KR20140015095A - Fabricatin method of absorber layer for thin-film solar cell - Google Patents
Fabricatin method of absorber layer for thin-film solar cell Download PDFInfo
- Publication number
- KR20140015095A KR20140015095A KR1020120082837A KR20120082837A KR20140015095A KR 20140015095 A KR20140015095 A KR 20140015095A KR 1020120082837 A KR1020120082837 A KR 1020120082837A KR 20120082837 A KR20120082837 A KR 20120082837A KR 20140015095 A KR20140015095 A KR 20140015095A
- Authority
- KR
- South Korea
- Prior art keywords
- ink
- particles
- milling
- solar cell
- weight
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 23
- 239000010409 thin film Substances 0.000 title abstract description 68
- 239000006096 absorbing agent Substances 0.000 title description 2
- 239000002245 particle Substances 0.000 claims abstract description 111
- 239000000203 mixture Substances 0.000 claims abstract description 52
- 229920000642 polymer Polymers 0.000 claims abstract description 41
- 239000011230 binding agent Substances 0.000 claims abstract description 39
- -1 chalcogenide compound Chemical class 0.000 claims abstract description 35
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 71
- 238000003801 milling Methods 0.000 claims description 56
- 238000000576 coating method Methods 0.000 claims description 40
- 150000004770 chalcogenides Chemical class 0.000 claims description 37
- 239000011248 coating agent Substances 0.000 claims description 37
- 229910052798 chalcogen Inorganic materials 0.000 claims description 33
- 150000001787 chalcogens Chemical class 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 29
- 238000004519 manufacturing process Methods 0.000 claims description 26
- 239000012298 atmosphere Substances 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 229910002535 CuZn Inorganic materials 0.000 claims description 9
- 239000001856 Ethyl cellulose Substances 0.000 claims description 9
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 9
- 229920001249 ethyl cellulose Polymers 0.000 claims description 9
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- 239000000020 Nitrocellulose Substances 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- 229920001220 nitrocellulos Polymers 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 229920005862 polyol Polymers 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 5
- 238000004132 cross linking Methods 0.000 claims description 5
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 4
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 4
- 229920000896 Ethulose Polymers 0.000 claims description 4
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 claims description 4
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 4
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 claims description 4
- 229920000159 gelatin Polymers 0.000 claims description 4
- 235000019322 gelatine Nutrition 0.000 claims description 4
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 4
- 229920000609 methyl cellulose Polymers 0.000 claims description 4
- 239000001923 methylcellulose Substances 0.000 claims description 4
- 235000010981 methylcellulose Nutrition 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- 239000008273 gelatin Substances 0.000 claims 2
- 235000011852 gelatine desserts Nutrition 0.000 claims 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000011669 selenium Substances 0.000 description 151
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 119
- 239000010949 copper Substances 0.000 description 94
- 239000002105 nanoparticle Substances 0.000 description 77
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 42
- 239000000758 substrate Substances 0.000 description 42
- 239000011521 glass Substances 0.000 description 31
- 239000000843 powder Substances 0.000 description 30
- 229910052717 sulfur Inorganic materials 0.000 description 27
- 229920002274 Nalgene Polymers 0.000 description 21
- 239000010408 film Substances 0.000 description 21
- 229910052711 selenium Inorganic materials 0.000 description 21
- 238000009210 therapy by ultrasound Methods 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 20
- 239000004926 polymethyl methacrylate Substances 0.000 description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 14
- 229910052802 copper Inorganic materials 0.000 description 12
- 239000005361 soda-lime glass Substances 0.000 description 11
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 235000011941 Tilia x europaea Nutrition 0.000 description 10
- 150000001786 chalcogen compounds Chemical class 0.000 description 10
- 239000004571 lime Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 230000008018 melting Effects 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 229910052738 indium Inorganic materials 0.000 description 5
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical group NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910052733 gallium Inorganic materials 0.000 description 4
- UODXCYZDMHPIJE-UHFFFAOYSA-N menthanol Chemical compound CC1CCC(C(C)(C)O)CC1 UODXCYZDMHPIJE-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- 238000002525 ultrasonication Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 2
- 239000001828 Gelatine Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000000224 chemical solution deposition Methods 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011246 composite particle Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 229940043237 diethanolamine Drugs 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 238000007647 flexography Methods 0.000 description 2
- 238000007646 gravure printing Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 238000010902 jet-milling Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000000813 microcontact printing Methods 0.000 description 2
- AIDQCFHFXWPAFG-UHFFFAOYSA-N n-formylformamide Chemical compound O=CNC=O AIDQCFHFXWPAFG-UHFFFAOYSA-N 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- 238000007645 offset printing Methods 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 238000005201 scrubbing Methods 0.000 description 2
- 229940091258 selenium supplement Drugs 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000007764 slot die coating Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 1
- RUJPNZNXGCHGID-UHFFFAOYSA-N (Z)-beta-Terpineol Natural products CC(=C)C1CCC(C)(O)CC1 RUJPNZNXGCHGID-UHFFFAOYSA-N 0.000 description 1
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- FFNVEROTSCOVKO-UHFFFAOYSA-N 2-(2-hydroxypropoxy)propan-1-ol prop-1-ene Chemical compound C=CC.C=CC.C=CC.CC(COC(C)CO)O FFNVEROTSCOVKO-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- AUJWGOMQUMBHEL-UHFFFAOYSA-M S(=O)([O-])O.[Se](=O)(O)O.[Na+] Chemical compound S(=O)([O-])O.[Se](=O)(O)O.[Na+] AUJWGOMQUMBHEL-UHFFFAOYSA-M 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 229940088601 alpha-terpineol Drugs 0.000 description 1
- 229920003144 amino alkyl methacrylate copolymer Polymers 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940031098 ethanolamine Drugs 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 150000002472 indium compounds Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 229960004011 methenamine Drugs 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- VPQBLCVGUWPDHV-UHFFFAOYSA-N sodium selenide Chemical compound [Na+].[Na+].[Se-2] VPQBLCVGUWPDHV-UHFFFAOYSA-N 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 229940117986 sulfobetaine Drugs 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- QJVXKWHHAMZTBY-GCPOEHJPSA-N syringin Chemical compound COC1=CC(\C=C\CO)=CC(OC)=C1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 QJVXKWHHAMZTBY-GCPOEHJPSA-N 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Electromagnetism (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention provides a device having excellent solar cell characteristics by producing a dense solar cell photoactive layer thin film while preventing crack formation of the thin film using an ink composition for a solar cell photoactive layer including a chalcogenide compound particle, a binder polymer and an organic solvent. to provide.
Description
The present invention relates to an ink composition for a solar cell photoactive layer and a method of manufacturing a compound semiconductor-based solar cell photoactive layer using the same.
Conventional vapor deposition based CI (G) S, CZT (S, Se) absorption layer manufacturing and solar cell manufacturing processes have limitations of high process cost despite their excellent characteristics. In order to solve this problem, the fabrication of CI (G) S and CZT (S, Se) absorption layers using a solution process is considered as an essential technology for commercialization of CI (G) S and CZT (S, Se) thin film solar cells. Various research methods have been reported for the production of CI (G) S thin film through particle-based solution process. A typical example is a method of preparing particle-based CI (G) S, CZT (S, Se) thin films by synthesizing particles having various properties, dispersing the synthesized particles in a specific solvent, and coating the particles. However, the process of preparing CI (G) S, CZT (S, Se) ink composition by dispersing the particles in the solvent and manufacturing the thin film is caused by cracking due to the stress in the thin film generated by removing the solvent inside the thin film. There are limitations in the manufacturing process. The resulting cracks cause not only non-uniformity of the properties of the finally fabricated solar cell, but also severe degradation of solar cell properties due to inadequate device structure. Therefore, when manufacturing a CI (G) S, CZT (S, Se) thin film using a particle-based solution process, it is necessary to research and development that can form cracks while forming a dense film.
The present invention has been made to solve the above problems, and an object of the present invention is to provide an ink composition for a photovoltaic cell photoactive layer which can form a dense film while preventing crack formation during thin film solar cell photoactive layer production. Another object of the present invention is to provide a thin film solar cell photoactive layer capable of maximizing excellent physical properties and light efficiency, including a dense film, and a solar cell including the same.
The ink composition for a solar cell photoactive layer according to the present invention comprises a binder polymer, a solvent and chalcogenide particles of CuIn x Ga 1-x Se y S 1-y or CuZn x Sn 1-x Se y S 1-y , CuIn x Ga 1-x Se y S 1-y or CuZn x Sn 1-x Se y S 1-y Precursor material forming particles, particles of at least one element selected from Group 11 to 14, chalcogen elements and And chalcogenide particles of one or more elements selected from Groups 11-14. The composition comprises 0.1 to 30 parts by weight of the binder polymer and 50 to 900 parts by weight of the solvent based on 100 parts by weight of the chalcogenide particles.
In particular, the binder polymer is characterized in that it contains 0.1 to 30% by weight of the chalcogenide particles. At this time, the binder polymer is polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyvinylpyrrolidone (PVP), polyvinylidene fluoride (PVDF), polymethyl methacrylate (PMMA), self-crosslinking acrylic Resin emulsion, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, hydroxy cellulose, methyl cellulose, nitrocellulose, ethyl cellulose, styrene butadiene rubber (SBR), C1-C10 alkyl (meth) acrylate and unsaturated carbohydrate Copolymers of acids, gelatine, thixotons, starches, polyether-polyols, polystyrenes with amine groups terminated, polyethylene oxides, polyurethanes, resins containing carboxyl groups, phenolic Resins, mixtures of ethylcellulose and phenolic resins, ester polymers, methacrylate polymers, self-crosslinking (meth) acrylic acid copolymers, ethylenic fires It comprises a copolymer having a weapon, ethyl cellulose, acrylate-based, epoxy resin-based, and any one or more selected from the aforementioned mixture.
Method for producing a photovoltaic cell active layer according to the present invention is a) a binder polymer in the solvent, chalcene compound particles of CuIn x Ga 1 - x Se y S 1 -y or CuZn x Sn 1-x Se y S 1-y , Or preparing a mixed solution containing the precursor material for forming the chalcogenide particles, b) milling the prepared solution to produce a homogeneous ink composition, and c) applying the ink composition to form a coating film. And d) heat treating the coating film.
In step a), the precursor material includes particles of at least one element selected from group 11 to 14, chalcogen element and particles of chalcogenide at least one selected from group 11 to 14. At least one element selected from Groups 11 to 14 may include at least one element selected from Cu, In, Ga, Zn, and Sn, and the chalcogen element includes S and Se.
The chalcogenide compound of at least one element selected from Groups 11 to 14 may include chalcogenide (O, S and / or Se) compound particles of at least one element selected from Cu, In, and Ga. For example, the chalcogenide compound is Cu 2 O, CuO, In 2 O 3 , Ga 2 O 3 , Cu 2 Se, CuSe, CuSe 2 , (In x Ga 1 -x ) 4 (S y Se 1 -y ) 3 , (In x Ga 1 -x ) (S y Se 1 -y ), (In x Ga 1 -x ) 6 (S y Se 1 -y ) 7 , (In x Ga 1-x ) 9 (S y Se 1-y ) 11 , (In x Ga 1- x ) 2 (S y Se 1 -y ) 3 and Cu z (In x Ga 1 -x ) 5 (S y Se 1 -y ) 2 , one or more It may include selected particles. In this case, x may be a real number of 0 ≦ x ≦ 1, y may be a real number of 0 ≦ y ≦ 1, and z may be a real number of 0.7 ≦ y ≦ 1.
In addition, the chalcogenide compound particles of at least one element selected from Groups 11 to 14 in step a) is a chalcogenide (O, S and / or Se) compound particles of at least one element selected from Cu, Zn, and Sn. It may include. For example, the chalcogenide compound may include Cu 2 O, CuO, ZnO, SnO, SnO 2 , CuSe, CuSe 2 , Sn (S a Se 1 -a ), Sn 2 (S a Se 1 -a ) 3 , Sn (S a Se 1 -a ) 2, Zn (S a Se 1-a ), and Cu c (Zn b Sn 1 -b ) (S a Se 1 -a ) particles. In this case, a may be a real number of 0 ≦ a ≦ 1, b may be a real number of 0 ≦ b ≦ 1, and c may be a real number of 0.5 ≦ y ≦ 1.
The binder polymer of step a) is characterized in that it contains 0.1 to 30% by weight of the chalcogenide particles.
The milling may be at least one selected from ion beam milling, ball milling, satellite milling, jet milling, slit milling, two-roll milling, three-roll milling, basket milling, gravel milling, attrition milling, scrubbing mixing milling and sand milling. Milling.
Forming a coating film by applying the ink composition is spin coating, bar coating, blade coating, dip coating, slot die coating, drop casting, ink-jet printing, micro-contact printing, It is carried out by one or more coating methods selected from printing, gravure printing, gravure-offset printing, flexography printing and screen printing.
The heat treatment may be performed at 400 to 550 ° C., chalcogen atmosphere.
The present invention includes a solar cell photoactive layer produced by the above-described method for manufacturing a solar cell photoactive layer.
The present invention includes a solar cell provided with a solar cell photoactive layer manufactured by the method for producing a photovoltaic cell active layer described above.
The solar cell photoactive layer manufacturing method according to the present invention is excellent in uniformity through a very simple, safe and easy process using an ink composition for a photovoltaic cell active layer that can improve the battery characteristics while significantly controlling the generation of cracks in the thin film. As well as having a fine microstructure, there is an advantage that can be produced a photoactive layer consisting of coarse grains having a micrometer order size.
Figure 1 shows the surface OM image after drying of the CuInSe 2 thin film based on the ink composition without the binder polymer of Comparative Example 1.
Figure 2 shows the surface OM image after the heat treatment under Se atmosphere of the ink composition-based CuInSe 2 thin film without the binder polymer of Comparative Example 1.
Figure 3 shows the surface SEM image after the heat treatment under Se atmosphere of the ink composition-based CuInSe 2 thin film without the binder polymer of Comparative Example 1.
Figure 4 shows the dark IV characteristics (efficiency: 0%) of the solar cell fabricated using the ink composition-based CuInSe 2 thin film without the binder polymer of Comparative Example 1.
Figure 5 shows the surface SEM image after the heat treatment in Se atmosphere of the ink composition-based CuInSe 2 thin film without the binder polymer of Comparative Example 2.
FIG. 6 is a surface SEM image of an ink composition-based CuInSe 2 thin film without a binder polymer of Comparative Example 6 after heat treatment under Se atmosphere.
7 shows the surface OM image after drying of the ink composition-based CuInSe 2 thin film to which the binder polymer of Example 1 is added.
FIG. 8 shows the surface OM image after heat treatment in Se atmosphere of the ink composition-based CuInSe 2 thin film to which the binder polymer of Example 1 was added.
9 is a surface SEM image after heat treatment in Se atmosphere of the ink composition-based CuInSe 2 thin film to which the binder polymer of Example 1 is added.
FIG. 10 illustrates solar cell characteristics (efficiency: 8.3%) prepared using the ink composition-based CuInSe 2 thin film to which the binder polymer of Example 1 was added.
FIG. 11 is a surface SEM image of the ink composition-based CuInSe 2 thin film to which the binder polymer of Example 5 is added after heat treatment in a Se atmosphere.
12 is a surface SEM image of the ink composition-based CuInSe 2 thin film to which the binder polymer of Example 9 is added after heat treatment in a Se atmosphere.
Hereinafter, a method of manufacturing the ink composition and the photoactive layer of the present invention will be described in detail with reference to the accompanying drawings. The following drawings are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention. Therefore, the present invention is not limited to the following drawings, but may be embodied in other forms, and the following drawings may be exaggerated in order to clarify the spirit of the present invention. Hereinafter, the technical and scientific terms used herein will be understood by those skilled in the art without departing from the scope of the present invention. Descriptions of known functions and configurations that may be unnecessarily blurred are omitted.
As a result of deepening the research on the compound semiconductor-based solar cell photoactive layer, the applicant has cracked due to the stress inside the thin film generated by removing the solvent when the thin film is manufactured through the particle-based solution process by the ink composition to which the binder polymer is added. It has been found that the generation can be surprisingly controlled, and through this, a solar cell photoactive layer having an improved photoelectric conversion efficiency having a compact structure can be manufactured and thus filed the present invention.
The ink composition according to the present invention comprises a binder polymer and a solvent, chalcogenide particles of CuIn x Ga 1-x Se y S 1-y or CuZn x Sn 1-x Se y S 1-y or the chalcogenide compound Precursor material to form particles. At this time, the precursor material includes particles of at least one element selected from group 11 to 14, chalcogen element and particles of chalcogenide of at least one element selected from group 11 to 14. At this time, the ink of the present invention includes an ink composition for a solar cell photoactive layer. Heat treatment temperature for manufacturing a photovoltaic cell active layer according to the present invention may be 400 to 550 ℃.
Specifically, at least one element selected from Groups 11 to 14 may include at least one element selected from Cu, In, Ga, Zn, and Sn, and the chalcogen element includes S and Se. The chalcogenide compound of at least one element selected from Groups 11 to 14 may include chalcogenide (O, S and / or Se) compound particles of at least one element selected from Cu, In, and Ga. As an example, the chalcogenide compound is Cu 2 O, CuO, In 2 O 3 , Ga 2 O 3 , Cu 2 Se, CuSe, CuSe 2 , (In x Ga 1 -x ) 4 (S y Se 1 -y ) 3 , (In x Ga 1 -x ) (S y Se 1 -y ), (In x Ga 1 -x ) 6 (S y Se 1 -y ) 7 , (In x Ga 1 -x ) 9 (S y Se 1 -y ) 11 , one or more of (In x Ga 1 -x ) 2 (S y Se 1-y ) 3 and Cu z (In x Ga 1 -x ) 5 (S y Se 1 -y ) 2 It may include selected particles. In this case, in the chalcogenide particles, x may be a real number each of 0 ≦ x ≦ 1, y may be a real number each of 0 ≦ y ≦ 1, and z may be a real number of 0.7 ≦ y ≦ 1. In addition, the chalcogenide particles of one or more elements selected from Groups 11 to 14 may include chalcogenide (O, S and / or Se) compound particles of one or more elements selected from Cu, Zn, and Sn. For example, the chalcogenide compound is Cu 2 O, CuO, ZnO, SnO, SnO 2 , CuSe, CuSe 2 , Sn (S a Se 1 -a ), Sn 2 (S a Se 1 -a ) 3 , Sn (S a Se 1 -a ) 2, Zn (S a Se 1-a ), and Cu c (Zn b Sn 1 -b ) (S a Se 1 -a ) particles. In this case, in the chalcogenide particles, a may be a real number of 0 ≦ a ≦ 1, b may be a real number of 0 ≦ b ≦ 1, and c may be a real number of 0.5 ≦ y ≦ 1. At this time, the bonding between the binder polymer according to the present invention and the CuIn x Ga 1 - x Se y S 1 -y or CuZn x Sn 1 - x Se y S 1 -y forming precursor materials together with the solvent used is the inside of the thin film in the preparation of the thin film The removal of the solvent can minimize the occurrence of cracks due to the stress inside the thin film and can form a dense structure.
The chalcogenide particles according to the present invention may include, in another embodiment, copper nanoparticles and chalcogenide particles of one or more elements selected from Groups 12 to 14. In this case, copper is a nanoparticle having a nano size to obtain a sintering driving force and low temperature reactivity with the chalcogenide particles, the average particle size of the copper nanoparticles may be 5nm to 200nm, the copper nanoparticles and Group 12 to Chalcogenide particles of one or more elements selected from Group 14 may have a uni-modal, bi-modal or higher distribution. For example, at a low temperature heat treatment temperature, in order to produce a single-phase, multi-phase chalcogenide compound having an average grain size of micrometer order, the average size of the chalcogenide particles is 1/100 of the average size of the copper nanoparticles. It is preferred to have a size of 1 to 1/10. The chalcogenide particles of one or more elements selected from group 12 to 14 may be amorphous chalcogenide particles, thereby reacting with the copper nanoparticles at a low temperature within a process allowable temperature, thereby more quickly and uniformly Polycyclic chalcogenides of the phase can be prepared.
In another embodiment, the chalcogenide particles according to the present invention include a first chalcogenide compound of a Group 11 metal and a second chalcogenide compound of a Group 11 metal having a lower melting point than that of the first chalcogenide compound. Composite particles, and precursors of one or more elements selected from Groups 12-14. Specifically, at least one of a multi-particle and a group 12 to 14 of the first chalcogen compound having a higher melting point and a second chalcogen compound having a lower melting point than the first chalcogen compound having a high melting point are mixed in a single particle. Including a precursor of the selected element, the high melting point first chalcogenide maintains a solid phase at a heat treatment temperature for manufacturing a photoactive layer of a solar cell, and the low melting point second chalcogenide may form a molten phase (liquid phase).
In another embodiment, the chalcogenide particles according to the present invention can be produced in a very fast and homogeneous single-phase multi-element chalcogenide by the second chalcogenide compound forming the molten phase and the first chalcogenide maintaining the solid phase. . In this case, the chalcogenide compound may be a nanoparticle as a composite particle in which the high melting point first chalcogenide compound and the low melting point second chalcogenide compound are homogeneously mixed, and the average particle diameter is preferably 5 to 500 nm. The first chalcogen compound may include Cu 2 Se, and the second chalcogen compound may include CuSe, CuSe 2 or a mixture thereof, and the first chalcogen may be 100 parts by weight of the second chalcogen compound. It may contain 10 to 80 parts by weight of the compound. When the weight ratio of the second chalcogen compound to the first chalcogen compound is outside the above range, there is a risk of low temperature reactivity and a decrease in film quality due to the low melting point of the second chalcogen compound, and a risk of loss of chalcogen elements. There is this.
In another embodiment, the chalcogenide particles according to the present invention may be formed by reacting a polyelectrolyte, a copper compound, and an indium compound selected from polyethyleneimine, polyacrylic acid sodium salt, and ammonium polyacrylate salt under an aqueous solvent, which is water, alcohol, or a mixture thereof. And forming a complex including indium, and then adding one or more selenium compounds selected from sodium selenite sulfite (Na 2 SeSO 3 ), alkyl selenide, sodium selenide, and ammonium selenide to CI (G) S nanoparticles can be used.
In the present invention, the binder polymer is characterized in that it contains 0.1 to 30% by weight of the chalcogenide particles. If the content of the binder polymer is out of the range, it is difficult to control the occurrence of cracks from the internal stress that may occur while the solvent inside the thin film is removed during thin film production.
The binder polymer is polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyvinylpyrrolidone (PVP), polyvinylidene fluoride (PVDF), polymethyl methacrylate (PMMA), self-crosslinkable acrylic resin Emulsion, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, hydroxy cellulose, methyl cellulose, nitrocellulose, ethyl cellulose, styrene butadiene rubber (SBR), C1-C10 alkyl (meth) acrylate and unsaturated carboxyl Acid copolymer, gelatine, thixoton, starch, polyether-polyol, polystyrene with amine groups terminated, polyethylene oxide, polyurethane, resins containing carboxyl groups, phenolic resins , Mixture of ethyl cellulose and phenolic resin, ester polymer, methacrylate polymer, self-crosslinking (meth) acrylic acid copolymer, ethylenically unsaturated At least one selected from a copolymer having a fire group, an ethyl cellulose type, an acrylate type, an epoxy resin type, and a mixture thereof.
The organic solvent in the present invention includes any one or more selected from water, apolar solvents, polyol solvents, amine solvents, phosphine solvents, alcohol solvents, polar solvents and mixtures thereof.
The polyol-based solvent may be diethylene glycol, diethylene glycol ethyl ether, diethylene glycol buthyl ether, triethylene glycol, polyethylene glycol (ethylene glycol), molecular weight; 200-100,000), polyethylene glycol diacrylate, polyethylene glycol dibenzonate, dipropylene glycol, tripropylene Dipropylene glycol, glycerol and any one or more selected from these mixtures.
The amine solvent may include a saturated or unsaturated acid, one or two or more selected from linear, branched and cyclic having 6 to 30 carbon atoms. As an example of the amine solvent, diethylamine, triethylamine, 1,3-propanediamine, 1,4-butanediamine, 1,4-butane diamine), 1,5-pentane diamine, 1,6-hexanediamine, 1,7-heptane diamine, 1, Diethylene diamine including 8-octane diamine, diethylene triamine, toluene diamine, m-phenylenediamine, diphenylmethane diamine (diphenyl methane diamine), hexamethylene diamine, triethylene tetramine, tetraethylenepentamine, hexamethylene tetramine, ethanolamine, diethanol amine ( one or more selected from diethanolamine, triethanolamine and oleylamine May comprise a solvent.
The phosphine solvent may include one or more solvents selected from trioctylphosphine and trioctylphosphineoxide, acid.
The alcohol solvent includes one or more solvents selected from methyl cellosolve, ethyl cellosolve, butyl cellosolve, and alcohol having 1 to 8 carbon atoms. can do.
The nonpolar solvent is toluene, chloroform, chlorobenzene, dichlorobenzene, anisole, xylene, and hydrocarbon solvent having 6 to 14 carbon atoms. It may include one or more solvent selected from.
The polar solvent is formamide (formamide), diformamide (diformamide), acetonitrile (acetonitrile), tetrahydrofuran (tetrahydrofuran), dimethylsulfoxide, acetone (acetone), α-terpineol ( Terpineol), β-terpineol, dihydro terpineol (Dihydro-terpineol) and water may include a solvent selected from one or more.
The ink composition according to the present invention comprises 0.1 to 30 parts by weight of the binder polymer and 100 parts by weight of the CuIn x Ga 1 - x Se y S 1 -y or CuZn x Sn 1 - x Se y S 1 -y forming precursor material. 50 to 900 parts by weight. The content of the binder polymer and the organic solvent used on the basis of the particulate form must satisfy the above range to obtain a more homogeneous granularity through the milling process, which is applied to the coating process to maintain the mechanical strength and homogeneity of the thin film. While improving, it is one of the main variables that can prevent the film quality degradation by the organic matter that is decomposed and removed during adhesion and drying and heat treatment.
Method for producing a photovoltaic cell active layer according to the present invention is a) chalcogen compound (CuIn x Ga 1 - x Se y S 1 -y or CuZn x Sn 1-x Se y S 1-y ) particles or the knife in a solvent Preparing a homogeneous ink composition by milling the prepared solution; and c) applying the ink composition to form a coating film. And d) heat treating the coating film.
In the step a), further comprising a dispersant in the solution to form a homogeneous film in the thin film coating process. The dispersant may be, for example, fatty acid salts (soaps), α-sulfofatty acid ester salts (MES), alkylbenzene sulfonate salts (ABS), linear alkylbenzene sulfonate salts (LAS), alkyl sulfate salts (AS), alkyl Low molecular weight anionic compounds including ether sulfate ester salts (AES) and alkyl sulfate triethanol; Low molecular weight non-ionic compounds including fatty acid ethanol amides, polyoxyethylene alkyl ethers (AE), polyoxyethylene alkyl phenyl ethers (APE), sorbitol and sorbitan; Low molecular weight cationic compounds including alkyltrimethylammonium salts, dialkyldimethylammonium chlorides and alkylpyridinium chlorides; Low molecular weight positively charged compounds including alkylcarboxybetaines, sulfobetaine, and lecithin; A polymeric water-based dispersant including a formalin condensate of a naphthalene sulfonate, a polystyrene sulfonate, a polyacrylate, a copolymer salt of a vinyl compound and a carboxylic acid monomer, carboxymethylcellulose, and polyvinyl alcohol; Polymeric non-aqueous dispersing agent comprising a polyacrylic acid partial alkyl ester and a polyalkylene polyamine; And polymeric cationic dispersants comprising polyethyleneimine and aminoalkyl methacrylate copolymers.
The process of milling the solution prepared in step b) is ion beam milling, ball milling, satellite milling, jet milling, slit mill, 2-roll milling, 3-roll milling, basket milling, gravel milling, attrition milling, scrubbing At least one milling process selected from mixed milling and sand milling, and preferably at least one milling process selected from ball milling, satellite milling, three-roll milling and attrition milling.
Forming the coating film by applying the ink composition in step c) is spin coating, bar coating, blade coating, dip coating, slot die coating, drop casting, ink-jet printing, micro-contact printing (micro-contact) Performed by one or more coating methods selected from printing, imprinting, gravure printing, gravure-offset printing, flexography printing and screen printing do.
Heat treatment of the coating film of the ink composition in step d) may be performed at 400 to 550 ℃, preferably 500 to 530 ℃. The heat treatment produces a chalcogenide film having a very dense, stable and homogeneous composition.
The heat treatment may be performed in a chalcogen atmosphere. The chalcogen atmosphere includes an atmosphere in which sulfur (S), selenium (Se), or a mixed gas thereof exists.
In detail, the heat treatment of the coating film can be performed by supplying a chalcogen-containing gas or by heat-treating the chalcogen powder together with the coating film and using the chalcogen powder as a source of chalcogen gas.
More specifically, the coating film is heat-treated knife kojen atmosphere is sulfur (S), selenium (Se) or comprising an atmosphere that is a mixed gas exists, knives kojen gas atmosphere is a knife, such as H 2 S or H 2 Se kojen The gas containing the element S or Se may be supplied or the chalcogen element S or Se may be volatilized and then supplied or the chalcogen powder which is a powder of the chalcogen element may be heat-treated together with the coating film, May be used as a source of chalcogen gas.
As a practical example, when supplying chalcogen gas, a chalcogen-containing gas containing H 2 S, H 2 Se, chalcogen element (S, Se) vapor or a mixed gas thereof is supplied at a flow rate of 5 to 300 sccm .
As a practical example, in the case where the chalcogen powder itself containing the S powder, the Se powder, or the mixed powder thereof is vaporized to form a chalcogen atmosphere in the chamber in which the heat treatment of the coating film is performed, And may be different from each other.
Specifically, when chalcogen powder is used as a chalcogen gas source, the chalcogen powder can be heated to 80 to 250 캜.
When the chalcogen powder is used as the chalcogen gas source, the chalcogen powder in the heat treatment apparatus may be placed in a region different from that in which the coating film is located. At this time, the heat treatment can be performed using an apparatus equipped with a heating element and a controller so that two or more uniform zones can be independently formed in a single heat treatment space capable of flowing the fluid, The heating temperature of the chalcogen powder can be controlled by controlling the position of the chalcogen powder in the heat treatment apparatus.
The heat treatment of the coating film may be carried out at any pressure, but in a non-limiting example, the heat treatment may be performed at a vacuum or an atmospheric pressure.
The present invention includes a photoactive layer produced by the above-described manufacturing method.
The present invention includes a solar cell provided with a photoactive layer manufactured by the above-described manufacturing method.
Hereinafter, the present invention will be described in detail with reference to the following examples. However, it is to be understood that the same is by way of illustration and example only and is not to be construed as limiting the scope of the present invention. Various modifications and variations are possible in light of the above teachings.
(Example 1)
10 g of zirconia balls with a diameter of 1 mm were placed in a 20 ml nalgene bottle, and a solution containing 1.68 g of ethylene glycol, 0.72 g of ethanol, and 0.01 g of polyvinylpyrrolidone (PVP; MW 55,000) was added thereto for 1 minute. Ultrasound was performed. 0.6 g of Cu 2 Se, CuSe, and In 2 O 3 synthetic particles were added to the solution, followed by milling at 20 Hz for 1 hour with a vibrating ball mill to disperse the ink. Then, after separating the ball and ink, the ink was subjected to external ultrasonic treatment for 1 minute. After the Mo electrode is deposited soda and a bar coating ink prepared in the lime glass substrate, and dried at 80 ℃, heating the Se powder in 230 ℃ and the CuInSe 2 thin film by heating the glass substrate on which the ink is applied at 530 ℃ temperature Photoactive layer was prepared. The pressure in the heat treatment chamber was 10 -5 torr. For fabricating the solar cell, CdS thin films were deposited by chemical bath deposition, ZnO and Al-doped ZnO thin films were deposited by sputtering, and Al electrodes were deposited by thermal evaporation.
(Example 2)
10 g of zirconia balls having a diameter of 1 mm were placed in a 20 ml nalgene bottle, and a solution containing 1.68 g of ethylene glycol, 0.72 g of ethanol, and 0.01 g of polyvinyl alcohol (PVA) was added thereto, followed by ultrasonication for 1 minute. . 0.6 g of Cu 2 Se, CuSe, and In 2 O 3 synthetic particles were added to the solution, followed by milling at 20 Hz for 1 hour with a vibrating ball mill to disperse the ink. Then, after separating the ball and ink, the ink was subjected to external ultrasonic treatment for 1 minute. After the Mo electrode is deposited soda and a bar coating ink prepared in the lime glass substrate, and dried at 80 ℃, heating the Se powder in 230 ℃ and the CuInSe 2 thin film by heating the glass substrate on which the ink is applied at 530 ℃ temperature Photoactive layer was prepared. The pressure in the heat treatment chamber was 10 -5 torr.
(Example 3)
10 g of zirconia balls with a diameter of 1 mm were placed in a 20 ml nalgene bottle, a solution containing 1.68 g of ethylene glycol, 0.72 g of ethanol, and 0.01 g of polyvinyl butyral (PVB) was added thereto, followed by ultrasonication for 1 minute. It was. 0.6 g of Cu 2 Se, CuSe, and In 2 O 3 synthetic particles were added to the solution, followed by milling at 20 Hz for 1 hour with a vibrating ball mill to disperse the ink. Then, after separating the ball and ink, the ink was subjected to external ultrasonic treatment for 1 minute. After the Mo electrode is deposited soda and a bar coating ink prepared in the lime glass substrate, and dried at 80 ℃, heating the Se powder in 230 ℃ and the CuInSe 2 thin film by heating the glass substrate on which the ink is applied at 530 ℃ temperature Photoactive layer was prepared. The pressure in the heat treatment chamber was 10 -5 torr.
(Example 4)
10 g of zirconia balls having a diameter of 1 mm were placed in a 20 ml nalgene bottle, and a solution containing 1.68 g of ethylene glycol, 0.72 g of ethanol, and 0.01 g of ethylcellulose was added thereto, followed by ultrasonication for 1 minute. 0.6 g of Cu 2 Se, CuSe, and In 2 O 3 synthetic particles were added to the solution, followed by milling at 20 Hz for 1 hour with a vibrating ball mill to disperse the ink. Then, after separating the ball and ink, the ink was subjected to external ultrasonic treatment for 1 minute. After the Mo electrode is deposited soda and a bar coating ink prepared in the lime glass substrate, and dried at 80 ℃, heating the Se powder in 230 ℃ and the CuInSe 2 thin film by heating the glass substrate on which the ink is applied at 530 ℃ temperature Photoactive layer was prepared. The pressure in the heat treatment chamber was 10 -5 torr.
(Example 5)
10 g of zirconia balls with a diameter of 1 mm are placed in a 20 ml nalgene bottle, and toluene, Cu nanoparticles and In 2 Se 3 nanoparticles, PMMA (MW: 120,000) are mixed, and at 20 Hz with a vibrating ball mill. The ink was prepared by dispersion by milling for 1 hour. The molar ratio of Cu to In of the Cu nanoparticles and In 2 Se 3 particles is 1: 1, and 400 parts by weight of toluene and 1 part by weight of PMMA are used based on 100 parts by weight of the combined Cu nanoparticles and In 2 Se 3 particles. It was. Then, after separating the ball and ink, the ink was subjected to external ultrasonic treatment for 1 minute. After the Mo electrode is deposited soda and a bar coating ink prepared in the lime glass substrate, and dried at 80 ℃, heating the Se powder in 230 ℃ and the CuInSe 2 thin film by heating the glass substrate on which the ink is applied at 530 ℃ temperature Photoactive layer was prepared. The pressure in the heat treatment chamber was 10 -5 torr.
(Example 6)
10 g of zirconia balls with a diameter of 1 mm were placed in a 20 ml nalgene bottle, mixed with toluene, Cu nanoparticles, Ga 2 Se 3 nanoparticles and In 2 Se 3 nanoparticles, PMMA (MW: 120,000), Ink was prepared by dispersion by milling at 20 Hz for 1 hour with a vibrating ball mill. Cu nanoparticles and Ga 2 Se 3 And a molar ratio of Cu: (In + Ga) of the In 2 Se 3 particles is 1: 1, and a molar ratio of In: Ga of the Ga 2 Se 3 and In 2 Se 3 particles is 7: 3. Cu nanoparticles, Ga 2 Se 3 400 parts by weight of toluene and 1 part by weight of PMMA were used based on 100 parts by weight of the nanoparticles and the In 2 Se 3 nanoparticles. Then, after separating the ball and ink, the ink was subjected to external ultrasonic treatment for 1 minute. After coating the ink prepared on the soda-lime glass substrate on which the Mo electrode was deposited, dried at 80 ° C., the Se powder was heated to 230 ° C., and the ink-coated glass substrate was heat-treated at 530 ° C. to obtain Cu (In 0). .7 Ga 0 .3) (to prepare a photoactive layer of S, Se) 2 thin film. The pressure in the heat treatment chamber was 10 -5 torr.
(Example 7)
10 g of zirconia balls with a diameter of 1 mm are placed in a 20 ml nalgene bottle, toluene, Cu nanoparticles, ZnS (Aldrich) particles, SnS (Aldrich) particles, PMMA (MW: 120,000), and then a vibrating ball. The ink was prepared by milling and dispersing for 1 hour at 20 Hz with a miller. It added to toluene so that the molar ratio of Cu: Zn: Sn between particles might be 2: 1: 1. In this case, 400 parts by weight of toluene and 1 part by weight of PMMA were used based on 100 parts by weight of the particulate particulate mixture of the Cu nanoparticles, ZnS, and SnS. Then, after separating the ball and ink, the ink was subjected to external ultrasonic treatment for 1 minute. The ink prepared on the soda lime glass substrate on which the Mo electrode was deposited was bar coated and dried at 80 DEG C and then the glass substrate coated with ink was heat-treated at a temperature of 530 DEG C while supplying H 2 S gas at a flow rate of 100 SCCM Cu 2 ZnSnS 4 thin films.
(Example 8)
10 g of zirconia balls with a diameter of 1 mm are placed in a 20 ml nalgene bottle, toluene, Cu nanoparticles, ZnS (Aldrich) particles, SnS (Aldrich) particles, PMMA (MW: 120,000), and then a vibrating ball. The ink was prepared by milling and dispersing for 1 hour at 20 Hz with a miller. It added to toluene so that the molar ratio of Cu: Zn: Sn between particles might be 2: 1: 1. In this case, 400 parts by weight of toluene and 1 part by weight of PMMA were used based on 100 parts by weight of the particulate particulate mixture of the Cu nanoparticles, ZnS, and SnS. Then, after separating the ball and ink, the ink was subjected to external ultrasonic treatment for 1 minute. After coating the ink prepared on the soda-lime glass substrate on which the Mo electrode was deposited, drying at 80 ° C., heating the Se powder to 230 ° C., and heating the ink-coated glass substrate at a temperature of 530 ° C. to obtain Cu 2 ZnSn ( S, Se) 2 thin film was prepared a photoactive layer. The pressure in the heat treatment chamber was 10 -5 torr.
(Example 9)
10 g of zirconia balls with a diameter of 1 mm are placed in a 20 ml nalgene bottle, toluene, Cu 2 Se nanoparticles, CuSe nanoparticles and In 2 Se 3 nanoparticles, PMMA (MW: 120,000), and then shaken. Ink was prepared by dispersing by milling for 1 hour at 20 Hz with a ball mill. The molar ratio of Cu to In of the Cu nanoparticles and In 2 Se 3 particles is 1: 1, and 400 parts by weight of toluene and 1 part by weight of PMMA are used based on 100 parts by weight of the combined Cu nanoparticles and In 2 Se 3 particles. It was. Then, after separating the ball and ink, the ink was subjected to external ultrasonic treatment for 1 minute. After the Mo electrode is deposited soda and a bar coating ink prepared in the lime glass substrate, and dried at 80 ℃, heating the Se powder in 230 ℃ and the CuInSe 2 thin film by heating the glass substrate on which the ink is applied at 530 ℃ temperature Photoactive layer was prepared. The pressure in the heat treatment chamber was 10 -5 torr.
(Example 10)
10 g of zirconia balls with a diameter of 1 mm are placed in a 20 ml nalgene bottle, toluene, Cu 2 Se nanoparticles, CuSe nanoparticles, Ga 2 Se 3 nanoparticles and synthetic In 2 Se 3 nanoparticles, PMMA (MW: 120,000) was mixed and then dispersed by milling at 20 Hz for 1 hour with a vibrating ball mill to prepare an ink. The molar ratio of Cu: (In + Ga) of Cu nanoparticles to Ga 2 Se 3 and In 2 Se 3 particles is 1: 1, and the molar ratio of In: Ga of Ga 2 Se 3 and In 2 Se 3 particles is 7: 3. to be. Cu nanoparticles, Ga 2 Se 3 400 parts by weight of toluene and 1 part by weight of PMMA were used based on 100 parts by weight of the nanoparticles and the In 2 Se 3 nanoparticles. Then, after separating the ball and ink, the ink was subjected to external ultrasonic treatment for 1 minute. After the Mo electrode is deposited soda and a bar coating ink prepared in the lime glass substrate, and dried at 80 ℃, heating the Se powder in 230 ℃ and heat-treating the glass substrate, the ink is applied at 530 ℃ temperature Cu (In 0.7 Ga 0.3 ) (S, Se) 2 thin film was prepared. The pressure in the heat treatment chamber was 10 -5 torr.
(Example 11)
10 g of zirconia balls with a diameter of 1 mm are placed in a 20 ml nalgene bottle, and toluene, Cu 2 Se nanoparticles, CuSe nanoparticles, ZnS (Aldrich) particles, SnS (Aldrich) particles, PMMA (MW: 120,000) After mixing, the ink was prepared by dispersing by milling at 20 Hz for 1 hour with a vibrating ball mill. It added to toluene so that the molar ratio of Cu: Zn: Sn between particles might be 2: 1: 1. In this case, 400 parts by weight of toluene and 1 part by weight of PMMA were used based on 100 parts by weight of the combined Cu nanoparticles and ZnS and SnS particles. Then, after separating the ball and ink, the ink was subjected to external ultrasonic treatment for 1 minute. The ink prepared on the soda lime glass substrate on which the Mo electrode was deposited was bar coated and dried at 80 DEG C and then the glass substrate coated with ink was heat-treated at a temperature of 530 DEG C while supplying H 2 S gas at a flow rate of 100 SCCM Cu 2 ZnSnS 4 thin films.
(Example 12)
10 g of zirconia balls with a diameter of 1 mm are placed in a 20 ml nalgene bottle, and toluene, Cu 2 Se nanoparticles, CuSe nanoparticles, ZnS (Aldrich) particles, SnS (Aldrich) particles, PMMA (MW: 120,000) After mixing, the ink was prepared by dispersing by milling at 20 Hz for 1 hour with a vibrating ball mill. It added to toluene so that the molar ratio of Cu: Zn: Sn between particles might be 2: 1: 1. In this case, 400 parts by weight of toluene and 1 part by weight of PMMA were used based on 100 parts by weight of the particulate nanoparticles including Cu nanoparticles and ZnS and SnS particles. Then, after separating the ball and ink, the ink was subjected to external ultrasonic treatment for 1 minute. The ink was prepared by ball milling for 60 minutes at 20 Hz. After coating the ink prepared on the soda-lime glass substrate on which the Mo electrode was deposited, drying at 80 ° C., heating the Se powder to 230 ° C., and heating the ink-coated glass substrate at a temperature of 530 ° C. to obtain Cu 2 ZnSn ( S, Se) 2 thin film was prepared a photoactive layer. The pressure in the heat treatment chamber was 10 -5 torr.
(Comparative Example 1)
10 g of zirconia balls having a diameter of 1 mm were placed in a 20 ml nalgene bottle, and a solution containing 1.68 g of ethylene glycol and 0.72 g of ethanol was added thereto, followed by ultrasonication for 1 minute. 0.6 g of Cu 2 Se, CuSe, and In 2 O 3 synthetic particles were added to the solution, followed by milling at 20 Hz for 1 hour with a vibrating ball mill to disperse the ink. Then, after separating the ball and ink, the ink was subjected to external ultrasonic treatment for 1 minute. After the Mo electrode is deposited soda and a bar coating ink prepared in the lime glass substrate, and dried at 80 ℃, heating the Se powder in 230 ℃ and the CuInSe 2 thin film by heating the glass substrate on which the ink is applied at 530 ℃ temperature Photoactive layer was prepared. The pressure in the heat treatment chamber was 10 -5 torr. For fabricating the solar cell, CdS thin films were deposited by chemical bath deposition, ZnO and Al-doped ZnO thin films were deposited by sputtering, and Al electrodes were deposited by thermal evaporation.
(Comparative Example 2)
10 g of zirconia balls with a diameter of 1 mm were placed in a 20 ml nalgene bottle, toluene, Cu nanoparticles, and In 2 Se 3 nanoparticles were mixed, and milled at 20 Hz for 1 hour with a vibrating ball mill. Disperse to prepare ink. The molar ratio of Cu: In of the Cu nanoparticles and the In 2 Se 3 particles was 1: 1, and the amount of toluene was 400 parts by weight based on 100 parts by weight of the combined particulates of the Cu nanoparticles and the In 2 Se 3 particles. Then, after separating the ball and ink, the ink was subjected to external ultrasonic treatment for 1 minute. After the Mo electrode is deposited soda and a bar coating ink prepared in the lime glass substrate, and dried at 80 ℃, heating the Se powder in 230 ℃ and the CuInSe 2 thin film by heating the glass substrate on which the ink is applied at 530 ℃ temperature Photoactive layer was prepared. The pressure in the heat treatment chamber was 10 -5 torr.
(Comparative Example 3)
10 g of zirconia balls with a diameter of 1 mm are placed in a 20 ml nalgene bottle, and toluene, Cu nanoparticles, Ga 2 Se 3 nanoparticles, and In 2 Se 3 nanoparticles are mixed, followed by a vibration ball mill at 20 Hz. The ink was prepared by dispersion by milling for 1 hour. The molar ratio of Cu: (In + Ga) of Cu nanoparticles to Ga 2 Se 3 and In 2 Se 3 particles is 1: 1, and the molar ratio of In: Ga of Ga 2 Se 3 and In 2 Se 3 particles is 7: 3. to be. Cu nanoparticles, Ga 2 Se 3 The amount of toluene was 400 parts by weight based on 100 parts by weight of the particle combined with the nanoparticles and the In 2 Se 3 nanoparticles. Then, after separating the ball and ink, the ink was subjected to external ultrasonic treatment for 1 minute. After coating the ink prepared on the soda-lime glass substrate on which the Mo electrode was deposited, dried at 80 ° C., the Se powder was heated to 230 ° C., and the ink-coated glass substrate was heat-treated at 530 ° C. to obtain Cu (In 0). .7 Ga 0 .3) (to prepare a photoactive layer of S, Se) 2 thin film. The pressure in the heat treatment chamber was 10 -5 torr.
(Comparative Example 4)
10 g of zirconia balls with a diameter of 1 mm are placed in a 20 ml nalgene bottle, and toluene, Cu nanoparticles, ZnS (Aldrich) particles and SnS (Aldrich) particles are mixed, and then vibrated ball mill for 1 hour at 20 Hz. The ink was prepared by dispersing by milling. It added to toluene so that the molar ratio of Cu: Zn: Sn between particles might be 2: 1: 1. In this case, the amount of toluene was 400 parts by weight based on 100 parts by weight of the particulate nanoparticles including the Cu nanoparticles and the ZnS and SnS particles. Then, after separating the ball and ink, the ink was subjected to external ultrasonic treatment for 1 minute. The ink prepared on the soda lime glass substrate on which the Mo electrode was deposited was bar coated and dried at 80 DEG C and then the glass substrate coated with ink was heat-treated at a temperature of 530 DEG C while supplying H 2 S gas at a flow rate of 100 SCCM Cu 2 ZnSnS 4 thin films.
(Comparative Example 5)
10 g of zirconia balls with a diameter of 1 mm are placed in a 20 ml nalgene bottle, and toluene, Cu nanoparticles, ZnS (Aldrich) particles and SnS (Aldrich) particles are mixed, and then vibrated ball mill for 1 hour at 20 Hz. The ink was prepared by dispersing by milling. It added to toluene so that the molar ratio of Cu: Zn: Sn between particles might be 2: 1: 1. In this case, the amount of toluene was 400 parts by weight based on 100 parts by weight of the particulate nanoparticles including the Cu nanoparticles and the ZnS and SnS particles. Then, after separating the ball and ink, the ink was subjected to external ultrasonic treatment for 1 minute. After coating the ink prepared on the soda-lime glass substrate on which the Mo electrode was deposited, drying at 80 ° C., heating the Se powder to 230 ° C., and heating the ink-coated glass substrate at a temperature of 530 ° C. to obtain Cu 2 ZnSn ( S, Se) 2 thin film was prepared a photoactive layer. The pressure in the heat treatment chamber was 10 -5 torr.
(Comparative Example 6)
10 g of zirconia balls with a diameter of 1 mm are placed in a 20 ml nalgene bottle, and toluene, Cu 2 Se nanoparticles, CuSe nanoparticles, and In 2 Se 3 nanoparticles are mixed, and then subjected to a vibrating ball mill at 20 Hz. The ink was prepared by dispersion by milling for a time. The molar ratio of Cu: In of the Cu nanoparticles and the In 2 Se 3 particles was 1: 1, and the amount of toluene was 400 parts by weight based on 100 parts by weight of the combined particulates of the Cu nanoparticles and the In 2 Se 3 particles. Then, after separating the ball and ink, the ink was subjected to external ultrasonic treatment for 1 minute. After the Mo electrode is deposited soda and a bar coating ink prepared in the lime glass substrate, and dried at 80 ℃, heating the Se powder in 230 ℃ and the CuInSe 2 thin film by heating the glass substrate on which the ink is applied at 530 ℃ temperature Photoactive layer was prepared. The pressure in the heat treatment chamber was 10 -5 torr.
(Comparative Example 7)
10 g of zirconia balls with a diameter of 1 mm are placed in a 20 ml nalgene bottle, and toluene, Cu 2 Se nanoparticles, CuSe nanoparticles, Ga 2 Se 3 nanoparticles, and In 2 Se 3 nanoparticles are mixed, and then vibrated. Ink was prepared by dispersing by milling for 1 hour at 20 Hz with a ball mill. The molar ratio of Cu: (In + Ga) of Cu nanoparticles to Ga 2 Se 3 and In 2 Se 3 particles is 1: 1, and the molar ratio of In: Ga of Ga 2 Se 3 and In 2 Se 3 particles is 7: 3. to be. Cu nanoparticles, Ga 2 Se 3 The amount of toluene was 400 parts by weight based on 100 parts by weight of the particle combined with the nanoparticles and the In 2 Se 3 nanoparticles. Then, after separating the ball and ink, the ink was subjected to external ultrasonic treatment for 1 minute. After coating the ink prepared on the soda-lime glass substrate on which the Mo electrode was deposited, dried at 80 ° C., the Se powder was heated to 230 ° C., and the ink-coated glass substrate was heat-treated at 530 ° C. to obtain Cu (In 0). .7 Ga 0 .3) (to prepare a photoactive layer of S, Se) 2 thin film. The pressure in the heat treatment chamber was 10 -5 torr.
(Comparative Example 8)
10 g of zirconia balls with a diameter of 1 mm are placed in a 20 ml nalgene bottle, toluene, Cu 2 Se nanoparticles, CuSe nanoparticles, ZnS (Aldrich) particles and SnS (Aldrich) particles are mixed, followed by a vibrating ball mill. The ink was prepared by dispersion by milling at 20 Hz for 1 hour. It added to toluene so that the molar ratio of Cu: Zn: Sn between particles might be 2: 1: 1. Then, after separating the ball and ink, the ink was subjected to external ultrasonic treatment for 1 minute. The ink prepared on the soda lime glass substrate on which the Mo electrode was deposited was bar coated and dried at 80 DEG C and then the glass substrate coated with ink was heat-treated at a temperature of 530 DEG C while supplying H 2 S gas at a flow rate of 100 SCCM Cu 2 ZnSnS 4 thin films.
(Comparative Example 9)
10 g of zirconia balls with a diameter of 1 mm are placed in a 20 ml nalgene bottle, toluene, Cu 2 Se nanoparticles, CuSe nanoparticles, ZnS (Aldrich) particles and SnS (Aldrich) particles are mixed, followed by a vibrating ball mill. The ink was prepared by dispersion by milling at 20 Hz for 1 hour. It added to toluene so that the molar ratio of Cu: Zn: Sn between particles might be 2: 1: 1. At this time, the amount of toluene was 400 parts by weight based on 100 parts by weight of the mixed material. Then, after separating the ball and ink, the ink was subjected to external ultrasonic treatment for 1 minute. After coating the ink prepared on the soda-lime glass substrate on which the Mo electrode was deposited, drying at 80 ° C., heating the Se powder to 230 ° C., and heating the ink-coated glass substrate at a temperature of 530 ° C. to obtain Cu 2 ZnSn ( S, Se) 2 thin film was prepared a photoactive layer. The pressure in the heat treatment chamber was 10 -5 torr.
As shown in Table 1, the photoactive layer thin film prepared from the ink to which the binder polymer was not added was cracked, whereas the photoactive layer thin film prepared from the ink to which the binder polymer was added was not cracked. . In addition, the photoactive layer thin film prepared from the ink without the organic binder is cracked (FIGS. 1 to 3, 5, 6), whereas the photoactive layer thin film prepared from the ink with the organic binder is not cracked. ((FIGS. 7-9, 11, 12)) can be confirmed. The effect of inhibiting crack formation in the photoactive layer thin film due to the addition of such an organic binder is a very important factor in solar cell fabrication. As shown in Table 2 above, when cracking occurs, a desirable heterojunction is not made. While the battery does not work (FIG. 4), when the cracking of the photoactive layer thin film is suppressed through the addition of an organic binder, it is possible to fabricate a thin film solar cell having a dramatically increased efficiency of 8.3%, showing a dramatically increased efficiency of 8.3%. It could be confirmed that (FIG. 10).
While the present invention has been described in detail with reference to the preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. All of which fall within the scope of the present invention.
Claims (10)
The chalcogenide compound particles are formed of a precursor material including particles of at least one element selected from group 11 to 14, a chalcogen element and chalcogenide particles of at least one element selected from groups 11 to 14 Ink composition.
The composition is an ink composition for a solar cell photoactive layer comprising 0.1 to 30 parts by weight of a binder polymer and 50 to 900 parts by weight of a solvent based on 100 parts by weight of chalcogenide particles.
The binder polymer is polyvinyl alcohol, polyvinyl butyral, polyvinylpyrrolidone, polyvinylidene fluoride, hydroxyethyl cellulose, carboxymethyl cellulose, hydroxy cellulose, methyl cellulose, nitrocellulose, ethyl cellulose, ethyl hydroxyethyl Cellulose, styrenebutadiene rubber, copolymer of C1-C10 alkyl (meth) acrylate and unsaturated carboxylic acid, nitrocellulose, gelatin, tinsotone, starch, polyether-polyol, polystyrene with amine groups terminated, Any one or two or more selected from the group consisting of polyethylene oxide, polyurethane, resin containing carboxyl group, self-crosslinking (meth) acrylic acid copolymer, ester polymer, copolymer having ethylenically unsaturated group, phenolic resin and epoxy resin Ink composition for a solar cell photoactive layer which is a mixture.
b) milling the mixed solution to produce a homogeneous ink composition, and
c) coating and heat treating the ink composition
≪ / RTI >
Step a) is an ink composition for a photovoltaic cell active layer comprising 0.1 to 30 parts by weight of the binder polymer and 50 to 900 parts by weight of the solvent with respect to 100 parts by weight of the chalcogenide particles.
The binder polymer is polyvinyl alcohol, polyvinyl butyral, polyvinylpyrrolidone, polyvinylidene fluoride, hydroxyethyl cellulose, carboxymethyl cellulose, hydroxy cellulose, methyl cellulose, nitrocellulose, ethyl cellulose, ethyl hydroxyethyl Cellulose, styrenebutadiene rubber, copolymer of C1-C10 alkyl (meth) acrylate and unsaturated carboxylic acid, nitrocellulose, gelatin, tinsotone, starch, polyether-polyol, polystyrene with amine groups terminated, Any one or two or more selected from the group consisting of polyethylene oxide, polyurethane, resin containing carboxyl group, self-crosslinking (meth) acrylic acid copolymer, ester polymer, copolymer having ethylenically unsaturated group, phenolic resin and epoxy resin Method for producing a photovoltaic cell active layer is a mixture.
The milling is a method of manufacturing a solar cell photoactive layer is any one or more milling selected from ball milling, satellite milling, three-roll milling and attrition milling.
The heat treatment is 400 to 550 ℃, the method of manufacturing a solar cell photoactive layer is performed in a chalcogen atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020120082837A KR20140015095A (en) | 2012-07-27 | 2012-07-27 | Fabricatin method of absorber layer for thin-film solar cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020120082837A KR20140015095A (en) | 2012-07-27 | 2012-07-27 | Fabricatin method of absorber layer for thin-film solar cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20140015095A true KR20140015095A (en) | 2014-02-06 |
Family
ID=50264882
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020120082837A KR20140015095A (en) | 2012-07-27 | 2012-07-27 | Fabricatin method of absorber layer for thin-film solar cell |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR20140015095A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108231922A (en) * | 2018-01-12 | 2018-06-29 | 莆田市超维二维科技发展有限公司 | A kind of novel graphite alkene photovoltaic cell |
-
2012
- 2012-07-27 KR KR1020120082837A patent/KR20140015095A/en active Search and Examination
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108231922A (en) * | 2018-01-12 | 2018-06-29 | 莆田市超维二维科技发展有限公司 | A kind of novel graphite alkene photovoltaic cell |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8329501B1 (en) | High-throughput printing of semiconductor precursor layer from inter-metallic microflake particles | |
| US8372734B2 (en) | High-throughput printing of semiconductor precursor layer from chalcogenide nanoflake particles | |
| US8889469B2 (en) | Multi-nary group IB and VIA based semiconductor | |
| US8623448B2 (en) | High-throughput printing of semiconductor precursor layer from chalcogenide microflake particles | |
| US8729543B2 (en) | Multi-nary group IB and VIA based semiconductor | |
| US20110294254A1 (en) | Low cost solar cells formed using a chalcogenization rate modifier | |
| US20070163638A1 (en) | Photovoltaic devices printed from nanostructured particles | |
| US20070163383A1 (en) | High-throughput printing of nanostructured semiconductor precursor layer | |
| US20070169813A1 (en) | High-throughput printing of semiconductor precursor layer from microflake particles | |
| US20100089453A1 (en) | High-Throughput Printing of Semiconductor Precursor Layer From Microflake Particles | |
| US20070169812A1 (en) | High-throughput printing of semiconductor precursor layer from nanoflake particles | |
| US20080280030A1 (en) | Solar cell absorber layer formed from metal ion precursors | |
| US20070163637A1 (en) | High-throughput printing of semiconductor precursor layer from nanoflake particles | |
| US20070163642A1 (en) | High-throughput printing of semiconductor precursor layer from inter-metallic microflake articles | |
| JP2008537640A (en) | Formation of compound films for metal dispersants and photovoltaic device active layers | |
| US8642455B2 (en) | High-throughput printing of semiconductor precursor layer from nanoflake particles | |
| EP1997149A2 (en) | High-throughput printing of semiconductor precursor layer from inter-metallic microflake particles | |
| EP1997150A2 (en) | High-throughput printing of semiconductor precursor layer from inter-metallic nanoflake particles | |
| JP2012515708A (en) | Selenization of precursor layers containing CuInS2 nanoparticles | |
| EP1861916A2 (en) | Mettalic dispersion and formation of compound film for photovoltaic device active layer | |
| WO2009051862A2 (en) | Semiconductor thin films formed from non-spherical particles | |
| KR101298026B1 (en) | Fabrication method of photo active layer for solar cell | |
| Lee et al. | Electrophoretic deposition of Ga–Cu core–shell nanocomposites for CuGaS2 thin films | |
| KR20140015095A (en) | Fabricatin method of absorber layer for thin-film solar cell | |
| KR20130057915A (en) | Hybrid ink for czts film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| AMND | Amendment | ||
| E902 | Notification of reason for refusal | ||
| AMND | Amendment | ||
| E601 | Decision to refuse application | ||
| AMND | Amendment |