基于TiO2纳米管阵列的高效正面透光型染料敏化太阳能电池的制备及其光电性能

[Article]物理化学学报(Wuli Huaxue Xuebao )Acta Phys.-Chim.Sin .2014,30(3),446-452MarchReceived:November 15,2013;Revised:December 31,2013;Published on Web:January 2,2014.*Corresponding author.Email:lanzhang@;Tel:+86-189********.The project was supported by the National Natural Science Foundation of China (U1205112,51002053),Key Project of the Ministry of Education of China (212206),Program for Prominent Young Talents in Fujian Province University,China;Program for New Century Excellent Talents in Fujian Province University,China,and Promotion Program for Yong and Middle-aged Teacher in Science and Technology Research of Huaqiao University,China (ZQN-YX102).国家自然科学基金(U1205112,51002053),教育部科技重点项目(212206),福建省高校杰出青年研究人才计划项目,福建省高校新世纪优秀人才支持计划项目和华侨大学中青年教师科研提升资助计划(ZQN-YX102)资助©Editorial office of Acta Physico -Chimica Sinicadoi:10.3866/PKU.WHXB 201401022基于TiO 2纳米管阵列的高效正面透光型染料敏化太阳能电池的制备及其光电性能高素雯1兰章1,2,3,*吴晚霞1阙兰芳1吴季怀1,2,3林建明1,2,3黄妙良1,2,3(1华侨大学材料科学与工程学院,福建厦门361021;2环境友好功能材料教育部工程中心,福建厦门361021;3福建省高等教育功能材料重点实验室,福建厦门361021)摘要:报道了一种基于TiO 2纳米管(TNT)阵列正面透光型光阳极的高效染料敏化太阳能电池.将TNTs 在450°C 烧结后能避免其有序结构在HF 处理过程中被破坏,使膜内高速电子传输通道被保留,有利于染料敏化太阳能电池(DSSC)实现高速电荷传输.再用HF 、TiCl 4、HF 和TiCl 4混合等溶剂对TNTs 进行处理,提高其表面粗糙度以吸附更多染料.染料吸附量的增加能提高光阳极在300-570nm 波段光子捕获效率,该波段是染料吸收光子的主要区域.然而,在染料吸收光子较弱的长波段区域(570-800nm)光子捕获效率的增加主要源于光阳极光散射率的提高.光阳极光子捕获效率的提高使DSSC 的内外量子效率在全波段(300-800nm)均有所增加,从而使短路电流明显提高.从电化学阻抗数据可知,与电子传输性能密切相关的电化学参数如电荷传输电阻、界面电荷复合电阻、电容、电子寿命、电子扩散长度和电子收集效率等在含处理过的TNTs 光阳极DSSC 中均有所改善,从而提高电池光电转换效率.含HF 和TiCl 4混合溶剂处理TNTs 光阳极的DSSC 最高光电转换效率能达到7.30%,比未处理的DSSC (5.38%)提高35.69%.关键词:TiO 2纳米管阵列;染料敏化太阳能电池;光阳极;HF;TiCl 4中图分类号:O644;O649Fabrication and Photovoltaic Performance of High EfficiencyFront-Illuminated Dye-Sensitized Solar Cell Based onOrdered TiO 2Nanotube ArraysGAO Su-Wen 1LAN Zhang 1,2,3,*WU Wan-Xia 1QUE Lan-Fang 1WU Ji-Huai 1,2,3LIN Jian-Ming 1,2,3HUANG Miao-Liang 1,2,3(1Institute of Materials Physical Chemistry,Huaqiao University,Xiamen 361021,Fujian Province,P .R.China ;2EngineeringResearch Center of Environment-Friendly Functional Materials,Ministry of Education,Xiamen 361021,Fujian Province,P .R.China ;3Key Laboratory of Functional Materials for Fujian Higher Education,Xiamen 361021,Fujian Province,P .R.China )Abstract:An efficient front-illuminated dye-sensitized solar cell (DSSC)based on ordered TiO 2nanotube (TNT)arrays was prepared.Sintering at 450°C avoided damage of the ordered TNTs during HF treatment.Fast electron transport channels were maintained in the membrane,for efficient charge transportat in the DSSC.The sintered TNT membranes were subsequently treated with HF,TiCl 4,and HF combined with446GAO Su-Wen et al.:High Efficiency TiO2Nanotube Arrays Based Front-Illuminated DSSCsNo.3TiCl4.This formed a rougher surface,and allowed increased dye loadings.The increased dye loading improved the light harvesting efficiency of the photoanode at300-570nm wavelength range,which is the main absorption region of the adsorbed dye.The adsorbed dye had a low absorption at570-800nm wavelength range.The enhanced light harvesting efficiency of the photoanode originated from its increased diffuse reflectance.The incident-photon-to-current and absorbed-photon-to-current conversion efficiencies were increased over the entire300-800nm wavelength range.This resulted in an increased short-circuit current density of the DSSC.Electrochemical impedance spectroscopy indicated that electron transport and related parameters including charge transport resistance,interfacial charge recombination resistance,distributed chemical capacitance,electron lifetime,effective electron diffusion length,and collection efficiency were significantly improved in the DSSC containing the treated TNT photoanode.This also resulted in an enhanced photovoltaic performance.The maximum power conversion efficiency from combining HF and TiCl4treatments was7.30%,which was a35.69%enhancement compared with the non-treated DSSC(5.38%).Key Words:TiO2nanotube array;Dye-sensitized solar cell;Photoanode;HF;TiCl41IntroductionDye-sensitized solar cells(DSSCs)have been a researching focus among new types of solar cells since O′Regan and Grätzel first reported.1Compared with conventional silicon so-lar cells,DSSCs have an absolute advantage of low-cost and easy preparation.2,3Generally,the DSSC is composed of a dye-sensitized photoanode,an electrolyte typically containing the iodine/iodide redox couple,and a counter electrode.4The pho-toanode is usually composed of TiO2nanoparticles(TNPs).5 However,the TNPs based photoanodes have some drawbacks affecting the photovoltaic performance of DSSCs.For exam-ple,the existed random networks and large interfaces will re-sult in serious charge recombination between electrons and io-dide ions in the electrolyte;numerous boundaries among TNPs will trap electrons and induce short electron diffusion length.6 To solve the problems,researchers have attempted to synthe-size and utilize some ordered one-dimensional TiO2nanorods,7 nanowires,8and nanotubes in DSSCs.9As a promising alternative to traditional TNPs based photo-anodes in DSSCs,TiO2nanotubes(TNTs)have been attracting intensive interests.10Highly ordered,one-dimensional TNTs have been widely used in DSSCs,sensors,photocatalysis and water splitting.11-13Applied in DSSCs,TNTs have some outstanding properties.For one hand,one-dimensional TNTs can provide a vertical electron transport path which can effectively reduce charge recombination;for another hand,the less grain boundar-ies lead to higher electron mobility and faster electron trans-port speed compared with the TNPs based photoanodes.14How-ever,mainly due to low surface area,the photovoltaic perfor-mance of TNTs based DSSCs is still much lower than that of the TNPs based DSSCs.One efficient way to increase the sur-face area of TNT membranes and further increase the photovol-taic performance of DSSCs is to form secondary or hierarchi-cal structure.15,16However,the as-formed particle-connected secondary structure in the TNT membranes will partly destroy the fast ordered electron transport channels.Here,some im-provements are carried out to fabricate highly photovoltaic per-formance of TNTs based DSSCs through maintaining the fast ordered electron transport channels in the TNT membranes and increasing surface roughness for enhancing dye loading amounts at the same time.2Experimental2.1MaterialsAll solvents and reagents were of AR grade quality and were used as received.2-propanol,concentrated nitric acid(65% (w)aqueous solution),ethanol,ethylene glycol,ammonium flu-oride,hydrofluoric acid,H2O2(30%(w)aqueous solution),tet-ra-n-butyl titanate,acetic acid,acetonitrile,titanium tetrachlo-ride,tetrabutyl ammonium iodide,4-tert-butyl pyridine,sodi-um iodide,iodine,and H2PtCl6∙6H2O were purchased from Sin-opharm Chemical Reagent Co.Ltd.,China.Ti-foils(0.2mm thick,99%(w)purity)were purchased from Baoji Yunjie Met-al Production Co.Ltd.Conductive glasses FTO glasses(fluo-rine doped tin oxide over-layer,sheet resistance15Ω∙□-1) were purchased from Nippon Sheet Glass Co.JP.N719dye (Ru[LL'-(NCS)2],L=2,2'-bipyridyl-4,4'-dicarboxylic acid,L'=2, 2'-bipyridyl-4,4'-ditetrabutylammonium carboxylate)from Dye sol.2.2Preparation of TiO2nanotube membranesTi foils(2cm×3cm)were treated with ultrasonic cleanser in deionized water,2-propanol,and ethanol for5min,respective-ly,and then rinsed with ethanol and dried at room temperature. The cleaned Ti foils were polished in a solution containing H2O(50%(volume fraction)),concentrated nitric acid(50% (volume fraction)),and NH4F(1.7%(w)vs the total weight of H2O and concentrated nitric acid).The polished Ti foils were subjected to a two-step anodization in electrolyte containing ethyl-ene glycol,H2O(0.5%(volume fraction)vs ethylene glycol), and ammonium fluoride(0.25%(w)vs ethylene glycol)at room ly,the polished Ti foils were firstly an-odized at60V for4h.After thermally treated at250°C for2h447Acta Phys.-Chim.Sin.2014V ol.30and cooled down to room temperature,they were anodized again at60V for5min.After two-step anodization,the Ti foils were rinsed with ethanol,dried at room temperature,and then immersed into H2O230%(w)aqueous solution for1h to de-tach the TNT membranes.2.3Preparation of photoanodes and assembling offront-side illuminated dye-sensitized solar cells The detached TNT membranes about12.5m m were incised into several pieces with area of0.1cm2(0.25cm×0.4cm)and adhered to FTO glasses using the paste containing10-20nm anatase TiO2nanoparticles prepared with the same method re-ported in the reference.17The thickness of the TiO2adhesive un-der-layer was about1μm.After sintered at450°C for30min, the TNT photoanodes were further treated with HF,TiCl4,and HF combining with TiCl4.The details are as follows.HF treat-ment:the TNT photoanodes were dipped in0.35%(volume fraction)HF aqueous solution at room temperature for1h,and then sintered again at450°C for30min.TiCl4treatment:the TNT photoanodes were dipped in0.05mol∙L-1TiCl4aqueous solution at90°C for30min,and then sintered again at450°C for30min.HF combining with TiCl4treatments:the TNT pho-toanodes were treated with HF solution and TiCl4solution with the methods as above mentioned in sequence.The as-prepared TNT photoanodes were sensitized in0.25mmol∙L-1anhydrous ethanol solution of N719dye for24h at room temperature. The sensitized TNT photoanodes were rinsed with anhydrous ethanol and dried in air.Pt counter electrode was prepared with the same method reported in the reference.18The DSSC was as-sembled as follows.Firstly,a drop of electrolyte was dripped into the sensitized TNT photoanode,and then a piece of Pt counter electrode was placed above the photoanode.Secondly, the two electrodes were clipped together and a cyanoacrylate adhesive was used as sealant to seal the cell.Bisphenol A ep-oxy resin was used in a further sealing process.The liquid elec-trolyte contained0.4mol∙L-1sodium iodide,0.1mol∙L-1tetra-butyl ammonium iodide,0.5mol∙L-14-tert-butylpyridine,and 0.05mol∙L-1iodine in acetonitrile solution.2.4MeasurementsThe surface morphologies and thickness of TNT membranes were characterized by a field emission scanning electron mi-croscopy(FESEM,S-4800,HITACHI,Japan).X-ray diffrac-tion(XRD)measurements were carried out with a Bruker D8 ADV ANCE(Germany),using Cu Kα1radiation(λ=0.15418 nm).A UV-Vis2550spectrophotometer(Shimadzu,Japan)was employed to measure UV-Vis absorption and reflectance spec-tra.Electrochemical impedance spectroscopy(EIS)measure-ments were performed using a CHI660C electrochemical workstation(CH Instrument Inc.,USA).The impedance spec-tra were analyzed by an equivalent circuit model interpreting the characteristics of DSSCs with Zview software.19Photovolta-ic tests were carried out by measuring photocurrent-voltage (I-V)characteristic curves under simulated AM1.5G solar illu-mination at100mW∙cm-2from a xenon arc lamp(CHF-XM500,Trusttech Co.,Ltd,China)in ambient atmosphere and recorded with a CHI660C electrochemical workstation.All of the samples were measured three times and the average data were taken.Incident-photon-to-current conversion efficiency (IPCE)curves were measured as a function of wavelength from300to800nm using the Newport IPCE system(New-port,USA).3Results and discussionFig.1shows X-ray diffraction patterns of TNT membranes treated with HF and TiCl4solutions,respectively,and the origi-nal non-treated sample after sintered at450°C for30min.The standard2q characteristic peaks of anatase TiO2according to the JCPDS#21-1272are at25.3°,37.55°,47.85°,53.75°, 55.05°,and62.35°,which are all existed in the three samples, so the crystal structures of the samples are all anatase.20The dif-fraction intensity of HF solution treated sample is stronger than the other two samples,so its crystallinity is higher than the oth-ers.Fig.2shows SEM images of top and cross-sectional views of TNT membranes without and with HF,TiCl4,and HF combin-ing with TiCl4treatments.It is seen that the non-treated TNT membrane is composed with highly ordered TNT array with smooth surfaces.After HF treatment,the top ends of former in-dividual TNTs are connected together to form a thin porous lay-er on up-side of the membrane;and the original structure of or-dered TNT walls does not obviously change except for a little rougher.However,after TiCl4or HF combining with TiCl4treat-ments the morphologies of TNT membranes are changed signif-icantly compared with that of the non-treated TNT membrane. Firstly,the porous top-side morphology disappears and is sub-stituted by a compact layer composed with nanoparticles.Sec-ondly,there appear many nanoparticles both on the inner and outer surfaces of TNT paring Fig.2(e,f)and Fig.2 (g,h),one can see that the nanoparticles on the top-side of the membrane in HF combining with TiCl4treated sample are big-ger than the others.Fig.3shows SEM images of back-side view of TNTmem-Fig.1X-ray diffraction patterns of TNT membranes aftersintered at450°C for30min(a)HF treated,(b)TiCl4treated,(c)non-treated448GAO Su-Wen et al .:High Efficiency TiO 2Nanotube Arrays Based Front-Illuminated DSSCsNo.3branes as prepared and corroded by 30%(w )H 2O 2aqueous so-lution and the cross-sectional image of TNT photoanode.One can observe that the back-side of TNT membrane is composed with ordered close-end semisphere-like TNT layer by the sec-ondary anodization.Due to the miss of thermal treatment,the formed secondary TNT layer can be easily corroded by H 2O 2re-agent.21From Fig.3(b,c),we can see that the thin TNTs under layer disappear after H 2O 2corrosion;and the newly formed un-der layer is porous,which is beneficial for strongly adhered to FTO glasses with TiO 2nanoparticle paste.Moreover,the through structure as shown in Fig.3(d)can provide a direct electron transport channel to FTO glasses by omitting the close-end under layer in the membrane,and improve the penetrabili-ty of electrolyte in the photoanode.22Fig.4(A,B)shows the UV-Vis diffused reflectance spectra of TNT membranes and absorption spectra of TNT photoanodes.The light scattering ability of the TNT membranes is improved obviously after HF and TiCl 4treatments as shown in Fig.4(A).The changed top-side morphologies and the increasedrough-Fig.2SEM images of top and cross-sectional views of TNTmembranes(a,b)non-treated samples;(c,d),(e,f),(g,h):HF,TiCl 4,and HF+TiCl 4treated samples,respectivelyFig.3SEM images of back-side views of TNT membranes(a)two-step anodized sample,(b,c)samples after corroded by 30%(w )H 2O 2aqueous solution;(d)cross-sectional image of TNTphotoanodeFig.4UV-Vis diffused reflectance spectra of TNT membranes (A);absorption (B)and LHE (C)spectra of TNT photoanodesThe curves from a to d are related to the HF combining with TiCl 4,TiCl 4,HFtreated samples,and non-treated one,respectively.449Acta Phys.-Chim.Sin.2014V ol.30ness of the TNT walls as discussed above mainly response for the changed diffused reflectance of the TNT membranes.From Fig.4(B),it is seen that the treated samples all show enhanced light absorbance compared with the non-treated one.The in-creased roughness of TNTs can increase dye-loading amounts (as listed in Table1),resulting in the enhanced light absor-bance in the short-wavelength region(300-570nm);and the in-creased light scattering ability of the TNT membranes is main-ly responsible for the enhanced light absorbance in the long-wavelength region(570-800nm).23The light harvesting effi-ciency(LHE)[LHE(l)=1-10-ABS(l),where ABS(l)is absor-bance of the photoanodes of the samples]shown in Fig.4(C) can reflect the effects of the treatments more directly.24 Photovoltaic performance of DSSCs based on TNT photo-anodes with different treatments is presented in Fig.5,and the corresponding parameters:short-circuit current density(J sc), open-circuit voltage(V oc),fill factor(FF),and power conver-sion efficiency(PCE)are listed in Table1.We can see that the values of J sc of DSSCs with the treated photoanodes are all im-proved compared with the original non-treated one;and the TiCl4treatment shows higher efficiency in enhancing J sc than that of HF treatment.Moreover,by HF combining with TiCl4 treatments,J sc of the DSSC can further attain to a higher value. As aforementioned,the increased dye-loading amounts and light harvesting efficiency are the main reasons for the en-hanced J sc,which can be verified by measuring the IPCE perfor-mance of the DSSCs.As shown in Fig.6(A),one can observe that the DSSCs with the treated photoanodes show enhanced IPCE;and the change tendencies are consistent with that of J sc.The absorbed-photon-to-current conversion efficiency(APCE),which is derived from the IPCE and LHE[APCE(%)=IPCE(%)/LHE(%)],24,25is also shown in Fig.6(B)to more directly demonstrate the im-proved photon-to-electron conversion ability of DSSCs with the treated photoanodes.From the data,it is seen that TiCl4 treatment can efficiently enhance the APCE of the DSSC in all wavelength region;and by combining with HF treatment,a higher APCE is obtained.The TiCl4and HF combining with TiCl4treated samples have maximum APCE about84.90%at 510nm and89.55%at530nm,respectively.Moreover,the two samples also show high APCE(exceeding20%)in the near-infrared long-wavelength region(700-770nm).Howev-er,the DSSC with non-treated one shows a lower APCE(be-low10%)in the same wavelength region.From the photovoltaic parameters of the DSSCs presented in Table1,it is found that the changes of V oc are small;whereas the values of FF are decreased obviously after treatments.The reason may be owing to the increased density of the TNT mem-branes by fitting the new generated TiO2nanoparticles,which results in hindering the deep penetration of electrolyte into TNTs and enhancing the resistance of the DSSCs.Even so,ow-ing to the largely enhanced J sc,the PCE of the DSSCs with the treated photoanodes is still improved.The best PCE of the DSSCs can attain to7.30%by HF combining with TiCl4treat-ments,with35.69%enhancement compared with the non-treat-ed DSSC(5.38%).The EIS measurements are carried out to deeply detect the electron transport and kinetic properties in the DSSCs with non-treated and treated TNT photoanodes as shown in Fig.7 (A).A transmission line model(Fig.7(B))is used to describeTable1Photovoltaic parameters of DSSCs as shown in Fig.5Photoanodeabcd 108C dye/(mol∙cm-2)4.7184.4204.0883.960J sc/(mA∙cm-2)14.9012.4610.189.52V oc/V0.7460.7600.7520.746FF0.6570.7110.7430.757PCE/%7.306.735.695.38Fig.5Photocurrent density-voltage curves of DSSCs based onTNT photoanodesThe curves from a to d represent the same samples as shown inFig.4.Fig.6IPCE(A)and APCE(B)spectra of DSSCs based onTNT photoanodesThe curves from a to d represent the same samples as shown in Fig.4. 450GAO Su-Wen et al .:High Efficiency TiO 2Nanotube Arrays Based Front-Illuminated DSSCsNo.3the kinetic processes of the DSSCs.The corresponding parame-ters:charge transport resistance R tr (R tr =r tr L ),interfacial charge recombination resistance R r (R r =r ct /L ),distributed chemical ca-pacitance C u (C u =c u L ),electron lifetime t n (t n =R r C u ),effective electron diffusion length L n [L n =L (R r /R tr )0.5],and collection effi-ciency ηcol =R r /(R r +R tr )are summarized in Table 2(where L is the thickness of the TNT membrane).26From the data,one can observe that HF treatment can sup-press the recombination reaction efficiently (due to the obvi-ously increased R r compared with the non-treated one),so the ηcol and L n increase,resulting in the improved photovoltaic per-formance of the DSSC.For TiCl 4treatment,the value of R r is increased greatly.Owing to the increased value of R tr at the same time,the enhancements of ηcol and L n are little lower than that of HF treated sample,whereas they are still higher thanthat of the non-treated one,so the DSSC can generate high J sc by combining with the largely increased t n .Using HF combin-ing with TiCl 4treatments,the values of EIS key parameters such as R r ,ηcol ,L n ,and t n are all further enhanced,so the PCE of the DSSC can attain to a higher value.It also can be seen that the TiCl 4and HF combining with TiCl 4treated samples show higher R tr than that of the non-treated one,which may re-sult in lower values of FF.The values of C u ,reflecting the sur-face area variation,are increased in the DSSCs with treated TNT photoanodes,which is consistent with the increased roughness of the TNTs.4ConclusionsHigh efficiency front-side illuminated dye-sensitized solar cells based on ordered TNTs have been successfully prepared.It is found that the high temperature sintering process can avoid damage of the ordered TNTs by HF treatment and main-tain the fast electron transport channels in the membranes.Fol-lowing with HF,TiCl 4,and HF combining with TiCl 4treat-ments,the TNTs become rougher,resulting in the increased dye loading amounts,light scattering ability,and light harvest-ing efficiency,which are all beneficial for improving the IPCE of DSSCs.The EIS analysis reveals that some key parameters describing the kinetic processes of DSSCs are made better af-ter the HF or TiCl 4treatment,especially the sample treated with HF combining with TiCl 4,which can attain to the highest power conversion efficiency about 7.30%,with 35.69%en-hancement compared with the non-treated DSSC (5.38%).References(1)O'Regan,B.;Grätzel,M.Nature 1991,353,737.doi:10.1038/353737a0(2)Bella,F.;Bongiovanni,R.;Kumar,R.S.;Kulandainathan,M.A.;Stephanc,A.M.J.Mater.Chem.A 2013,1,9033.doi:10.1039/c3ta12135f (3)Xin,X.;He,M.;Han,W.;Jung,J.;Lin,Z.Angew.Chem.Int.Edit.2011,50,11739.doi:10.1002/anie.201104786(4)Grätzel,M.Nature 2001,414,338.doi:10.1038/35104607(5)Shu,W.;Liu,Y .;Peng,Z.;Chen,K.;Zhang,C.;Chen,pd .2013,563,229.doi:10.1016/j.jallcom.2013.02.086(6)Frank,J.;Kopidakis,N.;Lagemaat,J.Coord.Chem.Rev .2004,248,1165.doi:10.1016/r.2004.03.015(7)(a)Liu,R.H.;Zhang,S.;Xia,X.Y .;Yun,D.Q.;Bian,Z.Q.;Zhao,Y .L.Acta Phys.-Chim.Sin .2011,27,1701.[刘润花,张森,夏新元,云大钦,卞祖强,赵永亮.物理化学学报,2011,27,1701.]doi:10.3866/PKU.WHXB20110734(b)Lan,Z.;Wu,J.H.;Lin,J.M.;Huang,M.L.J.Inorg.Mater .2011,26,119.[兰章,吴季怀,林建明,黄妙良.无机材料学报,2011,26,119.](8)(a)Xiao,Y .M.;Wu,J.H.;Yue,G.T.;Lin,J.M.;Huang,M.L.;Fan,L.Q.;Lan,Z.Acta Phys.-Chim.Sin .2012,28,578.[肖尧Fig.7Nyquist plots of DSSCs based on TNT photoanodes at 0.6V applied forward bias under dark condition (A)and theequivalent circuit model (B)(A)The lines are fitting results with the equivalent circuit model.The curves from a to d represent the same samples as shown in Fig.4.(B)In the equivalentcircuit model,where r ct is the charge-transfer resistance of the charge recombination process between electrons in the TiO 2film and I 3-in the electrolyte;C u is the chemical capacitance of the TiO 2film;r tr is the transport resistance of the electrons in the TiO 2film;Z d is the Warburg element showing the Nernst diffusion of I 3-in the electrolyte;R Pt and C Pt are the charge-transfer resistance and double-layer capacitance at the counter electrode (platinized TCO glass),respectively;R s is the series resistance,including the sheet resistance ofthe TCO glass and the contact resistance of the cell.Table 2Parameters determined by fitting the EIS experimental data to the equivalent circuit shown inFig.7451Acta Phys.-Chim.Sin.2014V ol.30明,吴季怀,岳根田,林建明,黄妙良,范乐庆,兰章.物理化学学报,2012,28,578.]doi:10.3866/PKU.WHXB201201032(b)Feng,X.;Shankar,K.;Varghese,O.K.;Paulose,M.T.;Latempa,J.;Grimes,C.A.Nano Lett.2008,8,3781.(9)(a)Zhang,Z.Y.;Sang,L.X.;Sun,B.;Zhang,X.M.;Ma,C.F.Acta Phys.-Chim.Sin.2010,26,2935.[张知宇,桑丽霞,孙彪,张晓敏,马重芳.物理化学学报,2010,26,2935.]doi:10.3866/PKU.WHXB20101131(b)Hyeokapark,J.;Guakang,mun.2008,2867.(10)(a)Li,H.H.;Chen,R.F.;Ma,Z.;Zhang,S.L.;An,Z.F.;Huang,W.Acta Phys.-Chim.Sin.2011,27,1017.[李欢欢,陈润锋,马琮,张胜兰,安众福,黄维.物理化学学报,2011,27,1017.]doi:10.3866/PKU.WHXB20110514(b)Mor,G.K.;Shankar,K.;Paulose,M.;Varghese,O.K.;Grimes,G.A.Nano Lett.2006,6,215.(11)Jun,Y.;Park,J.H.;Kang,mun.2012,48,6456.doi:10.1039/c2cc30733b(12)(a)Su,Y.L.;Li,Y.;Du,Y.X.;Lei,L.C.Acta Phys.-Chim.Sin.2011,27,939.[苏雅玲,李轶,杜瑛珣,雷乐成.物理化学学报,2011,27,939.]doi:10.3866/PKU.WHXB20110401(b)Chang,W.T.;Hsueh,Y.C.;Huang,S.H.;Liu,K.I.;Kei,C.C.;Perng,T.P.J.Mater.Chem.A2013,1,1987.(13)Zhang,Z.;Wang,P.Energy Environ.Sci.2012,5,6506.doi:10.1039/c2ee03461a(14)Kuang,D.;Brillet,J.;Chen,P.;Takata,M.;Uchida,S.;Miura,H.;Sumioka,K.;Zakeeruddin,S.M.;Grätzel,M.ACS Nano2008,2,1113.doi:10.1021/nn800174y (15)Zhang,T.;Hu,X.;Fang,M.;Zhang,L.;Wang,Z.CrystEngComm2012,14,7656.doi:10.1039/c2ce25323b (16)Tao,L.;Xiong,Y.;Liu,H.;Shen,W.J.Mater.Chem.2012,22,7863.doi:10.1039/c2jm00005a(17)Lan,Z.;Wu,J.H.;Lin,J.M.;Huang,M.L.J.Mater.Chem.2011,21,15552.doi:10.1039/c1jm12812d(18)Lan,Z.;Wu,J.H.;Lin,J.M.;Huang,M.L.J.Mater.Chem.2012,22,3948.doi:10.1039/c2jm15019k(19)Wang,Q.;Moser,J.E.;Grätzel,M.J.Phys.Chem.B2005,109,14945.doi:10.1021/jp052768h(20)Lan,Z.;Wu,J.H.;Lin,J.M.;Huang,M.L.J.Mater.Sci.:Mater.Electron.2010,21,833.doi:10.1007/s10854-009-0003-4 (21)Choi,J.;Park,S.H.;Kwon,Y.S.;Lim,J.;Song,I.Y.;Park,T.mun.2012,48,8748.doi:10.1039/c2cc33629d (22)Yip,C.T.;Guo,M.;Huang,H.;Zhou,L.;Wang,Y.;Huang,C.Nanoscale2012,4,448.doi:10.1039/c2nr11317a(23)Huang,F.;Chen,D.;Zhang,X.L.;Caruso,R.A.;Cheng,Y.B.Adv.Funct.Mater.2010,20,1301.doi:10.1002/adfm.v20:8 (24)Yanagida,M.;Yamaguchi,T.;Kurashige,M.;Hara,K.;Katoh,R.;Sugihara,H.;Arakawa,H.Inorg.Chem.2003,42,7921.doi:10.1021/ic034674x(25)Wang,Z.S.;Li,F.Y.;Huang,C.H.J.Phys.Chem.B2001,105,9210.doi:10.1021/jp010667n(26)Bisquert,J.;Belmonte,G.G.;Santiago,F.F.;Ferriols,N.S.;Bogdanoff,P.;Pereira,E.C.J.Phys.Chem.B2000,104,2287.doi:10.1021/jp993148h452基于TiO2纳米管阵列的高效正面透光型染料敏化太阳能电池的制备及其光电性能作者：高素雯， 兰章， 吴晚霞， 阙兰芳， 吴季怀， 林建明， 黄妙良， GAO Su-Wen， LAN Zhang， WU Wan-Xia ， QUE Lan-Fang， WU Ji-Huai， LIN Jian-Ming， HUANG Miao-Liang作者单位：高素雯,吴晚霞,阙兰芳,GAO Su-Wen,WU Wan-Xia,QUE Lan-Fang(华侨大学材料科学与工程学院,福建厦门,361021)， 兰章,吴季怀,林建明,黄妙良,LAN Zhang,WU Ji-Huai,LIN Jian-Ming,HUANG Miao-Liang(华侨大学材料科学与工程学院，福建厦门361021; 环境友好功能材料教育部工程中心，福建厦门361021; 福建省高等教育功能材料重点实验室，福建厦门361021)刊名：物理化学学报英文刊名：Acta Physico-Chimica Sinica年，卷(期)：2014(3)本文链接：/Periodical_wlhxxb201403007.aspx。