Tqp chi khoa hgc Trifng B^i hgc Quy Nhan So 4, Tgp VIII nam 2014 NGHIEN c t f u CHE T^O PIN MAT TRCJl MANG MONG CuIn(Al)S2 BANG PHl/CfNG P H A P PHUN PHU NHIET PHAN TOAN PHAN N G U Y I N DLfC HI^U'''', V[.]
Tqp chi khoa hgc Trifng B^i hgc Quy Nhan - So 4, Tgp VIII nam 2014 NGHIEN c t f u CHE T^O PIN MAT TRCJl MANG MONG CuIn(Al)S2 BANG PHl/CfNG P H A P PHUN PHU NHIET PHAN TOAN PHAN N G U Y I N DLfC HI^U', VO THI THANH TUY^N^, TRAN THANH THAP l.GICflTHlfeU CHUNG Trong thdi gian gan day, vide nghidn ctfu che tao phan tfi pin mat ttdi (PMT) cd hidu sua't cao, gia thdnh re vd thdn thien vdi mdi trtfdng dang thu hdt stf quan tam d^c bidt cfia cdc nhd khoa hpc ttong va ngodi ntfdc Cdc nghidn cffu tdp trung chfi yeu theo hai htfdng [1-4]: Thff nha't, lffa chpn vat lidu mdi dd thay thd vdt Ueu ttuyen thdng Cdc vat Udu truydn thd'ng nhff Si ddn tinh the, mang mdng Si vd dinh hinh (a-Si: H), cfing vdi cdc cd'u true kim loai/ didn mdi/ bdn dan (MIS tunnel) hodc cdc cd'u trfic chuyen tidp di cha't, da khdng ddp tfng hdi hda cac yen c l u cfia PMT vd hidu suat chuydn ddi ndng Itfdng, gid thdnh va than thien vdi mdi trtfdng, Chinh vi vay, vi$c nghidn cffu tim cac he vat Ueu mdi thay the' dang ttd ndn cd'p bach hdn bao gid hd't Trong sd cdc hd vdt hdu mdi nay, thi CuIn(AI)S2 (gpi tat la vat Ueu CI(A)S) Id hd v$t lieu cd nhieu hffa hen hdn ca Ddi vdi he vat li$u nay, cdc tinh todn \^ thuyet da dff dodn pin mdt ttdi mdng mdng CIS cd thd dat hidu sud't chuydn ddi quang dien ra't cao (~ 30%) vi vat Udu CIS cd dp rdng vung ca'mE - 1,5 eV cd the phu gan nhff hoan todn phd mat trdi, cd hd sd ha'p thu rd't cao (~ 10^ c m ' ) va thdn thidn mdi trtfdng Thff hai, vd mat cdng nghd che tao theo xu hffdng nghien ciJu phdt trien cdc cdng nghe lang dpng mdng mdng gid tha'p va khdng sfi" dung chdn khdng, nhff phffdng phdp phdn ffng pha ldp ion ILGAR (Ion Layer Gas Reaction) [I], phffdng phap lang dpng tiiih didn BSD (Electto Static Deposition) [2], phffdng phdp phun phfi nhiet phdn SPD (Spray Pyrolysis Deposition) [3, 4, 7], Trong so cac phffdng phdp trdn, phffdng phdp SPD thu hut sff quan tdm rd't ldn cfia nhidu nhd khoa hpc vl phffdng phap ddn gidn, dd didu khidn phan va cau tnic vi md cua mang lang dpng, de dang idng dpng mdng tten dien tich ldn vd gid tha'p [3, 4] Hidn nay, chung tdi da nghidn cdu phdt trien phffdng phdp phun phu nhiet phan ho ttd sidu am U S ? (Ulttasonic Spray Pyrolysis) ttdn cd sd nguydn ly cua phffdng phdp SPD [4, 7] Trong bdi bdo nay, chffng tdi thdng bdo kdt qua nghien ctfu lang dpng cac ldp chd-c nang (ldp cfia sd ZnO: In (IZO), ldp ddm In^^^, ldp hap tiiu CuIn(Al)S,) (CI(A)S)) vd pin mat ttdi mdng mdng ca'u tiiic dao glass/ IZO/ In^^J CI(A)S/ Ag chd tao bdng phtfdng phdp phun phfi nhiet phan todn phan FSPD (FuU Spray Pyrolysis Deposition) NGUYENBIJCmiu-, VOTHITHANHTirYPlJ' T R A N T H A N H T H A I ' 66 CAU T R O C P I N M A T TRCJI M A N G MONG VA HE THlfC NGHIEM 2.1 ca'u true pin mat trdi mang mdng Pin mat trdi mang mdng ca'u mac dao glass/ IZO/ CdS/ CIAS/ Ag (gpi tat pin matfl-diCIAS) dffpc bieu dien nhff tren Hinh la Ca'u tnic gdm c4c ldp chffc nang sau: - Ldp oxit din dien sufl't IZO dffdc lang dpng tren de kinh ddng vai tro nhff ldp cffa sd ddng ±di cung la dien cffc tie'p xiic mat trffdc - Ldp ddm In^Sy - Ldp hap fliu CIAS - Mat tren Idp hap ttiu CIAS lang dpng mpt ldp mdng kim loai Ag (Sj^, ~ 50 nm) ddng vai tro nhff dien cffc cflng tac cua pin mat trdi Gian dd nang Iffdng cua pin mat trdi CIAS (Hinh 1) mfl ta bang phan mem SCAPS-ID dffdc bidu didn trdn Hinh lb aE —^=e~® ^ / " A/ i.r* p-CIAS AA^rr r â_đ^ã E, E.N n-Znttln I| ^ t 1.2 IG Khoang cich (^m) Anil sdng m^t triri (a) (b) Hinh 1(a) Cdu htnh pin mdt tr&i Hinh 1(b) Gidn dd ndng luong cia pin mdng mdng cdu triic ddo glass /ZnO: In/ melt trdi mdng mong cd'u true ddo (a) In2S3/ CIAS /Ag: duac bang md phong SCAPS-IB Ldp cffa s^ IZO cd dp rflng viing cam quang rpng (E^ = 3,3 eV) v& ldp ddm In^Sj (E^ = 2,54 eV) chp phep phan ldn photon dnh sing dffdc hap fliu bdi ldp hSfpfliuCIAS cd dfl rflng vung cSfm quang nhd hdn (E = 1,45 -1,50 eV) Cap didn tff -15 tx6n% phdt sinh bdi cac phpton ldp hap thu se dffdc tach bdi didn trffdng khuS'ch tan cia chuyen tiep In^Sj/CIAS v4 gdp cho ddng quang dipn phat smh Dien ap hd mach cia pm mat trdi dffdc quyet dinh bdi didn aptid'pxuc ngoai V,, Can Iffu ^ rang, stf khic ve ltfc didn tff tai phan bien cffa tiep xiic di chat In^Sj/CIAS dan den sff thay ddi dOt ngpt ADE^ vimg din (xem Hinh lb) NGHIEN Cl?UCHg TAO PIN MAT TR^I MANQ MONO CuIn(Al)S, 2.2 H$ thifc nghidm He phun phu nhiet phan ho ttd sieu am USP (Ulttasonic Spray Pyrolysis) dffdc thi^t kd' va phat trien tren nguydn tac cua he phun phO nhiet phan va dtfdc bieu dien ttong Hinh CS'u tao cua hd phun phu nhiet phdn bfl ttd sieu am gdm cac kho'i chffc nang sau: - He bdm dung dich (1): NE-1000 Tdc dfl bdm: v = 0,001 ml/h - 2120 ml/h - Hd phat sidu dm: dlu phdt sieu am f^^ = 130 KHz (2) va bfl dieu khien (3) - Cd cau dinh hffdng (4) - Bfl cung c^p khi: binh nen N^ (5) va van dieufle'tlim Iffdng (6) Bfl phan ndy cimg vdi cd ca'u dich chuyen dlu phun (8) dieu khi^n hffdng va tdc dp ddng spl de'n de - Hd cung cl^p nhiet: Le nung (7) va bp dieu kliien nhiet dp (3) - Ca cd'u dich chuydn dau phun (8): Diiu chinh khoang cdch giffa dau phun va dd' (a) (b) Hinh 2(a) Mo Kinh thiet ke'vd Hinh 2(b) HI phun phi nhiet phdn ho tra sieu dm Nguyin ly hoat dgng: Dffdi tdc dung cua hd bdm (1), dlu phdt sidu am (2) vd bp diiu khien (3), dung dich precursor tien chd't dffdc tan nho bang sieu am cd dudng kinh trung btah cia cdc hat sol taoflianhdffdc xdc dinh fliee congfliffcLang nhff sau [7]: I 8ttij,, = 0,34 P,./^ 68 N G U Y S N BI?C HIEU', V O Tm THANH TUYEN', TRAN T H A N H THAF Trong dd, D^ la dffdng kinh hat sol, C7„_,ld sffc cdng be mat, P, Id ri ttpng cia chd't long vd f„^ Id tan sfl' rung Nhd ddng mang N^ (5) cac hat sol tao thdnh dffdc dffa den va cham vao be mat de' nung ndng Nhidt dp cia dd' dffdc dieu khien qua bfl dieu khien nhidt dp (7) cho phepfliid'tlap tai mflt gid tri nhidt dp xac dinh vdi dp chinh xac cap (± 1°C) O mflt nhidt dp xac dinh cia de, cac hdp cha't ttong cac sol ttai qua qud trinh nhidt phan, thtfc hien phanffnghda hpc va ti^p fliep la hdp nha't cdc hdp phan vdi dffa de'n hinh mang mdng cd phin mong mudn Cac san phim dd bay hdi khac vd dung mfli dff se thoat di d dang pha hdi THUC NGHIEM VA THAO LUAN 3.1 ThiJc nghi?m - Ldm s^ch de' kinh: Ngam de ttong dung dich axit HCl Sau dd, ngdm • dung moi axeton, etanol kit hdp vdi rung sidu dm Rffa bang nffdc khff ion vd sdfy khfl bang den hong ngoai - Lang dpng Idp ciia sS: Mdng mdng ZnO pha tap In vdi ti Id mol [Zn]/[In] = 0,012 va chieu ddy ~ 250 nm dffdc lang dpng tten dd' kinh bang phun phi nhidt phan hp ttd sieu dm USP Cac thong sd cong nghe khac dtfdc mfl td chi tilt ttong [4] - Lang dpng Idp dpm: Mang mdng In^S^ vdi cliieu ddy - 120 nm dffdc lang dpng len tten de glass/IZO bang phun phi nhiet phan hp ttd sieu am USP Cdc dung dich tien chd't InCl, (0,05M), (NHj)jCS (0,05M) dffdc hea vdi ti le mpl [hil/[S] = 1/3 Mdng In^S^ dffdc lang dpng vdi nhiet dp d l Tg = 380°C Cac thflng sd cdng nghe sff dung tffdng tff nhff lang dpng ldp IZO - Lang dpng Idp hd'p thii: Mdng CIS va CIAS vdi chieu day ~ 2,2 i m dtfdc lang dpng ldn ttdn de glass/IZO/In^S, tai nhidt dfl d l T^ = 370°C bang phffdng phap phun phi nhidt phan lap lai hfl ttd sidu dm URSP Mang CIS lang dpng vdi ri Id mpl [Cu]/[In] = 1,1; mdng CLAS lang dpng vdi d Id mol [Cu]/[In] = 1, tAl]/[In] = 0,12 vd mau sau lang dpng dffdc i nhiet ttong mfli trffdng hdi Itfu hu^nh [7] * Cac ky thu$t do: Cau Oruc vd flnh chat quang-didn cia cdc ldp chffc nang IZO, In^Sj, CIS, CIAS dffdc khao sat bang phffdng phdp phan tich phd nhieu xa tia X (hd nhieu xa X'Pert PRO-PANalytical si dung bffc xa Cu-Ka vdi btfdc sdng 1,540560 A), phtfdng phap phd tmyen qua UV-VIS (he UV-VIS Spectto-photometer, HP Agilent 8453) va phtfdng phap hidu ffng Hall (fliie't bi HaU Measurement system 7600 Series) NGHlfiN Ctfu CHE TAP PIN MAT TRpI MANG MONG CuIii(Al)S, 69 Sdc tnAig J-V cia cac pin mat ttdi che' tao dffdc khao sdt ttdn he thie't hi Keittiley 4200-SCS vdi SOLAR SIMULATOR cong suat 300 W Cflng sua't ngudn sang ehuin Id lOOmW/cm^ sff dung d che'dfl AM 1.5 3.2 Kd't qua va thao Iu$n 3.2.1 Cdu true vd tinh chdt quang-di^n cia cdc ldp chdc ndng pin mat tr&i CI(A)S Gidn dd nhieu xa tia X cia cdc ldp chffc ndng ttong cau ttie pin mat ttdi CI(A)S (Hinh 1) dffdc biiu didn tten Hinh Tff Hinh 3a cd tiie tiid'y, cdc dinh nhidu xa dac trffng (100), (002), (101), (102), (110), (103) cia mdng IZO xuat hidn day di vd ro rdng, khdngfliafystf xua't hidn cia cac pha la Bieu chtfng td rang, mdu IZO cd cau trie hecxagonal wurtzite (theo flie PDF 36-1451) Trdn Hinh 3b, gian dd flll hien cac dinh ddc mmg tai cdc mat phing (109), (220), (323) va (440) tffdng ffng vdi cd'u tiac tettagonal cia pha P-ln^S, (tiieo thS PDF 25-390) Hinh 3c, d flil hidn phd nhieu xa tia X cia mdng CIS va CIAS vdi cdc dinh hffdng ffu tidn (112), (200,004), (220,204) vd (312,116) Theo thflng bdo [1-3], cdc dinh nhieu xa ttdn Udn quan dd'n pha tettagonal (theo ttie PDF 27-0159) Theo xdc ditlh dfl rpng vung ca'm quang E cia mdng mdng [3,5], tff dff lidu phd truyln qua, E dtfdc tinh bang phffdng phdp ngoai suy dtfa vao dd thi quan he (ahv)^ vdi hv (Hinh 4) Chung tdi da xac dinh dfl rflng ving cam ttfdng tfng vdi tffng ldp chffc nang nhff sau: Ef° = 3,3 eV, E^='' = 2,54 eV, Ef' = 1,45 eV va E f " = 1,49 eV Cac thflng sd didn cia ldp chffc ndng IZO, In^S^, CIS va CIAS dffdc trinh bay ttong Bdng Mang IZO cd loai din n vd cd didn ttd sua't tha'p (10"^ Q.cm) Mang IHJSJ cd loai din n, dien ttd sua't 432 n.cm Trong do, cdc mdng CIS va CIAS the hien loai din p, cd ndng dp hat tai khpdng IO"" -^ 10'^ cm"^ Bang I Cdc thong sddien cia cdc Up chic ndng IZO, In^^, CIS vd CIAS Mang mong Di$n trd sudft (Q.cm) Dp linh dpng (cmW.s) Ndng dfl hat tai (cm') Logi din IZO 1,01 X l a ' 12,5 2,07 X 10" n In,S3 383,1 45,2 1,37x10" n CIS 19,3 11,3 3,34 X 10" P CIAS 63,8 23,8 6,04 X 10" P NGUYEN BtfC HIEU- VO T M THANH TI rYF.N* T R A N THANH THAI' W CIAS Id) s "f X ^ lc] S s CIS — -"""^ 1 lb) 3.JeV i as (c) i f "^75 (em 1' J ' "" lo,S, (.1 , i» 1 IZO - S w T 111 s § / 1,45 BV 2S 30 35 40 4S SO 55 60 65 14 I'S IJ 26 (dd) Hinh Gidn nhieu xa tia X cua cdc ldp Hinh Do thi (cchvf ~ hv tucfng ibig cdc l chvcc ndng (a) IZO, (b) In^^ (c) CIS (d) CIAS chiic ndng (a) IZO, (b) In^^ (c) CIS, (d) C 3.2.2 Khdo sdt cdc thong so'ddc tritng cda pin mat trdi CI(A)S Cdc pin matti-dikhao sat cd cd'u trfic: glass/IZO/In^S^/CIS/Ag (ky hieu CEL-01) va glass/IZO/In^Sj/CIAS/Ag (ky hieu CEL-02) Trdn Hinh bidu didn dnh chup pin mat trdi dUdc chd' tao thfi nghidm Cdc thdng sd quang didn cfia pin mattirdiche' tao CEL-OI vd CEL-02 dtfdc xdc dinh tCf dac tnXag J-V sang (Hinh 6) va dtfdc trinh bay Bdng J-V Si Nca.- 11^^ J^ ôããô f-9-H J-VằIDS CO ã01 - O — J - V *lngCEL.D2 ^ ^ ^ Dita &p (mV) IRnh Anh chup pin mat trdi che tao sau cat rdi vd gan dien cUc Hinh Ddc trung J-V cua CEL-01 vd CEL-02 NGHIEN CCfU CHE TAO PIN MAT TRdlMANGMONGCuIn(AI)S, Bdng Cdc thong sd quang diin cua pin mat trdi CEL-01 vd CEL-02 MSu Di^n ap hd mach (mV) CEL-OI CEL-02 348 421 M^t dO dong ng^n m^ch Jsc (mA/cm-) 10,17 11,09 He so' lap d^y FF (%) 21,93 28,18 Hi$u su^'t (%) 0,96 1,35 Ttf kdt qud bidu didn Bang 2, dd dang nhan tha'y, cac thdng sd quang dien ddc tnrtig cua pin CEL-02 da dtfdc cdi thidn dang ke so vdi pin CEL-OI So sdnh gian dd nhidu xa ciia cac mdng chd tao CIS va CIAS nhtf bidu dien tien Hinh 3c, d Dd ddng nhan tha'y, ca hai loai mang deu thd hidn su" kdt tinh tdt vdi pha tetragonal ndn nguydn nhan stf cai thien tien khdng phdi dnh htfdng ciia cd'u tnic kd't tinh Theo chiing tdi, nguyen nhdn ciia stf cai thien cac thdng sd quang didn cua pin mat trdi mdng mdng lien quan de'n rpng vung cam quang ciia ldp hap thu Vi ldp hdp thu CL\S (E = 1,49 eV) cd rong vCing cam cao hdn CIS (E = l,45eV) vd gia tri hodn todn phd hdp vdi gid tri tinh toan 1;^ thuydt cho hieu sudt td't nha't do'i vdi pin mat trdi mdng mdng [5] Hdn the' ni?a, didu cung hoan toan thd'ng nha^t vdi kd't qua tinh todn theo phtfdng phdp md phdng nhtf cdng bd [6, 7] Mat khac, vai trd c0a Idp hdp thu CI(A)S tac ddng den cdc qua trinh vdt ly xay ben chuyen tid'p p-n (qua trinh hd'p thu photon, qua tiinh phat sinh-tai hdp hat tai) cua PMT khao sat dtfdc phdn tich, danh gid cu the tiong thdng bdo [4, 7] KET LUAN Cdc mdng mdng IZO, In^S^, CIS vd CIAS dtfdc lang dong bang phtfdng phdp USP vd URSP vdi cac thdng sd cdng nghe che tao td'itfu.Cac dac tiifng cd'u tide, tinh cha't quang-didn ciia cdc mdng dtfdc khao sat Ke't qua khao sdt chotiid'ycac tiidng sd quang-didn ciia cdc loai mdng IZO, In^Sj, CIS va CIAS phii hdp de su" dung lam cac ldp chtfc ndng tiong cd'u tiiic pin mat trdi CI(A)S Cac thdng sd quang didn cua pin mdt trdi glass/IZO/In^Sj/CIAS/Ag da dtfdc cai thien dang kd so vdi pin mat trdi glass/IZO/In^Sj/CIS/Ag Kd't qua phdn tich cho thd'y dp rpng viing cam cao cua ldp hd'p thu Id nguyen nhan cdi thidn ddng ke cac thdng so quang didn cua pin mat tidi Ke't qua nghien ctfu da khdng dinh pin mat trdi mdng mong cd'u triic dao glass/IZO/In,S3/CI(A)S/Ag da dtfdc chd tao tiianh cdng bang phtfdng phap FSPD Day la tien de cho phep md khd nang suf dung phtfdng phap FSPD nhtf mot phtfdng phdp cdng nghd hiJu hieu de che tao cdc pin matti-dicd'utiTicdao, cd hieu sua't chuyen ddi quang didn cao va gia tiia'p 72 NGUYEN BtfCHIEU'.VOTHl THANH TUYEN" TRAN THANH THAI' TAI L I | U THAM KHAO [1] K Das, S K Panda, S Chaudhuri, Fabrication of nanostructured CuInS, thin films by ion layer gas reaction method, Appl Surf Sci., 253 (2007) 5166-5172 [2] S Nakamura, A Yamamoto, Electrodeposited CulnS^based thin-film solar cells, Sol Energy Mater Sol CeUs, 75 (2003) 81-86 [3] M Kninks, O Bijakina, T Varema, V Miklib, E Mellikova, Structural and optical properties of sprayed CuInS^ films, Thin solid films, 338 (1999) 125-130 [4] Tran Thanh Thai, Nguyen Due Hieu, Luu Thi Lan Anh, Pham Phi Hung, Vo Thach Son, Vu Thi Bich, Fabrication and characteristics of full sprayed ZnO/CdS/CuInS^ solar cells, Joumal of The Korean Physical Society, 61 (2012) 1494-1499 [5] T Markvart L Castaiier, Solar cells: Materials, manufacture and operation, Elsevier, [6] Stephen J Fonash, Solar Cell Device Physics, Elsevier, (2010) [7] Tran Thanh Thai, Nghien ciu vat ly vd cdng nghe pin mat trdi mdng mdng cau true ddo Glass/ZnO: In/CdS/CulnS/Metal che tqo bdng phuong phdp phun phu nhiet phdn todn phan (FSPD), Luan dn tien si Vdt ly, (2012) (2005) SUMMARY STUDY OF FABRICATION OF CuIn(Al)SjTHIN FILM SOLAR CELLS BY FULL SPRAY PYROLYSIS DEPOSITION TECHNIQUE Nguyen Due Hieu, Vo Thi Thanh Tuyen, Tran Thanh Thai This paper reports the successful fabrication of full deposited glass/IZO/In^Sj/ CIS(CIAS)/Ag solar cells with supersttate structure by using ulttasonic spray pyrolysis method (FSPD) The physical properties of the constituent layers are investigated with the result that the CIS (CIS) and CIAS films exhibited die best crystallites wiUi tettagonal structure and the optical band gap of tfie CIAS films is obtained as 1.49 eV Some physical properties of both ZnO and In^Sj thin fUms are also stodied The performance of the best cells obtained is V ^ = 421 mV, J^^ = 11.09 mA/cm\ FF = 28.18% and Tl = 1.35% The results shows ttiat FSPD method is a very promising technique appHed to prepare solar cells based on CIAS absorbers in a supersttate structure with low cost and high efficiency •Vi?ii Vit ly Ky thujt Tniflng Dai hoc B4ch khoa Hi Npi "Khoa H6a hoc, Tnrdng Dai hoc Quy Nhcfn TnrSng Dai hoc Quy Nhdn Ngiy nhSn bai: 06/5/2014; Ngiy nhSn dang; 15/10/2014 ... TRCJI M A N G MONG VA HE THlfC NGHIEM 2.1 ca''u true pin mat trdi mang mdng Pin mat trdi mang mdng ca''u mac dao glass/ IZO/ CdS/ CIAS/ Ag (gpi tat pin matfl-diCIAS) dffpc bieu dien nhff tren Hinh... Cl?UCHg TAO PIN MAT TR^I MANQ MONO CuIn(Al)S, 2.2 H$ thifc nghidm He phun phu nhiet phan ho ttd sieu am USP (Ulttasonic Spray Pyrolysis) dffdc thi^t kd'' va phat trien tren nguydn tac cua he phun phO... dlu phun (8) dieu khi^n hffdng va tdc dp ddng spl de''n de - Hd cung cl^p nhiet: Le nung (7) va bp dieu kliien nhiet dp (3) - Ca cd''u dich chuydn dau phun (8): Diiu chinh khoang cdch giffa dau phun