不同元素替代掺杂化合物M_0_04_Ti__省略__M_Ni_Al_Mg_的热电

第28卷　第2期Vol 128　No 12材　料　科　学　与　工　程　学　报Journal of Materials Science &Engineering 总第124期Apr.2010Article ID :167322812(2010)022*******R eceived d ata :2009210214;Modif ied d ata :2009212204Found ation item :national natural science foundation of China (10904144、50701043、10774145)is gratefully acknowledged Biography :ZHAN G Jian (1982-),Ph. D.candidate ,E 2mail :zhangjian @.Corresponding author :QIN Xiao 2Y ing (1960-),Ph. D.E 2mail :xyqin @.Thermoelectric Properties of Doped CompoundsM 0.04Ti 0.96S 2(M =Ni ,Al ,Mg)ZHANG Jian ,QIN Xiao 2ying ,L I Di ,XIN H ong 2xing ,SONG Chun 2jun(K ey Laboratory of Materials Physics ,Institute of Solid State Physics ,Chinese Academy of Sciences ,H efei 230031,China)【Abstract 】　Element doped compo unds M 0.04Ti 0.96S 2(M =Ni ,Al ,Mg )were prepared by solid 2state reaction ,and t heir t ransport and t hermoelect ric p roperties were investigated f rom 5K to 310K.The result s indicated t hat elect ric resistivity ρincreased as M (=Ni ,Al ,Mg )was int roduced ,at low temperat ures ρ～T curves for M 0.04Ti 0.96S 2(M =Ni ,Al ,Mg )were found to obey t he Mott ’s two 2dimensional hopping law ln ρ～T -1/3,indicating t hat TiS 2possess 2D t ransport characteristics.The appearance of Mott ’s 2D law could originate f rom potential disorder int roduced by M substit ution for Ti in S 2Ti 2S slabs.Moreover ,it was found t hat t he absolute t hermopower |S |for Al ,Mg doped compounds increased significantly in t he wholetemperat ure range investigated ,and specifically t he |S |of Al 0.04Ti 0.96S 2is about 500μV/K ,it is ～2times as great as t hat of TiS 2at 310K.Z T of t he Mg doped compound Mg 0.04Ti 0.96S 2is ～1.6times as great as t hat of TiS 2at 310K ,indicating t hat element doping is an effective app roach to enhance t hermoelect ric performance of TiS 2.【K ey w ords 】　TiS 2;t hermoelect ric ;resistivity ;t hermal conductivityC LC number :O482.6 Document Code :A不同元素替代掺杂化合物M 0.04Ti 0.96S 2(M =Ni ,Al ,Mg)的热电性质张　建,秦晓英,李　地,辛红星,宋春军(中国科学院固体物理研究所材料物理重点实验室,安徽合肥　230031) 【摘　要】　层状结构TiS 2具有准二维结构,高热电势(室温时S ≈250μV/K )和大的热电功率因子,作为热电材料具有很好的开发和应用前景。

通过固相反应法,我们分别用原子量大于和小于Ti 的原子部分替代Ti 位引入替位缺陷(Ni Ti ″,Al Ti ′,Mg Ti ″),合成了不同元素替代掺杂化合物M 0.04Ti 0.96S 2(M =Ni ,Al ,Mg ),在52310K 的温度范围内研究了各化合物的电阻率、热导率及热电势率与温度的对应关系。

结果表明Ni 、Al 、Mg 三种元素的掺杂均引起了主体材料从金属性到半导体导电性质的转变,且在低温范围内呈现莫特二维变程跳跃电导规律,ln σ∝T -1/3,表明了TiS 2的二维导电机制。

值得注意的是:①Mg 、Al 的掺杂引起了热电势绝对值的显著增高,特别是Al 掺杂的化合物在310K 时热电势率为-500μV/K ,达到了纯TiS 2的200%;②Ni 掺杂也在整个研究温区引起热导率的明显下降,而Mg 、Al 的掺杂却在整个研究温区引起热导率的明显升高。

由于电阻率的增大,Ni 、Al 的掺杂均没能使得材料的ZT 值有所提高,而Mg 的掺杂明显地提高了TiS 2的ZT 值,在310K 其ZT 值是纯TiS 2的1.6倍。

这表明元素掺杂是提高材料的热电优值的有效途径之一。

【关键词】　TiS 2;热电;电阻率;热导率1　Int roductionTiS2has an anisot ropic st ruct ure wit h a t rigonal space group,P3m.It is known to exist in two polytypes(1T,2H)wit h octahedral and t rigonal p rismatic coordinations,respectively.The main difference between t he1T2TiS2and2H2TiS2layers is t he type of t he local coordination of t he metal: octahedral(1T)versus t rigonal2prismatic(2H)[1]. The most stable form of TiS2(1T2TiS2,crystallizes in a layered CdI22like st ruct ure)consist s of sheet s of face2sharing TiS6octahedra forming of S2Ti2S sandwich layers,where a Ti sheet is sandwiched between two sulf ur sheet s.Atoms wit hin S2Ti2S sheet s are bound by st rong covalent interactions; bonding between t he layers is determined by weak van der Waals forces.Alt hough t he st ruct ure of TiS2is quite simple, t he nat ure of t he elect ronic st ruct ure of layered material TiS2has been in disp ute over t he past decades.Up to now,for instance,whet her it is semico nductor or semimetal has not been clarified[2216].Through t he measurement s of t he Hall coefficient,Seebeck coefficient and resistivity as a f unction of p ressure,Klip stein and Friend[2]found t hat t he band overlap between S3p states and Ti3d states increased at a rate of 4.5meV/Kbar,and concluded t hat TiS2is a semiconductor wit h a gap of 0.18±0.06eV.And many researches reported by Greenway and Nische[3],Chen et al[4],Barry et al[5],Shep herd and Williams[6]and Allan et al[7] indicated t hat TiS2is a semiconductor.On t he cont rary,some t heoretical calculations indicate t hat TiS2is a tely Benesh et al[8]got a semimetallic ground state for TiS2by using t he L A PW met hod as a f unction of pressure.Similarly, band calculations based on t he augmented sp herical wave(ASW)met hod by Fang et al[9],t he linear2 muffin2tin2orbital(L M TO)met hod by Wu et al[10212],and t he FP2LA PW met hod[13,14]showed t hat TiS2possessed a semi2metallic ground state. Meanwhile,many experiment s[15,16]indicated t hat t he electrical resistivity of TiS2almo st exclusively exhibit s metallic behavior.So far,no semico nductor behavior in it s conductivity of TiS2has ever been observed experimentally.On t he ot her hand,layered2struct ured TiS2is well known for it s capability of intercalation by a wide range of bot h organic and inorganic materials into it s van der Waals gap[17].For instance,since Li+can easily intercalate and leave van der Waals gap of TiS2,it has been st udied as a p romising cat hode material for rechargeable lit hium2ion batteries[17219]. Besides Li[2,20,21],t ransitio n metals,such as Fe,Co and Ni[22,23],have been successf ully inserted into t he gap of TiS2,and influences of t his intercalation on t he p hysical properties of t he corresponding compounds were investigated and explored. Specially,Imai et al reported t hat TiS2has large t hermopower S and power factor(S2/ρ,ρis electrical resistivity)at room temperat ure[24], indicating t hat TiS2is a potential candidate for t hermoelect ric applications.Very recently,t he work in o ur group indicated t hat large enhancement of t hermoelect ric properties for TiS2can be realized by intercalating proper Bi into it s ven der Waals gap[25].As outlined above,in order to tailor or improve t he p hysical properties of TiS2,numerous works conducted so far concent rated mainly on intercalation of guest atoms or molecules.Alternatively,at least in principle,t he p roperties of TiS2can also be t uned by substit utional doping,such as substit ution of foreign atoms for Ti in t he S2Ti2S sheet s of TiS2. Unfort unately,to our knowledge,so far no systematic work[26229]has been reported mainly due to difficulties in materials synt hesis,which is caused by simultaneous intercalations of t he foreign atoms.The aim of present work is to synt hesize t he element doped compounds M0.04Ti0.96S2(M=Ni,Al,Mg), and to investigate t he effect s of substit utional doping wit h element M on t heir t ransport properties and t hermoelect ric performance in t he temperat ure range f rom5K to310K.Our result s showed t hat element doping could not only cause significant changes of it s t ransport p roperties,but also give rise to enhancement of t hermoelect ric performance of TiS2 when doped p roperly.・832・材料科学与工程学报2010年4月2　Experimental DetailsPolycrystals of element doped compounds M0.04 Ti0.96S2(M=Ni,Al,Mg)samples were prepared by a solid2state reaction met hod.Titanium(99.9 wt.%),sulf ur(99.999wt.%)and nickel(99.0 wt.%)or aluminum(99.0wt.%)or magnesium (99.0wt.%)powders were weighed accurately to give t he desired compo sition,which were mixed intimately to give a homogeneous mixt ure and sealed in an evacuated quartz t ube,and t hen heat2t reated in a horizontal f urnace at880K for7days wit h a fixed heating rate of0.5K/min.The bulk specimens for t ransport p roperty measurement s were obtained by hot2p ressing at673K in vacuum.The p hase st ruct ures and t he compo sitions of t he obtained samples were checked using x2ray powder diff raction(XRD)and energy dispersive spect ro scopy (EDS),respectively.XRD analysis was carried out on a Philip s diff ractometer using Cu2Kαradiation. The accurate lattice parameters were determined f rom t he d2values of t he XRD peaks using a standard least2 squares refinement met hod wit h a Si standard for calibration.The measurement s of t ransport p roperties(DC resistivity,t hermal conductivity,and t hermopower)were carried out on a p hysical p roperty measurement system(PPMS)(Quant um Design)in t he temperat ure range from5to310K.3　Result s and Discussion3.1　Phase determination and change of lattice parameters after M addition analyzed by x2ray diffractionFig.1shows XRD patterns for t he synt hesized specimens wit h different element doped compo unds M0.04Ti0.96S2(M=Ni,Al,Mg).One can see f rom Fig.1t hat all t he main peaks on t he XRD patterns match well wit h t hose for TiS2,indicating t hat t he doped specimens have t he same crystallograp hic st ruct ure as t hat of TiS2.The values of t he lattice parameters a and c for all t he samples have been calculated f rom t he XRD data,which are shown in Fig.2.It can be seen t hat t he lattice parameter c of doped compounds M0.04Ti0.96S2(c= 5.6933!, 5.6946!,5.7144!for M=Ni,Al,Mg respectively) have minor changes compared to t hat of TiS2(c= 5.7044!)except Mg0.04Ti0.96S2,may due to more Mg atoms intercalated to t he van der waals gap s of TiS2t han Ni or Al t hat can be verified by t hat t he resistivity value of Mg0.04Ti0.96S2has decreased compared wit h t hat of p ure TiS2as t he resistivity value of Ni or Al doped compounds increased. Moreover,t he lattice parameter a is found to decrease f rom 3.4098!to 3.4054!, 3.4038!, 3.4039!for M=Al,Mg,Ni respectively.Many investigations showed t hat[28230]lattice parameter a of t he intercalated compounds A y TiS2(here A stands for intercalated element s)was always found to increase wit h increasing content of intercalated element s(For example,lattice parameter a changed f rom3.4083! to3.4156!in Bi y TiS2[28]wit h y increasing f rom0to 0.25;and t he parameter a of Li y TiS2[29]and Ti1+y S2[30]also increased wit h increasing y).Therefore, t he decrease of parameter a reflect s t hat substit ution of M(for Ti)has occurred after M addition,for atomic radius of M is smaller t han t hat of Ti(atomic radius R Ti=2.00!,R Al=1.82!,R Mg=1.72!, R Ni= 1.62!),if M atoms replace Ti atoms to int roduce defect s(Ni Ti″,Al Ti′,Mg Ti″),which are smaller t han Ti Ti×in size,and form covalent bonds[31]t he lattice of M0.04Ti0.96S2will shrink as compared wit h t hat of TiS2.Fig.1　XRD patterns of doped compoundsM0.04Ti0.96S2(M=Ni,Al,Mg).3.2　The effect of M doping on DC resistivityThe temperat ure dependences of t he elect rical resistivity for specimens wit h different element substit utions are shown in Fig.3.One can see t hat・932・第28卷第2期张　建,等.不同元素替代掺杂化合物M0.04Ti0.96S2(M=Ni,Al,Mg)的热电性质　Fig.2　Lattice parameters a and c for doped compoundsM0.04Ti0.96S2(M=Ni,Al,Mg).t heρ2T curve for p ure TiS2sample(x=0)shows a metal2like behavior(i.e.,dρ/d T>0)in t he whole temperat ure range investigated.Fitting t he resistivity to a power law,(ρ(T)-ρ0)∝Tγ,givesγ=2.2,in agreement wit h p revious result s reported by Klip stein et al[32].In cont rast,t heρ2T curves for t he substit uted compounds Ni0.04Ti0.96S2show a semico nductor2like behavior(i.e.,dρ/d T<0)in whole investigated temperat ure range,and M0.04Ti0.96 S2(M=Al,Mg)also show a semiconductor2like behavior as temperat ure decreases to a critical temperat ure T c(=52.3K,104.3K for M=Al,Mg, respectively),alt hough t hey still exhibit metal2like behavior in high temperat ure regions.This is quite cont rary to t hat for p urely intercalated compo unds A y TiS2,who se metallic behavior enhances wit h increasing intercalated element s[33,34],In addition, t he elect rical resistivity of doped compounds M0.04 Ti0.96S2(M=Ni,Al,Mg)is greater t han t hat of p ure TiS2(in whole investigated temperat ure range for Ni or Al substit ution,below184K for Mg substit ution),which is also cont rary to t he p heno mena in p urely intercalated TiS2where it s resistivity always decreased,as has been observed in Bi y TiS2[25]and Li y TiS2[33,34].These result s indicated f urt her t hat substit ution instead of intercalation of M took place mainly in t he compounds,for as M(Ni2+, Al3+or Mg2+)substit uted for Ti4+,acceptors (Ni Ti″,Al Ti′,Mg Ti″)will be int roduced and elect ron concentration in t he compounds will decrease due to compensation effect,giving rise to increase in resistivity.Nevert heless,one notices t hat t he electrical resistivity of compound Mg0.04Ti0.96S2is smaller t han t hat of doped compounds M0.04Ti0.96S2 (M=Ni,Al)(comparing curve(b)wit h curves(c)and(d)in Fig.3).This p henomenon indicated t hat t here were more Mg2+intercalation into t he van der Waals gap s t han Ni2+or Al3+,for intercalation of M would result in charge t ransfer f rom t he guest atoms to TiS2host,giving rising to increase in elect ron concentration.One can notice t hat t he resistivity of Ni doped compound Ni0.04Ti0.96S2is far larger t han t hat of Mg(or Al)doped compound Mg0.04Ti0.96S2 (or M0.04Ti0.96S2),which may due to Ni substit ution is more p ure t han Mg(or Al)substit ution in t he dopedcompounds.Fig.3　Dependence of t he electrical resistivityρon temperature for doped compounds M0.04Ti0.96S2(M=Ni,Al,Mg).Fig.4　Plot s of lnσversus1/T1/3for doped compoundsM0.04Ti0.96S2(M=Ni,Al,Mg). On t he ot her hand,co nsidering t hat M substit ution for Ti in S2Ti2S conduction planes may give rise to potential disorder,which would be strong enough to lead to considerable localized states,at very low temperat ures p honon assisted t unneling or hopping may dominate t he conductio n process.By best fitting t he experimental data to Mott’s variable range hopping(V R H)law,we find t hat t he conductivity data of M0.04Ti0.96S2(M=Ni,Al,Mg) in corresponding temperat ure ranges are in good agreement wit h Mott’s two2dimensional(2D)VR H law,i.e.:・42・材料科学与工程学报2010年4月σ=σ0exp-T0T1/3(1)where T0=8/(πkN(E F)l2v)is t he hopping barrier, andσ0is a co nstant.Figure4shows t he plot s of lnσversus T-1/3for t hree doped specimens.It can be seen t hat t here are good linear relations between lnσand T-1/3at lower temperat ure range,suggesting t hat TiS2has2D t ransport characteristics.The fitted values of T0are3892K,0.05K and2.5K for M=Ni, Al,Mg,respectively.3.3　The effect of M doping on thermal conductivityThe temperat ure dependences of total t hermal conductivityκfor M0.04Ti0.96S2(M=Ni,Al,Mg)are shown in Fig.5.It can be seen t hat M substit ution for Ti causes increase in t he t hermal conductivity (t here is an exception as M=Ni).Similar to t hat of TiS2,t he t hermal conductivityκof t he doped compounds shows weak temperat ure dependence above60K,below whichκof all t he compo unds increases rapidly and approximately linearly wit h increasing temperat ure.The total t hermal conductivityκcan be expressed by t he sum of lattice component(κl)and elect ronic compo nent(κe)asκ=κl+κe.Theκe values can be estimated f rom Wiedemann2Franz’s law asκe=L T/ρ(here L is t he Lorentz number,and L=2.44×10-8V2K-2for free electrons).Co nsequently,κL can be estimated f romκandκe,as shown in Fig. 6.It can be seen by comparing Fig.6wit h Fig.7t hat t he values and temperat ure dependences of lattice conductivityκl are similar to t ho se of t he total t hermal conductivityκ. This result indicates t hat t hermal conductivity of M0.04Ti0.96S2come mainly fro m t heir lattice conductivity.One can notice t hat M(=Al,Mg) doping causes increase in t he lattice conductivity of M0.04Ti0.96S2compared wit h t hat of p ure TiS2,but t he lattice conductivity decreases as M=Ni.This increase of lattice t hermal conductivityκL of Mg0.04 Ti0.96S2or Al0.04Ti0.96S2may originate f rom increase in acoustic velocity caused by lighter weight of Mg or Al atoms(t han t hat of Ti atoms),and t he decease ofκL of Ni0.04Ti0.96S2may originate f rom decrease in acoustic velocity caused by heavier weight of Ni ato ms(t han t hat of Ti atoms).3.4　The effect of M doping on thermopow erFig.5　Plot s of t hermal conductivityκversus temperature for doped compounds M0.04Ti0.96S2(M=Ni,Al,Mg).Fig.6　Plot s of lattice t hermal conductivityκversus temperature for doped compounds M0.04Ti0.96S2(M=Ni,Al,Mg).Fig.7　Variation of t hermopower S wit h temperature for doped compounds M0.04Ti0.96S2(M=Ni,Al,Mg). The variations of t he Seebeck coefficient(S)for M0.04Ti0.96S2(M=Ni,Al,Mg)wit h temperat ure are shown in Fig.7.The negative values of t he Seebeck coefficient fo und for all of t he specimens over t he entire temperat ure range show t hat t he major charge carriers in M0.04Ti0.96S2are elect rons.Moreover,one can see f rom Fig.7t hat t he Seebeck coefficient of all t he doped compounds M0.04Ti0.96S2(M=Al,Mg)is larger t han t hat of p ure TiS2.At310K,|S|= 300μV/K of Mg0.04Ti0.96S2,which is about21% larger t han t hat(248μV/K)of TiS2,and more obviously,|S|=505μV/K of Al0.04Ti0.96S2at310K, which is about104%larger t han t hat(248μV/K)of TiS2.However,for Ni substit uted compound,|S|・142・第28卷第2期张　建,等.不同元素替代掺杂化合物M0.04Ti0.96S2(M=Ni,Al,Mg)的热电性质　became smaller t han t hat of p ure TiS2.The temperat ure behavior of Seebeck coefficient for t he doped compounds M0.04Ti0.96S2(M=Ni,Al, Mg)is more or less similar to t hat of p ure TiS2:t he absolute t hermopower|S|for every compound is found to increase continuously wit h increasing temperat ure in t he whole temperat ure range investigated.The small valley observed at t he temperat ure around60K for each of t hem in t he plot of S vs.T could be ascribed to t he p honon2drag effect[28].At t he temperat ures above150K t he t hermopower for M0.04Ti0.96S2(M=Ni,Al,Mg)has approximately linear relationship to temperat ure. The diff usive part of t hermopower(T2linear t hermopower)can be described by formula[27]:S=π2k2Te E F(2)where k and e are Boltzmann constant and elect ron charge,respectively.This formula indicates t hat t he slope of t he plot S vs.T is inversely proportional to Fermi level.Best fit of t he data to formula(2)yields estimation of t he Fermi level E F for all t he compounds,as listed in table1.One can see t hat E F =0.237eV,0.119eV,0.045eV for M=Ni,Mg,Al respectively,E F of Al0.04Ti0.96S2is obviously smaller t han t hat of Mg0.04Ti0.96S2or Ni0.04Ti0.96S2,t his agrees wit h t hat t he|S|of Al0.04Ti0.96S2is largest in t he t hree doped specimens.T able1　Slope of the plot S vs.T and E F calculatedfrom the formula(2)M Ni Al MgSlop/μV-1・K-2-0.3100-0.6190-1.6408E F/eV0.2370.1190.0453.5　The effects of doping M on thermoelectric propertiesFig.8shows t he temperat ure dependence of dimensionless figure of merit Z T(=T S2/ρκ)for TiS2and t he doped compo unds M0.04Ti0.96S2(M=Ni, Al,Mg).The Z T values for all t he specimens increase wit h increasing temperat ure.However,t he Z T of all t he doped compounds M0.04Ti0.96S2(M=Ni, Al)is smaller t han t hat of p ure TiS2almost over whole temperat ure range,because t heir larger t hermal conductivity and resistivity.It is to be observed t hat Z T of Mg0.04Ti0.96S2reaches0.027at 310K,which is abo ut60%larger t han t hat of TiS2, exhibiting a spectacular improvement of it s t hermoelect ric performance after proper elementdoping.Fig.8　Variation of ZT wit h temperature for doped compoundsM0.04Ti0.96S2(M=Ni,Al,Mg).4　ConclusionsWe have st udied t he transport and t hermoelect ric properties of element doped compounds M0.04Ti0.96S2(M=Ni,Al,Mg)in t he range of5K to310K.The result s indicated t hat electric resistivityρincreased as M(=Ni,Al,Mg) int roduced,at low temperat uresρ～T curves for M0.04Ti0.96S2(M=Ni,Al,Mg)were found to obey t he Mott’s two2dimensional hopping law lnρ～T-1/3,indicating t hat TiS2possess2D t ransport characteristics.The appearance of Mott’s2D law could originate from potential disorder introduced by M substit ution for Ti in S2Ti2S slabs.Moreover,it was found t hat t he absolute t hermopower|S|for Al, Mg doped compounds increased significantly in t he whole temperat ure range investigated,and specifically t he|S|of Al0.04Ti0.96S2is about500μV/ K,it is～2times as great as t hat of TiS2at310K, which could be explained by lower Fermi level(E F= 0.045eV)of Al0.04Ti0.96S2.The increase ofρand|S| can be ascribed to decrease in electron concent ration due to M substit ution for Ti.Z T of t he Mg doped compound Mg0.04Ti0.96S2is～1.6times as great as t hat of TiS2at310K,indicating t hat element substit ution is an effective app roach to enhance t hermoelect ric performance of TiS2.・242・材料科学与工程学报2010年4月R eferences[1]　V.V.Ivanovskaya,G.Seifert.[J].Solid State Commun,2004,130:175～180.[2]　P. 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