CN102024858B - Ink, thin film solar cell and manufacturing methods thereof - Google Patents
Ink, thin film solar cell and manufacturing methods thereof Download PDFInfo
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- CN102024858B CN102024858B CN2010101498707A CN201010149870A CN102024858B CN 102024858 B CN102024858 B CN 102024858B CN 2010101498707 A CN2010101498707 A CN 2010101498707A CN 201010149870 A CN201010149870 A CN 201010149870A CN 102024858 B CN102024858 B CN 102024858B
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- 239000010409 thin film Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 55
- 239000010408 film Substances 0.000 claims abstract description 20
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 58
- 239000011669 selenium Substances 0.000 claims description 58
- 238000007639 printing Methods 0.000 claims description 45
- 239000002904 solvent Substances 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 38
- 239000000843 powder Substances 0.000 claims description 35
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 34
- 239000000126 substance Substances 0.000 claims description 27
- 229910052711 selenium Inorganic materials 0.000 claims description 26
- 239000010949 copper Substances 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 229910052738 indium Inorganic materials 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 11
- 229910052733 gallium Inorganic materials 0.000 claims description 11
- 238000013019 agitation Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 238000004528 spin coating Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000005864 Sulphur Substances 0.000 claims description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- 239000002562 thickening agent Substances 0.000 claims description 6
- 230000010148 water-pollination Effects 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- 230000001680 brushing effect Effects 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000010422 painting Methods 0.000 claims description 3
- 238000007650 screen-printing Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 229910021420 polycrystalline silicon Inorganic materials 0.000 abstract 1
- 229920005591 polysilicon Polymers 0.000 abstract 1
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 7
- 239000002245 particle Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229940065287 selenium compound Drugs 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000012163 sequencing technique Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 108091092878 Microsatellite Proteins 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000011712 cell development Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
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- 150000003346 selenoethers Chemical class 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Images
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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- 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
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- Photovoltaic Devices (AREA)
Abstract
The invention discloses ink used for preparing an absorbing layer of a semiconductor thin film solar cell, the thin film solar cell and the manufacturing methods thereof, in particular the ink used for preparing a CuInGaSe thin film solar cell and a method for manufacturing the thin film solar cell by using the ink. A CuInGaSe polysilicon film photovoltaic absorbing layer with the thickness of 1.5 to 2.5 mu m can be obtained by coating for only one time by the method.
Description
Technical field
The present invention relates to photovoltaic solar cell manufacturing technology field, be specifically related to a kind of semiconductor thin-film solar cell, particularly relate to and manufacture printing ink (ink) and copper-indium-galliun-selenium film solar cell and their manufacture method that copper-indium-galliun-selenium film solar cell is used.
Background technology
Continuous increase along with energy resource consumption, main source as the energy, the CO2 emission that a large amount of uses of oil and coal cause is pollution of ecological environment seriously, and oil and coal resources also face exhausted condition, therefore, seek low-carbon emission and inexhaustible regenerative resource becomes more and more urgent, the solar cell based on photovoltaic effect is a kind of so renewable new forms of energy just.Current, people pay attention to increasingly to the development and utilization of solar energy, and market increases day by day to the demand of large tracts of land more, the novel solar battery that lighter and thinner and production cost is lower.In these novel solar batteries, the alloy firm solar cell based on silicon materials developed in recent years, for example amorphous silicon and cadmium telluride diaphragm solar battery, the characteristics such as, low energy consumption few, low-cost by the silicon amount with it and high volume production, become new trend and the new focus of solar cell development.Although thin-film solar cells has above-mentioned advantage, amorphous silicon thin-film solar cell has the shortcomings such as the low and stability of photoelectric conversion efficiency is not good enough; Cadmium telluride diaphragm solar battery has the use restriction of environmental requirement to cadmium metal.
In recent years, academia has developed again based semiconductor copper-indium-gallium-selenium compound (CuInGaSe
2, thin-film solar cells CIGS).Copper-indium-galliun-selenium film solar cell have production cost low, pollute little, do not fail, the characteristics such as stable performance, capability of resistance to radiation are strong, low light level performance is good, photoelectric conversion efficiency occupies first of various thin-film solar cells, conversion efficiency close to existing market main product crystal silicon solar energy battery, cost is 1/3rd of crystal silicon cell, is called in the world " very promising novel cheap films solar cell of next epoch ".In addition, this battery has soft, uniform appearance of black, to the have higher requirements ideal chose in place of outward appearance, as glass curtain wall of building etc., no matter in fields such as modernization skyscrapers, very big market is arranged, be to have wide market prospects at the ground generating by solar or in the application of space microsatellite electrical source of power.
The classical production process of copper-indium-galliun-selenium film solar cell can be divided into two kinds substantially, coevaporation method and precast body film+selenizing two step method, and these two kinds of methods all need physical coating (PVD) equipment and evaporation equipment, and manufacturing cost is higher.Recently, American I BM company has adopted the method for solution spin coating to produce the CIGS thin-film solar cells, and its conversion efficiency has reached 12.8%.With traditional vacuum coating method, compare, the method of the manufacture thin-film solar cells of this solution spin coating is owing to not needing physical coating equipment and evaporation equipment, greatly reduce manufacturing cost, thereby be conducive to realize that the quick print technique of reel-to-reel reaches high volume production.In addition, the solution spin-coating method can increase substantially the uniformity of large area film component, and can significantly improve the raw material (utilance of (Cu, In, Ga, Se) etc.; The utilization rate of raw materials of coevaporation method or sputtering method is less than 50% usually, and the solution cladding process can reach and is greater than 90%.At first the solution spin-coating method that IBM Corporation adopts prepares and contains Cu
2S, In
2Se
3, S and Ga hydrazine solution, then with this solution spin coating, make precursor thin-film, change into through heat treatment (400～525 ℃) copper-indium-gallium-selenium compound membrane that has component controllability and good crystallinity concurrently.
Yet, due to the restriction that is subject to maxima solubility, the solid constituent content of this solution low (being less than 15%w/w), therefore the solution spin-coating method that IBM Corporation adopts will just can reach the requirement that film thickness is greater than 1.2 μ m through the coating of 8～10 times, and each coating all needs through heat treatment, and the heat treatment time in 10 whens coating will be longer, therefore for the suitability for industrialized production that realizes high volume production, the method also has larger limitation.
Summary of the invention
The object of the present invention is to provide a kind of printing ink, thin-film solar cells and manufacture method thereof for semiconductor thin-film solar cell, particularly, a kind of ink coats of manufacturing copper-indium-galliun-selenium film solar cell and utilize this printing ink to manufacture the method for thin-film solar cells particularly, method of the present invention can only apply once can obtain the Copper Indium Gallium Selenide polycrystal film photovoltaic absorption layer that thickness is 1.5～2.5 μ m.
One object of the present invention is to provide a kind of printing ink, and it comprises semiconducting compound microcrystalline powder, solvent carrier and is dissolved in simple substance or the compound containing Cu, In, Ga, Se, S in described solvent carrier.
Optionally, the chemical formula of described semiconducting compound is CuIn
xGa
1-xSe
2-yS
y, x=0～1 wherein, y=0～2.
Optionally, the diameter of described semiconducting compound microcrystalline powder is 50～1000nm.
Optionally, described solvent carrier is hydrazine solution NH
2NH
2Or other hydrophily or non-hydrophilic solvent.
Optionally, described simple substance or compound are Se, S, Cu
2X, In
2X
3, Ga
2X
3, wherein, X is Se and/or S.
Optionally, also comprise selectivity dispersant, stabilizer or thickener in described printing ink.
Another object of the present invention is to provide a kind of manufacture method of printing ink, comprises the following steps:
A, prepare solvent carrier;
B, prepare the semiconducting compound microcrystalline powder;
C, described solvent carrier and described semiconducting compound microcrystalline powder are mixed, form described printing ink after grinding.
Optionally, described step c is replaced by the following step:
Described semiconducting compound microcrystalline powder is mixed with hydrophilic solvent, after grinding, form aaerosol solution;
Described aaerosol solution and described solvent carrier are mixed to form to described printing ink.
Optionally, described step a comprises the following steps:
A1, add Cu in anhydrous hydrazine
2S and sulphur, obtain solution A after electromagnetic agitation;
A2, add In in anhydrous hydrazine
2Se
3And sulphur, obtain solution B after electromagnetic agitation;
A3, mixed solution A and solution B obtain solvent carrier.
Optionally, the chemical formula of described semiconducting compound is CuIn
xGa
1-xSe
2-yS
y, x=0～1 wherein, y=0～2.
Optionally, described semiconducting compound adopts the selenium grain of equimolar copper powder, indium grain, gallium grain and two times moles to react acquisition in nitrogen or inert gas atmosphere, and reaction temperature is that 200～550 ℃, pressure are 0～100Psi, and the reaction time is 0.5～10 hour.
Optionally, in described step a2, also add Ga in anhydrous hydrazine
2Se
3And/or (In
0.7Ga
0.3)
2Se
3.
Optionally, the chemical formula of described semiconducting compound is CuInSe
2Or CuIn
xGa
1-xSe
2-yS
y, x=0～1 wherein, y=0～2.
Optionally, described semiconducting compound adopts the selenium grain of equimolar copper powder, indium grain and two times moles to react acquisition in nitrogen or inert gas atmosphere, and reaction temperature is that 350 ℃, pressure are 50Psi, and the reaction time is 2 hours.
Optionally, after grinding, in described printing ink, the diameter of semiconducting compound suspended powder is 50～1000nm.
A further object of the present invention is to provide a kind of thin-film solar cells, comprises the first electrode and the photovoltaic absorption layer formed at described the first electrode surface, and described photovoltaic absorption layer comprises the semiconducting compound microcrystalline powder, and its chemical formula is CuIn
xGa
1-xSe
2-yS
y, x=0～1 wherein, y=0～2, the diameter of described semiconducting compound microcrystalline powder is 50～1000nm.
Another purpose of the present invention is to provide a kind of manufacture method of thin-film solar cells, comprises the following steps:
Prepare the first electrode at substrate surface;
Apply one deck printing ink as photovoltaic absorption layer at described the first electrode surface;
At described photovoltaic absorption layer surface preparation the second electrode;
Wherein, described printing ink comprises: semiconducting compound microcrystalline powder, solvent carrier and be dissolved in simple substance or the compound containing Cu, In, Ga, Se, S in described solvent carrier, the chemical formula of described semiconducting compound is CuIn
xGa
1-xSe
2-yS
y, x=0～1 wherein, y=0～2, the diameter of described semiconducting compound microcrystalline powder is 50～1000nm.
Optionally, described solvent carrier is hydrazine solution NH
2NH
2Or other hydrophily or non-hydrophilic solvent.
Optionally, described simple substance or compound are Se, S, Cu
2X, In
2X
3, Ga
2X
3, wherein, X is Se and/or S.
Optionally, also comprise selectivity dispersant, stabilizer or thickener in described printing ink.
Optionally, the preparation method of described the first electrode is magnetron sputtering method.
Optionally, the method for described coating includes but not limited to brushing, excellent painting, dipping, spin coating, silk screen printing, impression, spraying.
The accompanying drawing explanation
By the more specifically explanation of the preferred embodiments of the present invention shown in accompanying drawing, above-mentioned and other purpose of the present invention, Characteristics and advantages will be more clear.In whole accompanying drawings, identical Reference numeral is indicated identical part.Deliberately do not draw in proportion accompanying drawing, focus on illustrating purport of the present invention.
The flow chart that Fig. 1 is printing ink manufacture method the first embodiment according to the present invention;
The flow chart that Fig. 2 is printing ink manufacture method the second embodiment according to the present invention.
Described diagram is illustrative, and nonrestrictive, at this, can not excessively limit the scope of the invention.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement much to be different from alternate manner described here, and those skilled in the art can be in the situation that do similar popularization without prejudice to intension of the present invention.Therefore the present invention is not subject to the restriction of following public specific embodiment.
Main purpose of the present invention is a kind of printing ink of preparation, this printing ink is for applying the absorbed layer that forms the CIGS thin-film solar cells, printing ink of the present invention can apply the film thickness that once can reach 1.5～2.5 μ m, need thereby overcome the shortcoming applied through repeatedly in the prior art, greatly improved production efficiency.The core concept of the manufacture method that the present invention takes is the Cu that contains in prior art
2S, Ga
2Se
3, In
2Se
3, S hydrazine solution in add the Copper Indium Gallium Selenide crystallite particle (diameter is 50～1000nm) prepared.The concentration of solia particle in mixed solution of adding can be regulated according to actual conditions, and namely the mass ratio of solids content can be regulated between 15%～60% (w/w), thereby has realized quick coating processes, and primary coating can meet the requirements of thickness.In addition, due to the interpolation of Copper Indium Gallium Selenide crystallite particle, greatly promote the growth of CIGS crystal grain, reached therefrom the photoelectric conversion efficiency of higher thin-film solar cells.Copper Indium Gallium Selenide crystallite particle can be by chemical fabrication method, or first makes the Copper Indium Gallium Selenide crystal, then realizes as methods such as ball millings by the method for physical grinding.Below in conjunction with specific embodiment, the present invention is elaborated.
Of the present inventionly for the printing ink that generates the CIGS absorbing layer of thin film solar cell, comprise semiconducting compound microcrystalline powder, solvent carrier and be dissolved in simple substance or the compound containing Cu, In, Ga, Se, S of described solvent carrier, wherein the chemical formula of semiconducting compound is CuIn
xGa
1-xSe
2-yS
y, x=0～1, y=0～2.The diameter of described semiconducting compound microcrystalline powder is 50～1000nm, is preferably 0.4～0.8 μ m, and described solvent carrier is hydrophily or non-hydrophilic solvent, is preferably hydrazine solution NH
2NH
2.Described simple substance or compound are Se, S, Cu
2X, In
2X
3, Ga
2X
3, wherein, X is Se and/or S.Also comprise selectivity dispersant, stabilizer or thickener in described printing ink.
The flow chart that Fig. 1 is printing ink manufacture method the first embodiment according to the present invention, as shown in Figure 1, the first embodiment of printing ink manufacture method of the present invention comprises step: prepare solvent carrier (S101), concrete grammar is to add Cu in anhydrous hydrazine
2S and sulphur obtain solution A after electromagnetic agitation, add In in anhydrous hydrazine
2Se
3And sulphur, obtaining solution B after electromagnetic agitation, mixed solution A and solution B obtain solvent carrier; And the step (S102) for preparing the semiconducting compound microcrystalline powder, the chemical formula of this semiconducting compound is CuIn
xGa
1-xSe
2-yS
y, x=0～1 wherein, y=0～2.As an embodiment, above-mentioned copper-indium-gallium-selenium semiconductor compound can adopt the selenium grain of equimolar copper powder, indium grain, gallium grain and two times moles to react acquisition in nitrogen or inert gas atmosphere, reaction temperature is that 350 ℃, pressure are 50Psi, reaction time is 2 hours, then it is smashed to pieces to the particle fine powder into about 300 microns, form the copper-indium-gallium-selenium compound microcrystalline powder.Subsequently described solvent carrier and described microcrystalline powder are mixed, through ball mill grinding, the semiconducting compound microcrystalline powder is ground into atomic little suspended powder, its diameter can reach 50～1000nm, for example 0.6 micron, this suspension form printing ink of the present invention (S103) again after electromagnetic agitation.At this, it should be noted that, step S101 and S102 can carry out simultaneously, also sequencing can be arranged.
The flow chart that Fig. 2 is printing ink manufacture method the second embodiment according to the present invention, as shown in Figure 2, the second embodiment of printing ink manufacture method of the present invention, comprise step: prepare solvent carrier (S201), concrete grammar is identical with aforementioned the first embodiment's, and preparing semiconducting compound microcrystalline powder (S202), concrete grammar is identical with aforementioned the first embodiment's.The second embodiment of printing ink manufacture method of the present invention also comprises step S203: described semiconducting compound microcrystalline powder for example, is mixed to (mass ratio 1: 1) with hydrophilic solvent (isopropyl alcohol), in grinding in ball grinder, the semiconducting compound microcrystalline powder is ground into atomic little suspended powder, its diameter can reach 50～1000nm, for example 0.6 micron, form aaerosol solution.Then described aaerosol solution is mixed with described solvent carrier, form printing ink of the present invention (S204) after electromagnetic agitation.At this, it should be noted that, step S201 and step S202 and S203 can carry out simultaneously, also sequencing can be arranged.
In other embodiments of the invention, in the process of preparation solution B, in anhydrous hydrazine, can also add Ga
2Se
3And/or (In
0.7Ga
0.3)
2Se
3.In this case, semiconducting compound can adopt CuInSe
2Or CuIn
xGa
1-xSe
2-yS
y, x=0～1 wherein, y=0～2.Described CuInSe
2Adopt the selenium grain of equimolar copper powder, indium grain and two times moles to react acquisition in nitrogen or other inert gas atmosphere, reaction temperature is that 350 ℃, pressure are 50Psi, and the reaction time is 2 hours.Formed CuInSe
2(Cu-In selenide) smash into about 300 micro particles fine powders, then with hydrophilic solvent, mixes (1: 1 weight), through ball mill, is milled into the approximately aaerosol solution of 0.6 micron of average grain diameter.Again aaerosol solution is mixed with described solvent carrier, form printing ink of the present invention after electromagnetic agitation.
The copper-indium-galliun-selenium film solar cell that utilizes printing ink of the present invention to prepare, as an embodiment, comprise the first electrode and the photovoltaic absorption layer formed at described the first electrode surface, described photovoltaic absorption layer comprises the semiconducting compound microcrystalline powder, and its chemical formula is CuIn
xGa
1-xSe
2-yS
y, x=0～1 wherein, y=0～2, the diameter of described semiconducting compound microcrystalline powder is 50～1000nm.The manufacture method of copper-indium-galliun-selenium film solar cell of the present invention, comprise the following steps: to prepare the first electrode at substrate surface, at first get a cleaning and receive lime glass as substrate (3mm is thick), the method plating one deck that then adopts magnetron sputtering approximately the molybdenum of 0.6 micron thick as the first electrode.Then apply one deck printing ink as photovoltaic absorption layer precast body film at the first electrode surface, described printing ink comprises semiconducting compound microcrystalline powder, solvent carrier and is dissolved in simple substance or the compound containing Cu, In, Ga, Se, S in described solvent carrier, and the chemical formula of described semiconducting compound is CuIn
xGa
1-xSe
2-yS
y, x=0～1 wherein, y=0～2, the diameter of described semiconducting compound microcrystalline powder is 50～1000nm, for example 0.6 μ m.Solvent carrier wherein is hydrazine solution NH
2NH
2Or other hydrophily or non-hydrophilic solvent.Simple substance or compound are Se, S, Cu
2X, In
2X
3, Ga
2X
3, wherein, X is Se and/or S.Also comprise selectivity dispersant, stabilizer or thickener in described printing ink.The method applied includes but not limited to brushing, excellent painting, dipping, spin coating, silk screen printing, impression, spraying.The precast body film, under nitrogen operation, is heated to 300 ℃ and keep 5 minutes.After 20 minutes, form fine and close Copper Indium Gallium Selenide sulfide film through 500-550 ℃ of annealing again.Utilize subsequently the chemical bath method, form the N-type CdS film of the about 50nm of thick layer on formed copper indium diselenide film, magnetron sputtering one deck insulating properties ZnO (about 50nm) then, sputter layer of ZnO again: Al (3%) (0.5 micron), just formed the CI G S thin-film solar cells of standard.This solar cell, under the 1.5AM standard light is shone (1000W/m2), has photovoltaic effect, Voc=0.55V, and Jsc=30mA/cm2, FF=70%, power conversion effect is 11.7%.
The above, be only preferred embodiment of the present invention, not the present invention done to any pro forma restriction.Any those of ordinary skill in the art, do not breaking away from technical solution of the present invention scope situation, all can utilize the technology contents of above-mentioned announcement to make many possible changes and modification to technical solution of the present invention, or be revised as the equivalent embodiment of equivalent variations.Therefore, every content that does not break away from technical solution of the present invention,, all still belong in the protection range of technical solution of the present invention any simple modification made for any of the above embodiments, equivalent variations and modification according to technical spirit of the present invention.
Claims (18)
1. a printing ink, is characterized in that: comprise semiconducting compound microcrystalline powder, solvent carrier and be dissolved in simple substance or the compound containing Cu, In, Ga, Se, S in described solvent carrier; Wherein, the chemical formula of described semiconducting compound is CuIn
xGa
1-xSe
2-yS
y, x=0～1 wherein, y=0～2.
2. printing ink as claimed in claim 1, it is characterized in that: the diameter of described semiconducting compound microcrystalline powder is 50～1000nm.
3. printing ink as claimed in claim 1, it is characterized in that: described solvent carrier is hydrazine solution NH
2NH
2Or other hydrophily or non-hydrophilic solvent.
4. printing ink as claimed in claim 1, it is characterized in that: described simple substance or compound are Se, S, Cu
2X, In
2X
3, Ga
2X
3, wherein, X is Se and/or S.
5. printing ink as claimed in claim 1, is characterized in that: also comprise stabilizer or thickener in described printing ink.
6. the manufacture method of a printing ink, comprise the following steps:
A, prepare solvent carrier;
B, prepare the semiconducting compound microcrystalline powder;
C, described solvent carrier and described semiconducting compound microcrystalline powder are mixed, form described printing ink after grinding, wherein,
Described step c is replaced by the following step:
Described semiconducting compound microcrystalline powder is mixed with hydrophilic solvent, after grinding, form aaerosol solution;
Described aaerosol solution and described solvent carrier are mixed to form to described printing ink.
Described step a comprises the following steps:
A1, add Cu in anhydrous hydrazine
2S and sulphur, obtain solution A after electromagnetic agitation;
A2, add In in anhydrous hydrazine
2Se
3And sulphur, obtain solution B after electromagnetic agitation;
A3, mixed solution A and solution B obtain solvent carrier.
7. method as claimed in claim 6, it is characterized in that: the chemical formula of described semiconducting compound is CuIn
xGa
1-xSe
2-yS
y, x=0～1 wherein, y=0～2.
8. method as claimed in claim 7, it is characterized in that: described semiconducting compound adopts the selenium grain of equimolar copper powder, indium grain, gallium grain and two times moles to react acquisition in nitrogen or inert gas atmosphere, reaction temperature is that 200～550 ℃, pressure are 0～100Psi, and the reaction time is 0.5～10 hour.
9. method as claimed in claim 7, is characterized in that: in described step a2, also add Ga in anhydrous hydrazine
2Se
3And/or (In
0.7Ga
0.3)
2Se
3.
10. method as claimed in claim 9, it is characterized in that: the chemical formula of described semiconducting compound is CuInSe
2Or CuIn
xGa
1-xSe
2-yS
y, x=0～1 wherein, y=0～2.
11. method as claimed in claim 10, it is characterized in that: described semiconducting compound adopts the selenium grain of equimolar copper powder, indium grain and two times moles to react acquisition in nitrogen or inert gas atmosphere, reaction temperature is that 350 ℃, pressure are 50Psi, and the reaction time is 2 hours.
12. method as claimed in claim 6 is characterized in that: after grinding, in described printing ink, the diameter of semiconducting compound suspended powder is 50～1000nm.
13. the manufacture method of a thin-film solar cells, comprise the following steps:
Prepare the first electrode at substrate surface;
Apply one deck printing ink as photovoltaic absorption layer precast body film at described the first electrode surface, heating and the rear photovoltaic absorption layer that forms of annealing;
At described photovoltaic absorption layer surface preparation the second electrode;
Wherein, described printing ink comprises: semiconducting compound microcrystalline powder, solvent carrier and be dissolved in simple substance or the compound containing Cu, In, Ga, Se, S in described solvent carrier, the chemical formula of described semiconducting compound is CuIn
xGa
1-xSe
2-yS
y, x=0～1 wherein, y=0～2, the diameter of described semiconducting compound microcrystalline powder is 50～1000nm.
14. method as claimed in claim 13 is characterized in that: described solvent carrier is hydrazine solution NH
2NH
2Or other hydrophily or non-hydrophilic solvent.
15. method as claimed in claim 13 is characterized in that: described simple substance or compound are Se, S, Cu
2X, In
2X
3, Ga
2X
3, wherein, X is Se and/or S.
16. method as claimed in claim 13 is characterized in that: also comprise selectivity dispersant, stabilizer or thickener in described printing ink.
17. method as claimed in claim 13 is characterized in that: the preparation method of described the first electrode is magnetron sputtering method.
18. method as claimed in claim 13 is characterized in that: the method for described coating includes but not limited to brushing, excellent painting, dipping, spin coating, silk screen printing, impression, spraying.
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| Application Number | Priority Date | Filing Date | Title |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101498707A CN102024858B (en) | 2010-04-19 | 2010-04-19 | Ink, thin film solar cell and manufacturing methods thereof |
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| Publication Number | Publication Date |
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| CN102024858B true CN102024858B (en) | 2013-12-04 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI485872B (en) * | 2012-11-05 | 2015-05-21 | Ind Tech Res Inst | Paste and method for manufacturing light absorption layer of solar cell |
| CN103346206A (en) * | 2013-06-09 | 2013-10-09 | 深圳市亚太兴实业有限公司 | Method for preparing copper indium gallium selenide thin film with sulfur-rich surface |
| US9960314B2 (en) * | 2013-09-13 | 2018-05-01 | Nanoco Technologies Ltd. | Inorganic salt-nanoparticle ink for thin film photovoltaic devices and related methods |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101000865A (en) * | 2006-01-12 | 2007-07-18 | 国际商业机器公司 | Method for fabricating an inorganic nanocomposite and method for fabricating solar battery |
| EP1870943A2 (en) * | 1998-07-02 | 2007-12-26 | International Solar Electric Technology, Inc. | An oxide-based method of making compound semiconductor films and making related electronic devices |
| CN101471394A (en) * | 2007-12-29 | 2009-07-01 | 中国科学院上海硅酸盐研究所 | Method for preparing optical absorption layer of copper indium gallium sulphur selenium film solar battery |
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| JP2001053314A (en) * | 1999-08-17 | 2001-02-23 | Central Glass Co Ltd | Method for manufacturing compound semiconductor film |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1870943A2 (en) * | 1998-07-02 | 2007-12-26 | International Solar Electric Technology, Inc. | An oxide-based method of making compound semiconductor films and making related electronic devices |
| CN101000865A (en) * | 2006-01-12 | 2007-07-18 | 国际商业机器公司 | Method for fabricating an inorganic nanocomposite and method for fabricating solar battery |
| CN101471394A (en) * | 2007-12-29 | 2009-07-01 | 中国科学院上海硅酸盐研究所 | Method for preparing optical absorption layer of copper indium gallium sulphur selenium film solar battery |
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