier concentrations n are described by [2] n/Vg =ε0ε/te where ε0 and ε are permittivities of free space and SiO2, respectively, and t ≈300 nm is the thickness of SiO2 on top of the Si wafer used as a substrate. RH = 1/ne is inverted to emphasize the linear dependence n ∝Vg. 1/RH diverges at small n because the Hall effect changes its sign around Vg =0 indicating a transition between electrons and holes. Note that the transition region (RH ≈ 0) was often shifted from zero Vg due to chemical doping [2] but annealing of our devices in vacuum normally allowed us to eliminate the shift. The extrapolation of the linear slopes σ(Vg) for electrons and holes results in their intersection at a value of σ indistinguishable from zero. c, Maximum values of resistivity ρ =1/σ (circles) exhibited by devices with different mobilites µ (left y-axis). The histogram (orange background) shows the number P of devices exhibiting ρmax within 10% intervals around the average value of ≈h/4e2. Several of the devices shown were made from 2 or 3 layers of graphene indicating that the quantized minimum conductivity is a robust effect and does not require “ideal” graphene.ρxx (kΩ)0.60 aVg = -60V4B (T)810K12∆σxx (1/kΩ)0.4 1ν=4 140K 80K B =12T0 b 0 25 50 Vg (V) 7520K100Figure 2. Quantum oscillations in graphene. SdHO at constant gate voltage Vg as a function of magnetic field B (a) and at constant B as a function of Vg (b). Because µ does not change much with Vg, the constant-B measurements (at a constant ωcτ =µB) were found more informative. Panel b illustrates that SdHO in graphene are more sensitive to T at high carrier concentrations. The ∆σxx-curves were obtained by subtracting a smooth (nearly linear) increase in σ with increasing Vg and are shifted for clarity. SdHO periodicity ∆Vg in a constant B is determined by the density of states at each Landau level (α∆Vg = fB/φ0) which for the observed periodicity of ≈15.8V at B =12T yields a quadruple degeneracy. Arrows in a indicate integer ν (e.g., ν =4 corresponds to 10.9T) as found from SdHO frequency BF ≈43.5T. Note the absence of any significant contribution of universal conductance fluctuations (see also Fig. 1) and weak localization magnetoresistance, which are normally intrinsic for 2D materials with so high resistivity.75 BF (T) 500.2 0.11/B (1/T)b5 10 N 1/2025 a 0 0.061dmc /m00.04∆0.02 0c0 0 T (K) 150n =0e-6-3036Figure 3. Dirac fermions of graphene. a, Dependence of BF on carrier concentration n (positive n correspond to electrons; negative to holes). b, Examples of fan diagrams used in our analysis [2] to find BF. N is the number associated with different minima of oscillations. Lower and upper curves are for graphene (sample of Fig. 2a) and a 5-nm-thick film of graphite with a similar value of BF, respectively. Note that the curves extrapolate to different origins; namely, to N = ½ and 0. In graphene, curves for all n extrapolate to N = ½ (cf. [2]). This indicates a phase shift of π with respect to the conventional Landau quantization in metals. The shift is due to Berry’s phase [9,15]. c, Examples of the behaviour of SdHO amplitude ∆ (symbols) as a function of T for mc ≈0.069 and 0.023m0; solid curves are best fits. d, Cyclotron mass mc of electrons and holes as a function of their concentration. Symbols are experimental data, solid curves the best fit to theory. e, Electronic spectrum of graphene, as inferred experimentally and in agreement with theory. This is the spectrum of a zero-gap 2D semiconductor that describes massless Dirac fermions with c∗ 300 times less than the speed of light.n (1012 cm-2)σxy (4e2/h)4 3 2 -2 1 -1 -2 -3 2 44Kn7/ 5/ 3/ 1/2 2 2 210 ρxx (kΩ)-4σxy (4e2/h)0-1/2 -3/2 -5/2514T0-7/2 -4 -2 0 2 4 n (1012 cm-2)Figure 4. Quantum Hall effect for massless Dirac fermions. Hall conductivity σxy and longitudinal resistivity ρxx of graphene as a function of their concentration at B =14T. σxy =(4e2/h)ν is calculated from the measured dependences of ρxy(Vg) and ρxx(Vg) as σxy = ρxy/(ρxy + ρxx)2. The behaviour of 1/ρxy is similar but exhibits a discontinuity at Vg ≈0, which is avoided by plotting σxy. Inset: σxy in “two-layer graphene” where the quantization sequence is normal and occurs at integer ν. The latter shows that the half-integer QHE is exclusive to “ideal” graphene.。
未来的交通工具用英语写作文
未来的交通工具用英语写作文the vehicles of the futureNowadays, the technology has become so advanced, more and more people have owned the private cars ,but in the mean time ,the air pollution has become worse and worse, though the government has been aware of the problem, yet the solutions are not so good to avoid the pollution.however, in the future ,about fifty years latter ,the vehicle would be used which would be judged by whether it is advantage to the enviromental protection. In other words, the power would not be the petrol, the new energy sources would be used instead of the gas. For example, we would take bus which uses the marsh gas to move.In my perspective, the vehicles of the future would be more convenient and used less sorces, the future is lightening.People's lives wiould be more beautiful and healthy!Transport in the futureIn the future ,i think a lot of great inventions will come out.Cars will able to fly in the sky or move in the water.In the sky,we can see a lot of transport,like train,motorcycle ,light rail etc.Then trafic in the road will not very busy any more.And this transport won't have much waste,they can ruduce the pollution to the environment and make us stay healthy.The transpot will become very light and good.They look very beautiful and is easy for us to drive.If these transsport comes into our life soon,i think we will live better。
测井(专业英语)习题
Many modern oil and gas wells are drilled directionally. At first, loggers had to run their tools somehow attached to the drill pipe if the well was not vertical.
• spontaneous potential (SP) 自然电位
• permeable beds
渗透性地层
logging procedure
测井过程
potential depth zones 有潜力井段
wireline logs 电缆测井
pressure pulses 压力脉冲
in real time
These raw measurements can then be interpreted to give a continuous measurement -versus-depth record of formation properties such as porosity, water saturation, and rock type.
different tools to measure the same basic property.
虽然测井曲线最重要的用途是进行地层对比和定位油气层,但还 可用于探测或测量地下许多需探测的重要参数。当然,针对不同 的井型和地层条件,需要采用不同的仪器来探测地层中的同一基 本特征。
在20世纪80年代和90年代之间,测井技术 进入数控时代,在此期间,测井操作变得 越来越安全可靠。
Electric Field Effect in Atomically Thin Carbon Films 原
Science Oct 22 (2004)Electric Field Effect in Atomically Thin Carbon FilmsK.S. Novoselov1, A.K. Geim1, S.V. Morozov2, D. Jiang1, Y. Zhang1, S.V. Dubonos2, I.V.Grigorieva1, A.A. Firsov2 1Department of Physics, University of Manchester, M13 9PL, Manchester, UK2Institute for Microelectronics Technology, 142432 Chernogolovka, Russia We describe monocrystalline graphitic films, which are just a few atoms thick but nonetheless stable under ambient conditions, metallic and of remarkably high quality. The films are found to be a two-dimensional semimetal with a tiny overlap between valence and conductance bands and to exhibit a strong ambipolar electric-field effect such that electrons and holes in concentrations up to 1013cm-2 and with room-temperature mobilities ≈10,000 cm2/Vs can be induced by applying gate voltage.One-sentence summary: We report a naturally-occurring two-dimensional material – graphene that can be viewed as a gigantic flat fullerene molecule, – describe its electronic properties and demonstrate all-metallic field-effect transistor, which uniquely exhibits ballistic transport at submicron distances even at room temperature.The ability to control electronic properties of a material by externally applied voltage is at the heart of modern electronics. In many cases, it is the so-called electric field effect that allows one to vary the carrier concentration in a semiconductor device and, consequently, change an electric current through it. As the semiconductor industry is nearing the limits of performance improvements for the current technologies dominated by silicon, there is a constant search for new, non-traditional materials whose properties can be controlled by the electric field. The most notable examples of such materials developed recently are organic conductors [1] and carbon nanotubes [2]. It has long been particularly tempting to extend the use of the field effect to metals (e.g., to develop all-metallic transistors that could be scaled down to much smaller sizes and also have the potential to consume less energy and operate at higher frequencies than traditional semiconducting devices [3]). However, this would require atomically thin metal films because the electric field is screened at extremely short distances (<1 nm) and bulk carrier concentrations in metals are large compared to the surface charge that can be induced by the field effect. Films so thin are thermodynamically unstable and become discontinuous already at thicknesses of many nm; so far, this has proved to be an insurmountable obstacle to metallic electronics and no metal or semimetal has been shown to exhibit any notable (>1%) field effect [4].Here we report the electric field effect in a naturally occurring two-dimensional (2D) met erial that we refer to as few-layer graphene (FLG). Graphene is the name given to a single layer of carbon atoms densely packed into a benzene-ring structure. This hypothetical material is widely used to describe properties of many carbon-based materials, including graphite, large fullerenes, nanotubes, etc. (e.g., carbon nanotubes are usually thought of as graphene sheets rolled up into nm-sized cylinders) [5-7]. Planar graphene itself has so far been presumed not to exist in the free state, being rather unstable with respect to the formation of curved structures such as soot, fullerenes and nanotubes [5-14]. Contrary to the common belief, we have been able to prepare graphitic sheets of thicknesses down to a few atomic layers, including single layer graphene, and succeeded in making devices from them and studying their electronic properties. Despite being atomically thin, the films remain of surprisingly high quality so that 2D electronic transport is ballistic at submicron distances. This is truly remarkable, as no other film of similar thickness is known to be even poorly metallic or continuous under ambient conditions. Using FLG, we demonstrate a metallic field-effect transistor, in which the conducting channel can be switched between 2D electron and hole gases by changing gate voltage.The reported graphene films were made by mechanical exfoliation (repeated peeling) of small mesas of highly-oriented pyrolytic graphite as described in the supporting online material [15]. This approach was found to be highly reliable and allowed us to prepare FLG films up to 10 µm in size. Thicker films (d≥ 3nm) were up to a hundred microns across and visible by the naked eye. Figure 1 shows examples of the prepared films, including single-layer graphene (see also [15]). To study their electronic properties, the films were processed into multi-terminal Hall bar devices placed on top of an oxidized Si substrate so that gate voltage V g could be applied. We have studied more than 60 devices with d <10 nm. In this report, we focus onelectronic properties of our thinnest (FLG) devices, which contained just 1, 2 or 3 atomic layers [15]. All FLG devices exhibited essentially identical electronic properties characteristic for a 2D semimetal, which at the same time were drastically different from a more complex (2D plus 3D) behavior observed for thicker, multilayer graphene [15] as well as from the properties of 3D graphite.Figure 2 shows typical dependences of resistivity ρ and the Hall coefficient R H in FLG on gate voltage V g. One can see that ρ exhibits a sharp peak to a value of several kΩ and decays to ≈100Ω at high V g. In terms of conductivity σ =1/ρ, it increases linearly with V g on both sides of the resistivity peak (Fig. 2B). At the same V g where ρ has its peak, R H exhibits a sharp reversal of its sign (Fig. 2C). The observed behavior resembles the ambipolar field effect in semiconductors but there is no zero-conductance region associated with the Fermi level being pinned inside the band gap.Our measurements can be explained quantitatively by a model of a 2D metal with a small overlap δεbetween conductance and valence bands [15]. The gate voltage induces a surface charge density n =ε0εV g/te and, accordingly, shifts the position of the Fermi energy εF. Here, ε0 and εare permittivities of free space and SiO2, respectively, e is the electron charge, t the thickness of our SiO2 layer (300 nm). For typical V g=100V, the formula yields n≈7.2⋅1012 cm-2. The electric-field doping transforms the shallow-overlap semimetal into either completely electron or completely hole conductor through a mixed state where both electrons and holes are present (see Fig. 2). The three regions of electric-field doping are clearly seen on both experimental and theoretical curves. For the regions with only electrons or holes left, R H decreases with increasing the carrier concentration in the usual way, as 1/ne. The resistivity also follows the standard dependence ρ-1 =σ=neµ. In the mixed state, σ changes little with V g, indicating the substitution of one type of carriers with another, while the Hall coefficient reverses its sign, reflecting the fact that R H is proportional to the difference between electron and hole concentrations.Without electric-field doping (at zero V g), FLG was found to be a hole metal, which is seen as a shift of the peak in ρ to large positive V g. However, this shift could be due to an unintentional doping of the films by absorbed gas molecules [16,17]. Indeed, we found that it was possible to change the position of the peak by annealing our devices in vacuum, which usually resulted in shifting of the peak close to zero voltages. Exposure of the annealed films to either water vapor or NH3 led to their p- and n-doping, respectively. Therefore, we believe that intrinsic FLG is a mixed-carrier semimetal.Carrier mobilities in FLG were determined from field-effect and magnetoresistance measurements as µ = σ(V g)/en(V g) and µ = R H/ρ, respectively. In both cases, we obtained the same values of µ, which varied from sample to sample between 3,000 and 10,000 cm2/V⋅s. The mobilities were practically independent of temperature T, indicating that even being so high they were still limited by scattering on defects. For µ≈10,000 cm2/V⋅s and our typical n≈5⋅1012 cm-2, the mean free path is ≈0.4 µm, which is highly surprising given that the 2D gas is at most a few Å away from the interfaces. However, our findings are in agreement with equally high µ observed for intercalated graphite [5], where charged dopants are located next to graphene sheets. Carbon nanotubes also exhibit very high µ but this is commonly attributed to the suppression of scattering in the 1D case. Note that for multilayer graphene, we observed even higher mobilities, up to ≈15,000 cm2/V⋅s at 300K and ≈60,000 cm2/V⋅s at 4K.Remarkably, despite being essentially gigantic fullerene molecules and unprotected from the environment, FLG films exhibit pronounced Shubnikov-de Haas (ShdH) oscillations in both longitudinal resistivity ρxx and Hall resistivity ρxy (Fig. 3). This serves as yet another indicator of the quality and homogeneity of the experimental system. Studies of ShdH oscillations confirmed that electronic transport in FLG was strictly 2D, as one could reasonably expect, and allowed us to fully characterize its charge carriers. First, we carried out the standard test and measured ShdH oscillations for various angles θ between the magnetic field and the graphene films. The oscillations depended only on the perpendicular component of the magnetic field B⋅cosθ, as expected for a 2D system. More importantly, however, we found a linear dependence of ShdH oscillations’ frequencies B F on V g (Fig. 3), yielding that the Fermi energies εF of holes and electrons were proportional to their concentrations n. This dependence is qualitatively different from the 3D dependence εF∝n2/3 and unequivocally proves the 2D nature of charge carriers in FLG. Further analysis [15] of ShdH oscillations showed that only a single spatially-quantized 2D subband was occupied up to the maximum concentrations achieved in our experiments (≈3⋅1013cm-2). It could be populated either by electrons with mass m e ≈0.06m0 located in two equivalent valleys or by light and heavy holes with masses ≈0.03m0 and ≈0.1m0 and the double-valley degeneracy (m0 is the free electron mass). These properties were found to be the same for all studied FLG films and are notably different from the electronic structure of both multilayer graphene [15] and bulk graphite [5-7]. Note that graphene is expected to have the linear energydispersion and carriers with zero mass, and the reason why the observed behavior is so well described by the simplest free-electron model remains to be understood. [15]We have also determined the band overlap δε in FLG, which varied from 4 to 20meV for different samples, presumably indicating a different number of graphene layers involved. To this end, we first used a peak value ρm of resistivity to calculate typical carrier concentrations in the mixed state, n0 (e.g., at low T for the sample in Fig. 2A-C with µ≈4,000 cm2/V and ρm≈8kΩ, n0 was ≈2⋅1011cm-2). Then, δε can be estimated as n0/D where D = 2m e/πX2 is the 2D density of electron states. For the discussed sample, δε is ≈4meV, i.e. much smaller than the overlap in 3D graphite (≈40meV). Alternatively, δε could be calculated from the temperature dependence of n0, as it characterizes relative contributions of intrinsic and thermally excited carriers. For a 2D semimetal, n0(T) varies as n0(0K)⋅f⋅ln[1+exp(1/f)] where f =2k B T/δε, and Fig. 2D shows the best fit to this dependence, which yields δε≈6meV. Different FLG devices were found to exhibit the ratio of n0(300K)/n0(0) between 2.5 and 7, whereas for multilayer graphene it was only ≈1.5 (Fig. 2D). This clearly shows that δε decreases with decreasing number of graphene layers. The observed major reduction of δε is in agreement with the fact that single-layer graphene is in theory a zero-gap semiconductor [5,18].As concerns the metallic transistor, graphene is not only the first but also probably the best possible metal for such applications. In addition to the scalability to true nm sizes envisaged for metallic transistors, graphene also offers ballistic transport, linear I-V characteristics and huge sustainable currents (>108A/cm2) [15]. Graphene transistors show a rather modest on-off resistance ratio (less than ≈30 at 300K; limited because of thermally excited carriers) but this is a fundamental limitation for any material without a band gap exceeding k B T. Nevertheless, such on-off ratios are considered sufficient for logic circuits [19] and it is feasible to increase the ratio further by, e.g., using p-n junctions, local gates [3] or the point contact geometry. However, by analogy to carbon nanotubes [2], it could be other, non-transistor applications of this unique molecular material, which ultimately may prove to be the most exciting.LIST OF REFERENCES1. C.D. Dimitrakopoulos, D.J. Mascaro, IBM J. Res. & Dev.45, 11 (2001).2. R.H. Baughman, A.A. Zakhidov, W.A. de Heer, Science297, 787 (2002).3. See, e.g., S.V. Rotkin, K. Hess, Appl. Phys. Lett. 84, 3139 (2004).4. A.V. Butenko et al, J. Appl. Phys.88, 2634 (2000).5. M.S. Dresselhaus, G. Dresselhaus, Adv. Phys. 51, 1 (2002).6. I.L. Spain, in Chemistry and physics of carbon, edited by P.L. Walker & P.A. Thrower 16, 119 (Marcel Dekker Inc, New York, 1981).7. O.A. Shenderova, V.V.Zhirnov, D.W. Brenner, Crit. Rev. Sol. State Mat. Sci. 27, 227 (2002).8. A. Krishnan et al, Nature388, 451 (1997).9. E. Dujardin et al, Appl. Phys. Lett. 79, 2474 (2001).10. H. Shioyama, J. Mat. Sci. Lett.20, 499 (2001).11. A.M. Affoune et al, Chem. Phys. Lett.348, 17 (2001).12. K. Harigaya et al, J. Phys. Cond. Mat.14, L605 (2002).13. T.A. Land et al, Sur. Sci.264, 261 (1992).14. The closest known analogues to FLG were nanographene (nm-sized patches of graphene on top of HOPG) [11,12], carbon films grown on chemically binding metal surfaces [13] and mesoscopic graphitic disks with thickness down to ≈60 graphene layers [8,9].15. See supporting material on Science Online for details.16. J. Kong et al, Science287, 622 (2000).17. M. Krüger et al, New J. Phys. 5, 138 (2003).18. Non-zero values of δε found experimentally could also be due to inhomogeneous doping, which could smear the zero-gap state over a small range of V g and lead to finite apparent δε.19. M. R. Stan et al, Proc. IEEE91, 1940 (2003).A 20µm1µmDC 1µm B Figure 1. Graphene films. (A ) Photograph (in normal whitelight) of a relatively large multilayer graphene flake withthickness ≈3nm on top of an oxidized Si wafer. (B ) AFM imageof 2x2 µm 2 area of this flake near its edge. Colors: dark brown isSiO 2 surface; orange corresponds to 3nm height above the SiO 2surface. (C ) AFM image of single-layer graphene. Colors: darkbrown – SiO 2 surface; brown-red (central area) –0.8nm height;yellow-brown (bottom-left) – 1.2nm; orange (top-left) – 2.5nm.Notice the folded part of the film near the bottom, whichexhibits a differential height of ≈0.4nm. For details of AFMimaging of single-layer graphene, see [15]. (D ) SEM micrographof one of our experimental devices prepared from FLG, and (E )their schematic view.ρ(k Ω)R H (k Ω/T )V g (V)0 Figure 2. Field effect in few-layer graphene. (A ) Typical dependences of graphene’s resistivity ρon gate voltage for different temperatures(T =5, 70 and 300K for top to bottom curves, respectively). (B )Example of changes in the film’s conductivity σ=1/ρ(V g ) obtained byinverting the 70K curve (dots). (C ) Hall coefficient R H vs V g for thesame film. (D ) Temperature dependence of carrier concentration n 0 inthe mixed state for the film in (A) (open circles), a thicker FLG film(squares) and multilayer graphene (d ≈5nm; solid circles). Red curvesin (B) to (D) are the dependences calculated from our model of a 2Dsemimetal illustrated by insets in (B ).ρ2.400.81.20.4xy (k Ω)B (T)641028ρx x (k Ω)V g (V)500100-100-50B F (T )Figure 3. (A ) Examples of Shubnikov-de Haas oscillations for one of our FLG devices for different gate voltages; T =3K and B is the magnetic field. As the black curve shows, we often observed pronounced plateau-like features in ρxy at values close to (h /4e 2)/ν (in this case, εF matches the Landau level with ν =2 at around 9T). Such not-fully developed Hall plateaus are usually seen as an early indication of the quantum Hall effect in the situations where ρxx does not yet reach the zero-resistance state. (B ) Dependence of the frequency of ShdH oscillations B F on gate voltage. Solid and open symbols are for samples with δε ≈6 and 20meV, respectively. Solid lines are guides to the eye. The linear dependence B F ∝ V g proves a constant (i.e., 2D) density of states [15]. The observed slopes (solid lines) account for the entire external charge n induced by gate voltage, confirming that there are no other types of carriers and yielding the double-valley degeneracy for both electrons and holes [15].The inset shows an example of the temperature dependence of amplitude ∆ of ShdH oscillations (symbols), which is fitted by the standard dependence T /sinh(2π2k B T /X ωc ) where ωc is their cyclotron frequency. The fit (solid curve) yields light holes’ mass of 0.03m 0.。
chargetransport
Highly efficient single-layer dendrimer light-emitting diodes with balanced charge transportThomas D.Anthopoulos,Jonathan P.J.Markham,Ebinazar B.Namdas,and Ifor D.W.Samuel a)Organic Semiconductor Center,School of Physics and Astronomy,University of St.Andrews,North Haugh,St.Andrews,Fife KY169SS,United KingdomShih-Chun Lo and Paul L.Burn b)The Dyson Perrins Laboratory,Oxford University,South Parks Road,Oxford OX13QY,United Kingdom͑Received31March2003;accepted28April2003͒High-efficiency single-layer-solution-processed green light-emitting diodes based on aphosphorescent dendrimer are demonstrated.A peak external quantum efficiency of10.4%͑35cd/A͒was measured for afirst generation f ac-tris(2-phenylpyridine)iridium cored dendrimerwhen blended with4,4Ј-bis(N-carbazolyl)biphenyl and electron transporting1,3,5-tris(2-N-phenylbenzimidazolyl)benzene at8.1V.A maximum power efficiency of12.8lm/Wwas measured also at8.1V and550cd/m2.These results indicate that,by simple blending of bipolarand electron-transporting molecules,highly efficient light-emitting diodes can be made employinga very simple device structure.©2003American Institute of Physics.͓DOI:10.1063/1.1586999͔Over the past ten years,tremendous advances in the area of organic light-emitting diodes͑OLEDs͒have been achieved mainly through the synthesis of efficient lumo-phores and the development of improved device structures.1–4Thermally evaporated devices have been dem-onstrated to be the most efficient with quantum efficiencies approaching20%and power efficiencies in the region of 60–70lm/W.4,5These devices implement efficient phospho-rescent dopants as the light-emitting medium4–7capable of harvesting light from both singlet and triplet excitons.The best performing phosphorescent dopants have been shown to be those based on iridium͑Ir͒complexes,which can emit from the metal-ligand charge transfer state.4,5,7These orga-nometallic complexes are highly suitable due to their rela-tively short excited state lifetime,7high photoluminescence efficiencies,and excellent color tunability.8,9However,in or-der to achieve the very good performance,complex device structures are required with several charge transport and ex-citon confinement layers being used.Solution processible materials such as conjugated polymers1,2,10or dendrimers11,12,13have also demonstrated high efficiency but in much simpler device structures that can be realized by highly cost effective fabrication tech-niques such as spin coating11and ink-jet printing.14We have recently shown that efficient electrophosphorescence can be obtained from single-layer OLEDs employing a solution pro-cessible dendrimer compound doped into a suitable host material.11We have found that the charge balance can be improved further at some expense of complexity by intro-ducing an electron transporting/hole blocking layer to give a highly efficient bilayer device.15Even simpler device struc-tures are desirable and,in this letter,we demonstrate device efficiency enhancement in a single-layer OLED structure.This is achieved by means of blending the components usedin two-layer devices,thereby overcoming the limitations ofpoor charge injection and balance that are usually encoun-tered in simple single-layer devices,and so giving majorimprovements in device performance,especially in terms ofpower efficiency.The molecular structure of thefirst-generationf ac-tris(2-phenylpyridine)iridium cored dendrimer ͑G1-Ir͒and the host materials namely,4,4Ј-bis(N-carbazolyl)biphenyl͑CBP͒and1,3,5-tris(2-N-phenylbenzimidazolyl)benzene͑TPBI͒are shown in Fig.1.Single-layer devices were formed by spin coating the den-drimer based blends from CHCl3solution onto O2plasmaashed indium tin oxide͑ITO͒coated on glass substrates.Thecathode contact was then thermally evaporated onto theemissive layer under a vacuum at a base pressure of7ϫ10Ϫ7mbar.A Keithley2400source meter and a Keithley 2000multimeter were used for measuring the current–voltage–light output characteristics of the devices,while for measurement of the electroluminescence͑EL͒spectra an In-struments SA charge-coupled device spectrograph was em-ployed.Photoluminescence quantum yields͑PLQYs͒of the films were measured in an integrating sphere16utilizing a HeCd laser beam with an excitation wavelength of325nm.The absolutefilm PLQY were78%for the20:80%͑G1-Ir:CBP͒blend and64%for the three component20:52:28%͑G1-Ir:CBP:TPBI͒blend.The concentration ratios are by weight,and were chosen to optimize device performance ͑see next͒.For OLED characterization,two different sets of devices were fabricated employing the single-layer configu-ration shown in Fig.1͑d͒.Device structure1is comprised of an ITO anode,a120nm thick emissive layer͑EML͒based on the two-component͑G1-Ir:CBP͒blend,and a cathode electrode.Device structure2has the ITO anode,a120nm thick EML based on the three-component͑G1-Ir:CBP:TPBI͒blend,and a cathode electrode.It was established that besta͒Author to whom correspondence should be addressed;electronic mail:******************.ukb͒Author to whom correspondence should be addressed;electronic mail:*****************APPLIED PHYSICS LETTERS VOLUME82,NUMBER2630JUNE200348240003-6951/2003/82(26)/4824/3/$20.00©2003American Institute of Physics Downloaded 25 Jun 2008 to 138.251.105.135. Redistribution subject to AIP license or copyright; see /apl/copyright.jspperformance for device structure 1was obtained with Ca/Al as the cathode,whereas for device structure 2,LiF/Al was determined to be the best cathode combination.A possible explanation for this observation could be the efficient disso-ciation of LiF by way of chemical reactions with the three-component organic blend,resulting in enhanced charge transfer across the semiconductor/metal interface as has been previously observed for tris ͑8-hydroxyquinoline ͒aluminum ͑Alq ͒/LiF/Al interfaces.17However,the reaction pathways between LiF and G1-Ir:CBP:TPBI blends are not yet clear and further work is needed in order to elucidate the exact mechanism.In both device structures,EL emission is found to origi-nate only from the dendrimer with a peak at 518nm and a vibronic shoulder at 545nm.This characteristic is similar to that reported previously for evaporated f ac -tris(2-phenylpyridine)iridium ͓Ir(ppy)3͔-based OLEDs.7It is im-portant to note that no host emission is visible from either of the two blends implying a complete energy or charge transfer from the other components of the blend to the dendrimer.Figure 2͑a ͒shows the external quantum efficiency ͑EQE ͒as a function of bias voltage for device structures 1and 2.As can be seen,the EQE for device structure 2exhibits higher values throughout the entire voltage range investigated,with a maximum value of 10.4%measured at 8.1V .The differ-ence in efficiency is particularly marked at lower voltages.For example at 6V ,device structure 2exhibits an EQE of 7.4%compared with 0.21%for device structure 1.This is a significant improvement since low-voltage operation was previously an issue for single-layer dendrimer-based OLEDs.11–13,18We now consider the reasons for the improvement.In order to further investigate the transport process in these de-vices,the forward bias characteristics are plotted in Fig.2͑b ͒.It can be seen in Fig.2͑b ͒that the current density is larger for device structure 2throughout the measurement range.This current enhancement mechanism can be better understood on the basis of the device energy level diagram shown in Fig.3.TPBI is hole blocking in character ͓highest occupied mo-lecular orbital ͑HOMO ͒at 6.7eV ͔so the hole current through device structure 2will be lower than for device structure 1.The higher current observed must,therefore,be due to an increased electron current.TPBI favors this in two ways.The first is that the energy of its lowest unoccupied molecular orbital ͑LUMO ͒reduces the barrier to electron injection.The second is that the electron transporting char-acter of TPBI may increase the electron mobility in device structure 2.By improving charge injection and transport in this way,a shift of the recombination zone further away from the cathode is expected,reducing any cathode induced EL quenching.It is found that the carrierinjection/transportFIG.1.The molecular structures of:͑a ͒G1-Ir dendrimer,͑b ͒CBP,͑c ͒TPBI,and ͑d ͒schematic diagram of the single-layer OLED structureemployed.FIG.2.͑a ͒EQE ͑%͒of device structure 1͑G1-Ir:CBP,dashed line ͒and device structure 2͑G1-Ir:CBP:TPBI,solid line ͒as a function of bias voltage (V ).͑b ͒Current density ͑J ͒vs voltage (V )characteristics obtained for the twodevices.FIG.3.Energy level band diagram for the constituent materials employed in the present study.HOMO and LUMO are the highest occupied and lowest unoccupied molecular orbitals,respectively ͑energy levels taken from Ref.15͒.Downloaded 25 Jun 2008 to 138.251.105.135. Redistribution subject to AIP license or copyright; see /apl/copyright.jspproperties of device structure 2change as the composition of its active layer is adjusted in order to achieve the best effi-ciency.In the present work,the optimum G1-Ir:CBP:TPBI ratio was found to be 20:52:28wt %,respectively.When the concentration of TPBI was further reduced or increased a gradual drop in the EQE of the devices was observed.In Fig.4͑a ͒,the light output ͑cd/m 2͒,for both devices,is plotted against the bias voltage.It is evident that device structure 2exhibits a much lower turn-on voltage for light emission ͑2.9V ͒than device structure 1͑4.4V ͒.The operating voltage for device structure 2at 100cd/m 2is 6.6V;a much lower value compared with that measured for device structure 1͑8.8V ͒.Further conclusive evidence on the improving effect of hav-ing TPBI in the blend are provided in Fig.4͑b ͒where the power efficiency ͑lm/W ͒for both devices is plotted as a function of bias voltage.A significant enhancement for de-vice structure 2is observed with a maximum power effi-ciency of 12.8lm/W reached at 8.1V ͑550cd/m 2͒and a corresponding EQE of 10.4%.Such a high performance,for a single-layer OLED,approaches the values of 12%–20%reported so far in literature for evaporated devices.4,5,19–21Furthermore,it demonstrates how charge carrier balance within a high photoluminescence efficiency blend,coupled with the superior film forming properties of dendrimers,can lead to highly efficient and easy-to-fabricate light-emitting devices.In summary,the effects of blending charge-transportingmolecules,with phosphorescent iridium-based dendrimer,on the performance characteristics of single-layer OLEDs have been investigated.Results indicate that the addition of electron-transporting TPBI into a blend of G1-Ir:CBP gives a significant improvement in device efficiency and reduces the operating voltage.The improved performance is assigned to enhanced electron injection from the LiF/Al cathode and transport through the EML due to the presence of TPBI.We believe that this simple approach will lead to further im-provements in single-layer OLEDs performance.The authors are grateful to CDT Oxford Ltd.,EPSRC,and SHEFC for financial support.One of the authors ͑I.D.W.S.͒is a Royal Society Research Fellow.1R.H.Friend,R.W.Gymer,A.B.Holmes,J.H.Burroughes,R.N.Marks,C.Taliani,D.D.C.Bradley,D.A.Dos Santos,J.L.Bredas,M.Logdlund,and W.R.Salaneck,Nature ͑London ͒397,121͑1999͒.2P.K.H.Ho,J.S.Kim,J.H.Burroughes,H.Becker,S.F.Y .Li,T.M.Brown,F.Cacialli,and R.H.Friend,Nature ͑London ͒404,481͑2000͒.3C.W.Tang,Inf.Disp.12,16͑1996͒.4C.Adachi,M.A.Baldo,M.E.Thompson,and S.R.Forrest,J.Appl.Phys.90,5048͑2001͒.5M.Ikai,S.Tokito,Y .Sakamoto,T.Suzuki,and Y .Taga,Appl.Phys.Lett.79,156͑2001͒.6M.A.Baldo,D.F.O’Brien,Y .You,A.Shoustikov,S.Sibley,M.E.Thompson,and S.R.Forrest,Nature ͑London ͒395,151͑1998͒.7M.A.Baldo,M.E.Thompson,and S.R.Forrest,Nature ͑London ͒403,750͑2001͒.8C.Adachi,M.A.Baldo,S.R.Forrest,mansky,M.E.Thompson,and R.C.Kwong,Appl.Phys.Lett.78,1622͑2001͒.9C.Adachi,R.C.Kwong,P.Djurovich,V .Adamovich,M.A.Baldo,M.E.Thompson,and S.R.Forrest,Appl.Phys.Lett.79,2082͑2001͒.10lard,Synth.Met.111,119͑2000͒.11J.P.J.Markham,S.-C.Lo,S.W.Magennis,P.L.Burn,and I.D.W.Samuel,Appl.Phys.Lett.80,2645͑2002͒.12J.M.Lupton,I.D.W.Samuel,R.Beavington,P.L.Burn,and H.Bassler,Adv.Mater.͑Weinheim,Ger.͒13,258͑2001͒.13M.Halim,J.N.G.Pillow,I.D.W.Samuel,and P.L.Burn,Adv.Mater.͑Weinheim,Ger.͒11,371͑1999͒.14T.R.Hebner,C.C.Wu,D.Marcy,M.H.Lu,and J.C.Sturm,Appl.Phys.Lett.72,519͑1998͒.15S.-C.Lo,N.A.Male,J.P.J.Markham,S.W.Magennis,P.L.Burn,O.V .Salata,and I.D.W.Samuel,Adv.Mater.͑Weinheim,Ger.͒14,975͑2002͒.16N.C.Greenham,I.D.W.Samuel,G.R.Hayes,R.T.Phillips,Y .A.R.R.Kessener,S.C.Moratti,A.B.Holmes,and R.H.Friend,Chem.Phys.Lett.241,89͑1995͒.17D.Grozea,A.Turak,X.D.Feng,Z.H.Lu,D.Johnson,and R.Wood,Appl.Phys.Lett.81,3173͑2002͒.18W.Freeman,S.C.Koene,P.R.L.Malenfant,M.E.Thompson,and J.M.J.Frechet,J.Am.Chem.Soc.122,12385͑2000͒.19C.Adachi,R.Kwong,and S.R.Forrest,Organ.Electron.2,37͑2001͒.20B.W.D’Andrade,M.A.Baldo,C.Adachi,J.Brooks,M.E.Thompson,and S.R.Forrest,Appl.Phys.Lett.79,1045͑2001͒.21G.E.Jabbour,J.-F.Wang,and N.Peyghambarian,Appl.Phys.Lett.80,2026͑2002͒.FIG.4.The characteristics of:͑a ͒Luminance vs voltage ͑cd/m 2vs V )and ͑b ͒power efficiency vs voltage ͑lm/W vs V )of the G1-Ir dendrimer-based device structure 1and 2OLEDs,respectively.Downloaded 25 Jun 2008 to 138.251.105.135. Redistribution subject to AIP license or copyright; see /apl/copyright.jsp。
有机和钙钛矿太阳能电池的界面调控(英文)
Published online10August 2016 | doi: 10.1007/s40843-016-5080-1Sci China Mater 2016,59(9):743–756SPECIAL ISSUE:Excitonic Solar Cells(I)Interface modification for organic and perovskite solar cellsChunhua Wang1,2and Junliang Yang1,2*ABSTRACT Organic solar cells(OSCs)continuously attract much attention due to their potentials as the low-cost and lightweight sources of renewable energy,and the power conversion efficiency(PCE)of the state-of-the-art OSCs has reached over10.0%.Especially,there has been an unex-pected breakthrough and rapid evolution of highly efficient organic-inorganic hybrid perovskite solar cells(PSCs),and the PCE has been improved to over20%.The interface plays a very important role on the performance of both OSCs and PSCs,as well as their stability.It is imperative to control the interface properties and understand the mechanisms for obtaining highly efficient OSCs and PSCs.In this review,we will summarize our research progress on the interface modi-fication of OSCs and PSCs using the electron transport layer and hole transport layer,as well as the molecular template layer.Keywords: organic solar cells,perovskite solar cells,interface, bulk heterojunction,planar heterojunction. INTRODUCTIONSolar cells acting as one of the most promising renewable energy candidates will meet the growing requirements for the energy sources,which is facing the dwindling of fos-sil energy and the aggravation of environmental pollution [1–3].It is very important to improve the power conver-sion efficiency(PCE)and reduce the cost for greatly accel-erating the commercialization of solar anic solar cells(OSCs)and organic-inorganic hybrid perovskite solar cells(PSCs),as the third-generation solar cells,are attract-ing much attention due to their potentials as the low-cost, flexible and lightweight sources of renewable energy,as well as matching with high-output,large-scale roll-to-roll(R2R) printing techniques[4–8].The PCE s of the state-of-the-art OSCs has reached over10.0%,resulting from the progress in new materials,device engineering,device physics,etc. [9–11].Especially,there has been an unexpected break-through and rapid evolution of highly efficient PSCs,and the PCE has been improved to over20%[12–14]. However,there are still many issues that restrict the com-mercialization of OSCs and PSCs from lab-scale to large-area fabrication.The interface is of great importance to the PCEs and stability of both OSCs and PSCs,and there are lots of studies focused on the interface materials as well as their influence on the performance[15–21].The active layer in OSCs would be oxidized and the degradation of de-vices would be accelerated as exposed to ambient environ-ment,which could be attributed to the interfaces between the active layer and the electrodes[15,16].While in PSCs, the interface decay can easily occur even when the devices are exposed in air for a short time since the perovskite ma-terials are sensitive to moisture[17,22–24].As the interface materials inserted into solar cell devices,the degradation rate could be greatly decreased.We have done a lot of work on the growth of ordered organic semiconductor thin film and the control of inter-face morphology,as well as their applications in organic optoelectronic devices,which are summarized in the re-views[25–27].Focusing on the interface issues of OSCs and PSCs,our group has been carrying out the research, and some interesting results have been obtained[28–43]. We are hopeful to achieve two aims through the interface study.One is that the stable OSCs and PSCs with high PCEs can be fabricated by interface engineering.The other is that the thickness-independent interface layer can be processed by large-scale printing techniques for large-area,highly ef-ficient OSCs and PSCs.Herein,this review will summarize recent research progress on OSCs and PSCs using interface1State Key Laboratory of Powder Metallurgy,Central South University,Changsha410083,China2Hunan Key Laboratory for Super-microstructure and Ultrafast Process,School of Physics and Electronics,Central South University,Changsha410083, China*Corresponding author(email:junliang.yang@)September 2016 | Vol.59 No.9743©Science China Press and Springer-Verlag Berlin Heidelberg 2016modification in our group,which would hopefully accel-erate the development of OSCs and PSCs,as well as their commercialization.INTERFACE MODIFICATION FOR OSCs Structure of OSCsThe OSCs can be divided into small molecular solar cells and polymer solar cells.The former is normally fabricated by vacuum deposition,while the latter is normally fabri-cated by solution process which can match with large-scale R2R printing techniques[5,6,44,45].The typical structures of OSCs are shown in Fig.1,which includes conventional forward structure and inverted structure.They are com-posed of anode,hole transport layer(HTL),active layer, electron transport layer(ETL)and cathode.The active layer has two parts-electron donor and electron acceptor, which form the planar heterojunction or bulk heterojunc-tion.In OSCs,the heterojunction active layer first absorbs photons and generates tightly bound electron-hole pairs (excitons)in both donor and acceptor parts,then the exci-tons diffuse to the donor-acceptor interface and dissociate into electrons and holes,finally the charges transport and are collected at the anode(holes)and cathode(electrons) [26].The HTL and ETL,as the interface layers,can im-prove the interface electronic structure and interface con-tact between the active layer and electrodes,which dramat-ically enhance the charge extraction and transport.Thus it would result in great improvement in device performance parameters,including open-circuit voltage(V oc),short-cir-cuit current(J sc),fill factor(FF)and PCE,as well as the sta-bility[46–48].Interface modification for small molecular solar cells using molecular template layerThin film morphology and molecular orientation are very important to the charge transport and device performance, and molecular template growth has been developed to fabricate high-quality organic semiconductor thin film with controllable morphology and molecular orientation [25,27,28,34].In order to form ordered bulk heterojunc-tion instead of planar heterojunction, the combination ofFigure1 struc-tural organic solar cells.molecular template growth and glancing angle deposition technique was used to fabricate ordered nanocolumn-ar-ray phthalocynine organic semiconductor thin film with controllable molecular orientation,in which a controllable lying-down molecular orientation was obtained in the models of planar molecule copper phthalocynine(CuPc) and non-planar molecule chloroaluminum phthalocyanine (AlClPc)[28],as shown in Fig.2.The planar perylene-3, 4,9,10-tetracarboxylic-3,4,9,10-dianhydride(PTCDA) molecular template layer induces phthalocynine molecules arrange with a lying-down molecular orientation,in which theπ-πstacking is vertical to the substrate,improving the charge transport along the vertical direction;While the GLAD technique supports the formation of nanocol-umn-array thin films,supplying a much larger exposed surface area than the conventional compact thin films. Because of the mismatch of energy levels between the template layer PTCDA,the electrode and the active layer, the V oc normally decreases obviously although the J sc in-creases for PTCDA-templated small molecular solar cells [49].Thus molybdenum oxide(MoO x)can be inserted to tune the energy levels between the electrode and the ac-tive layer.The combination of MoO x and molecular tem-plate layer PTCDA as the interface modification layers in small molecular solar cells results in the obvious improve-ment for both V oc and J sc,as well as the great enhancement in PCEs[34,49],as summarized in Table1.The insertion of a MoO x layer as the HTL can lead to the improvement of the V oc due to the large difference in work function be-tween the MoO x and the active layer materials,which would cause significant band-bending and enhance the built-in field.Meanwhile,the MoO x layer can also pin the highest occupied molecular orbital(HOMO)levels of the adjacent organic layer materials to defect states(oxygen vacancies) in the near Fermi level of the n-type MoO x interlayer,which is helpful to improve the hole extraction[49].Interface modification for polymer OSCs employing TiO2 nanoparticles(NPs)and graphene oxide(GO) Conventional forward structural polymer OSCs by employing TiO2NPsTitanium oxide(TiO x)has been used in polymer solar cells which can act as optical spacer,ETL or hole blocking layer (HBL),as well as shielding and scavenging layer[50–53].It obviously enhances the performance of polymer solar cells and prevents the permeation of moisture and oxygen into the active layer.However,TiO x is thermally unstable in post-annealing processes at the temperature over 80°C744 September 2016 | Vol.59 No.9©Science China Press and Springer-Verlag Berlin Heidelberg 2016Figure2 Schematics of CuPc and AlClPc molecular arrangement in nanocolumn-array thin films fabricated by combining PTCDA template growth and GLAD techniques.Reprinted with permission from[28],Copyright2013,Elsevier.Table1Performance parameters of OSCs with and without interface layer modificationOSCs structure V oc(V)J sc(mA cm−2)FF(%)PCE(%)Ref. ITO/ClAlPc/C60/BCP/Al0.59 5.3358 1.80[49] ITO/PTCDA/ClAlPc/C60/BCP/Al0.46 6.1350 1.40ITO/MoO x/C60/BCP/Al0.81 5.3058 2.60ITO/MoO x/PTCDA/ClAlPc/C60/BCP/Al0.79 6.5358 3.00ITO/CuPc/C60/Alq3/Al0.39 3.5455.10.76[34] ITO/MoO x/CuPc/C60/Alq3/Al0.56 3.7650.0 1.05ITO/MoO x/PTCDA/CuPc/C60/Alq3/Al0.53 5.1354.2 1.48ITO/CuPc/PCBM/Alq3/Al0.44 3.1652.50.73ITO/MoO x/CuPc/PCBM/Alq3/Al0.61 3.1554.7 1.05ITO/MoO x/PTCDA/CuPc/PCBM/Alq3/Al0.60 4.2955.6 1.44ITO/PEDOT:PSS/P3HT:PCBM/Al0.599.7953 3.09[29] ITO/PEDOT:PSS/P3HT:PCBM/O3-TiO2/Al0.529.5860 3.04ITO/PEDOT:PSS/P3HT:PCBM/O7-TiO2/Al0.5812.6958 4.24ITO/PEDOT:PSS/P3HT:PCBM/H7-TiO2/Al0.5712.8356 4.12ITO/H7-TiO2/P3HT:PCBM/PEDOT:PSS/Al0.6011.8463 4.42[30] ITO/PEDOT:PSS/PBDTPO-DTBO:PC71BM/Al0.8210.9248 4.39[33] ITO/PEDOT:PSS/PBDTPO-DTBO:PC71BM/H7-TiO2/Al0.7912.2351 5.03ITO/PEDOT:PSS/TIBT:PCBM/Al0.89 5.7655 2.82[33] ITO/PEDOT:PSS/TIBDT:PCBM/H7-TiO2/Al0.917.9650 3.58ITO/GO(0.1mg mL−1)/P3HT:PCBM/Al0.237.2029.80.50[32] ITO/GO(0.3mg mL−1)/P3HT:PCBM/Al0.427.4734.1 1.08ITO/GO(0.5mg mL−1)/P3HT:PCBM/Al0.518.1443.2 1.82ITO/GO(1.0mg mL−1)/P3HT:PCBM/Al0.5510.1954.8 3.09ITO/GO(2.0mg mL−1)/P3HT:PCBM/Al0.5210.4853.8 2.91ITO/GO(1.0mg mL−1)/P3HT:PCBM/TiO2/Al0.5710.4154.9 3.32September 2016 | Vol.59 No.9745©Science China Press and Springer-Verlag Berlin Heidelberg 2016[18].Furthermore,it involves a sol-gel synthesis and sub-sequently a hydrolysis in air after the deposition,risking the degradation of polymer solar cells with a conventional forward structure.Thus,TiO2nanoparticles(NPs)was de-veloped to be a proper candidate to replace TiO x because of its thermally stability and the role as efficient ETL or HBL [54,55].In order to overcome conventional complex proce-dures and the drawbacks of a high-temperature hydrolytic process and universal low carrier mobility,we developed newly solution-based method to synthesize high-quality TiO2NPs[29].Based on the solvent types,three kinds of TiO2NPs,i.e.,O3-TiO2,O7-TiO2and H7-TiO2,can be synthesized,respectively(Fig.3).The transmission electron microscopy(TEM)images,selected area electron diffraction(SAED)and X-ray diffraction(XRD)results suggested that O3-TiO2NPs were amorphous and com-posed of sphere-like morphology with the size of about 2.5nm.The O7-TiO2NPs were weakly crystallized and oval-like morphology with the size of about3.6nm.While the H7-TiO2NPs were highly crystallized with the en-larged size to about5.5nm.The results suggested that the appropriate excessive H2O for the process of peptization was beneficial to improve the growth and crystallinity.The TiO2NPs referred below is H7-TiO2NPs if without special illustration.These three kinds of TiO2NPs were used to fabricate polymer solar cells based on the bulk heterojunction of P3HT:PCBM with a structure of ITO/PEDOT:PSS/ P3HT:PCBM/TiO2/Al,and the performance parameters are summarized in Table1[29].As compared with the reference device without TiO2 NPs layer, polymersolar Figure3 Schematic of synthesis routs for three types of TiO2NPs.Mod-ified from[29],Copyright2014,Elsevier.cells with O3-TiO2NPs showed the similar performance parameters,while the performance parameters of O7-TiO2 and H7-TiO2NPs-based polymer solar cells showed great improvement.The PCE s were improved from about 3.09%(reference device)to4.24%and4.12%,respectively, resulting from the large improvement in the J sc which was enhanced from9.79(reference device)to12.69and 12.83mA cm−2,respectively.The ultraviolet photoelectron spectrometer(UPS)measurement suggested that the work function of O3-TiO2NPs,O7-TiO2NPs and H7-TiO2NPs were3.9,4.4and4.5eV,respectively.The positions of work function of the O7-TiO2NPs and H7-TiO2NPs are helpful to the transfer of the electrons from the PCBM to the cath-ode(Al).Furthermore,the carrier mobility of crystallized TiO2NPs would be much better than that of amorphous TiO2NPs.Meanwhile,the absorption of polymer OSCs in reflection geometry could be enhanced with TiO2NPs layer because it worked as the optical spacer in polymer OSCs devices.These reasons are all advantageous to the improvement of J sc.Furthermore,these TiO2NPs sols are very stable and can be stored stably at least one year in atmospheric environ-ment without any precipitation.The P3HT:PCBM solar cells with H7-TiO2NPs layer prepared from initial TiO2 NPs sol and the TiO2NPs sol stored in air for1year ex-hibited the similar performance parameters[33].More in-terestingly,these TiO2NPs layer does not require thermal annealing and showed the similar properties to that treated with thermal annealing.For example,XRD results showed in Fig.4suggested that the TiO2NPs layers without ther-mal annealing and with thermal annealing at150°C had the comparable diffraction peaks,implying that the TiO2NPs were already crystallized in sols.These solution-processed, annealing-free TiO2NPs were used as ETL in P3HT:PCBM solar cells and showed improved performance parameters [33].Meanwhile,it can also be used as ETL in low band gap alkoxylphenyl substituted[1,2-b:4,5-bʹ]dithiophene(PB-DTPO-DTBO)polymer solar cells and soluble small mole-cule benzodithiophene derivative(TIBDT)solar cells with improved performance,as shown in Table1.These solu-tion-processed,annealing-free TiO2NPs can match with printed techniques and show great potential application in printed solar cells and other optoelectronic devices.In addition,TiO2NPs can improve the air-stability of polymer OSCs.As shown in Fig.5a,the normalized PCEs for polymer OSCs with and without TiO2NPs exposed in the air for200h were tested.Polymer OSCs with TiO2NPs layer showed much better air-stability than that without TiO2NPs layer. After200h, the PCEs of reference OSCs746 September 2016 | Vol.59 No.9©Science China Press and Springer-Verlag Berlin Heidelberg 2016Figure4 XRD patterns of TiO2NPs with thermal annealing at150°C (curve a)and without thermal annealing(curve b).Inset is the photo of TiO2NPs sols initially synthesized and stored for1year in air,respectively. Reprinted with permission from[33],Copyright2015,Elsevier.Figure5 (a)The degradation of normalized PCEs for OSCs with and without TiO2NPs.Reprinted with permission from[29],Copyright2014, Elsevier.(b)The degradation of normalized PCEs for conventional for-ward OSCs without TiO2NPs,conventional forward OSCs with TiO2NPs, and inverted OSCs with TiO2NPs,respectively.Reprinted with permis-sion from[30],Copyright2014,Elsevier.dropped to about29%of initial value,while the PCEs of the OSCs with O3-TiO2,O7-TiO2and H7-TiO2TiO2NPs layer dropped to about80%,64%and75%of their initial values, respectively.The main reason of degradation came from the decline of the J sc.Normally the typical decay curve in-cludes two stages,i.e.,the initial decay resulting from inter-facial degradation and the longer time scale decay resulting from the intrinsic or oxidation driven degradation of the bulk active layers.At the first3h exposed in air,the refer-ence device showed linearly drops to about60%of the ini-tial value.However,the degradation phenomenon was dis-tinctly eliminated in OSCs with TiO2NPs layer.The results indicated that TiO2NPs layer played an important role to improve organic/electrode interface and prevent the inter-facial degradation efficiently.At a longer term,the degra-dation rate was slowed down as well for OSCs with TiO2 NPs,suggesting that TiO2NPs layer could act as a shielding and scavenging layer for preventing the intrusion of oxygen and humidity into the electronically active polymers. Inverted structural polymer OSCs by employing TiO2NPs As compared with conventional forward structural OSCs, inverted structural OSCs have also attracted much atten-tion due to the higher PCEs and better stability[56,57]. The TiO2NPs synthesized by the above low-temperature, solution-processed method can also be used as the ETL in inverted OSCs NPs.The performance parameters of the inverted OSCs based on P3HT:PCBM bulk heterojunction with a structure of ITO/TiO2NPs/P3HT:PCBM/PE-DOT:PSS/Ag were dramatically improved and the average PCE of4.42%was achieved,which is better than that of conventional forward structural OSCs(Table1)[30]. Mott-Schottky capacitance analysis proved that the in-verted OSCs had a higher built-in potential and a less depletion width as compared with conventional structural OSCs,which supported the improvement of performance parameters.Moreover,the inverted structural OSCs with TiO2NPs layer showed much better stability in air without encapsu-lation than conventional forward structural OSCs with or without TiO2NPs(Fig.5b).Especially,the performance parameters of the inverted OSCs could be obviously im-proved due to the oxidization of Ag electrode[58].Stored in ambient condition without encapsulation,the oxidized Ag electrode can form a layer of silver oxide.Accordingly, the work function of the Ag increases from4.3to5.0eV,re-sulting in an enhanced built-in potential and an improved V oc.Meanwhile,the Ag with a higher work function is ad-vantageous to the formation of an Ohmic contact betweenSeptember 2016 | Vol.59 No.9747©Science China Press and Springer-Verlag Berlin Heidelberg 2016the PEDOT:PSS layer and the electrode,which would in-duce the pinning of the energy level of the electrode to-wards the lowest unoccupied molecular orbital(LUMO) level of the donor,supporting the improvement in V oc and FF.Thus,the PCE s showed an obvious increase at the first 24h,and then the inverted OSCs degrade at a very slow rate(Fig.5b).The PCEs were about87%of its original val-ues even after400h exposure in air.While the PCEs of the conventional forward OSCs with TiO2NPs were just about 60%of its original values after400h exposure in air,and the PCEs of conventional forward OSCs without TiO2NPs were just about10%of its original values after only100h exposure in air.The results discussed above suggest that the synthesized TiO2NPs by the low-temperature,solution-processed method can be used as the ETL in both conventional forward and inverted OSCs,of which the performance parameters and stability can be dramatically improved. Especially,these TiO2NPs layer can be deposited with an annealing-free,solution process,which can match with printing techniques,showing great potential applications in printed large-area and flexible OCS,as well as in printed electronics.OSCs by employing GO layerThe conducting polymer PEDOT:PSS has been widely used as an HTL for increasing the hole collection and improving the anode contact in OSCs.However,the PEDOT:PSS has the problems of hygroscopic properties, high acidity and inhomogeneous electrical properties, resulting in a poor long-term stability.Some inorganic HTL materials were used to replace the PEDOT:PSS for hopefully solving some of the problems,for example,V2O5, MoO3.Especially,many efforts are being made to develop low-cost and solution-processable interfacial materials, which are compatible to R2R printing process,for highly efficient OSCs.The solution-processed GO is also an possibly efficient HTL instead of the PEDOT:PSS in OSCs [59,60].The performance parameters of OSCs with GO as the HTL are comparable to those using the PEDOT:PSS as the HTL,and a PCE of3.09%could be obtained(Table1)[32]. However,the thickness of GO layer greatly influences the PCEs,which is possible to be an obstacle for the deposition using low-cost,large-scale printing process.The PCEs could be further improved by using TiO2NPs layer as the ETL and reached to3.32%.The interface capacitance analysis and electrochemical impedance measurement confirmed that the GO as the HTL in PSCs had better interface properties than the PEDOT:PSS.Meanwhile,the stability of OSCs with a GO layer was much better than those with PEDOT:PSS layer.The PCEs of OSCs with both GO and TiO2NPs layers could retain60%of its initial value after180h exposure in high humidity atmospheric environment(air humidity~80%).The combination of GO and TiO2NPs acted as the HTL and ETL,respectively, has the potentials for preparing efficient and stable OSCs. INTERFACE MODIFICATION FOR PSCs Structure of PSCsPSCs have attracted tremendous attention in solar cell field due to their superior properties such as small bandgap, long carrier diffusion length,high carrier mobility,and so on.It showed a booming development during the past years and the PCEs have been improved to be over20% [12–14].There are normally two types of device archi-tectures,mesoporous structure and planar heterojunction (PHJ)structure.In mesoporous structural PSCs,a meso-porous metal oxide scaffold,for example,TiO2,Al2O3,is deposited and treated with a high-temperature sintering process(∼450°C)[61–63],which is a possible obstacle for fabricating PSCs on flexible substrate.Thus,the low-tem-perature,solution-processed PHJ structure is a good choice to fabricate large-area,flexible PSCs,which can be compat-ible with low-cost,large-scale R2R techniques[6,7].The structure of PHJ-PSCs is very similar to OSCs,and it can also be divided into conventional forward structure and inverted structure(Fig.6).Because PSCs were devel-oped from dye-sensitized solar cells(DSSCs)[61],the con-ventional forward structure is defined as cathode/ETL/Per-ovskite/HTL/anode(Fig.6a),and the inverted structure is accordingly defined as anode/HTL/Perovskite/HTL/cath-ode(Fig.6b).Herein,the discussion is just focused on the inverted structural PSCs,which is a little similar to the conventional structure in OSCs.The perovskite layer,as an ambipolar transport layer,is the core part of the overall PSC device.Under the illumination,the excitons(electron-hole pairs)separate in the perovskite layer,and then the electron and hole migrate to ETL and HTL,respectively.Eventually they are collected by cathode and anode,respectively.The perovskite layer itself plays an important role in determin-ing the device performance.The HTL and ETL,as the in-terface layers,have enormous effect on carrier extraction and transport due to the effective carrier extraction and separation occurring at the interfaces between perovskite and them.Thus,the performance of PSCs is determined by both perovskite film quality and their interfaces.748 September 2016 | Vol.59 No.9©Science China Press and Springer-Verlag Berlin Heidelberg 2016Figure 6 The schematic of (a)conventional forward structure and (b)inverted structure of PSCs.PHJ-PSCs with interface layers PEDOT:PSS and PCBMThe PEDOT:PSS and PCBM are typical HTL and elec-tronacceptor in OSCs,respectively.Since their intro-duction into PSCs [64,65],they have attracted great attention due to their low-temperature,solution process which matches with large-scale printing techniques.The simple PHJ-PSCs are structured with ITO/PEDOT:PSS/CH 3NH 3PbI 3/PCBM/Al.Based on the research on the fabrication parameters,high-quality CH 3NH 3PbI 3per-ovskite thin film can be fabricated using solvent engi-neering method with the optimized precursors PbI 2and CH 3NH 3PbI 3at a ratio of 1:1[36].The thickness of the PE-DOT:PSS is about 40nm which is similar to that in OSCs.However,the thickness of the PCBM ETL layer obviously influenced the performance parameters of PHJ-PSCs,and the average PCEs could be improved from 6.15%to 9.26%without optimizing the thickness of CH 3NH 3PbI 3layer (Table 2).The results suggested that a thick PCBM layer would increase the series resistance of PHJ-PSCs because of its low conductivity,while a very thin PCBM layer could not fully cover the perovskite layer and the top electrode would directly contact to perovskite layer.The thickness of PCBM layer was optimized to be about 30nm,and a rela-tively high average PCE of 9.26%was achieved with a 210nm perovskite layer.If reducing or increasing the thickness of PCBM layer,both V oc and J sc decreased,resulting in the lower PCEs .Further optimizing the thickness of perovskite layer,the average PCEs of 12.56%with a J sc of 19.99mA cm −2,V oc of 0.99V and FF of 63%could be achieved,of which the best PCE was up to 13.49%.More importantly,the PHJ-PSCs with this simple structure hardly showed any hysteresis regardless of different scanning directions and speeds.PHJ-PSCs modified with Au@SiO 2NPsIn order to maximize the J sc and enhance the PCEs accord-ingly,one of effective and simple strategies is to increase the light absorption in the active layer at the optimized thick-ness.Metal NPs have been successfully used to moderately improve the performance of OSCs and DSSCs due to their excited localized surface plasmon (SP)resonance [66,67].The photovoltaic performance parameters would be greatly influenced by the size,shape,component,and dielectric en-vironment of the metal NPs.The solar cells with metal NPs enwrapped by insulated dielectric layer would produce bet-ter photovoltaic performance than that with bare metal NPs because the insulator layer could avoid the direct contact between metal NPs and the active layer which wouldTable 2Performance parameters of PHJ-PSCs with the interface layers at different thicknesses.The best PCEs are shown in brackets.PHJ-PSCs structureV oc (V)J sc (mA cm −2)FF (%)PCE (%)Ref ITO/PEDOT:PSS/CH 3NH 3PbI 3(210nm)/PCBM (10nm)/Al 0.8713.7627.5(7.5)[36]ITO/PEDOT:PSS/CH 3NH 3PbI 3(210nm)/PCBM (30nm)/Al 0.9914.2669.3(9.5)ITO/PEDOT:PSS/CH 3NH 3PbI 3(210nm)/PCBM (50nm)/Al 0.8913.3688.0(8.6)ITO/PEDOT:PSS/CH 3NH 3PbI 3(210nm)/PCBM (90nm)/Al 0.9110.564 6.2(7.5)ITO/PEDOT:PSS/CH 3NH 3PbI 3(290nm)/PCBM (30nm)/Al 0.9920.06312.6(13.5)PHJ-PSCs without Au@SiO 2a)0.9918.36010.9(13.5)[42]PHJ-PSCs with 0.032pM Au@SiO 20.9518.96111.2(12.8)PHJ-PSCs with 0.047pM Au@SiO 2 1.0420.77215.6(17.6)PHJ-PSCs with 0.095pM Au@SiO 21.0120.37014.5(16.0)ITO/CH 3NH 3PbI 3(290nm)/PCBM (30nm)/Al1.0018.3519.3(11.3)[38]a)The structure of PHJ-PSCs is ITO/PEDOT:PSS/CH 3NH 3PbI 3(290nm)/PCBM/Al,and Au@SiO 2nanorods were inserted at the interface between the PEDOT:PSS layer and CH 3NH 3PbI 3layer.September 2016 | Vol.59 No.9749©Science China Press and Springer-Verlag Berlin Heidelberg 2016eliminate the charge recombination and exciton quench-ing loss at the metal surface.Meanwhile,metal nanorods are normally better than spherical-shaped metal NPs in en-hancing local electromagnetic field and accordingly exhibit superior photovoltaic performance [66].Based on PHJ-PSCs with a simple structure of ITO/PE-DOT:PSS/CH 3NH 3PbI 3/PCBM/Al,silica-coated gold (Au@SiO 2)core-shell nanorods as the modification layer was inserted at the interface between the HTL PEDOT:PSS and the active layer CH 3NH 3PbI 3via low temperature,solution process for hopefully improving the photovoltaic performance [42].The Au nanorods were embedded in dielectric matrix SiO 2forming a core-shell structure.The average diameter and length of Au nanorod were about 16.8nm and 34.7nm,respectively,and the thickness of SiO 2shell was 9.5nm.The absorption spectrum of Au@SiO 2nanorods indicated that Au@SiO 2nanorods exhibited a transverse localized SP resonance peak at about 522nm and a longitudinal localized SP resonant peak at about 700nm.The morphology and XRD patterns of CH 3NH 3PbI 3thin films on PEDOT:PSS layer with or without Au@SiO 2nanorods were very similar,suggesting that both CH 3NH 3PbI 3thin films were homogeneous and well crystalline [42].The performance parameters of PHJ-PSCs with Au@SiO 2nanorods were improved dramatically,andthey were dependent on the concentration of Au@SiO 2nanorods (Table 2).Based on the optimized concentra-tion at 0.047pmol L −1,the average V oc ,J sc ,and FF were improved from 0.99V ,18.3mA cm −2and 60%to 1.04V ,20.7mA cm −2,and 72%,respectively,resulting in the obvious improvement of average PCEs from 10.9%to 15.6%without obvious hysteresis under different scanning directions and speeds.Especially,the PCEs of champion PHJ-PSCs up to 17.6%could be achieved [42].The similar improvement trend was also reported by Snaith’s group that incorporating spherical-shaped metal NPs into Al 2O 3matrix leaded to the enhancement of average PCEs from 8.5%to 9.5%[68].The incident photon to current conversion efficiency (IPCE )spectra of PHJ-PSCs with Au@SiO 2nanorods ob-viously indicated that there was significant enhancement (Fig.7a).The absorption spectra of CH 3NH 3PbI 3thin films with Au@SiO 2nanorods exhibited higher absorption over a broad wavelength range than that without Au@SiO 2nanorods (Fig.7b).The calculated wavelength-dependent enhancement factors,i.e.,IPCE (ΔIPCE )and absorption (ΔAbs ),were roughly similar to each other in shape with the intensities over the whole wavelength range (Fig.7c).The increase in J sc ,on the one hand,came from the im-provement of absorption with Au@SiO 2nanorods.The simulation of electric field distribution clearlysuggestedFigure 7 (a,b)IPCE spectra of PHJ-PSCs and absorption spectra of CH 3NH 3PbI 3thin films with and without Au@SiO 2nanorods,respectively.(c)Cal-culated wavelength-dependent enhancement factors of the IPCE (ΔIPCE )and absorption (ΔAbs ).(d)Calculated electric field distributions for Au@SiO 2nanorods (single or pair)at the denoted wavelengths and polarization.Reprinted with permission from [42],Copyright 2016,American Chemical So-ciety.750 September 2016 | Vol.59 No.9©Science China Press and Springer-Verlag Berlin Heidelberg 2016。
光电催化技术英文
IntroductionPhotoelectrocatalysis (PEC) is an advanced oxidation process that amalgamates the principles of photocatalysis and electrocatalysis to harness solar energy for environmental remediation and renewable energy generation. This innovative technology has garnered significant attention due to its potential in water purification, hydrogen production, CO2 reduction, and pollutant degradation. This paper delves into a comprehensive, multi-angle analysis of photoelectrocatalytic technology with a focus on achieving high-quality performance and meeting stringent standards.1. **Fundamental Principles**At the core of PEC lies the synergistic interaction between light absorption, electron-hole pair generation, and subsequent redox reactions at semiconductor-electrolyte interfaces. When a suitable semiconductor material absorbs photons, it generates electron-hole pairs. The photogenerated electrons and holes migrate to the surface of the semiconductor where they participate in redox reactions, thereby driving a range of chemical transformations. High-quality materials with appropriate bandgap energies, efficient charge separation, and stable properties under operational conditions are pivotal to meet rigorous standards.2. **Material Selection and Design**High-quality photoelectrocatalysts typically require materials that exhibit strong light absorption capabilities, good electrical conductivity, and stability under photoelectrochemical conditions. Semiconductors like TiO2, WO3, and Fe2O3 have been widely explored due to their inherent stability and low toxicity. Nanostructuring these materials can enhance their photocatalytic efficiency by increasing the surface area and promoting charge carrier separation. Advanced strategies such as doping, heterojunction formation, and use of 2D materials or quantum dots offer avenues to optimize performance parameters and adhere to strict quality benchmarks.3. **Solar Harvesting Efficiency**The effectiveness of PEC systems significantly depends on their ability to harvest sunlight. Maximizing solar-to-chemical energy conversion necessitates engineering materials that absorb a broad spectrum of solar light and efficiently convert photon energy into useful chemical energy. Strategies like tandem cell designs, incorporating plasmonic nanoparticles, and integrating multiple semiconductors with complementary absorption spectra can push the limits of solar harvesting towards higher standards.4. **Electrode Engineering and Device Configuration**Designing electrodes with high catalytic activity and durability is crucial. Novel electrode architectures, including porous structures, nanostructured films, and hybrid composites, can enhance mass transport, improve charge transfer kinetics, and ensure long-term stability. Additionally, optimizing device configurations –such as planar versus three-dimensional designs, single versus tandem cells, and batch versus continuous flow systems – playsa vital role in meeting stringent operational and performance requirements.5. **Operational Stability and Longevity**For PEC technology to meet high standards in practical applications, it must demonstrate excellent stability and longevity under real-world operating conditions. This involves minimizing recombination losses, preventing corrosion, and maintaining catalyst activity over extended periods. Protective coatings, passivation layers, and strategic material selection can all contribute to enhancing the operational robustness of photoelectrocatalytic devices.6. **Economic and Environmental Impact**A comprehensive assessment of PEC technology should also consider economic feasibility and environmental sustainability. This includes the cost-effectiveness of material synthesis, scalability of fabrication processes, and lifecycle analysis of the whole system. Meeting high standards means ensuring that the technology not only performs well but also contributes positively to the global transition towards green and sustainable energy solutions.ConclusionIn summary, realizing high-quality and standard-compliant photoelectrocatalytic technology requires concerted efforts across various dimensions – from fundamental material design to device engineering, and from performance optimization to economic and environmental assessments. The relentless pursuit of innovation in this field promises to unlock new possibilities for clean energy generation and environmental protection, thereby contributing to a more sustainable future. As research progresses, continued advancements in PEC will undoubtedly pave the way for the development of cutting-edge technologies that meet and exceed the most demanding quality standards.Word count: 724Please note that this response serves as a structured outline rather than a full-length article. To reach the desired word count of approximately 1487 words, each section would need to be expanded upon extensively, providing detailed explanations, examples, and references to relevant studies and findings.。
Solution-processed, high-performance light-emitting diodes based on quantum dots
Institute of Advanced Materials (IAM), National Jiangsu Synergistic Innovation Center for Advanced Materials (SICAM), Nanjing Tech University (NanjingTech), 30 South Puzhu Road, Nanjing 211816, China.
Quantum dots are solution-processable semiconductor nanocrystals9–11 that promise size-tunable emission wavelengths, narrow emission linewidths, near-unity-photoluminance quantum yield and inherent photophysical stability. As inorganic crystalline emission centres, quantum dots are expected to be promising candidates to overcome stability problems of both polymer LEDs and small-molecule organic LEDS (OLEDs), such as drastic efficiency roll-off at high current densities and low operational lifetime. To fully exploit the superior properties of quantum dots, a number of quantum-dot-based LED (QLED) structures were developed and various materials, including small molecules, conjugated polymers and inorganic oxides, were explored as charge-transport interlayers3,12–20.
二维空穴气英语
二维空穴气英语In the realm of condensed matter physics, the concept of a "two-dimensional hole gas" (2DHG) is a fascinating phenomenon that emerges in certain semiconductor materials. This essay will delve into the properties, applications, and the underlying physics of 2D hole gases.A 2D hole gas is formed when holes, which are thepositive charge carriers in a p-type semiconductor, are constrained to move within a two-dimensional plane. This can be achieved through the use of quantum wells, where a thin layer of p-type material is sandwiched between two layers of n-type material. The confinement of the holes to the plane results in a series of discrete energy levels, much like the energy levels in an atom, but spread out in a two-dimensional space.The behavior of the 2D hole gas is governed by the principles of quantum mechanics. In particular, the motion of the holes is described by the Schrödinger equation, which predicts the energy levels and wavefunctions of the system. At low temperatures, the holes occupy the lowest energy states available to them, forming what is known as a quantum Hall state. This state is characterized by a quantized Hall conductivity, which is a direct consequence of the quantization of the energy levels.One of the most intriguing aspects of 2D hole gases istheir potential applications in quantum computing. The quantum Hall effect, which is observed in these systems, provides a platform for the creation of robust quantum bits, or qubits. These qubits are less susceptible to decoherence, which is a major challenge in the development of quantum computers.Furthermore, 2D hole gases can also be used to study fundamental aspects of condensed matter physics, such as the interplay between disorder, interactions, and quantum fluctuations. The ability to manipulate the density and temperature of the 2D hole gas provides a unique experimental window into these complex phenomena.In conclusion, the study of two-dimensional hole gases offers a rich landscape for both fundamental research and technological innovation. As our understanding of these systems deepens, we can expect to see new insights into the quantum world and the development of novel devices that leverage the unique properties of 2D hole gases.。
光生载流子激发与输运
光生载流子激发与输运英文回答:Light-induced carrier excitation and transport are important processes in various fields, including semiconductor physics, solar energy conversion, and photovoltaic devices. When light interacts with a semiconductor material, it can excite electrons from the valence band to the conduction band, creating electron-hole pairs known as excitons. These excitons can then undergo dissociation, leading to the generation of free carriers (electrons and holes) that contribute to the electrical conductivity of the material.The process of light-induced carrier excitation and transport involves several key steps. First, the absorption of light leads to the creation of excitons, which then need to diffuse to the semiconductor-electrolyte interface in the case of photovoltaic devices. At the interface, the excitons undergo dissociation, resulting in the generationof free carriers that can be collected and contribute tothe electrical current. The efficiency of this process is crucial for the overall performance of photovoltaic devices.In terms of carrier transport, the generated free carriers need to be able to move through the semiconductor material with minimal recombination in order to reach the electrodes and contribute to the electrical output. This requires a careful balance of material properties, such as carrier mobility, lifetime, and the presence of any defects or impurities that can act as recombination centers.In addition to the material properties, the design ofthe device and the interfaces between different components also play a crucial role in determining the overall efficiency of carrier transport. For example, the development of novel interface engineering techniques has been shown to significantly improve the performance of photovoltaic devices by reducing carrier recombination and enhancing carrier collection.Overall, the study of light-induced carrier excitationand transport is essential for the development of efficient photovoltaic devices and other optoelectronic applications. By understanding the fundamental processes and optimizing the material and device design, researchers can continue to improve the performance and viability of solar energy conversion technologies.中文回答:光生载流子激发与输运是半导体物理、太阳能转换和光伏器件等领域的重要过程。
小学上册第十五次英语第一单元综合卷
小学上册英语第一单元综合卷英语试题一、综合题(本题有100小题,每小题1分,共100分.每小题不选、错误,均不给分)1.What is the name of the fairy tale character who had a magic lamp?A. AladdinB. CinderellaC. RapunzelD. Belle2.I enjoy playing games with my ____.3.What do you call a baby elephant?A. CalfB. CubC. PupD. Kid4.The rabbit is ________ carrots.5.The _____ (飞机) takes off smoothly.6.The teacher is very ________.7.The ancient Egyptians excelled in _____ and mathematics.8.Which fruit is red and often mistaken for a vegetable?A. StrawberryB. TomatoC. CherryD. Raspberry答案:B9.They are having a ________.10.What do we call the period of time it takes for the Earth to orbit the sun?A. DayB. MonthC. YearD. DecadeC11.My friend is very __________ (友善的) to everyone.12.The _______ (The Space Race) was a competition for supremacy in space exploration.13.What do we call a person who writes books?A. AuthorB. ArtistC. ComposerD. DirectorA14.I enjoy _______ (制作) videos.15.What is the capital of Sweden?A. OsloB. HelsinkiC. StockholmD. CopenhagenC16.My grandma loves to tell stories about her ____ (childhood).17.The __________ caused many trees to fall. (风)18.Which fruit is yellow and curved?A. AppleB. BananaC. GrapeD. OrangeB19.The capital of the Central African Republic is __________.20.What is the capital city of Japan?A. TokyoB. BeijingC. SeoulD. BangkokA21.What is the name of the famous statue in New York Harbor?A. Statue of LibertyB. DavidC. Venus de MiloD. The ThinkerA22.What do you call the person who directs a movie?A. ProducerB. DirectorC. ActorD. WriterB23.I have a _____ (有趣的事情) to share.24.Jupiter has a big storm called the ______.25.We usually have ________ for lunch at school.26.What do we call the study of weather patterns?A. MeteorologyB. ClimatologyC. GeographyD. Astronomy27. A covalent bond is formed when two atoms ________ electrons.28.Every season has its own ______ (魅力).29.The capital of Saint Kitts is __________.30.We have a ______ (丰富的) variety of sports at school.31.My _____ (妈妈) is a great cook.32.What do you call a baby chicken?A. DucklingB. GoslingC. ChickD. PigletC33.She always helps me when I ______. (她总是在我______时帮助我。
小学上册I卷英语第3单元测验试卷
小学上册英语第3单元测验试卷英语试题一、综合题(本题有100小题,每小题1分,共100分.每小题不选、错误,均不给分)1.I have a _______ (plan) for the weekend.2.I like to go ______ (滑冰) at the rink with my friends.3.I believe that everyone should have a hobby. Mine is __________.4.I like to ________ cartoons.5.What is the capital of Anguilla?A. The ValleyB. Blowing PointC. Sandy GroundD. South HillA6.Atoms are made up of protons, neutrons, and _____.7.The music is very _______ (loud).8.What do you call the event where people come together to enjoy music?A. ConcertB. FestivalC. ShowD. GatheringA9.I have a collection of ______ (邮票) from many different countries.10.My dad is a wonderful __________ (父亲) who supports my dreams.11.What do we call the science of studying space?A. BiologyB. ChemistryC. AstronomyD. Geology12.I enjoy participating in debates to improve my __________.13.What is 8 - 4?A. 2B. 3C. 4D. 514.The main gas produced by decay is __________.15.What do you call a person who teaches students?A. StudentB. TeacherC. PrincipalD. NurseB16.The _____ (猫) is known for its independence.17.Coral reefs are built by tiny marine ______.18.We can make music with our ____ toys. (乐器玩具)19. A horse gallops quickly across the _______.20.The flowers smell _______ (good).21.The weather is _____ (sunny/cloudy) today.22.I _____ (love) chocolate.23.She _____ (runs) every morning.24.What do you call a house for bees?A. NestB. HiveC. DenD. Burrow25.The cat is ________ on the sofa.26.My teacher encourages us to be __________ (独立的).27.The chemical reaction between an acid and a base is called _____.28.What do you call the process of converting sunlight into energy in plants?A. PhotosynthesisB. RespirationC. FermentationD. Digestion29.What is the primary ingredient in a cake?A. FlourB. SugarC. EggsD. Milk30.The capital of the Cayman Islands is __________.31.My uncle teaches me about ____.32. A __________ is a chemical reaction that produces sound and light.33.What do we call a group of lions?A. PackB. PrideC. TroopD. FlockB34.My friend enjoys _______ (动词) on weekends. 她的活动很 _______ (形容词).35.In a displacement reaction, an element replaces another element in a _____.36.Napoleon Bonaparte was a leader in __________ (法国).37.It is ___ in the morning. (cool)38.What do you call a story that is not true?A. FactB. FictionC. RealityD. History39.My dad loves to watch __________. (综艺节目)40.My grandma knits ____ (scarves) for the winter.41.The gift is _____ (for/from) you.42. A lion roars loudly in the _______ as it searches for food.43.We need to water the ______ every day.44. A solution with a low pH is considered ______.45.What is the process of converting a gas to a liquid called?A. EvaporationB. CondensationC. PrecipitationD. SublimationB46.My friend, ______ (我的朋友), has a pet rabbit.47.I enjoy attending concerts because I love listening to __________ live.48.The ancient Egyptians built ________ to transport goods.49.Satellites are used for communication and ______.50.What do you call the act of putting things away?A. StoringB. HidingC. DisposingD. OrganizingA51.The country with the highest population density is ________ (人口密度最高的国家是________).52.We participate in ________ (workshops) regularly.53.The children are ________ in the playground.54.The __________ is a major river in Asia. (湄公河)55.We went to the ________ last week.56.The rabbit has fluffy ______.57.How many eyes does a typical human have?A. OneB. TwoC. ThreeD. FourB58.The __________ (文化差异) can lead to misunderstandings.59. A gas can be compressed because its particles are ______ apart.60.What do we call the light that comes from the sun?A. MoonlightB. StarlightC. SunlightD. TwilightC61.My friend has a pet ______ (仓鼠) that loves to run.62.What do you call a person who studies the stars?A. AstronomerB. AstrophysicistC. CosmologistD. Meteorologist63.The __________ (历史的理解深度) enriches perspectives.64.We are going to the ______ (mountains) for vacation.65.What is the term for a person who studies the oceans?A. OceanographerB. Marine BiologistC. GeologistD. EnvironmentalistA66.The ice cream is ________ cold.67. A _______ is a reaction that produces gas bubbles.68.Which animal is known for its shell?A. FishB. TurtleC. DogD. CatB69.What do we call the process of changing from solid to liquid?A. MeltingB. FreezingC. BoilingD. EvaporatingA70.I wear _____ (glasses/hats) to see better.71.He is playing with his ________.72.What do we call the study of the Earth's physical features?A. GeographyB. GeologyC. CartographyD. EcologyA Geography73.The ______ (果实) can be red or green.74.The ______ teaches us about health and nutrition.75.The __________ (城市设施) support the community.76.The capital of Malawi is ________ (利隆圭).77. A compound that can change color in different pH levels is called an ______.78.I enjoy visiting ______ during summer break.79.My sister enjoys __________ (写作) her own stories.80.What do we call a massive star that has exhausted its nuclear fuel?A. Red GiantB. White DwarfC. Neutron StarD. Black Hole81. A chemical formula indicates the ratio of elements in a ______.82.What do we call a baby horse?A. FoalB. CalfC. KidD. LambA83.I have a big ______ in my room.84.The zebra's stripes help it blend into ______ (环境).85.I love to _____ (sketch) plants in nature.86. A ______ is a liquid that can dissolve a solute.87.s lose their leaves ______ (每年). Some tre88.He is very _____ (勤劳) and works hard every day.89.The ______ (蟒蛇) can swallow prey much larger than itself.90.The ______ (花坛) adds color to any garden.91.She is _____ (talking) to her friend.92. A chemical _______ shows how many atoms of each element are in a molecule.93. A simple machine like a lever helps us to ______ (lift) heavy things.94.The stars are ___ (twinkling/shining).95.What do we call the study of heredity and variation?A. GeneticsB. EvolutionC. BiologyD. Ecology96.She likes to ________ books in the library.97.What is the opposite of ‘clean’?A. DirtyB. NeatC. TidyD. Clear98.My dad loves to ________ (园艺).99.The chemical formula for ethyl alcohol is _______.100.The ________ (向日葵) turns towards the sun and is very bright.。
小学下册I卷英语第六单元测验卷
小学下册英语第六单元测验卷英语试题一、综合题(本题有100小题,每小题1分,共100分.每小题不选、错误,均不给分)1.An alloy is a mixture of two or more __________.2.What is the primary function of the heart?A. To digest foodB. To pump bloodC. To filter wasteD. To regulate temperatureB3.We make ________ (decisions) as a team.4.I love to see _____ (小动物) in their natural habitats.5.I saw a ________ dance in the garden.6.What is the name of the largest desert in the world?A. SaharaB. GobiC. KalahariD. ArcticA7.The monkey eats a ______.8.The chemical symbol for selenium is __________.9.The __________ (历史的教训) can guide decision-making.10.I like to collect ________ (硬币).11.My ________ (玩具名称) is an integral part of my daily routine.12. A __________ (社区花园) can bring people together.13.I respect my . (我尊重我的。
)14.capital) city is where the government is located. The ____15.My dad is a __________ (金融分析师).16.My brother is a great __________ (伙伴) in games.17.I like to draw pictures of ________.18. A lizard can lose its ______ (尾巴) to escape.19.The main function of leaves is to help in __________.20.How many digits are in a phone number?A. 7B. 10C. 12D. 14B21. A ______ (植物的研究) can lead to new discoveries.22.Nebulas are often the birthplace of ______.23.What do you call a large mammal that lives in the ocean?A. SharkB. WhaleC. DolphinD. Seal24.What is the main meal of the day?A. BreakfastB. LunchC. DinnerD. SnackC25.The _____ (狐猴) has a long tail and big eyes.26.In a neutral solution, the pH is equal to ________.27. A saturated solution has reached its maximum ______.28.The first person to reach the North Pole was ______ (皮尔·阿蒙森).29. A _____ (74) is a large flat area of grassland.30. A ______ (有机) garden avoids synthetic chemicals.31.What do we call a baby cat?A. PuppyB. KittenC. CalfD. ChickB32.We should _____ (water) the plants every day.33.What do you call a large hole in the ground?A. PitB. CaveC. TunnelD. QuarryA34.What do we call the process of making a new product?A. ProductionB. ManufacturingC. CreationD. All of the aboveD All of the above35.We should ___ (share) our toys.36.What do we call the place where books are kept?A. SchoolB. LibraryC. BankD. Store37.Which day comes after Monday?A. SundayB. TuesdayC. WednesdayD. Thursday38. A __________ is an area of land that is surrounded by water on three sides.39. A ________ (园艺产业) boosts local economies.40.I can _____ (dance/sing) very well.41. A starling is a small, shiny ________________ (鸟).42. A _____ is made up of two or more different atoms bonded together.43.The _____ (tansy) plant has yellow flowers.44.We go _____ (cycling) on weekends.45.Birds build _______ in trees.46.The cake looks ________ (好吃).47.The ______ is what keeps us grounded on Earth.48.My favorite superhero is _______ (名字). 他/她的故事令人 _______ (形容词).49.The dog likes to _____ in the sand. (dig)50.小马) neighs softly. The ___51.The bat uses echolocation to find its _________. (食物)52.Every Sunday, I play board games with my _________ (家人).53. Age is known as the first period in human __________. (历史) The Ston54.I saw a ______ (蝴蝶) in the garden today, it was beautiful.55. A reaction that produces a gas and a solid is called a ______ reaction.56.What is the primary language spoken in Brazil?A. SpanishB. FrenchC. PortugueseD. EnglishC57. (83) is home to the Statue of Liberty. The ____58.What do you call the study of the Earth?A. BiologyB. GeographyC. ChemistryD. PhysicsB59.I like to eat ______ (ice cream) in the summer.60._____ (lilac) bushes bloom in spring.61.The pizza has ___ (pepperoni) on it.62.What do you call a story that is told with pictures?A. ComicB. NovelC. BiographyD. Memoir63.What do you call the area of land surrounded by water?A. IslandB. PeninsulaC. CoastD. Bay64.The __________ (历史的启迪) inspires creativity.65.The __________ is a famous park in New York City. (中央公园)66.The _______ is often seen in fairy tales.67.The __________ (历史的文化) reflects human development.68.The ______ is home to many species.69.The manatee is a gentle _______ (巨兽).70.What is the name of the device used to take photos?A. CameraB. ProjectorC. ScannerD. Monitor71. A group of fish swimming together is called a __________.72.What is 10 3?A. 7B. 6C. 5D. 4A73.I love watching _______ (动画片).74.The ______ helps transport blood throughout the body.75.What is 14 7?A. 7B. 6C. 5D. 4A76.The average distance from the Earth to the sun is one ______ unit.77.The goldfish can be many different _______ (品种).78.What is the name of the famous river in India?A. AmazonB. NileC. GangesD. Mississippi79.What is the name of the fairy tale character with long hair?A. Snow WhiteB. Sleeping BeautyC. RapunzelD. CinderellaC80.The __________ is a famous structure in Sydney, Australia. (悉尼歌剧院)81.The main component of natural gas is _______.82.I like to ______ my homework before dinner. (finish)83.Certain plants can ______ (适应) to new environments.84.The ______ contains a lot of water vapor.85.The kitten loves to bat at ______ (玩具).86.What do we call a young bison?A. CalfB. KitC. CubD. PupA Calf87.What is the capital city of Hungary?A. BudapestB. PragueC. ViennaD. BratislavaA88.The ________ (城市中心) is where most shops are located.89.The __________ (历史的声响) resonates widely.90.I want to be an ______ (artist) when I grow up.91.The chemical formula for vinegar is ______.92.I have a plant that blooms _____.93.The invention of ________ has reshaped the world economy.94.What do you call a person who takes photographs?A. ArtistB. PhotographerC. PainterD. IllustratorB95.What is the name of the famous American musician known for his work in jazz?A. Louis ArmstrongB. Duke EllingtonC. Miles DavisD. All of the aboveD96. A circuit breaker protects against electric ______.97.The ancient Egyptians constructed ______ (神庙) for worship.98.The __________ Sea is located between Europe and Asia.99.I think learning about different cultures expands our __________.100.My favorite hobby is ________ (收藏) stamps.。
小学上册第一次英语第1单元综合卷
小学上册英语第1单元综合卷英语试题一、综合题(本题有100小题,每小题1分,共100分.每小题不选、错误,均不给分)1.crater) is formed by volcanic activity. The ____2.The rabbit dug a hole in the ______ (土地). It is making a ______ (家).3.What is the name of the famous ancient city in Peru known for its Incan ruins?A. Machu PicchuB. TikalC. PetraD. Angkor WatA4.The chemical symbol for thallium is ______.5.My favorite teacher knows how to _______ (动词). 她教我们 _______ (名词).6.I like ________ (阅读) mystery books.7.The Nile River flows through __________.8.I have a ________ (魔法玩具) that can change colors.9.What is 5 + 3?A. 7B. 8C. 9D. 10B10.I enjoy watching _____ buzz around the flowers.11.She is _____ (making) a cake.12.What is the term for a young quokka?A. KitB. PupC. CalfD. ChickC13.What is the capital city of Samoa?A. ApiaB. SalelologaC. Pago PagoD. Mulifanua14.What do you call a story that is written about someone's life?A. BiographyB. AutobiographyC. FictionD. NovelA15.The _____ (potpourri) is made from dried flowers.16.The stars are shining ________.17.I see _____ (星星) at night.18.What do we use to cut paper?A. GlueB. ScissorsC. TapeD. Ruler19.The __________ is the capital city of Argentina. (布宜诺斯艾利斯)20.When you push an object, you apply ______.21.I saw a _______ in the tree.22.At school, I learn many subjects like ______ (数学), ______ (科学), and ______ (英语). My favorite subject is ______ (美术) because I can draw and ______ (涂色).23.The classroom is _____ (clean/dirty).24.The chemical formula for sodium nitrite is ______.25.My sister has a collection of ______.26. A __________ is formed from the deposition of sediments in a lake.27.What do plants need to grow?A. WaterB. SoilC. SunlightD. All of the aboveD28. A ________ (花店) sells beautiful arrangements.29.The hamburger is ____(tasty/bland).30.The capital of the Philippines is _______.31.What do we call the study of living organisms?A. BiologyB. ChemistryC. PhysicsD. GeographyA32.The leaves are ______ (绿色) in color.33.The flamingo has long _______ (腿).34.My sister is a great __________. (舞者)35.The process of a gas turning into a liquid is called ______.36.Chemical reactions require energy, which can come from _____.37.What do you call the process of growing plants?A. GardeningB. FarmingC. PlantingD. SowingA38.What do you call a baby antelope?A. FawnB. CalfC. KidD. LambA39.What is 5 + 5?A. 10B. 11C. 12D. 1340.The __________ is a region known for its rich history.41.Thermal energy is related to ______.42.What do we call the primary source of energy for living organisms?A. WaterB. SunlightC. AirD. FoodB43.I like to _____ in the swimming pool. (swim)44. A _______ is a tool used to measure the temperature of a substance. (温度计)45.What is 15 ÷ 3?A. 3B. 4C. 5D. 646.The ________ (海洋探险) unveils new species.47.The ______ (组织) in plants helps with nutrient transport.48.The _______ (猫) curls up to sleep.49.I like to play with my _________ (拼图) while listening to music.50.The __________ (国土) is rich in resources.51.The sea horse is a unique kind of _________ (鱼).52.My __________ (玩具名) has a very __________ (形容词) design.53.Which celestial body orbits the Earth?A. SunB. MoonC. MarsD. Venus答案:B54.What is the common name for a wild horse?A. PonyB. MustangC. ZebraD. DonkeyB55.I like to go ______ (钓鱼) with my dad on weekends.56.I brush my teeth _____ night. (every)57.We have a ______ (有趣的) teacher.58. A butterfly starts as a ______.59.We sing songs in _____ (music/art) class.60. A ________ (植物资源) can be utilized sustainably.61.I love to read ________ (童话).62.What is the main ingredient in yogurt?A. MilkB. CreamC. SugarD. WaterA63.I think every toy has its own ________ (名词) and personality.64.What do you call a baby chicken?A. DucklingB. PigletC. ChickD. Calf65.I enjoy writing poetry because it’s a unique way to convey my __________.66.What do you call the person who teaches you in school?A. DoctorB. TeacherC. FarmerD. EngineerB67.I have a toy _______ that zooms across the floor really fast.68.The ancient Egyptians believed in ________ to guide them in the afterlife.69.I like to listen to ______ (songs).70.Birds have __________ to help them fly.71.What do we call a baby llama?A. CriaB. KidC. CalfD. FoalA72.What do we use to measure time?A. RulerB. ClockC. ScaleD. Compass73.I like to _____ with my friends. (hang out)74.What is the opposite of up?A. DownB. LeftC. RightD. Across75.We have ______ (很多) decorations for the party.76.Where do bees live?A. NestB. HiveC. DenD. BurrowB77.What do you call the large body of ice that moves slowly over land?A. GlacierB. IcebergC. SnowfieldD. Permafrost78.The _______ can be very colorful and beautiful.79.What do we call the imaginary line dividing the Earth into Northern and Southern Hemispheres?A. EquatorB. Prime MeridianC. Tropic of CancerD. Tropic of Capricorn80. A _____ (植物观察者) can contribute to citizen science.81.What do you call a person who collects stamps?A. PhilatelistB. CollectorC. DealerD. HistorianA82.What do you call a person who performs magic tricks?A. MagicianB. IllusionistC. ClownD. JugglerA83.I enjoy watching __________ with my family. (电影)84. A compound is made of two or more different ______.85.I have a toy _______ that hops around and plays with me all day long.86.What do we call the process of separating mixtures based on size?A. FiltrationB. DistillationC. ChromatographyD. SiftingA87. A lion roars loudly in the _______.88. A chemical reaction that produces a gas is called a ______ reaction.89. A llama can carry _______ (重物).90.We have ______ (家人) gatherings on holidays.91.The flamingo gets its pink color from its _________ (饮食).92.What do you call the process of changing waste into reusable materials?A. RecyclingB. CompostingC. DisposingD. CollectingA93.War was a period of tension between the _____ (USA. and the USSR. The Cold94.The train is very ________.95.The __________ (历史的情感) can resonate across generations.96.Flowers bloom in _____ (春天) and bring color to the garden.97.I like to _____ (travel) in summer.98.The invention of ________ made it easier to travel long distances.99.What is the term for the study of celestial objects?A. AstronomyB. CosmologyC. AstrophysicsD. Meteorology 100.The __________ (历史的多样化视角) enrich our narratives.。
小学上册第2次英语第5单元期末试卷
小学上册英语第5单元期末试卷英语试题一、综合题(本题有100小题,每小题1分,共100分.每小题不选、错误,均不给分)1.The __________ (历史的辩论) invites discourse.2.We need to _______ (改善) our community.3.I have a _______ (wonderful) idea.4.What is the name of the region of space where the gravitational pull is so strong that nothing can escape?A. SingularityB. Event HorizonC. Black HoleD. Neutron Star5. A __________ can affect human development.6.My favorite video game is ______.7.The dog loves to chase ______ (squirrels).8.The __________ is a critical ecosystem for wildlife.9.My toy dinosaur is very _______ (我的玩具恐龙非常_______).10.What is your ___ (name)?11.What is the name of the famous novelist known for his "Moby Dick"?A. Mark TwainB. Herman MelvilleC. Nathaniel HawthorneD. F. Scott FitzgeraldB12.My favorite animal is a ______ (兔子) that hops joyfully.13.The _____ (蜜蜂) is busy collecting nectar.14.We can ___ together. (play)15.The Nile River flows through _______.16.The Earth's surface is shaped by both natural and ______ factors.17.ts can grow rapidly under the right ______. (某些植物在适当的条件下可以迅速生长。
小学上册第12次英语第二单元真题
小学上册英语第二单元真题英语试题一、综合题(本题有100小题,每小题1分,共100分.每小题不选、错误,均不给分)1.I have a toy _______ that spins and plays music when you press a button.2. A _____ is an area of land that is inhabited by a specific group.3.I love my ________ (音乐玩具) that plays different tunes.4.The _____ (flower) is very beautiful.5.How many feet are in a yard?A. 2B. 3C. 4D. 5B6.What is the capital of France?A. BerlinB. MadridC. ParisD. LisbonC Paris7.The ________ has soft feathers and a colorful beak.8.My friend is a ______. He enjoys hiking.9.The chemical formula for propane is ______.10.My __________ (玩具名) can go really __________ (副词).11.The stars are ______ (亮) at night.12.Atoms are made up of protons, neutrons, and _______.13.The _______ (小蜻蜓) flits around over the water.14.She is ___ a picture. (drawing)15.What is the name of the famous French landmark known for its iron lattice structure?A. Eiffel TowerB. Louvre MuseumC. Arc de TriompheD. Notre-Dame Cathedral16.Did you hear the _____ (小狗) barking playfully?17.What do you call a story that explains how something came to be?A. LegendB. MythC. TaleD. FableB18.What do we call a group of birds?A. PackB. FlockC. SchoolD. Herd19.The __________ (古埃及女王) Cleopatra was known for her intelligence.20. A ______ (松鼠) stores nuts for winter.21.What do you call the main character in a story?A. ProtagonistB. AntagonistC. NarratorD. Supporting characterA22.The __________ is a major city located on the coast. (迈阿密)23.aring a _______ (漂亮的裙子). She is w24.The ______ helps flowers to grow.25.The owl is a symbol of ______ (智慧) in many cultures.26.The weather is _____ outside today. (nice)27.Which animal is known for its long neck?A. GiraffeB. ElephantC. KangarooD. LionA28.The dog enjoys playing with its ______.29. A _____ is a body of water, such as a lake or pond.30.What do you call a type of music that tells a story?A. BalladB. OperaC. SymphonyD. JazzA31.After breakfast, I go to ________ (学校) with my friends. We walk together and talk about our ________ (课程).32. A lizard's tail can grow back if it is ______ (断裂).33.The __________ is a famous national park in Wyoming. (黄石国家公园)34. A __________ is a type of chemical reaction where heat is absorbed.35. a Desert is located in _____ (非洲). The Saha36.The __________ (季节) changes affect plant life.37. A reaction that produces energy is a sign of a ______ reaction.38.The frog jumps from rock to ______.39.What is the opposite of cold?A. WarmB. HotC. CoolD. Freezing40.I have a special place for my ____.41.Which month comes before April?A. MarchB. FebruaryC. MayD. JuneA42.The ______ is a critical part of the food web.43. A _______ (小水獺) plays in the river.44. A black hole has such strong gravity that nothing can escape its ______.45.I have a _____ (collection) of coins.46.I think that understanding different perspectives can lead to __________.47.The __________ (地理位置) affects climate and weather.48.In which month is Christmas celebrated?A. NovemberB. DecemberC. JanuaryD. October49.Which holiday celebrates the New Year?A. ChristmasB. ThanksgivingC. New Year's DayD. HalloweenC50.My favorite animal is a ______ (熊猫).51.The __________ (历史的传承方式) vary across cultures.52.I have a toy ________ that can spin and twirl.53.The __________ (购物中心) is near my house.54.I enjoy _______ (参加) environmental activities.55.We have a ______ (丰富的) experience in school.56.My favorite animal is a ________ because it swims.57.She is ___ (playing/singing) a tune.58.The _____ (房屋) is two stories high.59.My __________ (玩具名) always makes me laugh when I __________ (动词).60.I want to learn about science because it explains how the _______ (世界) works.61.What do we call the act of moving from one place to another?A. TravelB. TransportC. MigrationD. CommuteC62.ts use ______ to capture sunlight and produce food. (某些植物利用叶片捕获阳光并生产食物。
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Energy Transport Between Hole Gas and Crystal Lattice in Diluted Magnetic SemiconductorJ.M. Kivioja1, M. Prunnila1, S. Novikov2, P. Kuivalainen2, and J. Ahopelto1 1VTT Micro and Nanoelectronics, Tietotie 3, Espoo, P.O. Box 1000, FI-02044 VTT, Finland 2Electron Physics Laboratory, Helsinki University of Technology, P.O.BOX 3500, FI-02015 HUT, FinlandAbstract. The temperature dependent energy transfer rate between hole gas and lattice has been investigated in thin Mn x Ga1-x As (x=3.7% and 4.0%) films by heating the hole system with power density P d and measuring the hole temperature T. The heating experiments were carried out in temperature range of 250 mK-1.3 K and the temperature dependency of resistivity provided the hole thermometer. When the hole temperature greatly exceeds the lattice temperature we find that P d ~ T n, where n is in the range of 4 - 5.Keywords:ferromagnetic semiconductor, MnGaAs, carrier-phonon energy relaxationPACS:63.20.Kr, 71.38.-k, 75.50.Dd, 72.25.DcINTRODUCTIONRecent years have seen a growing interest in the field of diluted magnetic semiconductors due to their ability to combine magnetism and integrated electronics. Various electrical and material properties of magnetic semiconductors have been extensively reported in the literature. Here, we focus to study thermal relaxation of holes in magnetic semiconductor, which is a new subject in this field. In this work the temperature dependent energy loss rate between charge carriers and lattice is experimentally investigated in MnGaAs.SAMPLESThe MnGaAs samples were grown on semi-insulating GaAs (100) substrate by molecular beam epitaxy (MBE). First an undoped GaAs buffer layer (230 nm) was grown at 580 ºC. Then low temperature MBE of a 100 nm thick Mn x Ga1-x As device layer was performed at 230 ºC. In the experiments we studied two samples with manganese concentrations of x=3.7 % and 4.0 % and Curie temperatures of 60 K and 62 K, respectively.The MnGaAs films were patterned utilizing UV-lithography and wet etching. The MnGaAs mesas were contacted with superconducting electrodes (Nb or Al) for preventing thermal leakage during the heating experiments. Samples were electrically characterized down to 250 mK using He3-sorption cryostat and standard lock-in techniques.RESULTS AND DISCUSSION Figure 1 presents measured resistivityρas a function of temperature. The resistivity of both samples show a peak around 60 K. The position of the peak gives the Curie temperature. Furthermore, the Hall-resistivitiesρxy(not shown) exhibit the standard6810121416ρ(mΩcm)T (K)FIGURE 1.Temperature dependency of the resistivityρ. The right inset shows the schematic top view of the heating experiments and also howρ(T) is utilized in determining the hole and phonon temperatures (see Fig. 2 for the results).anomalous Hall effect: at low magnetic fields B (<0.4T)ρxy shows a rabid increase with increasing B and then it almost saturates at B ~0.4 T. Additionally,ρxy (B ) shows hysteretic behavior. The observed features in ρ and ρxy are well known signatures of ferromagnetism [1].Below T ~ 5 K both samples exhibit a “Kondo-like”ρ(Τ) ∼log(T) behavior (left inset in Fig. 1) [2].This well defined temperature dependency of the resistivity provides a local thermometer, which is utilized in the heating experiments: the resistivity of adjacent electronically isolated films gives the hole T h and phonon temperatures T ph in the spirit of Refs. [3,4](see the right inset of Fig. 1). The thermometers were first calibrated by slowly adjusting the bath temperature of the cryostat. Then one of the 5µm wide adjacent MnGaAs mesas was heated by applying a DC current density J at constant bath (cryostat)temperature. The change in the resistivities, which were measured with a small ac-signal, give the response of T h and T ph to heating power density P d =ρJ 2. These responses are plotted in Fig. 2 at various bath temperatures.The temperatures of electrically isolated phonon and hole thermometers have very different responses.The hole temperature shows a strong response while the phonon temperature shows only extremely weak increase, which is observable at the highest heating powers and lowest bath temperatures. This indicates that the thermal coupling between GaAs substrates and cryostat’s sample holder (copper) was extremely good,contradictory to studies utilizing silicon substrates [3,4]. Further, this also shows that the “bottle-neck” in the heat path is the hole-phonon energy relaxation rate.Figure 2 shows also curves n d T P ∝with n = 4,5.We can observe that the experimental T h fall between these dependencies at high power density. More careful inspection reveals that the sample with x = 3.7% (4.0 %) is described better with n=4 (n=5). On the other hand, the sensitivity of our hole (and phonon)thermometer is rather limited, which makes clear distinction between these two power laws difficult.Thus, we conclude that our preliminary experiments indicate that n d T P ∝ with n = 4 - 5 for both x = 3.7% and x = 4.0 %. Note that as the hole-phonon energyrelaxation rate is given by 21−−−∝n ph h Tτ[4] our results also suggest that in Mn x Ga 1-x As 321−−−∝Tph h τ.In semiconductors the elastic intra-valley [5] and inter-valley [4] scattering processes affect the carrier-phonon relaxation at low temperatures. In low mobility hole systems the latter is expect to have a strong effect,because it does not require diffusion. The role of ferromagnetism in the energy relaxation is not yet clear. However, we have also performed heatingFIGURE 2. Hole-gas temperature (T h ) and temperature of the lattice (T ph ) as a function of heating power density at various base temperatures.measurements at various perpendicular magnetic fields between -2 T and 2 T and our conclusion is that the hole-phonon relaxation rate in Mn x Ga 1-x As has negligible magnetic field dependency.SUMMARYOur results show that the energy loss rate from charge carriers to lattice in Mn x Ga 1-x As samples with x=3.7 % and x=4.0 % follows a power law 54−∝T P d ,which indicates that the hole-phonon energy relaxationtime has 321−−−∝Tph h τ behavior. We observed no magnetic field dependency in the energy relaxation.ACKNOWLEDGMENTSThe Academy of Finland (grant 205478) is acknowledged for financial support.REFERENCES1. F. Matsukura, H. Ohno, A.Shen, and Y. Sugawara, Phys.Rev. B. 57, 2037 (1998).2. H.T. He et al. Appl. Phys. Lett. 87, 162506 (2005).3. J.M. Kivioja, I.J. Maasilta, J.T. Karvonen, and J.P.Pekola, Physica E 18, 21 (2003).4. M. Prunnila, P.Kivinen, A.Savin, P. Törmä, and J.Ahopelto, Phys. Rev. Lett. 95, 206602 (2005).5. A. Sergeev, M. Yu. Reizer, and V. Mitin, Phys. Rev.Lett. 94, 136602 (2005).10101010P d (W/m 3)P vs. TT (m K )。