中国光学 掺碲硒化镓晶体的光学性能 2. 俄罗斯科学院西伯利亚分院气候与生态系统监测研究所, 托木斯克 , 俄罗斯 ; 3. 俄罗斯托木斯克洲立大学西伯利亚物理技术研究所, 托木斯克 , 俄罗斯 ; 4. 中国科学院长春光学精密机械与物理研究所, 吉林长春 )

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第 4 卷 第 6 期 2011 年 12 月 中国光学 ChineseOptics Vol.4 No.6 Dec.2011 文章编号 1674 2915(2011)06 0660 07 OpticalpropertiesofTe dopedgasecrystal KUShin an 1,CHUWei chen 1,LUOChih wei 1,ANDREEVYM 2,4,LANSKIGV 2, SHAIDUKOAV 2,IZAAKTI 3,SVETLICHNYIVA 3,VAYTULEVICHEA 3,ZUEVVV 2 (1.NationalChiaoTungUniversity,Hsinchu30010,Taiwan,China; 2.InstituteofMonitoringofClimaticandEcologicalSystemSBRAS,Tomsk634055,Rusia; 3.SiberianPhysics technicalinstituteoftsu,tomsk634050,rusia; 4.ChangchunInstituteofOptics,FineMechanicsandPhysics,ChineseAcademy ofsciences,changchun130033,china) Abstract:ε GaSecrystalsaregrownwiththestoichiometricGaSeof0 05%,0 1%,0 5%,1% and2% (maspercent)teandarecharacterizedbygase Te(0 01%,0 07%,0 38%,0 67% and2 07%(mas percent))crystals.thetransformationoftherigidlayerphononmodeswithdopingisstudiedforthefirst time.theabsorptionpeakoftherigidmodee (2) centeredat~0 59THzisrisingupintheintensitytilreac hingamaximalvalueonthefirststageofthedopingconcentrationlesthan0 38%(maspercent).This procescorelateswelwiththeimprovementintheopticalproperty.furtherdopingisresultinginthedecrease oftheintensitytilvanishingthee (2) absorptionpeakat1%(maspercent)te.simultaneouslywiththe E (2) absorptionpeakdecreasing,theabsorptionpeakoftherigidmodee (2) centeredat1 78THzisrisingup intheintensity.thetwoprocesescorelatewelwiththedegradationintheopticalqualityofgase Tecrys tal.thedopinglevelthatresultsinthehighestintensityoftheabsorptionpeakoftherigidlayermodee (2) is proposedasacriterionintheidentificationoftheoptimalte dopingingasecrystalthatisconfirmedbythz generationviaopticalrectification. Keywords:GaSe;GaSe Tecrystal;crystalgrowth;opticalproperty;THz 掺碲硒化镓晶体的光学性能 古新安 1, 朱韦臻 1, 罗志伟 1,ANDREEVYM 2,4,LANSKIGV 2,SHAIDUKOAV 2, IZAAKTI 3,SVETLICHNYIVA 3,VAYTULEVICHEA 3,ZUEVVV 2 (1. 国立交通大学, 新竹 30010, 中国台湾 ; 2. 俄罗斯科学院西伯利亚分院气候与生态系统监测研究所, 托木斯克 634055, 俄罗斯 ; 3. 俄罗斯托木斯克洲立大学西伯利亚物理技术研究所, 托木斯克 634050, 俄罗斯 ; 4. 中国科学院长春光学精密机械与物理研究所, 吉林长春 130033) 收稿日期 :2011 09 21; 修订日期 :2011 11 23 基金项目 :supportedbyrfbrproject(no.10 02 01452 a),presidiumsbrasundertheprojectvi.63.3.1ofvi.63.3 Prog.andJoinProj.betweenPresidiumSBRASandPresidiumNAS,BelarusNo.10of2010.

第 6 期 GUXin an,etal.:opticalpropertiesofte dopedgasecrystal 661 摘要 : 采用水平区熔法生长了碲 (Te) 掺杂浓度 ( 质量百分比 ) 分别为 0 05%,0 1%,0 5%,1%,2% 的硒化镓 (GaSe) 晶体, 并分别对掺杂浓度为 0 01%,0 07%,0 38%,0 67%,2 07% 的 GaSe Te 晶体的光学性能进行了表征 首次研究了 GaSe Te 晶体中刚性层声子模式的转换 吸收光谱测试结果表明 : 当 Te 掺杂浓度小于 0 38% 时, 振动中心位于 0 59THz 附近的 E (2) 刚性模式吸收峰强度可达最大值, 这一过程与 GaSe Te 晶体光学性能的提高密切相关 但 Te 掺杂浓度的进一步提高会导致 E (2) 刚性模式吸收峰强度逐渐减弱, 当 Te 掺杂浓度为 1% 时,E (2) 刚性模式吸收峰基本消失 这两个过程与 GaSe Te 晶体光学质量的下降密切相关 因此,E (2) 刚性模式吸收强度达到最高时对应的掺杂浓度即是 GaSe Te 晶体中 Te 的最佳掺杂浓度, 光整流产生太赫兹过程证实了此结论的正确性 关键词 : 硒化镓 ; 掺碲硒化镓 ; 晶体生长 ; 光学性能 ; 太赫兹 中图分类号 :O734;TN304.2 文献标识码 :A 1 Introduction Duetoasetofextremeopticalproperties,GaSehas been succesfuly employed to generate coherent radiationinthemid infraredanddowntothetera hertz(thz) frequency range [1 2]. On the other hand,low hardnesandeasycleavingleadtolow opticalpropertiesthathampertheapplicationsof large areacrystals.fortunately,gaseisagoodma trixmaterialfordopingwithvariousimpurities.an originalε polytypicstructureofgaseisstrengthened bydopingimpuritiesandotherphysicalproperties beingresponsibleforthefrequencyconversionefi ciencyandexploitationparametersarealsosignifi cantlymodified [3 9].Nevertheles,whileTHzgener ationbyopticalrectificationanddown conversionin GaSehasbeenstudiedindetail [2,10 11],thereare veryfewtasksdevotedtotheexperimentalstudyof THzrangeopticalpropertiesandgenerationindoped GaSe.OpticalpropertiesandeficiencyofTHzgen erationisstudiedexperimentalyins dopedgase (GaSe S) [12 17],GaSe In [15 16,18],GaSe Er [19 20], GaSe Al [21] andgase Te [15 16,18,22 23].Thestudies ofthephysicalpropertiesandthzgenerationinthe intricatecrystalsgrownfrom themeltgase AgGaS 2 (identifiedasdoubledopedgase S Ag)andGaSe AgGaSe 2 (identified asgase Ag) are repor ted [21,24],relatively. Beyondmid IR,theTHzabsorptionofanon linearcrystalplacesapracticallimitonfrequency rangeofopticalrectificationanddownconversion. TheTHzabsorptionofacrystalisusualyatributed toinfrared activephononmodesortheircombination modes.theimpactofthephononmodesincluding rigidlayermodee (2) centeredat0 586THzonre fractiveindicesand THzgeneration eficiency in GaSe ErwasstudiedexperimentalyinRef.[20]. Secondorderphononmodeswereidentifiedincenti meter sizedhighopticalqualitygase Scrystalsin Ref.[12 13].Norigidmodetransformationwith dopingwereeverbeenreportedbutrisingupofthe rigidmodee (2) at1 78THzinintensity [14],soas degeneracyoftherigid layermodee (2) in low dopedgase S [14,17] andgase Te [25].Thus,thea vailabledataon opticalpropertiesin centimeter sizeddopedgaseinthethzregionarestilincon sistent.besides,nooptimaldopingbyanimpurity ingasehaseverbeenreported. Thisworkreportsthegrowthofhexagonalstruc turegasedopedwith0 05%,0 1%,0 5%,1%, 2%,5% and10%(maspercent)teorgase Te (0 05%,0 1%,0 5%,1%,2%,5% and10% (maspercent))inthechargecompositionandfor thefisttimeinourknowledgeexperimentalstudyof therigidmodestransformationwithdopingiscaried out.criterionfordeterminationoftheoptimalte do pingisproposedandcheckedinanopticalrectifica tionexperiment.

662 中国光学第 4 卷 2 Crystalgrowthandcharacterization 2.1 CrystalGrowth CreationofGaSe 1-x Te x crystalsinvolvestwoprinci plesteps.initialysynthesispolycrystalinematerial withthemasof120-150ghasbeenproducedina two zonehorizontalfurnacebyusing high purity (99 9999%)galium(Ga),selenium(Se),and 99 9% telurium(te).a weightedchargeofga andsewereplacedintheboatslocatedathotand coldendsoftheampoule.chemicalreactionofthe reagentsuptogaseformationhasbeenproducedon thefirststagebysublimationofseat690 andin teractionofthevaporwithgameltat970,that is,thegasecompoundissynthesizedunderseleni umvaporpresureinthereactionampoule.thesec ondstageprovidesthemelthomogenizationat1000 duetodifusion,whereasonthethirdstagethe meltiscooledfor36handthehomogeneouslarge blockgaseingotsaregrown.theprocesofgase synthesisisperformedbythreesequentialstagesat diferenttemperatureprofilesovertheampoulesasit isdescribedindetailselsewhere [26 32].DopingbyTe atomswasdevelopedby0 05%,0 1%,0 5%, 1%,2%,5% and10% (maspercent)intothe boatwithgaliumduringsynthesisofthecompound. Thetemperaturegradientatthecrystalizationfront was10 /cm andcrystalpulingratewas10mm/ d.thesampleswerepreparedbycleavinganas growningotparaleltothec planelayerandused withoutanyadditionaltreatment.thelengthsofthe specimenspreparedandstudiedwere1 14,1 0, 1 0,0 98and0 86mm,respectively. 2.2 Crystalcompositionandstructure ThecompositionoftheGaSe Tecrystalwasprovided byz 8000atomic absorptionspectrometry,hitachi spectrometer(air acetyleneflame)andbyinductive ly coupled plasma opticalemision spectrometry (ICP OES)withspectrometeriCAP6500,Thermo Scientificafterdisolutionofsampleweightsinnitric acid.crystalsgrownfrom thechargewith0 05%, 0 1%,0 5%,1% and2%(maspercent)ofte are identified as GaSe Te(0 01%, 0 07%, 0 38%,0 67% and2 07%(maspercent))crys tals,respectively.theε polytypestructureofthe observedspecimenswasidentifiedbytheproposed nonlinearmethod [33] throughφ angledependenceof afemtosecondti sapphirelaseropticalrectification. Foralcrystals,rectifiedsignalversusφ anglewas clearsix petal flowertypewhichissimilartothatin ε GaSe,asitgoesfromtherelationforeficientnon linearsusceptibilitycoeficientd ef =d 22 cosθsin3φ forthetype Iofthreefrequencyinteractions. 2.3 Opticalproperties UV visibletransmisionofthecloselengthspeci mensobserved wasrecorded by Cary100 Scan (Varian,Inc.,Austria) spectrometer:wavelength rangeis190900nm,spectralresolutionis0 2-4nm,wavelength deviation is ±1 nm.mid IR transmisionwasrecorded byftir Nicolet6700 (ThermoElectronCorp.) spectrometer:operation wavelengthrangeis11000-375cm -1,spectral resolutionis0 09cm -1.Selectedspectraarepres entedinfig.1(a)and(b). Absolutevaluesoftheatenuationcoeficientsat maximalmid IR transparencyrangeweremeasured atchosenpointsonthecrystalfacedwithlowpower 1 0mmbeamatwavelengthof9 6μm CO 2 laser bandtominimizetheinfluenceofthesurfacedefects onthemeasurementresults. Terahertzrangeabsorptioncoeficientandn o spectrainthecrystalsweredeterminedbyahome madethz TDSspectrometerwith50fsTi sapphire lasersystem(800nm)describedelsewhere [14].The THzbeamwasnormalyincidenttothecrystalface. TheTHzabsorptionanddispersionspectraareshown infig.1(c)and(d).

第 6 期 GUXin an,etal.:opticalpropertiesofte dopedgasecrystal 663 Fig.1 UV visible(a),mid IR(b)transmision,THzo waveabsorption(c)andn o dispersionspectra(d)ingase Te. 3 Resultsanddiscusion Crystals grown from the charge with 0 05%, 0 1%,0 5%,1% and2%(maspercent)ofte areidentifiedas,respectively,ε GaSe Te(0 01%, 0 07%,0 38%,0 67% and2 07% (masper cent))singlecrystalsthataresuitableforthzgen erationviaopticalrectificationanddownconversion. Atmaximaltransparencyrangeofmid IRGaSe Te (0 01,0 07,0 38mas%)crystalsposeseso waveabsorptioncoeficientαfrom ~0 2cm -1 to 0 5cm -1.GaSe Te(0 67%,maspercent)crys talsischaracterizedbydramaticalyincreasedα 5cm -1 mainlyduetohighdensityofteprecipi tates.crystalsgrownfrom thechargewith5% and 10%(maspercent)Teappearasusefulnespoly crystalinelow optical qualitymaterial. InFig.1(a),itisseenthatthestructureof phononmodesinmid IRareindependentbutrigid modesin THzrangetransformingwith Te doping (Fig.1(c)).TherigidlayermodeE (2) at~0 59 THzisexpectedtobethemodeinwhichthelayer vibrationareasrigidunitsagainsteachotherand thatthereisnorelativedisplacementofthegaand Seatomswithinalayer.ForlowTe dopedcrystals thecenterofthee (2) modeiswelincoincidence withthedataforpuregaseinref.[34].measuring thephononabsorptionspectrainmm lengthcrystals wereporte (2) isrisinguptilreachingthehighest valueatte dopingbetween0 07% and0 38% (maspercent).thisprocescorelateswelwith theimprovementintheopticalqualityingase Te duetothedecreasinginthenumberofpointandlay erstackingdefects [35]. TherigidlayermodeE (2) isdecreasinginthe intensity tildegeneracy with furtherte doping. Simultaneously, the absorption peak ofthe rigid modee (2) centeredat1 78THzisrapidlyrisingup intheintensityandnoticeablyinfluencethen o dis persionatte doping 0 67%(maspercent)(Fig. 1(d)).Itisthemodeinwhichthelayersvibratea

664 中国光学第 4 卷 gainsteachotherwiththerelativedisplacementof twoga Sesub layerswithinafour atomlayer [36].It wasestablishedthatbothe (2) rigidlayermodedeg radationande (2) rigidmoderisingupcorelatewel withthedecreasinginthecrystalopticalqualitythat isduetonumerousreasonssuchasstructuraldefects (polytypism,stackingfaults,dislocations) [35,37 38], defectcomplexes [9,37],excitonphononandexciton impurityinteractions [37],interlayerinterstitials [35,39] andinternalstrains [40]. Noadistinctreasonwasformulatedtoexplain therisingupinintensityofe (2) rigidmodewithte doping. Posibly interlayerintercalation oflarger sizeofteatoms [9,37] leadstotheformationofthelo calstrainedregionsthatbondhardseandgalay ers. 4 Conclusion TherigidmodetransformationinGaSe Tecrystal wasstudiedforthefirsttime.thisprocescore lateswelwiththetransformationoftheopticalquali tyingase Te.Dopinglevelthatisresultinginthe highestintensityoftheabsorptionpeakofrigidlayer modee (2) isproposedasthecriterionofoptimalte dopingingase. References: [1] DMITRIEVVG,GURZADYANGG,NIKOGOSYANDN.HandbookforNonlinearOpticalCrystals[M].3rded.Berlin: Springer,1999. [2] LEEYS.PrinciplesofTerahertzScienceandTechnology[M].Berlin:Springer,2008. [3] ALLAKHVERDIEVKR,GULIEVRI,SALAEVEY,etal..Investigationoflinearandnonlinearopticalpropertiesof GaS x Se 1-x crystals[j].sov.j.quantumelectron.,1982,12:947 948. [4] SUHREDR,SINGH NB,BALAKRISHNAV,etal..ImprovedcrystalqualityandharmonicgenerationinGaSedoped withindium[j].opt.let.,1997,22:775 777. [5] SINGHNB,SUHREDR,ROSCH W,etal..ModifiedGaSecrystalsformid IRapplications[J].J.Cryst.Growth, 1999,198:588 592. [6] HSUYK,CHENCW,HUANGJY,etal..ErbiumdopedGaSecrystalformid IRapplications[J].Opt.Expres,2006, 14:5484 5491. [7] FENGZS,KANGZH,WUFG,etal..SHGindopedGaSe Incrystals[J].Opt.Expres,2008,16:9978 9985. [8] ZHANGHZ,KANGZH,JIANGY,etal..SHGphasematchinginGaSeandmixedGaSe 1-x S x,x 0 412,crystalsat roomtemperature[j].opt.expres,2008,16:9951 9957. [9] RAKZ,MAHANTISD,MANDALKC,etal..DopingdependenceofelectronicandmechanicalpropertiesofGaSe 1-x Te x andga 1-x In x Sefromfirstprinciples[J].Phys.Rev.B,2010,82:155203. [10] SHIW,DINGYJ.Amonochromaticandhigh powerterahertzsourcetunableintherangesof2.7~38.4and58.2~ 3540μmforvarietyofpotentialapplications[J].Appl.Phys.Let.,2004,84:1635 1637. [11] DINGYJ,SHIW.WidelytunablemonochromaticTHzsourcesbasedonphase matcheddiference frequencygeneration innonlinear opticalcrystals:anovelapproach[j].laserphys.,2006,16:562 570. [12] ATUCHINVV,ANDREEVYM,SARKISOVSY,etal..GaSe 1-x S x crystalsforterahertzfrequencyrange[c]//10 th An nualinternationalconferenceandseminaronmicro/nanotechnologiesandelectrondevices(edm 2009),July1 6, 2009,NovosibirskTomsk,Rusia,2009:96 99. [13] ANDREEVYM,BEREZNAYASA,VINNIKEM,etal..OpticalpropertiesofGaSe 1-x S x inthzrange[c]//eightsi berianconferenceonclimateandecologicalmonitoring,oct8 10,2009,Tomsk,Rusia,2009:375 376.(inRusian) [14] LUOZW,GUXA,ZHUW C,etal..OpticalpropertiesofGaSe Scrystalsinterahertzfrequencyrange[J].Opt.Preci sioneng.,2011,19:354 359.(inChinese) [15] ANDREEVYM,LANSKIGV,ORLOVSN,etal..Physicalproperties,phasematchingandfrequencyconversionin GaSe 1-x S x,ga 1-x In x SeandGaSe 1-x Te x [C]//17 th Int.Conf.onAdvancedLaserTechnologies,Sept26 Oct1,2009,

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666 中国光学第 4 卷 [37] MAMEDOVGM,KARABULUTM,ERTAPH,etal..Excitonphotoluminescence,photoconductivityandabsorptionin GaSe 0.9 Te 0.1 aloycrystals[j].j.lumines.,2009,129:226 230. [38] ABDULLAEVGB,ALLAKHVERDIEVKR,BABAEVSS,etal..RamanscateringfromGaSe 1-x Te x [J].SolidState Commun.,1980,34:125 128. [39] SHIGETOMIS,IKARIT.Opticalandelectricalcharacteristicsofp GaSedopedwithTe[J].J.Appl.Phys.,2004,95: 6480 6482. [40] MENESESEA,JANNUZZIN,FREITASJR,etal..PhotoluminescenceoflayeredGaSe 1-x Te x crystals[j].phys.stat. Sol.(b),1976,78:K35 K38. Authors biographies:kushin an(1985 ),Post graduatestudent,nationalchiaotunguniversity,taiwan,china.hisre searchinterestsincludenonlinearopticsandthzspectroscopy.e mail:ksa7471@hotmail.com CHUWei chen(1989 ),MasterStudent,NationalChiaoTungUniversity,Taiwan,China.Herresearch interestsincludenonlinearopticsandthzspectroscopy.e mail:s.dafodil@hotmail.com LUOChih wei(1975 ),M.Sc.,Profesor,NationalChiaoTungUniversity,Taiwan,China.Hisre searchinterestsincludethzspectroscopy,thinfilm,superconductorandtopologicalinsulator.e mail: cwluo@mail.nctu.edu.tw AndreevY(1946 ),M.Sc.,Profesor,InstituteofMonitoringofClimaticandEcologicalSystem,SB RAS,Rusia&VisitingProfesor,ChangchunInstituteofOptics,FineMechanicsandPhysics,Chinese AcademyofSciences,China.Hisresearchinterestsincludenonlinearoptics,crystalcharacterization,fs andthzpulses,molecularspectroscopy,daslidar,forceopticssystems.e mail:yuandreev@yandex.ru LanskiGrigory(1980 ),M.Sc.,Dr.,InstituteofMonitoringofClimaticandEcologicalSystem,SB RAS,Rusia.Hisresearchinterestsincludemathematicalmodelingofnonlinearopticsandprogramming. E mail:lansky@yandex.ru ShaidukoAnna(1979 ),M.Sc.,Dr.,InstituteofMonitoringofClimaticandEcologicalSystem,SB RAS,Rusia.Herresearchinterestsincludemathematicalmodeling.E mail:an1579@yandex.ru IzaakTatiana(1967 ),M.Sc.,Dr.,SiberianPhysics technicalinstituteoftsu,rusia.herresearch interestsincludespectroscopy,electro chemistry,silicondioxide.e mail:taina@mail.tomsknet.ru SvetlichnyiValery(1970 ),M.Sc.,Dr.,SiberianPhysics technicalinstituteoftsu,rusia.hisre searchinterestsincludelaserphysics,spectroscopy,nanostructure.e mail:taina@mail.tomsknet.ru VaytulevichElena(1967 ),M.Sc.,Dr.,SiberianPhysics technicalinstituteoftsu,rusia.herre searchinterestsincludepolymers,coloidalsystems,nanostructures.e mail:xim@pisem.net ZuevVladimir(1956 ),M.Sc.,Profesor,CorespondentAcademician,InstituteofMonitoringofCli maticandecologicalsystem,sbras,rusia.hisresearchinterestsincludenonlinearopticsandlidars. E mail:vvzuev@imces.ru