CN103346206A - Method for preparing copper indium gallium selenide thin film with sulfur-rich surface - Google Patents
Method for preparing copper indium gallium selenide thin film with sulfur-rich surface Download PDFInfo
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- CN103346206A CN103346206A CN2013102297802A CN201310229780A CN103346206A CN 103346206 A CN103346206 A CN 103346206A CN 2013102297802 A CN2013102297802 A CN 2013102297802A CN 201310229780 A CN201310229780 A CN 201310229780A CN 103346206 A CN103346206 A CN 103346206A
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- copper indium
- indium gallium
- gallium selenide
- sulphur
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- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 239000010409 thin film Substances 0.000 title claims abstract description 118
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 49
- 229910052717 sulfur Inorganic materials 0.000 title abstract description 5
- 239000011593 sulfur Substances 0.000 title abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 26
- 239000002105 nanoparticle Substances 0.000 claims abstract description 13
- 239000005864 Sulphur Substances 0.000 claims description 78
- 238000010438 heat treatment Methods 0.000 claims description 51
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 40
- 239000011159 matrix material Substances 0.000 claims description 39
- 239000012528 membrane Substances 0.000 claims description 32
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 28
- 229910052733 gallium Inorganic materials 0.000 claims description 28
- 238000002360 preparation method Methods 0.000 claims description 27
- 229910052711 selenium Inorganic materials 0.000 claims description 23
- 239000011669 selenium Substances 0.000 claims description 23
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 230000035515 penetration Effects 0.000 claims description 11
- 150000002258 gallium Chemical class 0.000 claims description 10
- 150000002471 indium Chemical class 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 229910052738 indium Inorganic materials 0.000 claims description 9
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 9
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- ALCDAWARCQFJBA-UHFFFAOYSA-N ethylselanylethane Chemical compound CC[Se]CC ALCDAWARCQFJBA-UHFFFAOYSA-N 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 229910000058 selane Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims 1
- -1 oxide of cupric Chemical compound 0.000 claims 1
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 230000006872 improvement Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000001228 spectrum Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 37
- 239000010408 film Substances 0.000 description 37
- 238000006243 chemical reaction Methods 0.000 description 32
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 26
- 229910002804 graphite Inorganic materials 0.000 description 26
- 239000010439 graphite Substances 0.000 description 26
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 26
- 238000005406 washing Methods 0.000 description 20
- 238000007747 plating Methods 0.000 description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 18
- 239000000376 reactant Substances 0.000 description 18
- 239000012265 solid product Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 14
- 239000005361 soda-lime glass Substances 0.000 description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 12
- 229910052791 calcium Inorganic materials 0.000 description 12
- 239000011575 calcium Substances 0.000 description 12
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 12
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 12
- 238000000053 physical method Methods 0.000 description 12
- 238000000137 annealing Methods 0.000 description 11
- 238000004140 cleaning Methods 0.000 description 11
- 238000001755 magnetron sputter deposition Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000013019 agitation Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 239000004575 stone Substances 0.000 description 9
- 238000010345 tape casting Methods 0.000 description 9
- 229940044658 gallium nitrate Drugs 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005693 optoelectronics Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 2
- 229910004613 CdTe Inorganic materials 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000002096 quantum dot Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- ZRKMQKLGEQPLNS-UHFFFAOYSA-N 1-Pentanethiol Chemical compound CCCCCS ZRKMQKLGEQPLNS-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- MGWAGIQQTULHGU-UHFFFAOYSA-N 2-ethylbutan-1-amine Chemical compound CCC(CC)CN MGWAGIQQTULHGU-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- ZUBZATZOEPUUQF-UHFFFAOYSA-N isopropylhexane Natural products CCCCCCC(C)C ZUBZATZOEPUUQF-UHFFFAOYSA-N 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 150000003342 selenium Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Photovoltaic Devices (AREA)
Abstract
The invention is suitable for the technical field of photovoltaic new energy materials and provides a method for preparing a copper indium gallium selenide thin film with the sulfur-rich surface. The method comprises the following steps: preparing copper indium gallium selenide nano particles, preparing copper indium gallium selenide nanocrystalline ink, preparing the copper indium gallium selenide thin film, and conducting sulfidizing on the copper indium gallium selenide thin film. The method is simple in process, convenient to operate and low in cost, facilitates large-scale production of a solar thin film cell, optimizes the energy band structure of the copper indium gallium selenide thin film, enables energy of solar spectra to be fully utilized, and further promotes the improvement of cell interface performance.
Description
Technical field
The invention belongs to photovoltaic new energy materials technical field, relate in particular to the preparation method of the CIGS thin-film of surperficial rich sulphur.
Background technology
Along with industrial expansion, Increase of population, non-renewable energies such as coal, oil, natural gas are consumed excessively, and then have caused the energy-intensive situation.Therefore people begin to pay attention to wind energy, geothermal energy, morning and evening can, regenerative resources such as solar energy.And wherein, it is big, inexhaustible that solar energy has an energy of containing, and advantages such as cleanliness without any pollution become the energy that application prospect is arranged most.The form of utilizing of solar energy mainly contains two kinds of heat energy and electric energy, as solar water heater, and solar cell etc.
Solar cell is of many uses, easy to carry with it, not got more and more people's extensive concerning by advantages such as region restriction.Its kind mainly comprise silicon solar cell, organic too can battery, DSSC, quantum dot solar cell, CdTe thin-film solar cells, GaAs solar cell and Copper Indium Gallium Selenide (CIGS) thin-film solar cells etc.At present, the silica-based solar cell technology is the most ripe, and optoelectronic transformation efficiency the highest (about 20.4%) occupies the photovoltaic market share about 85%.But because its cost height, complex process, apparatus expensive, pollution are big, along with problem aggravations such as its there is lack of raw materials aggravation, price rise steadily, people are seeking a kind of other solar cells that can the substituted for silicon solar cell.And organic too can battery, DSSC, quantum dot solar cell, the cost of manufacture height has also appearred in CdTe thin-film solar cells and GaAs thin-film solar cells, complex process, the shortcoming of different levels such as optoelectronic transformation efficiency is low is not so be widely used.Copper-indium-galliun-selenium film solar cell becomes the focus of current research topic because addressing the above problem the favor that enjoys people preferably.
At present, the preparation method of CIGS thin-film absorbed layer mainly contains vacuum and antivacuum two big class methods, and wherein vacuum method comprises magnetron sputtering method and vacuum coevaporation method, and antivacuum method mainly contains sol-gal process, electrochemical deposition method and nanocrystal solution method.The vacuum coevaporation method is present most widely used a kind of preparation CIGS film process, its prepared film purity is higher, surfacing, and compactness is good, optoelectronic transformation efficiency is the highest, reached 20.3%, still, this method requires the instrument and equipment of high vacuum, input cost is big, big energy-consuming, the uniformity of preparation large area film is relatively poor, therefore is difficult to realize large-scale production.Prepare in the CIGS thin-film process at electrochemical deposition method, because the sedimentation potential of copper, indium, gallium, each element of selenium is difficult to coupling, and make the stoichiometric proportion of film be difficult to control, and dephasign composition height, film compactness, tack are all very poor.
Summary of the invention
The purpose of the embodiment of the invention is to provide the preparation method of the CIGS thin-film of the rich sulphur in a kind of surface, is intended to solve that existing preparation method's complexity, product stoichiometric proportion are restive, dephasign composition height, film compactness and tack is poor, the film bandwidth is narrow problem.
The embodiment of the invention is achieved in that the Preparation Method of the CIGS thin-film of the rich sulphur in a kind of surface, may further comprise the steps:
Mantoquita, indium salt, gallium salt and selenium source compound are mixed synthetic Copper Indium Gallium Selenide nano particle with oleyl amine;
Described Copper Indium Gallium Selenide nanoparticulate dispersed is formed the nanocrystalline ink of Copper Indium Gallium Selenide in organic solvent;
Described Copper Indium Gallium Selenide nanometer ink is filmed at matrix, form Copper Indium Gallium Selenide presoma prefabricated membrane, obtain CIGS thin-film after the annealed processing;
Under the condition of sulphur source existence, described Cu-In-Ga-Se-S thin film is carried out vulcanizing treatment at 450-550 ° of C, obtain the CIGS thin-film of surperficial rich sulphur.
The present invention adopts antivacuum solwution method to prepare the CIGS thin-film of surperficial rich sulphur, method is simple, the equipment less investment, cost is low, efficient is high, and avoided the use (as hydrazine etc.) of a large amount of toxic reagents, meet requirement and theory that environmental protection is produced, the product appearance densification for preparing is smooth, change composition and the band structure thereof on Cu-In-Ga-Se-S thin film surface, improved absorption and the utilization of Cu-In-Ga-Se-S thin film to light, promoted the raising of battery interface performance.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explaining the present invention, and be not used in restriction the present invention.
The embodiment of the invention provides the preparation method of the CIGS thin-film of the rich sulphur in a kind of surface, may further comprise the steps:
S01. prepare the Copper Indium Gallium Selenide nano particle: mantoquita, indium salt, gallium salt and selenium source compound are mixed synthetic Copper Indium Gallium Selenide nano particle with oleyl amine;
S02. prepare the nanocrystalline ink of Copper Indium Gallium Selenide: described Copper Indium Gallium Selenide nanoparticulate dispersed is formed the nanocrystalline ink of Copper Indium Gallium Selenide in organic solvent;
S03. prepare CIGS thin-film: described Copper Indium Gallium Selenide nanometer ink is filmed at matrix, form Copper Indium Gallium Selenide presoma prefabricated membrane, obtain CIGS thin-film after the annealed processing;
S04. CIGS thin-film vulcanizing treatment: under the condition that exists in the sulphur source, described Cu-In-Ga-Se-S thin film is carried out vulcanizing treatment at 450-550 ° of C, obtain the CIGS thin-film of surperficial rich sulphur.
Particularly, among the above-mentioned steps S01, in order effectively to dissolve mantoquita, indium salt, gallium salt and selenium source compound, and stable in the synthesis temperature scope, volatility is little, the embodiment of the invention selects for use oleyl amine as the solvent of synthetic Copper Indium Gallium Selenide nano particle.The mode that mantoquita, indium salt, gallium salt and selenium source compound mix with oleyl amine is unrestricted, as preferred embodiment, can be to join in the oleyl amine together after mantoquita, indium salt, gallium salt and the selenium source compound, also can be respectively mantoquita, indium salt, gallium salt and selenium source compound to be joined in the oleyl amine, it is unrestricted that it adds order.Wherein, in a preferred embodiment, this mantoquita is at least a in chlorate, acetate, acetylacetonate, the oxide; Described indium salt is at least a in chlorate, acetate, acetylacetonate, the oxide; Described gallium salt is at least a in chlorate, acetate, acetylacetonate, the oxide; Described selenium source compound is at least a of selenium simple substance, diethyl selenide, hydrogen selenide, and as preferred embodiment, selenium simple substance is at least a in selenium powder, the selenium ball.
In the CIGS thin-film, the ratio of each component has certain influence to the band structure of film, especially the ratio of indium and gallium is bigger to the influence of film wideband structural, the content difference of gallium, the bandwidth difference of thin-film material is in the certain proportion scope, the bandwidth of the more big film of gallium content more big (between the 1.0-1.68), but when gallium content was too big, the performance of film also can be affected.In this step, the ratio for the preparation of mantoquita, indium salt, gallium salt and the selenium source compound of CIGS thin-film in this area all can be used in the embodiment of the invention.Discover repeatedly that through the inventor described indium, gallium element percentage composition ratio are: 0＜gallium/(indium+gallium)＜50% o'clock, the better performances of thin-film material, wherein, when gallium/(indium+gallium)=30%, the performance of film is best.
As preferred embodiment, for secluding air, avoid the generation of other side reactions, add raw material after, preferably in device, adopt the mode that feeds vacuum and nitrogen atmosphere to the reactant liquor gas washing that circulates, be full of reaction vessel with nitrogen then.Wherein, the gas washing number of times is preferably 2 times, and each gas washing time is preferably 15min.Of course it is to be understood that other safety under reaction condition and not with other gases that can be used for gas washing of product generation side reaction also in protection scope of the present invention.
Among this step S01, in described Copper Indium Gallium Selenide nano particle synthetic, synthesis temperature is preferably 220-300 ° of C, and the reaction time is 10-90min.Wherein, for homogeneous heating in the synthetic reaction process, mode of heating is selected the magnetic agitation mode of heating for use in the above-mentioned synthetic reaction.
Among the step S01, synthetic reaction is cooled to room temperature with reactant liquor after finishing, and filtering reacting liquid obtains solid product, after organic solvent cleaning 1～5 time, obtains clean Copper Indium Gallium Selenide nano particle.As specific embodiment, above-mentioned organic solvent is preferably at least a in ethanol, isopropyl alcohol, hexane or the chloroform.
Among the above-mentioned steps S02, adhesive force is good in order to obtain, the nanocrystalline ink of the Copper Indium Gallium Selenide of impurity less residue, and as further preferred embodiment, described organic solvent is at least a in amine, benzene class or the alkanethiol compounds.In the preferred embodiment, this organic solvent plays the effect of dispersant simultaneously, and the Copper Indium Gallium Selenide nano particle that makes reaction generate can evenly disperse, and can improve the adhesive force of the nanocrystalline ink of Copper Indium Gallium Selenide and matrix.As specific embodiment, at least a in the preferred pyridine of amine, butylamine, amylamine, hexylamine, the 2-ethyl butyl amine, at least a in the preferred toluene of benzene class, dimethylbenzene, benzene, ethylbenzene, the propyl benzene, at least a in the preferred hexyl mercaptan of alkanethiol class, butyl mercaptan, amyl hydrosulfide, the certain herbaceous plants with big flowers mercaptan.
The nanocrystalline ink of the Copper Indium Gallium Selenide of above-mentioned preparation, the thickness of the individual layer CIGS thin-film of its concentration and following step S03 preparation has direct relation, and the nanocrystalline body of Copper Indium Gallium Selenide is more big, and the individual layer CIGS thin-film for preparing is more thick.Therefore, in order to obtain the individual layer CIGS thin-film that thickness is suitable, be evenly distributed, the concentration of the nanocrystalline ink of described Copper Indium Gallium Selenide is 5-300mg/mL.
Matrix film described in the above-mentioned steps S03 without limits, can be used for matrix that CIGS thin-film smears in this area all in protection scope of the present invention.As concrete preferred embodiment, the above-mentioned matrix of filming is selected the calcium soda-lime glass matrix of plating Mo for use.The soda-lime glass of plating Mo can provide the Na source on the other hand on the one hand as the matrix of a film preparation, reaches film is carried out the purpose that Na mixes, thereby improve the performance of film.As specific embodiment, the preparation method of the calcium soda-lime glass matrix of plating Mo is: it is the 3.0cm size that calcium soda-lime glass matrix is cut into the length of side, clean calcium soda-lime glass matrix with acetone, ethanol, deionized water excusing from death respectively, obtain the matrix of surface cleaning, then plate the metal M o film of one deck 300-1500nm by magnetron sputtering at the matrix of cleaning.
In this S03 step, the nanocrystalline presoma prefabricated membrane of Copper Indium Gallium Selenide is prepared from by using physical method that Copper Indium Gallium Selenide nanometer ink is coated on the matrix.The present invention adopts antivacuum physical method, does not only need expensive equipment, has reduced cost of investment, and simple to operate, is convenient to large-scale industrial production.As concrete preferred embodiment, described physical method is preferably a kind of in knife coating, spin-coating method, czochralski method, drop-coating, the silk screen print method.Of course it is to be understood that in this area that other can be used for physical method that the nanocrystalline presoma prefabricated membrane of Copper Indium Gallium Selenide films all in protection scope of the present invention.Change for fear of the too high nanocrystalline ink of Copper Indium Gallium Selenide that causes of temperature, be coated with membrane process described in the embodiment of the invention and preferably finish at ambient temperature, room temperature condition is specially 20-30 ℃.
Among this step S03, described annealing method is preferably: the nanocrystalline presoma prefabricated membrane of dried Copper Indium Gallium Selenide and selenium powder be placed in the graphite box, then this stone mill box is placed in the tube furnace, feed N again
2Gas drains the air in the stove, and makes N
2Be full of furnace chamber.With the programming rate of 10-40 ° of C/min, to the body of heater heating, make the furnace chamber temperature be elevated to 450-550 ° of C then, behind the heating 10-100min, obtain CIGS thin-film.Wherein, N
2Gas is used for preventing the nanocrystalline presoma prefabricated membrane of Copper Indium Gallium Selenide generation side reaction as protective gas.Of course it is to be understood that other under these conditions can be as the gas of the nanocrystalline presoma protective gas of Copper Indium Gallium Selenide, all in protection scope of the present invention in this area.In the embodiment of the invention, the annealing in process prerequisite is for saturated selenium vapour pressure, and purpose is in order to prevent in the annealing heat treatment process, to cause original selenium loss in the film.As preferred embodiment, the selenium powder consumption is 1-10mmol, and the selenium amount can cause the loss that is not enough to replenish selenium in the film very little, and the selenium amount then can cause waste too much.
As preferred embodiment, the CIGS thin-film thickness for preparing is 800-3000nm.Discover repeatedly that through the inventor thickness of CIGS thin-film is bigger to the inhalation effects of light: the thickness of film too hour with reducing film to the absorption of light and then influencing the film photoelectric conversion ratio, makes the performance of product limited; Film thickness is more thick, and film is more high to the absorption of light, and the utilance of light is more high, and the performance of product is also just more good, will increase the film cost but thickness is too thick.When CIGS thin-film thickness is 800-3000nm, can satisfy the performance of CIGS thin-film, can control cost effectively again.
Wherein, among the above-mentioned steps S04, the concrete steps of described vulcanizing treatment are: CIGS thin-film and sulphur source are placed in the graphite box, adopt tube furnace as the heat treatment instrument, feed N in tube furnace
2Gas draining the air in the furnace chamber, and makes and is full of N in the furnace chamber
2, the speed with 10-40 ° of C/min heats up then, to the body of heater heating, makes the furnace chamber temperature be elevated to 450-550 ° of C, behind the heating 5-50min, obtains the CIGS thin-film of surperficial rich sulphur.Wherein, described sulphur source is at least a in sulphur powder, the hydrogen sulfide.
In the vulcanizing treatment of CIGS thin-film described in the embodiment of the invention, the consumption of sulphur is bigger to the Cu-In-Ga-Se-S thin film influence.The position that a spot of sulphur can replace selenium on the surface of CIGS thin-film forms the very thin copper indium gallium sulphur layer of one deck, can increase the bandwidth of film, thereby promote film to absorption and the utilization of light, and then improve the film photoelectric transfer ratio.When sulfur content is too low, do not reach the effect of surperficial rich sulphur; When sulfur content was too high, the corresponding minimizing of the content of selenium formed the copper indium gallium sulphur film at last in the film, will reduce the performance of film.When the consumption of sulphur was 0.5-5mmol, can access sulfur content was 1-30%, uniform Cu-In-Ga-Se-S thin film.
In the Cu-In-Ga-Se-S thin film of the surperficial rich sulphur that S04 prepares, element sulphur is bigger to the photoelectricity conversion performance influence of film in the length of penetration on CIGS thin-film surface, as preferred embodiment, the length of penetration of element sulphur on the CIGS thin-film surface is 10-200nm, more preferably 10-100nm among the present invention.
The preparation method of the copper indium gallium sulphur film of the rich sulphur in the described surface of the embodiment of the invention, adopt antivacuum solwution method to prepare the copper indium gallium sulphur film of surperficial rich sulphur, method is simple, equipment less investment, cost of manufacture are low, has only 1/3rd of silicon solar cell cost, and avoided the use (as hydrazine etc.) of a large amount of toxic reagents, meet requirement and theory that environmental protection is produced, and adopt liquid solution to prepare the CIGS thin-film of surperficial rich sulphur, can control the stoichiometric proportion of each composition accurately and effectively, reduce the dephasign composition.The Cu-In-Ga-Se-S thin film product of the surperficial rich sulphur that obtains with this method, the film densification is smooth, tack good, and it has changed composition and the band structure thereof on Cu-In-Ga-Se-S thin film surface, form the Cu-In-Ga-Se-S thin film material of surperficial rich sulphur, improve absorption and the utilization of Cu-In-Ga-Se-S thin film to light, promoted the raising of battery interface performance.
Embodiment one
(1) at room temperature, the 1.0mmol copper nitrate, the 0.8mmol indium nitrate, 0.2mmol gallium nitrate and 2.0mmol selenium powder add in the 50mL three-necked bottle, add the 20mL oleyl amine again, connect device.Then the mode by vacuum and nitrogen atmosphere circulation is to circulate gas washing 2 times of reactant liquor, each gas washing 15min.Be full of reaction vessel with nitrogen at last.Under magnetic agitation, to the reaction unit heating, when being elevated to 265 ° of C, keep temperature-resistant, reaction 40min.Then reactant liquor is cooled to room temperature, filtering reacting liquid obtains solid product, and with ethanol, isopropyl alcohol, the mixed liquor of one or more in hexane or the chloroform cleans 5 times, obtains the solid product of cleaning.
(2) subsequently this product being put into toluene formation concentration is the nanocrystalline ink of the stable colloidal solution-Copper Indium Gallium Selenide of 30mg/mL.
(3) calcium soda-lime glass matrix is cut into 3.0cm * 3.0cm size, cleans up with acetone, ethanol, deionized water excusing from death.By direct current magnetron sputtering process plating Mo on matrix, thickness is 500nm.Then at ambient temperature, in the air, the nanocrystalline ink of Copper Indium Gallium Selenide is coated on the matrix of plating Mo by physical methods such as knife coatings, form the thick nanocrystalline presoma prefabricated membrane of Copper Indium Gallium Selenide of 1000nm, be placed on the electric hot plate of 300 ° of C dry afterwards.The selenium powder of the nanocrystalline presoma prefabricated membrane of dried Copper Indium Gallium Selenide and 2mmol is placed in the graphite box, then this stone mill box is placed in the tube furnace, feed N again
2Gas drains the air in the stove, and makes N
2Be full of furnace chamber.With the programming rate of 15 ° of C/min, to the body of heater heating, make the furnace chamber temperature be elevated to 500 ° of C then, copper indium gallium sulphur presoma prefabricated membrane is carried out annealing in process.Stop heating behind the 40min, obtain CIGS thin-film.
(4) the sulphur powder of CIGS thin-film and 2mmol is placed in the graphite box, then this graphite box is placed tube furnace.In tube furnace, feed N subsequently
2Gas draining the air in the furnace chamber, and makes and is full of N in the furnace chamber
2, with the programming rate of 10 ° of C/min, to the body of heater heating, make the furnace chamber temperature be elevated to 480 ° of C then, CIGS thin-film is carried out vulcanizing treatment.Stop heating behind the 30min, obtain the Cu-In-Ga-Se-S thin film of surperficial rich sulphur at last.The thickness of Cu-In-Ga-Se-S thin film is 1200nm, and the length of penetration of element sulphur on the CIGS thin-film surface is 50nm.
Embodiment two
(1) at room temperature, the 1.0mmol copper chloride, the 0.8mmol indium nitrate, 0.3mmol gallium nitrate and 2.0mmol selenium powder add in the 50mL three-necked bottle, add the 20mL oleyl amine again, connect device.Then the mode by vacuum and nitrogen atmosphere circulation is to circulate gas washing 2 times of reactant liquor, each gas washing 15min.Be full of reaction vessel with nitrogen at last.Under magnetic agitation, to the reaction unit heating, when being elevated to 280 ° of C, keep temperature-resistant, reaction 40min is cooled to room temperature with reactant liquor then.Filtering reacting liquid obtains solid product, and with ethanol, isopropyl alcohol, the mixed liquor of one or more in hexane or the chloroform cleans 5 times, obtains the solid product of cleaning.
(2) subsequently this product being put into toluene formation concentration is the nanocrystalline ink of the stable colloidal solution-Copper Indium Gallium Selenide of 50mg/mL.
(3) calcium soda-lime glass matrix is cut into 3.0cm * 3.0cm size, cleans up with acetone, ethanol, deionized water excusing from death.By direct current magnetron sputtering process plating Mo on matrix, thickness is 1300nm.By physical methods such as knife coatings the nanocrystalline ink of Copper Indium Gallium Selenide is coated on the matrix of plating Mo then, forms the thick nanocrystalline presoma prefabricated membrane of Copper Indium Gallium Selenide of 1500nm, be placed on the electric hot plate of 300 ° of C dry afterwards.The selenium powder of the nanocrystalline presoma prefabricated membrane of dried Copper Indium Gallium Selenide and 2mmol is placed in the graphite box, then this stone mill box is placed in the tube furnace, feed N again
2Gas drains the air in the stove, and makes N
2Be full of furnace chamber.With the programming rate of 20 ° of C/min, to the body of heater heating, make the furnace chamber temperature be elevated to 480 ° of C then, copper indium gallium sulphur presoma prefabricated membrane is carried out annealing in process.Stop heating behind the 40min, obtain CIGS thin-film.
(4) the sulphur powder of CIGS thin-film and 2mmol is placed in the graphite box, then this graphite box is placed tube furnace.In tube furnace, feed N subsequently
2Gas draining the air in the furnace chamber, and makes and is full of N in the furnace chamber
2, with the programming rate of 20 ° of C/min, to the body of heater heating, make the furnace chamber temperature be elevated to 500 ° of C then, CIGS thin-film is carried out vulcanizing treatment.Stop heating behind the 25min, obtain the Cu-In-Ga-Se-S thin film light absorbing zone of surperficial rich sulphur at last.The thickness of Cu-In-Ga-Se-S thin film is 1800nm, and the length of penetration of element sulphur on the CIGS thin-film surface is 60nm.
Embodiment three
(1) at room temperature, the 1.0mmol stannous chloride, the 0.6mmol inidum chloride, 0.4mmol gallium nitrate and 2.0mmol selenium powder add in the 50mL three-necked bottle, add the 20mL oleyl amine again, connect device.Then the mode by vacuum and nitrogen atmosphere circulation is to circulate gas washing 2 times of reactant liquor, each gas washing 15min.Be full of reaction vessel with nitrogen at last.Under magnetic agitation, to the reaction unit heating, when being elevated to 250 ° of C, keep temperature-resistant, reaction 40min is cooled to room temperature with reactant liquor then.Filtering reacting liquid obtains solid product, and with ethanol, isopropyl alcohol, the mixed liquor of one or more in hexane or the chloroform cleans 5 times, obtains the solid product of cleaning.
(2) subsequently this product being put into toluene formation concentration is the nanocrystalline ink of the stable colloidal solution-Copper Indium Gallium Selenide of 100mg/mL.
(3) calcium soda-lime glass matrix is cut into 3.0cm * 3.0cm size, cleans up with acetone, ethanol, deionized water excusing from death.By direct current magnetron sputtering process plating Mo on matrix, thickness is 1000nm.By physical methods such as knife coatings the nanocrystalline ink of Copper Indium Gallium Selenide is coated on the matrix of plating Mo then, forms the thick nanocrystalline presoma prefabricated membrane of Copper Indium Gallium Selenide of 1800nm, be placed on the electric hot plate of 300 ° of C dry afterwards.The selenium powder of the nanocrystalline presoma prefabricated membrane of dried Copper Indium Gallium Selenide and 2mmol is placed in the graphite box, then this stone mill box is placed in the tube furnace, feed N again
2Gas drains the air in the stove, and makes N
2Be full of furnace chamber.With the programming rate of 25 ° of C/min, to the body of heater heating, make the furnace chamber temperature be elevated to 520 ° of C then, copper indium gallium sulphur presoma prefabricated membrane is carried out annealing in process.Stop heating behind the 40min, obtain CIGS thin-film.
(4) the sulphur powder of CIGS thin-film and 2mmol is placed in the graphite box, then this graphite box is placed tube furnace.In tube furnace, feed N subsequently
2Gas draining the air in the furnace chamber, and makes and is full of N in the furnace chamber
2, with the programming rate of 25 ° of C/min, to the body of heater heating, make the furnace chamber temperature be elevated to 520 ° of C then, CIGS thin-film is carried out vulcanizing treatment.Stop heating behind the 20min, obtain the Cu-In-Ga-Se-S thin film light absorbing zone of surperficial rich sulphur at last.The thickness of Cu-In-Ga-Se-S thin film is 2200nm, and the length of penetration of element sulphur on the CIGS thin-film surface is 40nm.
Embodiment four
(1) at room temperature, the 1.0mmol copper nitrate, the 0.5mmol indium acetate, 0.5mmol gallium nitrate and 2.0mmol hydrogen selenide add in the 50mL three-necked bottle, add the 20mL oleyl amine again, connect device.Then the mode by vacuum and nitrogen atmosphere circulation is to circulate gas washing 2 times of reactant liquor, each gas washing 15min.Be full of reaction vessel with nitrogen at last.Under magnetic agitation, to the reaction unit heating, when being elevated to 290 ° of C, keep temperature-resistant, reaction 40min is cooled to room temperature with reactant liquor then.Filtering reacting liquid obtains solid product, and with ethanol, isopropyl alcohol, the mixed liquor of one or more in hexane or the chloroform cleans 5 times, obtains the solid product of cleaning.
(2) subsequently this product being put into toluene formation concentration is the nanocrystalline ink of the stable colloidal solution-Copper Indium Gallium Selenide of 150mg/mL.
(3) calcium soda-lime glass matrix is cut into 3.0cm * 3.0cm size, cleans up with acetone, ethanol, deionized water excusing from death.By direct current magnetron sputtering process plating Mo on matrix, thickness is 800nm.By physical methods such as knife coatings the nanocrystalline ink of Copper Indium Gallium Selenide is coated on the matrix of plating Mo then, forms the thick nanocrystalline presoma prefabricated membrane of Copper Indium Gallium Selenide of 2000nm, be placed on the electric hot plate of 300 ° of C dry afterwards.The selenium powder of the nanocrystalline presoma prefabricated membrane of dried Copper Indium Gallium Selenide and 2mmol is placed in the graphite box, then this stone mill box is placed in the tube furnace, feed N again
2Gas drains the air in the stove, and makes N
2Be full of furnace chamber.With the programming rate of 30 ° of C/min, to the body of heater heating, make the furnace chamber temperature be elevated to 460 ° of C then, copper indium gallium sulphur presoma prefabricated membrane is carried out annealing in process.Stop heating behind the 40min, obtain CIGS thin-film.
(4) the sulphur powder of CIGS thin-film and 3mmol is placed in the graphite box, then this graphite box is placed tube furnace.In tube furnace, feed N subsequently
2Gas draining the air in the furnace chamber, and makes and is full of N in the furnace chamber
2, with the programming rate of 30 ° of C/min, to the body of heater heating, make the furnace chamber temperature be elevated to 460 ° of C then, CIGS thin-film is carried out vulcanizing treatment.Stop heating behind the 50min, obtain the Cu-In-Ga-Se-S thin film light absorbing zone of surperficial rich sulphur at last.The thickness of Cu-In-Ga-Se-S thin film is 2500nm, and the length of penetration of element sulphur on the CIGS thin-film surface is 80nm.
Embodiment five
(1) at room temperature, the 1.0mmol copper nitrate, the 0.7mmol indium nitrate, 0.3mmol gallium nitrate and 2.0mmol diethyl selenide add in the 50mL three-necked bottle, add the 20mL oleyl amine again, connect device.Then the mode by vacuum and nitrogen atmosphere circulation is to circulate gas washing 2 times of reactant liquor, each gas washing 15min.Be full of reaction vessel with nitrogen at last.Under magnetic agitation, to the reaction unit heating, when being elevated to 265 ° of C, keep temperature-resistant, reaction 40min is cooled to room temperature with reactant liquor then.Filtering reacting liquid obtains solid product, and with ethanol, isopropyl alcohol, the mixed liquor of one or more in hexane or the chloroform cleans 5 times, obtains the solid product of cleaning.
(2) subsequently this product being put into toluene formation concentration is the nanocrystalline ink of the stable colloidal solution-Copper Indium Gallium Selenide of 200mg/mL.
(3) calcium soda-lime glass matrix is cut into 3.0cm * 3.0cm size, cleans up with acetone, ethanol, deionized water excusing from death.By direct current magnetron sputtering process plating Mo on matrix, thickness is 900nm.By physical methods such as knife coatings the nanocrystalline ink of Copper Indium Gallium Selenide is coated on the matrix of plating Mo then, forms the thick nanocrystalline presoma prefabricated membrane of Copper Indium Gallium Selenide of 2300nm, be placed on the electric hot plate of 300 ° of C dry afterwards.The selenium powder of the nanocrystalline presoma prefabricated membrane of dried Copper Indium Gallium Selenide and 2mmol is placed in the graphite box, then this stone mill box is placed in the tube furnace, feed N again
2Gas drains the air in the stove, and makes N
2Be full of furnace chamber.With the programming rate of 15 ° of C/min, to the body of heater heating, make the furnace chamber temperature be elevated to 500 ° of C then, copper indium gallium sulphur presoma prefabricated membrane is carried out annealing in process.Stop heating behind the 40min, obtain CIGS thin-film.
(4) the sulphur powder of CIGS thin-film and 1mmol is placed in the graphite box, then this graphite box is placed tube furnace.In tube furnace, feed N subsequently
2Gas draining the air in the furnace chamber, and makes and is full of N in the furnace chamber
2, with the programming rate of 10 ° of C/min, to the body of heater heating, make the furnace chamber temperature be elevated to 480 ° of C then, CIGS thin-film is carried out vulcanizing treatment.Stop heating behind the 20min, obtain the Cu-In-Ga-Se-S thin film light absorbing zone of surperficial rich sulphur at last.The thickness of Cu-In-Ga-Se-S thin film is 2800nm, and the length of penetration of element sulphur on the CIGS thin-film surface is 30nm.
Embodiment six
(1) at room temperature, the 1.0mmol acetylacetone copper, the 0.8mmol Indium Tris acetylacetonate, 0.2mmol acetylacetone,2,4-pentanedione gallium and 2.0mmol selenium powder add in the 50mL three-necked bottle, add the 20mL oleyl amine again, connect device.Then the mode by vacuum and nitrogen atmosphere circulation is to circulate gas washing 2 times of reactant liquor, each gas washing 15min.Be full of reaction vessel with nitrogen at last.Under magnetic agitation, to the reaction unit heating, when being elevated to 265 ° of C, keep temperature-resistant, reaction 40min is cooled to room temperature with reactant liquor then.Filtering reacting liquid obtains solid product, and with ethanol, isopropyl alcohol, the mixed liquor of one or more in hexane or the chloroform cleans 5 times, obtains the solid product of cleaning.
(2) subsequently this product being put into toluene formation concentration is the nanocrystalline ink of the stable colloidal solution-Copper Indium Gallium Selenide of 10mg/mL.
(3) calcium soda-lime glass matrix is cut into 3.0cm * 3.0cm size, cleans up with acetone, ethanol, deionized water excusing from death.By direct current magnetron sputtering process plating Mo on matrix, thickness is 600nm.By physical methods such as knife coatings the nanocrystalline ink of Copper Indium Gallium Selenide is coated on the matrix of plating Mo then, forms the thick nanocrystalline presoma prefabricated membrane of Copper Indium Gallium Selenide of 2600nm, be placed on the electric hot plate of 300 ° of C dry afterwards.The selenium powder of the nanocrystalline presoma prefabricated membrane of dried Copper Indium Gallium Selenide and 2mmol is placed in the graphite box, then this stone mill box is placed in the tube furnace, feed N again
2Gas drains the air in the stove, and makes N
2Be full of furnace chamber.With the programming rate of 30 ° of C/min, to the body of heater heating, make the furnace chamber temperature be elevated to 500 ° of C then, copper indium gallium sulphur presoma prefabricated membrane is carried out annealing in process.Stop heating behind the 40min, obtain CIGS thin-film.
(4) the sulphur powder of CIGS thin-film and 5mmol is placed in the graphite box, then this graphite box is placed tube furnace.In tube furnace, feed N subsequently
2Gas draining the air in the furnace chamber, and makes and is full of N in the furnace chamber
2, with the programming rate of 10 ° of C/min, to the body of heater heating, make the furnace chamber temperature be elevated to 530 ° of C then, CIGS thin-film is carried out vulcanizing treatment.Stop heating behind the 30min, obtain the Cu-In-Ga-Se-S thin film light absorbing zone of surperficial rich sulphur at last.The thickness of Cu-In-Ga-Se-S thin film is 3000nm, and the length of penetration of element sulphur on the CIGS thin-film surface is 100nm.
Embodiment seven
(1) at room temperature, the 1.0mmol Schweinfurt green, the 0.8mmol indium acetate, 0.2mmol acetic acid gallium and 2.0mmol selenium ball add in the 50mL three-necked bottle, add the 20mL oleyl amine again, connect device.Then the mode by vacuum and nitrogen atmosphere circulation is to circulate gas washing 2 times of reactant liquor, each gas washing 15min.Be full of reaction vessel with nitrogen at last.Under magnetic agitation, to the reaction unit heating, when being elevated to 265 ° of C, keep temperature-resistant, reaction 40min is cooled to room temperature with reactant liquor then.Filtering reacting liquid obtains solid product, and with ethanol, isopropyl alcohol, the mixed liquor of one or more in hexane or the chloroform cleans 5 times, obtains the solid product of cleaning.
(2) subsequently this product being put into toluene formation concentration is the nanocrystalline ink of the stable colloidal solution-Copper Indium Gallium Selenide of 260mg/mL.
(3) calcium soda-lime glass matrix is cut into 3.0cm * 3.0cm size, cleans up with acetone, ethanol, deionized water excusing from death.By direct current magnetron sputtering process plating Mo on matrix, thickness is 1500nm.By physical methods such as knife coatings the nanocrystalline ink of Copper Indium Gallium Selenide is coated on the matrix of plating Mo then, forms the thick nanocrystalline presoma prefabricated membrane of Copper Indium Gallium Selenide of 1700nm, be placed on the electric hot plate of 300 ° of C dry afterwards.The selenium powder of the nanocrystalline presoma prefabricated membrane of dried Copper Indium Gallium Selenide and 2mmol is placed in the graphite box, then this stone mill box is placed in the tube furnace, feed N again
2Gas drains the air in the stove, and makes N
2Be full of furnace chamber.With the programming rate of 35 ° of C/min, to the body of heater heating, make the furnace chamber temperature be elevated to 500 ° of C then, copper indium gallium sulphur presoma prefabricated membrane is carried out annealing in process.Stop heating behind the 40min, obtain CIGS thin-film.
(4) the sulphur powder of CIGS thin-film and 1mmol is placed in the graphite box, then this graphite box is placed tube furnace.In tube furnace, feed N subsequently
2Gas draining the air in the furnace chamber, and makes and is full of N in the furnace chamber
2, with the programming rate of 35 ° of C/min, to the body of heater heating, make the furnace chamber temperature be elevated to 480 ° of C then, CIGS thin-film is carried out vulcanizing treatment.Stop heating behind the 10min, obtain the Cu-In-Ga-Se-S thin film light absorbing zone of surperficial rich sulphur at last.The thickness of Cu-In-Ga-Se-S thin film is 2000nm, and the length of penetration of element sulphur on the CIGS thin-film surface is 10nm.
Embodiment eight
(1) at room temperature, the 1.0mmol copper nitrate, the 0.8mmol indium nitrate, 0.2mmol gallium nitrate and 2.0mmol selenium powder add in the 50mL three-necked bottle, add the 20mL oleyl amine again, connect device.Then the mode by vacuum and nitrogen atmosphere circulation is to circulate gas washing 2 times of reactant liquor, each gas washing 15min.Be full of reaction vessel with nitrogen at last.Under magnetic agitation, to the reaction unit heating, when being elevated to 265 ° of C, keep temperature-resistant, reaction 40min is cooled to room temperature with reactant liquor then.Filtering reacting liquid obtains solid product, and with ethanol, isopropyl alcohol, the mixed liquor of one or more in hexane or the chloroform cleans 5 times, obtains the solid product of cleaning.
(2) subsequently this product being put into toluene formation concentration is the nanocrystalline ink of the stable colloidal solution-Copper Indium Gallium Selenide of 300mg/mL.
(3) calcium soda-lime glass matrix is cut into 3.0cm * 3.0cm size, cleans up with acetone, ethanol, deionized water excusing from death.By direct current magnetron sputtering process plating Mo on matrix, thickness is 500nm.By physical methods such as knife coatings the nanocrystalline ink of Copper Indium Gallium Selenide is coated on the matrix of plating Mo then, forms the thick nanocrystalline presoma prefabricated membrane of Copper Indium Gallium Selenide of 1800nm, be placed on the electric hot plate of 300 ° of C dry afterwards.The selenium powder of the nanocrystalline presoma prefabricated membrane of dried Copper Indium Gallium Selenide and 2mmol is placed in the graphite box, then this stone mill box is placed in the tube furnace, feed N again
2Gas drains the air in the stove, and makes N
2Be full of furnace chamber.With the programming rate of 15 ° of C/min, to the body of heater heating, make the furnace chamber temperature be elevated to 500 ° of C then, copper indium gallium sulphur presoma prefabricated membrane is carried out annealing in process.Stop heating behind the 40min, obtain CIGS thin-film.
(4) the sulphur powder of CIGS thin-film and 1mmol is placed in the graphite box, then this graphite box is placed tube furnace.In tube furnace, feed N subsequently
2Gas draining the air in the furnace chamber, and makes and is full of N in the furnace chamber
2, with the programming rate of 12 ° of C/min, to the body of heater heating, make the furnace chamber temperature be elevated to 480 ° of C then, CIGS thin-film is carried out vulcanizing treatment.Stop heating behind the 30min, obtain the Cu-In-Ga-Se-S thin film light absorbing zone of surperficial rich sulphur at last.The thickness of Cu-In-Ga-Se-S thin film is 2200nm, and the length of penetration of element sulphur on the CIGS thin-film surface is 20nm.
The above only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the preparation method of the CIGS thin-film of the rich sulphur in surface may further comprise the steps:
Mantoquita, indium salt, gallium salt and selenium source compound are mixed synthetic Copper Indium Gallium Selenide nano particle with oleyl amine;
Described Copper Indium Gallium Selenide nanoparticulate dispersed is formed the nanocrystalline ink of Copper Indium Gallium Selenide in organic solvent;
Described Copper Indium Gallium Selenide nanometer ink is filmed at matrix, form Copper Indium Gallium Selenide presoma prefabricated membrane, obtain CIGS thin-film after the annealed processing;
Under the condition of sulphur source existence, described Cu-In-Ga-Se-S thin film is carried out vulcanizing treatment at 450-550 ° of C, obtain the CIGS thin-film of surperficial rich sulphur.
2. the preparation method of the CIGS thin-film of the rich sulphur in surface as claimed in claim 1, it is characterized in that: in the described vulcanizing treatment process, the percentage composition of sulphur is 1-30% in the CIGS thin-film.
3. the preparation method of the CIGS thin-film of the rich sulphur in surface as claimed in claim 1 or 2, it is characterized in that: in the described vulcanizing treatment step, the length of penetration of element sulphur on the CIGS thin-film surface is 10-100nm.
4. the preparation method of the CIGS thin-film of the rich sulphur in surface as claimed in claim 1 is characterized in that: in the described vulcanizing treatment step, the sulphur source is at least a in sulphur powder, hydrogen sulfide, carbon disulfide, the thiocarbamide.
5. the preparation method of the CIGS thin-film of the rich sulphur in surface as claimed in claim 1, it is characterized in that: in the described vulcanizing treatment step, heating rate is 10-40 ° of C/min, and be 5-50min heating time.
6. the preparation method of the CIGS thin-film of the rich sulphur in surface as claimed in claim 1, it is characterized in that: in the step of described synthetic Copper Indium Gallium Selenide nano particle, the synthesis temperature of described Copper Indium Gallium Selenide nano particle is 220-300 ° of C.
7. the preparation method of the CIGS thin-film of the rich sulphur in surface as claimed in claim 1, it is characterized in that: in the step of described synthetic Copper Indium Gallium Selenide nano particle, described mantoquita, indium salt, gallium salt are respectively at least a in the chlorate, acetate, acetylacetonate, oxide of cupric, indium, gallium, and described selenium source compound is at least a of selenium simple substance, diethyl selenide, hydrogen selenide.
8. the preparation method of the CIGS thin-film of the rich sulphur in surface as claimed in claim 1, it is characterized in that: in the step of described synthetic Copper Indium Gallium Selenide nano particle, described indium, gallium element percentage composition ratio are: 0＜gallium/(indium+gallium)＜50%.
9. the preparation method of the CIGS thin-film of the rich sulphur in surface as claimed in claim 1 is characterized in that: in the step of the nanocrystalline ink of described preparation Copper Indium Gallium Selenide, described organic solvent is at least a in amine, benzene class or the alkanethiol compounds.
10. the preparation method of the CIGS thin-film of the rich sulphur in surface as claimed in claim 1, it is characterized in that: in the step of the nanocrystalline ink of described preparation Copper Indium Gallium Selenide, the concentration of the nanocrystalline ink of described Copper Indium Gallium Selenide is 5-300mg/mL.
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