CN104094412B - Utilize manufacture method and the CIGS system thin film of method making accordingly of the CIGS system used for solar batteries thin film of low melting point flux - Google Patents
Utilize manufacture method and the CIGS system thin film of method making accordingly of the CIGS system used for solar batteries thin film of low melting point flux Download PDFInfo
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- 239000010409 thin film Substances 0.000 title claims abstract description 103
- 230000004907 flux Effects 0.000 title claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 238000002844 melting Methods 0.000 title claims abstract description 22
- 239000011669 selenium Substances 0.000 claims abstract description 114
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 67
- 239000002105 nanoparticle Substances 0.000 claims abstract description 61
- OZAIFHULBGXAKX-UHFFFAOYSA-N precursor Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000010438 heat treatment Methods 0.000 claims abstract description 33
- BUGBHKTXTAQXES-UHFFFAOYSA-N selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 19
- 239000002002 slurry Substances 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 42
- 239000010949 copper Substances 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 24
- 229940091258 Selenium supplements Drugs 0.000 claims description 22
- 229910052738 indium Inorganic materials 0.000 claims description 22
- 229910052802 copper Inorganic materials 0.000 claims description 21
- 229910052733 gallium Inorganic materials 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 10
- 238000004528 spin coating Methods 0.000 claims description 10
- MHQOTKLEMKRJIR-UHFFFAOYSA-L Sodium selenate Chemical compound [Na+].[Na+].[O-][Se]([O-])(=O)=O MHQOTKLEMKRJIR-UHFFFAOYSA-L 0.000 claims description 8
- NVBFHJWHLNUMCV-UHFFFAOYSA-N Sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 claims description 8
- 229960001881 sodium selenate Drugs 0.000 claims description 8
- 239000011655 sodium selenate Substances 0.000 claims description 8
- 235000018716 sodium selenate Nutrition 0.000 claims description 8
- BVTBRVFYZUCAKH-UHFFFAOYSA-L Sodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 claims description 7
- 239000011781 sodium selenite Substances 0.000 claims description 7
- WILFBXOGIULNAF-UHFFFAOYSA-N [Sn]=S.[Zn].[Cu] Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 claims description 6
- 238000007641 inkjet printing Methods 0.000 claims description 6
- 229960001471 sodium selenite Drugs 0.000 claims description 6
- 235000015921 sodium selenite Nutrition 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- IIACRCGMVDHOTQ-UHFFFAOYSA-N Sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000002738 chelating agent Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000000366 colloid method Methods 0.000 claims description 3
- 235000013339 cereals Nutrition 0.000 claims 8
- 241000209094 Oryza Species 0.000 claims 2
- 235000007164 Oryza sativa Nutrition 0.000 claims 2
- 235000009566 rice Nutrition 0.000 claims 2
- 239000002529 flux Substances 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 32
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 30
- 238000004821 distillation Methods 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 230000002194 synthesizing Effects 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000005253 cladding Methods 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000005361 soda-lime glass Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N ethanolamine Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- RPPBZEBXAAZZJH-UHFFFAOYSA-N Cadmium telluride Chemical compound [Te]=[Cd] RPPBZEBXAAZZJH-UHFFFAOYSA-N 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N Diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- TYVNFQRMDPFYPC-UHFFFAOYSA-L disodium;selenate;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-][Se]([O-])(=O)=O TYVNFQRMDPFYPC-UHFFFAOYSA-L 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N 1,2-ethanediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- ZYVAQZSGKALVEU-UHFFFAOYSA-N 2-[2-[bis(2-hydroxy-2-oxoethyl)amino]ethyl-(2-hydroxy-2-oxoethyl)amino]ethanoic acid Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O.OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O ZYVAQZSGKALVEU-UHFFFAOYSA-N 0.000 description 1
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 1
- RAEOEMDZDMCHJA-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-[2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]ethyl]amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CCN(CC(O)=O)CC(O)=O)CC(O)=O RAEOEMDZDMCHJA-UHFFFAOYSA-N 0.000 description 1
- GBIBYNIYVUFTIT-UHFFFAOYSA-N 2-[bis(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O.OC(=O)CN(CC(O)=O)CC(O)=O GBIBYNIYVUFTIT-UHFFFAOYSA-N 0.000 description 1
- 229910005263 GaI3 Inorganic materials 0.000 description 1
- DWRNSCDYNYYYHT-UHFFFAOYSA-K Gallium(III) iodide Chemical compound I[Ga](I)I DWRNSCDYNYYYHT-UHFFFAOYSA-K 0.000 description 1
- -1 In-S Chemical class 0.000 description 1
- 229920002521 Macromolecule Polymers 0.000 description 1
- NOVHEGOWZNFVGT-UHFFFAOYSA-N NN.NN Chemical compound NN.NN NOVHEGOWZNFVGT-UHFFFAOYSA-N 0.000 description 1
- 229910003424 Na2SeO3 Inorganic materials 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N Triethylenetetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Tris Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000005712 crystallization Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- DEFVIWRASFVYLL-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl)tetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)CCOCCOCCN(CC(O)=O)CC(O)=O DEFVIWRASFVYLL-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N n-pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propanol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- 230000000717 retained Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- VYECFMCAAHMRNW-UHFFFAOYSA-N sulfamic acid Chemical group NS(O)(=O)=O.NS(O)(=O)=O VYECFMCAAHMRNW-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Abstract
The invention discloses manufacture method and the CIGS system thin film of method making accordingly of a kind of CIGS system used for solar batteries thin film utilizing low melting point flux.The manufacture method of the CIGS system thin film of the present invention, including: make the step (a) of CIGS system nano-particle；The making step (b) of the slurry containing the flux that above-mentioned CIGS system nano-particle and fusing point are 30 400 DEG C of scopes；The above-mentioned slurry of antivacuum coating on substrate and form the step (c) of CIGS system precursor thin-film；It is dried the step (d) of CIGS system precursor thin-film；Utilize selenium steam that above-mentioned CIGS system precursor thin-film is carried out the step (e) of selenizing heat treatment.Temperature low when making than former CIGS system thin film can be used accordingly to carry out selenizing heat treatment, thus reduce manufacturing cost, and also be able to be sufficiently complete the growth of thin film intercrystalline with low temperature.
Description
Technical field
The present invention relates to the manufacture method of a kind of solar cell CIGS system thin film, particularly relate to a kind of with antivacuum
When cladding process makes CIGS system thin film, formed in the step of precursor thin-film, when using fusing point than former selenizing heat treatment
The relatively low flux of temperature, thus reduce finished heat treatment temperature, it is also possible to fully carry out the CIGS of crystalline growth
It is manufacture method and the CIGS system thin film of method making accordingly of thin film.
Background technology
Solaode, according to the material of the use as light absorbing zone, is divided into various kind, currently used the most extensive
Be the silicon solar cell utilizing silicon.But silicon is under-supply recently, price is quick-fried to rise, the concern to thin-film type solar cell
Day by day increase.Thin-film type solar cell is fabricated to the thinnest thickness, and therefore material consumption is less, and lightweight, therefore applies
Scope is quite varied.Non-crystalline silicon and cadmium telluride (CdTe), copper and indium to the materials'use as this thin-film type solar cell
The research of selenium (CIS) or CIGS (CIGS) is the most active.
CIS system thin film or CIGS system thin film are one of I-III-VI compound semiconductors, and in experiment
In the thin-film solar cells that room makes, there is the highest conversion ratio (20.3%).Enable in particular to be fabricated to the thickness of less than 10 microns
Degree, and during life-time service, performance is also stable, thus as can the cheap high efficiency solaode of substituted for silicon, quite looked steadily
Mesh.
CIGS system thin film is to improve the relatively low open-circuit voltage of CIS system thin film and with Ga Substitute For Partial In
Or substitute S and the material developed with Se.CIGS system solaode utilizes the thin film of a few micrometers thickness to make solar-electricity
Pond, and this manufacture method mainly has the method using vacuum evaporation to carry out heat treatment after, antivacuum coating precursor species
Method.
Coating the CIGS system thin film of precursor species under non-vacuum, micropore is many, compactness is poor, therefore needs
Selenizing heat treatment to be carried out.The fusing point of the CuSe contributing to the thin film intercrystalline growth of CIGS system during selenizing heat treatment is 500
More than DEG C, it is therefore desirable to carry out under conditions of more than 500 DEG C.The manufacturing cost that accordingly, there exist CIGS system thin film rises
Problem.
The content relevant with above-mentioned background technology can refer to Korean granted patent the 10-1030780th, 10-1039667
Number etc..
Summary of the invention
When it is an object of the invention to make CIGS system thin film used for solar batteries under non-vacuum condition, form bag
Include the precursor thin-film of low melting point flux, i.e. use and carry out selenizing heat treatment than the lowest temperature, it is also possible to fully carry out
Thin film intercrystalline grows, thus finally improves the efficiency of the solaode comprising this thin film.
For achieving the above object, the CIGS system used for solar batteries thin film utilizing low melting point flux of the present invention
Manufacture method, including: make step a of CIGS system nano-particle；Containing above-mentioned CIGS system nano-particle and fusing point
The making step b of slurry for the flux of 30-400 DEG C of scope；The above-mentioned slurry of antivacuum coating on substrate and form copper and indium
Step c of gallium selenium system precursor thin-film；It is dried step d of above-mentioned CIGS system precursor thin-film；Selenium (Se) steam is utilized to incite somebody to action
Above-mentioned CIGS system precursor thin-film carries out step e of selenizing heat treatment.
Above-mentioned CIGS system nano-particle can be to be selected from: comprises selected from Cu-Se, In-Se, Ga-Se, Cu-S, In-S
And the binary nanoparticles of any one in molecular group of Ga-S grain；Comprise selected from Cu-In-Se, Cu-In-S, Cu-Ga-S
And the ternary nano granule of any one in molecular group of Cu-Ga-Se grain；Cu-In-Ga-Se quaternary nano-particle；Comprise
Selected from Cu-In-Ga-Se-(S, Se) and Cu-In-Al-Ga-(S, Se) any one five yuan of nano-particle in the group that forms；
The hexa-atomic nano-particle of Cu-In-Al-Ga-Se-S；Comprise selected from Cu-Zn-Sn-(Se, S) and Cu-In-Ga-Zn-Sn-(Se, S) grain
The copper-zinc-tin-sulfur system nano-particle of any one in molecular group；And comprise selected from Cu, In, Ga, Al, Zn, Sn, S and
The nano-particle of any one in the group of Se element powders composition.
Above-mentioned steps a can use in low temperature colloid method, solvent-thermal process method, microwave method and ultrasonic synthesis any one
Method.
Slurry in above-mentioned steps b can mix above-mentioned CIGS system nano-particle, above-mentioned flux, solvent, complexation
Agent, cross-linking agent make.
Above-mentioned flux can be the group selected from sulphamide, sodium selenate (ten water things), sodium selenite and sulfamic acid composition
In any one.
Above-mentioned steps c can use spraying process, ultrasonic spray method, spin coating method, scraper for coating method, silk screen print method and
Any one in ink jet printing method.
In above-mentioned steps d, can be dried 2-10 minute at a temperature of 60-300 DEG C, and repeat above-mentioned being dried for 2-10 time.
In above-mentioned steps e, can be under 250-450 DEG C of scope, selenizing heat treatment 30-120 minute.
Another of the present invention for achieving the above object utilizes the CIGS system used for solar batteries of low melting point flux thin
The manufacture method of film, including: the making of the CIGS system precursor solution containing the flux that fusing point is 30-400 DEG C of scope
Step l；Antivacuum coating contains above-mentioned flux on substrate CIGS system precursor solution and form CIGS system
Step m of precursor thin-film；It is dried step n of above-mentioned CIGS system precursor thin-film；Utilize selenium steam by above-mentioned copper and indium gallium
Selenium system precursor thin-film carries out step o of selenizing heat treatment.
Above-mentioned CIGS system precursor solution may include that the metal salt solution including Cu, In and Ga respectively；Containing copper
The hydrazine solution of indium gallium selenium system nano-particle.
Above-mentioned CIGS system nano-particle can be to be selected from: comprises selected from Cu-Se, In-Se, Ga-Se, Cu-S, In-S
And the binary nanoparticles of any one in molecular group of Ga-S grain；Comprise selected from Cu-In-Se, Cu-In-S, Cu-Ga-S
And the ternary nano granule of any one in molecular group of Cu-Ga-Se grain；Cu-In-Ga-Se quaternary nano-particle；Comprise
Selected from Cu-In-Ga-Se-(S, Se) and Cu-In-Al-Ga-(S, Se) any one five yuan of nano-particle in the group that forms；
The hexa-atomic nano-particle of Cu-In-Al-Ga-Se-S；Comprise selected from Cu-Zn-Sn-(Se, S) and Cu-In-Ga-Zn-Sn-(Se, S) grain
The copper-zinc-tin-sulfur system nano-particle of any one in molecular group；Comprise selected from Cu, In, Ga, Al, Zn, Sn, S and Se unit
The nano-particle of any one in the group of element powder constituent.
Above-mentioned metal salt solution can be selected from chloride, acetate, nitrate and sulfate composition group in any
One.
Above-mentioned steps n can use spraying process, ultrasonic spray method, spin coating method, scraper for coating method, silk screen print method and
Any one in ink jet printing method.
In above-mentioned steps o, can be under 250-450 DEG C of scope, selenizing heat treatment 30-120 minute.
For achieving the above object, the CIGS system used for solar batteries thin film utilizing low melting point flux of the present invention,
Can be with following steps for manufacturing, containing the slurry of the flux that CIGS system nano-particle and fusing point are 30-400 DEG C of scope
Making step；The above-mentioned slurry of antivacuum coating on substrate and formed CIGS system precursor thin-film and be dried step；Profit
With selenium steam, above-mentioned CIGS system precursor thin-film is carried out the step of selenizing heat treatment.
For achieving the above object, another of the present invention utilizes the CIGS system used for solar batteries of low melting point flux thin
Film, can with following steps for manufacturing, the CIGS system precursor solution containing the flux that fusing point is 30-400 DEG C of scope
Making step；Antivacuum coating contains above-mentioned flux on substrate CIGS system precursor solution and form CIGS
It is precursor thin-film the step being dried；Utilize selenium steam that above-mentioned CIGS system precursor thin-film is carried out selenizing heat treatment
Step.
Accompanying drawing explanation
Fig. 1 is the flow chart of the manufacture method of the CIGS system used for solar batteries thin film showing the present invention successively.
Fig. 2 is the flow process of the manufacture method of another CIGS system used for solar batteries thin film showing the present invention successively
Figure.
Detailed description of the invention
The manufacture method of the CIGS system used for solar batteries thin film of the present invention applies antivacuum cladding process, above-mentioned non-
Vacuum coat method can use the method utilizing the slurry containing CIGS system nano-particle, it would however also be possible to employ utilizes copper and indium gallium
The method of selenium slaine precursor solution.
First, after the method utilizing the slurry containing CIGS system nano-particle is illustrated, then to utilizing copper and indium
The method of gallium selenium slaine precursor solution illustrates.
Below, the manufacture method of the CIGS system thin film of the present invention is described with reference to Fig. 1.Above-mentioned CIGS system thin film
Manufacture method is divided into five steps.
First, CIGS system nano-particle-step a is made.
Above-mentioned CIGS system nano-particle, can mix the binary such as Cu-Se, In-Se, Ga-Se, Cu-S, In-S, Ga-S
Nano-particle uses, according to circumstances, it is also possible to comprise: IB-IIIA-VIA compound semiconductor i.e. Cu-In-Se is main Cu-
The ternary compounds such as In-S, Cu-Ga-S, Cu-Ga-Se；The quaternary compounds such as Cu-In-Ga-Se；Cu-In-Ga-Se-(S, Se),
Cu-In-Al-Ga-(S, Se), five yuan, the nano-particle of hexa-atomic compound such as Cu-In-Al-Ga-Se-S.
And then, it is also possible to comprise: with Group IIB element (Zn etc.)+IVA race's element (Sn etc.) displacement in above-mentioned CIS system or
Cu-Zn-Sn-(Se, S of the Group IIIA elements such as whole In, Ga, the Al in CIGS based compound)；Carry out aliquot replacement
Cu-In-Ga-Zn-Sn-(Se, S) etc. the nano-particle of copper-zinc-tin-sulfur based compound.
Further, according to the kind of above-claimed cpd, it is possible to use the element powder of Cu, In, Ga, Al, Zn, Sn, S, Se etc.
End.
Above-mentioned CIGS system nano-particle can use low temperature colloid method, solvent thermal (solvothermal) synthetic method, micro-
Method known to the technical field of the invention such as ripple method, ultrasonic synthesis makes.
Then, slurry-step b containing low temperature flux with CIGS system nano-particle is made.
Above-mentioned slurry be blended in above-mentioned steps a is made CIGS system nano-particle, solvent, chelating agent
(chelating agent), cross-linking agent and low temperature flux (flux) and make.
Now, above-mentioned solvent can use alcohols, ether class, ketone, the ethylene glycol such as methanol, ethanol, amylalcohol, propanol, butanol
Ether kind solvent etc..
Above-mentioned chelating agent can use ethanolamine (monoethanolamine), diethanolamine (diethanolamine), three
Ethanolamine (triethanolamine), ethylenediamine (ethylenenediamine), ethylenediaminetetraacetic acid
(ethylenediaminetetraacetic acid), nitrilotriacetic acid (nitrilotriacetic acid), ethoxy second two
Amine triacetic acid (hydroxyethyl ethylenediamine triacetic acid), glycoletherdiaminotetraacetic acid
(glycol ether diamine tetraacetic acid), teiethylene tetramine-hexacetic acid (triethylene tetraamine
Hexaacetic acid) etc. aminated compounds.
It addition, for be sufficiently mixed above-mentioned low temperature flux in above-mentioned slurry, it is also possible to add a small amount of solvent i.e. water.
Above-mentioned cross-linking agent can make spent glycol (ethylene glycol), propylene glycol (propylene glycol) etc.
Macromolecule alcohols.
Above-mentioned low temperature flux refers to, the CuSe fusing point phase having with helping the thin film crystallization growth of CIGS system in the past
Ratio, is preferably the material of 30-400 DEG C of scope fusing point below relatively low temperature that is 400 DEG C, it is defined as at copper and indium gallium of the present invention
In selenizing heat treatment step when selenium system thin film makes, it is possible to melt at relatively low temperatures, and make migration (migration)
The simplest, thus contribute to the material of crystalline growth.
Now, above-mentioned low temperature flux can use sulphamide (Sulfamide), sodium selenate (ten water things) (sodium
Selenate Decahydrate), sodium selenite (Sodium Selenite), sulfamic acid (Sulfamic acid) form
Any one in group.
The low temperature flux data enumerated above is as shown in table 1 below.
[table 1]
| Title | Chemical formula | CAS/Aldrich | Molecular weight | Fusing point (DEG C) |
| Sulphamide | (NH2)2SO2 | 7803-58-9/211370 | 96.11 | 90～92 |
| Sodium selenate (ten water things) | Na2SeO4-10H2O | 10102-23-5/450294 | 369.09 | 35 |
| Sodium selenite | Na2SeO3 | 10102-18-8/24485 | 172.94 | 350 |
| Sulfamic acid | NH2SO3H | 5329-14-6/481505 | 97.09 | ～220 |
As shown in Table 1, above-mentioned low temperature flux can melt under 350 DEG C of temperature below, thus than before selenizing heat
At a temperature of 500 DEG C of temperature during process are low, make migration of elements simpler, thus the crystalline growth in CIGS system thin film
Very well.
Na element included in above-mentioned low temperature flux, itself is to the crystalline growth of CIGS system thin film very
Helpful, Se Yu S is the element constituting thin film, although N Yu O is foreign body, but to the performance of CIGS system thin film almost without
Impact.Further, O oneself evaporates and is not retained in thin film in selenizing heat treatment process.
Then, substrate coats above-mentioned slurry and make CIGS system precursor thin-film-step c.
It is characterized as when making above-mentioned CIGS system precursor thin-film using antivacuum cladding process.As above-mentioned antivacuum
Cladding process, can use spraying process, ultrasonic spray method, spin coating method, scraper for coating method, silk screen print method, ink jet printing method
Etc. all antivacuum cladding processes known to the technical field of the invention.This antivacuum cladding process vapour deposition method together is compared, energy
Enough relatively reduce production costs.
Then, CIGS system precursor thin-film-step d of above-mentioned coating it is dried.
Above-mentioned dry being preferably is dried 2-10 minute at a temperature of 60-300 DEG C, and repeats above-mentioned being dried for 2-10 time.
Hereby it is possible to remove above-mentioned solvent, cross-linking agent.
Finally, utilize selenium (Se) steam that above-mentioned CIGS system precursor thin-film carries out selenizing (selenization) heat
Process-step e.
In the above-mentioned engineering utilizing selenium steam heating, heating selenium solid makes it evaporate and provides selenium steam, and lifting sets
The substrate temperature of above-mentioned thin film is had to complete.Now, the temperature of aforesaid substrate is the 250-450 lower than during former selenizing heat treatment
Under DEG C scope, carry out 30-120 minute being preferred.
Accordingly, above-mentioned CIGS system precursor thin-film is by selenizing, and above-mentioned low temperature flux is melted and completes knot
Crystals growth.
Further, the present invention provides the CIGS system thin film made by above-mentioned manufacture method.
Further, the present invention provides the solaode comprising above-mentioned CIGS system thin film as light absorbing zone.
Below, the manufacture method of another CIGS system used for solar batteries thin film of the present invention is described.Above-mentioned making side
Method is the method utilizing CIGS precursor solution.Fig. 2 shows above-mentioned manufacture method successively.
With reference to Fig. 2, first, CIGS system precursor solution-step l containing low temperature flux is made.
Above-mentioned CIGS system precursor solution is selected from: comprise the metal salt solution (metal of Cu, In, Ga respectively
Salt)；And comprise the binary of Se or S, ternary, quaternary, five yuan, hexa-atomic CIS system, CIGS system, copper-zinc-tin-sulfur system
Hydrazine (hydrazine) solution of any one in compound nano-particle.Above-claimed cpd nano-particle and another copper and indium gallium above-mentioned
The content described in step a of selenium system film manufacturing method is identical, and therefore detailed content is with reference to this part.
Now, above-mentioned metal salt solution can use alcohols solvent or water as solvent.Further, it is included in above-mentioned slaine
Slaine in solution can be chloride (chloride), acetate (acetate), nitrate (nitrate), sulfate
Etc. (sulfate) organic salt or inorganic salt.
Further, the above-mentioned binary compound containing Se, including Cu2Se、In2Se3And Ga2Se3Nano-particle, also may be used at this
To add Se.
Above-mentioned low temperature flux, with utilize above-mentioned slurry CIGS system thin film manufacture method step b in table 1
Holding identical, therefore detailed content is with reference to this part.
Then, the coating CIGS system precursor solution containing above-mentioned low temperature flux on substrate, and make copper and indium
Gallium selenium system precursor thin-film-step m.
Being characterized as when making above-mentioned CIGS system precursor thin-film using antivacuum cladding process, this concrete grammar is permissible
Use the institutes of the present invention such as spraying process, ultrasonic spray method, spin coating method, scraper for coating method, silk screen print method, ink jet printing method
Belong to all antivacuum cladding processes known to technical field.
Then, CIGS system precursor thin-film-step n of above-mentioned coating it is dried.
Finally, utilize selenium steam that above-mentioned CIGS system precursor thin-film is carried out selenizing heat treatment-step o.
Above-mentioned steps n and the method for step o and condition, with the system of another CIGS system thin film used for solar batteries above-mentioned
Making step d and step e in method identical, detailed content is with reference to this content.
Further, the present invention provides the CIGS system thin film made by above-mentioned manufacture method.
Further, the present invention provides the solaode comprising above-mentioned CIGS system thin film as light absorbing zone.
[embodiment 1]
CuI:0.343g, InI is mixed in glove box3: 0.673g, GaI3: 0.207g and the pyridine solvent 30ml of distillation,
And stir 30 minutes above in 100 DEG C of heating plates (Hot Plate).About stirring can confirm that opaque solution becomes after 10 minutes
Transparent.Mix this Cu, In mixture and the Na dissolved in the methanol 20ml of distillation2Se0.48g.This atomic ratio is Cu:In:
Ga:Se=0.9:0.68:0.23:1.91.
Then, mechanical agitation methanol/pyridine mixtures in 0 DEG C of ice bath, and react 1 minute and synthesize CIGS chlorination
Thing.After the 4000rpm CIGS chloride centrifugation to synthesizing about 30 minutes, ultrasonic Treatment 5 minutes, and with distilling
Methanol clean, repeat by-product and pyridine that this process completely removes in product, thus the Cu-In-Ga-Se of synthesis of high purity
Nano-particle.
Then, mix above-mentioned Cu-In-Ga-Se nano-particle 0.3g, chelating agent 0.3g, ethylene glycol 0.3g, methanol 1.2g,
A small amount of water that low temperature flux i.e. sulphamide 0.03g, solvent as low temperature flux use, then ultrasonic Treatment 60 minutes
And make slurry.
Then, on the soda-lime glass substrate of evaporation Mo thin film, utilize spin coating method to coat above-mentioned slurry.Now, on
The rotary speed stating glass substrate is set as that 800rpm, rotational time are set as 20 seconds.After coating, face divides three on hot plate
Step is dried.Now, first step is to be dried for 5 minutes at 60 DEG C, and second step is to be dried for 2 minutes at 200 DEG C,
Third step is to be dried for 10 minutes at 300 DEG C.
Finally, under 400 DEG C of substrate temperatures, supply Se steam, selenizing heat treatment 30 minutes and to complete CIGS system thin
Film.
[embodiment 2]
CuI:0.343g, InI is mixed in glove box3: 0.991g and the pyridine solvent 30ml of distillation, and 50 DEG C of heating
Stir 10 minutes above plate.About stirring can confirm that opaque solution went clear after 10 minutes.Mix this Cu, In mixture
With the Na dissolved in the methanol 20ml of distillation2Se0.5g.This atomic ratio is Cu:In:Se=0.9:1:2.
Then, mechanical agitation methanol/pyridine mixtures in 0 DEG C of ice bath, and react 1 minute and synthesize nano-particle.With
After the 4000rpm CIS chloride centrifugation about 30 minutes to synthesis, ultrasonic Treatment 5 minutes, and with the methanol distilled
Clean, repeat by-product and pyridine that this process completely removes in product, and the Cu-In-Se nano-particle of synthesis of high purity.
Get above-mentioned nano-particle Cu-In-Se nano-particle 0.3g ready, then by the condition identical with above-described embodiment 1
With method, complete CIS system thin film.
[embodiment 3]
In glove box, mix the pyridine solvent 30ml of CuI:0.762g and distillation, and in 100 DEG C of heating plates, stir 30
Minute.About stirring can confirm that opaque solution went clear after 10 minutes.Mix this Cu solution and the methanol in distillation
The Na dissolved in 10ml2Se0.25g.This atomic ratio is Cu:Se=1:2.Then, mechanical agitation methanol/pyridine in 0 DEG C of ice bath
Mixture, and react 1 minute and synthesize Cu2Se chloride.With the 4000rpm Cu to synthesis2Se chloride centrifugation about 30 points
Zhong Hou, ultrasonic Treatment 5 minutes, and clean with the methanol of distillation, repeat by-product and pyrrole that this process completely removes in product
Pyridine, and the Cu of synthesis of high purity2Se granule.
Further, in glove box, InI is mixed3: 1.487g and the pyridine solvent 30ml of distillation, and in 100 DEG C of heating plates
Stir 30 minutes.About stirring can confirm that opaque solution went clear after 10 minutes.Mix this In solution and in distillation
The Na dissolved in methanol 20ml2Se0.75g mixes.This atomic ratio is In:Se=2:3.Then, mechanical agitation first in 0 DEG C of ice bath
Alcohol/pyridine mixtures, and react 1 minute and synthesize In2Se3Chloride.With the 4000rpm In to synthesis2Se3Chloride is centrifuged
After separating about 30 minutes, ultrasonic Treatment 5 minutes, and clean with the methanol of distillation, repeat this process and completely remove in product
By-product and pyridine, and the In of synthesis of high purity2Se3Granule.
Further, in glove box, GaI is mixed3: 1.80g and the pyridine solvent 50ml of distillation, and stir in 100 DEG C of heating plates
Mix 30 minutes.About stirring can confirm that opaque solution went clear after 10 minutes.By this Ga solution and the methanol in distillation
The Na dissolved in 20ml2Se0.75g mixes.This atomic ratio is Ga:Se=2:3.Then, in 0 DEG C of ice bath mechanical agitation methanol/
Pyridine mixtures, and react 1 minute and synthesize Ga2Se3Chloride.With the 4000rpm Ga to synthesis2Se3Chloride centrifugation
After about 30 minutes, ultrasonic Treatment 5 minutes, and clean with the methanol of distillation, repeat the by-product that this process completely removes in product
Thing and pyridine, and the Ga of synthesis of high purity2Se3Granule.
The Cu that mixing is synthesized by said method2Se、In2Se3、Ga2Se3Nano-particle, and draw 0.3g, by with above-mentioned
The method that embodiment 1 is identical makes slurry, then completes CIGS system thin film.
[embodiment 4]
Make Cu-In-Ga-Se nano-particle by the method identical with above-described embodiment 1, and make containing low temperature of it
The CIGS system metal salt solution of flux sodium selenate (ten water things).
Utilize spin coating method, on the soda-lime glass substrate of evaporation Mo thin film, coat above-mentioned CIGS system slaine
Solution, be coated by the method identical with above-described embodiment 1, be dried and selenizing heat treatment and to complete CIGS system thin
Film.
[embodiment 5]
Prepare Cu-In-Se nano-particle by the method identical with above-described embodiment 2, make of it and flux containing low temperature
The CIS metal salt solution of agent sodium selenate (ten water things).
Utilize spin coating method, on the soda-lime glass substrate of evaporation Mo thin film, coat above-mentioned CIS metal salt solution,
Be coated by the method identical with above-described embodiment 1, be dried and selenizing heat treatment and complete CIGS system thin film.
[embodiment 6]
Cu is prepared by the method identical with above-described embodiment 32Se、In2Se3、Ga2Se3Nano-particle, makes of it and contains
The CIGS system metal salt solution of low temperature flux sodium selenate (ten water things).
Utilize spin coating method, on the soda-lime glass substrate of evaporation Mo thin film, coat above-mentioned CIGS slaine molten
Liquid, be coated by the method identical with above-described embodiment 1, be dried and selenizing heat treatment and complete CIGS system thin film.
When making CIGS system thin film used for solar batteries under non-vacuum condition, formed containing low melting point flux
Precursor thin-film such that it is able to carry out selenizing heat treatment at a temperature of lower than in the past, thus reduce production costs, and at low temperature
Under also be able to fully carry out thin film intercrystalline growth.
The preferred embodiments of the present invention described above, but the present invention is not limited to above-mentioned specific embodiment, has this
The people of the usual knowledge of bright art, can carry out various deformation implementation in the range of this technological thought.Therefore the present invention
Interest field and not based on specific embodiment, and should be according to the content of claims in adnexa depending on.
Claims (13)
1. the manufacture method of the CIGS system used for solar batteries thin film utilizing low melting point flux, it is characterised in that
Including:
A () makes the step of CIGS system nano-particle；
The making step of (b) slurry containing the flux that above-mentioned CIGS system nano-particle and fusing point are 30-400 DEG C of scope
Suddenly, wherein flux be selected from sulphamide, sodium selenate (ten water things), sodium selenite and sulfamic acid composition group in any one
Individual；
(c) on substrate the above-mentioned slurry of antivacuum coating and form the step of CIGS system precursor thin-film；
D () is dried the step of above-mentioned CIGS system precursor thin-film；
E () utilizes selenium steam above-mentioned CIGS system precursor thin-film to be carried out the step of selenizing heat treatment, at 250-450 DEG C of model
Under enclosing, selenizing heat treatment 30-120 minute.
The making side of the CIGS system used for solar batteries thin film utilizing low melting point flux the most according to claim 1
Method, it is characterised in that
Above-mentioned CIGS system nano-particle is selected from:
The binary of any one comprised in molecular group of Cu-Se, In-Se, Ga-Se, Cu-S, In-S and Ga-S grain is received
Rice grain；
Comprise the ternary of any one in molecular group of Cu-In-Se, Cu-In-S, Cu-Ga-S and Cu-Ga-Se grain
Nano-particle；
Cu-In-Ga-Se quaternary nano-particle；
Comprise any one five yuan in the group that Cu-In-Ga-Se-(S, Se) and Cu-In-Al-Ga-(S, Se) forms
Nano-particle；
The hexa-atomic nano-particle of Cu-In-Al-Ga-Se-S；
Comprise in Cu-Zn-Sn-(Se, S) and molecular group of Cu-In-Ga-Zn-Sn-(Se, S) grain any one
Copper-zinc-tin-sulfur system nano-particle；And
Comprise the nano-particle of any one in the group of Cu, In, Ga, Al, Zn, Sn, S and Se element powders composition.
The making side of the CIGS system used for solar batteries thin film utilizing low melting point flux the most according to claim 1
Method, it is characterised in that
Above-mentioned steps (a) uses any one side in low temperature colloid method, solvent-thermal process method, microwave method and ultrasonic synthesis
Method.
The making side of the CIGS system used for solar batteries thin film utilizing low melting point flux the most according to claim 1
Method, it is characterised in that
Slurry in above-mentioned steps (b) is to mix above-mentioned CIGS system nano-particle, above-mentioned flux, solvent, chelating agent, friendship
Connection agent makes.
The making side of the CIGS system used for solar batteries thin film utilizing low melting point flux the most according to claim 1
Method, it is characterised in that
Above-mentioned steps (c) uses in spraying process, spin coating method, scraper for coating method, silk screen print method and ink jet printing method any
A kind of.
The making side of the CIGS system used for solar batteries thin film utilizing low melting point flux the most according to claim 1
Method, it is characterised in that
In above-mentioned steps (d), it is dried 2-10 minute at a temperature of 60-300 DEG C, and repeats above-mentioned being dried for 2-10 time.
7. the copper and indium gallium used for solar batteries utilizing low melting point flux that the manufacture method as described in claim 1 makes
Selenium system thin film.
8. the manufacture method of the CIGS system used for solar batteries thin film utilizing low melting point flux, it is characterised in that
Including:
L the making step of () CIGS system precursor solution containing the flux that fusing point is 30-400 DEG C of scope, wherein helps
Flux is any one in the group of sulphamide, sodium selenate (ten water things), sodium selenite and sulfamic acid composition；
M () antivacuum coating on substrate contains the CIGS system precursor solution of above-mentioned flux, and form CIGS
It it is the step of precursor thin-film；
N () is dried the step of above-mentioned CIGS system precursor thin-film；
O () utilizes selenium steam above-mentioned CIGS system precursor thin-film to be carried out the step of selenizing heat treatment, at 250-450 DEG C of model
Under enclosing, selenizing heat treatment 30-120 minute.
The making side of the CIGS system used for solar batteries thin film utilizing low melting point flux the most according to claim 8
Method, it is characterised in that
Above-mentioned CIGS system precursor solution includes:
Include the metal salt solution of Cu, In and Ga respectively；Hydrazine solution containing CIGS system nano-particle.
The making of the CIGS system used for solar batteries thin film utilizing low melting point flux the most according to claim 9
Method, it is characterised in that
Above-mentioned CIGS system nano-particle is selected from:
The binary of any one comprised in molecular group of Cu-Se, In-Se, Ga-Se, Cu-S, In-S and Ga-S grain is received
Rice grain；
Comprise the ternary of any one in molecular group of Cu-In-Se, Cu-In-S, Cu-Ga-S and Cu-Ga-Se grain
Nano-particle；
Cu-In-Ga-Se quaternary nano-particle；
Comprise any one five yuan in the group that Cu-In-Ga-Se-(S, Se) and Cu-In-Al-Ga-(S, Se) forms
Nano-particle；
The hexa-atomic nano-particle of Cu-In-Al-Ga-Se-S；
Comprise in Cu-Zn-Sn-(Se, S) and molecular group of Cu-In-Ga-Zn-Sn-(Se, S) grain any one
Copper-zinc-tin-sulfur system nano-particle；
Comprise the nano-particle of any one in the group of Cu, In, Ga, Al, Zn, Sn, S and Se element powders composition.
The making of the 11. CIGS system used for solar batteries thin film utilizing low melting point flux according to claim 9
Method, it is characterised in that
Above-mentioned metal salt solution is any one in the group of chloride, acetate, nitrate and sulfate composition.
The making of the 12. CIGS system used for solar batteries thin film utilizing low melting point flux according to claim 8
Method, it is characterised in that
Above-mentioned steps (m) uses appointing in spraying process, spin coating method, scraper for coating method, silk screen print method and ink jet printing method
Meaning one.
The copper and indium used for solar batteries utilizing low melting point flux that 13. 1 kinds of manufacture methods as described in claim 8 make
Gallium selenium system thin film.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2012-0010638 | 2012-02-02 | ||
| KR1020120010638A KR101367760B1 (en) | 2012-02-02 | 2012-02-02 | Preparation method of cigs-based compound thin film using flux with low melting point and ci(g)s-based compound thin film preparated by the same |
| PCT/KR2013/000804 WO2013115582A1 (en) | 2012-02-02 | 2013-01-31 | Method for manufacturing photovoltaic ci(g)s-based thin film using flux having low melting point, and ci(g)s-based thin film manufactured by same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104094412A CN104094412A (en) | 2014-10-08 |
| CN104094412B true CN104094412B (en) | 2016-11-30 |
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