Cu_2Se、In_2Se_3、Ga_2Se_3混合球磨过程中的Cu(In,Ga)Se_2形成机制研究
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摘要
对球磨时间不同的Cu2Se、In2Se3和Ga2Se3混合粉末进行热压烧结制备CIGS靶材,发现在球磨时间较短时靶材出现分层,随着球磨时间延长分层缺陷消失。由此考察了粉末在球磨过程中发生的物理化学变化及其对分层的影响。结果表明:Cu2Se、In2Se3和Ga2Se3三种硒化物粉末在球磨过程中发生机械合金化反应形成黄铜矿相Cu(In,Ga)Se2(CIGS)。随着球磨时间的延长,黄铜矿相结构Cu In Se2(CIS)首先在Cu-Se二元化合物表面产生,并随着Ga原子的扩散逐步形成CIGS四元相。当球磨时间达到48 h时,粉末由黄铜矿相CIGS和少量Ga2Se3组成。由于Cu2-xSe与CIGS晶体结构相近,因此通过外延反应的方式有效促进了CIGS的合成。球磨过程中Cu-Se二元相的消失和CIGS相的形成有助于抑制烧结过程中分层缺陷的产生。
Sputtering targets of CIGS quaternary ceramic were fabricated by hot-press sintering the milled powder mixture of Cu2 Se, In2Se3 and Ga2Se3. When the milling time of the powders less than 4 h,the sintered targets delaminated, while the delamination disappeared with the prolonging milling time.Therefore the physico-chemical changes of the powder mixture during the milling process and their influence on the delamination of the targets were investigated. The results indicate that with the progress of the milling process, mechanical alloying(MA) occurred, and chalcopyrite Cu(In, Ga)Se2(CIGS) formed from Cu2 Se, In2Se3 and Ga2Se3; With the increasing milling time, Cu In Se2(CIS) formed on the surface of binary copper selenide firstly and CIGS was subsequently generated due to the inward diffusion of Ga;Thus the original blend powders became a mixture of CIGS and residual Ga2Se3 after milling for 48 h.Since CIGS and Cu2- xSe have a similar crystallographic structure, therefore this epitaxial relation may facilitate the formation of CIGS. The disappearance of Cu-Se binary compound and the formation of CIGS restrained the delamination of the CIGS targets in the sintering process.
Sputtering targets of CIGS quaternary ceramic were fabricated by hot-press sintering the milled powder mixture of Cu2 Se, In2Se3 and Ga2Se3. When the milling time of the powders less than 4 h,the sintered targets delaminated, while the delamination disappeared with the prolonging milling time.Therefore the physico-chemical changes of the powder mixture during the milling process and their influence on the delamination of the targets were investigated. The results indicate that with the progress of the milling process, mechanical alloying(MA) occurred, and chalcopyrite Cu(In, Ga)Se2(CIGS) formed from Cu2 Se, In2Se3 and Ga2Se3; With the increasing milling time, Cu In Se2(CIS) formed on the surface of binary copper selenide firstly and CIGS was subsequently generated due to the inward diffusion of Ga;Thus the original blend powders became a mixture of CIGS and residual Ga2Se3 after milling for 48 h.Since CIGS and Cu2- xSe have a similar crystallographic structure, therefore this epitaxial relation may facilitate the formation of CIGS. The disappearance of Cu-Se binary compound and the formation of CIGS restrained the delamination of the CIGS targets in the sintering process.
引文
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12 J.Zhu,Q.Li,L.Bai,Y.Sun,M.Zhou,Y.Xie,Metastable tetragonal Cu2Se hyperbranched structures:large-scale preparation and tunable electrical and optical response regulated by phase conversion,Chem.Eur.J.,18(41),13213(2012)
13 M.Marudachalam,R.W.Birkmire,H.Hichri,J.M.Schultz,A.Swartzlander,M.M.Al-Jassim,Phases,morphology,and diffusion in Cu InxGa1-xSe2thin films,J.Appl.Phys.,82(6),2896(1997)
14 C.D.Kim,M.S.Jin,W.T.Kim,Growth and characterization of ordered vacancy chalcopyrite Cu In3Se5and Cu(In,Ga)3Se5single crystals,J.Korean Phys.Soc.,30(3),750(1998)
15 W.Witte,R.Kniese,M.Powalla,Raman investigations of Cu(In,Ga)Se2thin films with various copper contents,Thin Solid Films,517(2),867(2008)
16 J.Weszka,Ph.Daniel,A.Burian,A.M.Burian,A.T.Nguyen,Raman scattering in In2Se3and In Se2amorphous films,J.Non.-Cryst.Solids.,265,98(2000)
17 B.Minceva-Sukarova,M.Najdoski,I.Grozdanov,C.J.Chunnilall,Raman spectra of thin solid films of some metal sulfides,J.Mol.Struct.,410,267(1997)
18 P.Dub?ek,B.Etlinger,K.Furi?,M.Kranj?ec,Raman spectra of(GaxIn1-x)2Se3,Phys.Status.Solidi.(a),122(1),K87(1990)
19 D.J.Chakrabarti,D.E.Laughlin,The Cu-Se(copper-selenium)system,J.Phase Equilib.,2(3),305(1981)
2 P.Jackson,D.Hariskos,R.Wuerz,O.Kiowski,A.Bauer,T.M.Friedlmeier,M.Powalla,Properties of Cu(In,Ga)Se2solar cells with new record efficiencies up to 21.7%,Phys.Status.Solidi.ARapid Res.Lett.,9(1),1(2014)
3 LI Chunlei,ZHUANG Daming,ZHANG Gong,LUAN Hexin,LIU Jiang,SONG Jun,The influence of selenization temperature on the properties of Cu In Ga Se2Thin Films,Chin.J.Mater.Res.,24(4),358(2010)(李春雷,庄大明,张弓,栾和新,刘江,宋军,硒化温度对铜钢稼硒太阳能电池吸收层性能的影响,材料研究学报,24(4),358(2010))
4 F.F.Liu,Y.Sun,Q.He,Z.Q.Zhou,Rapid thermal annealing on Cd S/Cu(In,Ga)Se2based solar cells,in:2013 International Conference on Materials for Renewable Energy and Environment(ICMREE),edited by IEEE(Chengdu,IEEE,2013)p.143
5 J.A.Frantz,R.Y.Bekele,V.Q.Nguyen,J.S.Sanghera,A.Bruce,S.V.Frolov,M.Cyrus,I.D.Aggarwal,Cu(In,Ga)Se2thin films and devices sputtered from a single target without additional selenization,Thin Solid Films,519(22),7763(2011)
6 C.P.Liu,C.L.Chuang,Fabrication of CIGS nanoparticle-ink using ball milling technology for applied in CIGS thin films solar cell,Powder Technol.,229,78(2012)
7 J.H.Shi,Z.Q.Li,D.W.Zhang,Q.Q.Liu,Z.Sun,S.M.Huang,Fabrication of Cu(In,Ga)Se2thin films by sputtering from a single quaternary chalcogenide target,Prog.in Photovolt.:Res.and Appl.,19(2),160(2011)
8 K.Utsumi,O.Matsunaga,T.Takahata,Low resistivity ITO film prepared using the ultra high density ITO target,Thin Solid Films,334(1),30(1998)
9 N.Zhang,D.M.Zhuang,G.Zhang,An investigation on preparation of CIGS targets by sintering process,Mater.Sci.Eng.B,166,34(2010)
10 J.Liu,D.M.Zhuang,H.X.Luan,M.J.Cao,M.Xie,X.L.Li,Preparation of Cu(In,Ga)Se2thin film by sputtering from Cu(In,Ga)Se2quaternary target,Prog.Nat.Sci.,23(2),133(2013)
11 P.Jackson,D.Hariskos,E.Lotter,S.Paetel,R.Wuerz,R.Menner,W.Wischmann,M.Powalla,New world record efficiency for Cu(In,Ga)Se2thin-film solar cells beyond 20%,Prog.in Photovolt.:Res.and Appl.,19(7),894(2011)
12 J.Zhu,Q.Li,L.Bai,Y.Sun,M.Zhou,Y.Xie,Metastable tetragonal Cu2Se hyperbranched structures:large-scale preparation and tunable electrical and optical response regulated by phase conversion,Chem.Eur.J.,18(41),13213(2012)
13 M.Marudachalam,R.W.Birkmire,H.Hichri,J.M.Schultz,A.Swartzlander,M.M.Al-Jassim,Phases,morphology,and diffusion in Cu InxGa1-xSe2thin films,J.Appl.Phys.,82(6),2896(1997)
14 C.D.Kim,M.S.Jin,W.T.Kim,Growth and characterization of ordered vacancy chalcopyrite Cu In3Se5and Cu(In,Ga)3Se5single crystals,J.Korean Phys.Soc.,30(3),750(1998)
15 W.Witte,R.Kniese,M.Powalla,Raman investigations of Cu(In,Ga)Se2thin films with various copper contents,Thin Solid Films,517(2),867(2008)
16 J.Weszka,Ph.Daniel,A.Burian,A.M.Burian,A.T.Nguyen,Raman scattering in In2Se3and In Se2amorphous films,J.Non.-Cryst.Solids.,265,98(2000)
17 B.Minceva-Sukarova,M.Najdoski,I.Grozdanov,C.J.Chunnilall,Raman spectra of thin solid films of some metal sulfides,J.Mol.Struct.,410,267(1997)
18 P.Dub?ek,B.Etlinger,K.Furi?,M.Kranj?ec,Raman spectra of(GaxIn1-x)2Se3,Phys.Status.Solidi.(a),122(1),K87(1990)
19 D.J.Chakrabarti,D.E.Laughlin,The Cu-Se(copper-selenium)system,J.Phase Equilib.,2(3),305(1981)
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