CN103811569B - Paste and method for forming light absorbing layer of solar cell - Google Patents

Paste and method for forming light absorbing layer of solar cell Download PDF

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CN103811569B
CN103811569B CN201210516825.XA CN201210516825A CN103811569B CN 103811569 B CN103811569 B CN 103811569B CN 201210516825 A CN201210516825 A CN 201210516825A CN 103811569 B CN103811569 B CN 103811569B
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slurry
dispersant
light
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layer
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CN103811569A (en
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黄渼雯
陈彦至
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Industrial Technology Research Institute ITRI
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
    • H01L31/0323—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2 characterised by the doping material
    • 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
    • Y02E10/541—CuInSe2 material PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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 relates to a slurry and a method for forming a light absorbing layer of a solar cell. The present invention provides a slurry comprising: 1 part by weight of antimony-doped CIGS nanoparticles; 0.05 to 0.15 parts by weight of a dispersant; and 4 to 7 parts by weight of an organic solvent in which the antimony-doped CIGS nanoparticles are suspended by a dispersant. The invention also provides a method for forming a light-absorbing layer of a solar cell, which comprises providing a substrate, forming a back electrode layer on the substrate; applying the paste to the back electrode layer; heating to remove the organic solvent to form a precursor layer; and thermally treating the precursor layer to form a light absorbing layer.

Description

The formation method of the light-absorption layer of slurry and solar cell
Technical field
System of the present invention, about solar cell, particularly forms about the slurry forming its light-absorption layer.
Background technology
CIGS coating technique mainly can be divided into the vacuum process technology such as common evaporation (Co-evaporation), sputter (Sputtering), and is coated with the antivacuum process technique such as (Coating), chemistry sprinkling pyrolysismethod (Chemicalspraypyrolysis), electro-deposition (Electrodeposition).The equipment of vacuum process and maintenance expense costliness thereof, although the high problem also having high cost of photoelectric conversion efficiency.Antivacuum process technique has the advantage of low equipment cost and high materials'use rate, and volume production quite has Advantages and Patontial, and therefore many companies and research institution drop into antivacuum process technique energetically.Chemistry sprays pyrolysismethod because of shortcomings such as compactness are poor and materials'use rate is lower in the middle of antivacuum processing procedure, less use recently.Galvanoplastic often meet with the problems such as the not good and bubble of plated film uniformity, and the manufacturer therefore dropped into is less.Coating process is expected most, and drop into the also maximum technology of manufacturer.
At present prepare with coating process the flow process that copper indium gallium selenium solar cell absorbs photosphere and roughly can be summarized as three steps: the preparation of predecessor slurry, with wet coating method slurry to be plated on molybdenum base material, again, in high temperature selenizing mode, the element in predecessor or compound to be reacted into CIGS thin-film.The form of predecessor slurry is broadly divided into corpuscular type and solution-type, no matter form why, all need form copper-indium-gallium-selenium compound through pyroreaction, therefore mostly needs the predecessor of preparation more than two to prepare light-absorption layer in the middle of existing technology.Although the CIGS thin-film efficiency of pyroreaction mode gained is verified, predecessor is prepared numerous and diverse and time-consuming, and is difficult to during pyroreaction avoid dephasign generate and be difficult to control the composition of film.
In sum, the light-absorption layer that new slurry forms solar cell is needed at present badly, to overcome the problem of aforementioned multiple predecessor slurry.
Summary of the invention
One embodiment of the invention provides a kind of slurry, comprising: the copper-indium-gallium-selenium nanoparticles of the antimony dopant of 1 weight portion; The dispersant of 0.05 to 0.15 weight portion; And 4 to 7 organic solvents of weight portion, wherein the copper-indium-gallium-selenium nanoparticles of antimony dopant is suspended in organic solvent by dispersant.
One embodiment of the invention provides a kind of formation method of light-absorption layer of solar cell, comprising: provide substrate, forms back electrode layer on substrate; Above-mentioned slurry is put on back electrode layer; Heat and form precursor layer to remove organic solvent; And heat treatment precursor layer is to form light-absorption layer.
Accompanying drawing explanation
In Fig. 1 system one embodiment of the invention, Copper Indium Gallium Selenide (CIGS:Sb) alloy powder of antimony dopant and antimony selenide (Sb 2se 3) XRD comparison diagram;
In Fig. 2 system one embodiment of the invention, Copper Indium Gallium Selenide (CIGS:Sb) alloy powder of antimony dopant and antimony selenide (Sb 2se 3) Ramman comparison diagram; And
In Fig. 3 system one embodiment of the invention, the XRD comparison diagram of the Copper Indium Gallium Selenide (CIGS:Sb) of the antimony dopant of different I n/Ga content.
Embodiment
One embodiment of the invention provides a kind of slurry, comprising: the copper-indium-gallium-selenium nanoparticles of the antimony dopant of 1 weight portion; The dispersant of 0.05 to 0.15 weight portion; And 4 to 7 solvents of weight portion, wherein the copper-indium-gallium-selenium nanoparticles of antimony dopant is suspended in organic solvent by dispersant.If the consumption of organic solvent is too much, then the solid content of slurry is easily too low, is unfavorable for coating process.If the consumption of organic solvent is too low, then slurry viscosity is easily too high, and be full of cracks problem easily appears in coating.If the consumption of dispersant is too low, in slurry, Copper Indium Gallium Selenide (CIGS:Sb) nano particle of antimony dopant is easy to assemble and cannot effectively disperse.If the consumption of dispersant is too high, then slurry is too sticky causes coating not easily, and is difficult to remove dispersant and easily have carbon residue problem in the step of subsequent heat formation light-absorption layer.
The composition of above-mentioned CIGS:Sb is as shown in Equation 1:
Cu 1-x(In 1-yga y) Se 2+z: Sb w(formula 1)
In formula 1,0≤x≤0.2,0.1≤y≤0.9,0≤z≤0.2, and 0 < w≤0.2.Weigh copper powder, indium powder, selenium powder according to stoichiometry, insert in high-pressure reactor containing the gallium nitrate of the crystallization water and antimony selenide, collocation organic solvent reacts, the product of formula 1.Because antimony (Sb) helps the long brilliant effect of melting, the precursor layer therefore containing CIGS:Sb can form the light-absorption layer of yellow copper structure after heat treatment.On the other hand, the CIGS:Sb slurry first forming formula 1 can simplify the preparation flow of multiple predecessor, and the stability of CIGS:Sb is high, the change of element ratio not easily occurs, the composition of light-absorption layer more easy to control when heat treatment.
In an embodiment of the present invention, organic solvent can be C 1-6monohydric alcohol (only containing a hydroxyl) methyl alcohol, normal propyl alcohol, other suitable monohydric alcohol or above-mentioned combination.In an embodiment of the present invention, dispersant can be (1) anionic: there is electronegative polar group, as carboxyl.(2) cationic: the polar group with positively charged, as amino.(3) electric neutrality type: as ethylene glycol.(4) nonionic: form as polyethoxylatedglycols (PEG), Alkylphenolethoxylates (APE) etc. mainly with Oxyranyle chain.For example, dispersant can be monoethanolamine.CIGS:Sb powder, dispersant and organic solvent are placed in suitable dispersal device as after ball mill, slurry.In an embodiment of the present invention, the average grain diameter of the CIGS:Sb particle in slurry is 10nm to 50nm.If the average grain diameter of CIGS:Sb particle is excessive, after wet, easily form hole in precursor layer.Even if after high-temperature heat treatment precursor layer, above-mentioned hole still can residue in the last light-absorption layer formed, and affects the usefulness of solar cell.
One embodiment of the invention also provides the formation method of the light-absorption layer of solar cell.For example, back electrode layer can first be applied on substrate.Substrate can be glass, PI film, metal forming or other suitable board-like material.Back electrode layer can be any electric conducting material as metal, alloy or other suitable electric conducting material.In an embodiment of the present invention, back electrode layer is molybdenum.Then put on back electrode layer by above-mentioned slurry, its applying method can be wet as scraper for coating method, infusion method, spraying process, method of spin coating or other suitable wet coating method.Then organic solvent is removed to form precursor layer.The last crystal making the long brilliant formation yellow copper structure of CIGS:Sb precursor layer again through a heat treatment processing procedure, namely completes light-absorption layer.
In an embodiment of the present invention, can drive before heating in the step of nitride layer and pass into selenium steam or sulfur vapor to avoid the volatilization of selenium element in heating process, and the sulfur vapor of trace contributes to the regulation and control of CIGS surface level, can help the lifting of efficiency.The selenium of light-absorption layer or the content of sulphur are increased, and then the band gap scope of adjustment light-absorption layer.
The temperature removing organic solvent formation precursor layer is 90 DEG C to 150 DEG C.If the temperature of heated slurry is too low, then organic solvent cannot be removed.Thus, organic solvent residual in precursor layer when heating processing at higher temperature afterwards, possible Quick-gasifying and form hole in light-absorption layer.If the temperature of heated slurry is too high, then may Quick-gasifying organic solvent and form hole in light-absorption layer.
Heat treatment precursor layer is 500 DEG C to 600 DEG C to form the temperature of light-absorption layer.The main purpose of this heating steps is to make the nano particle of CIGS:Sb to grow into the crystal of chalcopyrite, and removable residual organic solvent and dispersant.If the temperature of heating precursor layer is too low, be then not easily fully formed chalcopyrite crystallization.If the temperature of heating precursor layer is too high, then bottom substrate is easily damaged because of high temperature.
In order to the above-mentioned of the present invention and other object, feature and advantage can be become apparent, several embodiment cited below particularly coordinates appended diagram, is described in detail below:
[embodiment]
Embodiment 1
Stoichiometry according to table 1 weigh copper powder, indium powder, selenium powder, with containing the gallium nitrate of the crystallization water, put into 1L high-pressure reactor.600mL ethylenediamine solution is added in high-pressure reactor and stirs, then weigh antimony selenide (embodiment 1-8 does not need this step) according to the stoichiometry of table 1 and added high-pressure reactor.After complete sealed high pressure reactor, with air in nitrogen replacement high-pressure reactor, high-pressure reactor is placed in heater, by temperature increase to 200 DEG C, reacts and be cooled to room temperature after 24 hours.Separate solvent and alloy powder with filter type, after oven dry, verify that alloy powder composition is as table 1 with ICP-MS.Copper Indium Gallium Selenide (CIGS:Sb) alloy powder of the antimony dopant of Fig. 1 system embodiment 1-1 and antimony selenide (Sb 2se 3) XRD comparison diagram, and Fig. 2 system implements the CIGS:Sb alloy powder of 1-1 and Sb 2se 3ramman comparison diagram.From Fig. 1 and 2, the CIGS:Sb alloy powder that above-mentioned synthetic method is formed is not containing the dephasign of antimony selenide.The XRD comparison diagram of the CIGS:Sb of Fig. 3 system different I n/Ga content.As shown in Figure 3, CIGS:Sb alloy powder is not containing the dephasign of antimony selenide, and the composition of different I n/Ga can make characteristic absorption peak produce obvious displacement, it can thus be appreciated that just can control light-absorption layer composition at the synthesis phase of alloy powder.
Table 1
Embodiment 2
Then disperse the alloy powder of embodiment 1 to form slurry.For making slurry and molybdenum base material have good adhesion, the surface tension coefficient of solvent need be less than 40mN/m, and dispersant lies in 350 DEG C of i.e. heat decomposable chemicals, with the photoelectric conversion efficiency avoiding carbon residue to affect light-absorption layer.The CIGS:Sb getting 0.1g embodiment 1-3 how ground rice body is placed in the solvent of 2ml, then adds the dispersant of 0.01g, observes powder distributed state after 18 hours.Table 2 is the result of different solvents and dispersant powder, and solvent is better with the effect of monohydric alcohol, and dispersant is then best with the effect of the dispersant containing amido.
Table 2
Dispersion solvent Dispersant Distributed state
Test 1 Ethylene glycol Ether amine Most precipitation
Test 2 Glycol dimethyl ether Triethylamine A little precipitation
Test 3 Normal propyl alcohol Monoethanolamine Almost without precipitation
Test 4 Isobutanol PEG Precipitate completely
Test 5 Methyl alcohol Ether amine Almost without precipitation
Test 6 Ethanol PEG Most precipitation
Test 7 DME Octanol Precipitate completely
Test 8 Glycol dimethyl ether BDO Precipitate completely
Test 9 Ethylenediamine Cellulose Precipitate completely
Test 10 Ethylenediamine Octanol Precipitate completely
Embodiment 3
The solvent of the test 3 of Example 2 and dispersant make slurry.The CIGS:Sb alloy powder getting 10g embodiment 1-3 is placed in controlling wet-type finishing machine (JBM-b035), add 0.8g monoethanolamine, the normal propyl alcohol of 70ml and yttrium zirconium pearl 480g (particle diameter is 50 μm) again, grinding 3.5 hours under the condition of 35 DEG C and rotating speed 2000rpm.With screen cloth separating yttrium zirconium pearl ball and lapping liquid after having ground, then concentrate lapping liquid to desired concn (10-15wt%) in decompression distillation mode.The slurry brown color obtained.Test the particle size of CIGS:Sb particle in its slurry with dynamic light scattering (ZetasizerNanoZS), in known slurry, the average grain diameter of CIGS:Sb particle is 50nm.
Get plating molybdenum glass, by above-mentioned slurry wet on the molybdenum base material of 15cm × 30cm, through being repeatedly coated with still without the phenomenon observing disbonding.This to be coated with on the heating plate being placed under atmospheric environment 100-150 DEG C to remove solvent, to obtain the CIGS:Sb predecessor film that thickness is greater than 2.5 μm.Observe this predecessor film by SEM, and though be from above depending on or the SEM photo analysed and observe all to can be observed predecessor film stack ground very closely knit.
Get above-mentioned predecessor film and carry out high temperature selenizing processing procedure.Get 5cm 2the test piece of predecessor film be placed on quartz glass supporter, get 2g selenium powder and be positioned on quartz boat, and quartz boat and quartz glass supporter are put into the uniform temperature zone of six inch tube high temperature furnaces.Behind closed tube high temperature furnace two ends, with vacuum pump, tubular high temperature stove is evacuated to vacuum and passes into nitrogen again to normal pressure, repeat twice ventilation action and really make no oxygen in stove.Maintain this temperature 20 to 30 minutes after tubular high temperature furnace to 530 DEG C, stop heating afterwards with temperature in cooling water pipe to normal temperature, test piece can be taken out.To observe in the brilliant situation of predecessor film length at high temperature with sem analysis test piece, from above depending on and the size of the known CIGS:Sb crystal of SEM photo of side-looking be increased to about 1 μm by tens nanometer.Can confirm that CIGS:Sb crystal is yellow copper structure and exists without dephasign by XRD.
Comparative example 1
Similar to embodiment 3, dispersion solvent and the dispersant of difference test 5 in embodiment 2 grind.How ground rice body is placed in controlling wet-type finishing machine (JBM-b035) to get the CIGS:Sb of 10g, add 0.8g ether amine, the methyl alcohol of 70ml and yttrium zirconium pearl 480g (particle diameter is 50 μm) again, grinding 3.5 hours under the condition of 35 DEG C and rotating speed 2000rpm.With screen cloth separating yttrium zirconium pearl ball and grinding distribution liquid after having ground, then the grinding distribution liquid obtained is concentrated into desired concn (solid content 10-30wt%) in decompression distillation mode, driving thing ink color before institute obtains is dark-grey black.Test its particle size with dynamic light scattering (ZetasizerNanoZS), in known slurry, the average grain diameter of CIGS:Sb particle is 200nm.
Get plating molybdenum glass, by above-mentioned slurry wet on the molybdenum base material of 15cmx30cm, through being repeatedly coated with still without the phenomenon observing disbonding.This to be coated with on the heating plate being placed under atmospheric environment 100-150 DEG C to remove solvent, to obtain the CIGS:Sb predecessor film that thickness is greater than 3 μm.Observe this predecessor film by SEM, and though on being depending on or analyse and observe and all can be observed predecessor film there is many holes, the compaction rate of its storehouse is not as the predecessor film of embodiment 3.
Get above-mentioned predecessor film and carry out high temperature selenizing processing procedure.Get 5cm 2the test piece of predecessor film be placed on quartz glass supporter, get 2g selenium powder and be positioned on quartz boat, and quartz boat and quartz glass supporter are put into the uniform temperature zone of six inch tube high temperature furnaces.Behind closed tube high temperature furnace two ends, with vacuum pump, tubular high temperature stove is evacuated to vacuum and passes into nitrogen again to normal pressure, repeat twice ventilation action and really make no oxygen in stove.Maintain this temperature 20 to 30 minutes after tubular high temperature furnace to 530 DEG C, stop heating afterwards with temperature in cooling water pipe to normal temperature, test piece can be taken out.Take out test piece observe the brilliant situation of predecessor film length at high temperature with sem analysis, from above depending on SEM photo known CIGS:Sb crystal also have obviously long brilliant but have obvious hole, the storehouse packing that should come from predecessor film is not good.Be confined to the surface of light-absorption layer by the brilliant situation of the known length of SEM photo of analysing and observe, only observe few part melting under surface and nothing is obviously long brilliant.
From embodiment 3 and comparative example 1 relatively, in slurry, the Average Particle Diameters of CIGS:Sb particle can affect the melting degree of nano particle when high temperature significantly, situation brilliant in the length of film.
Comparative example 2
Similar to Example 3, difference is that nano particle contained in slurry is not the CIGS:Sb of embodiment 1-3 but the CIGS of embodiment 1-8.Observe the CIGS thin film after long crystalline substance with SEM, find that the length crystalline substance of film obviously has the phenomenon of layering, upper half storey has obviously long brilliant, and the long brilliant situation of lower half storey is less obvious.The size of current that the difference of long brilliant situation will produce after affecting light-absorption layer irradiation.The film of embodiment 3 and comparative example 2 is made assembly (please refer to solid-StateElectronics, vol.56, Iss.1, Feb.2011, Pages175-178) after, compare both current values.In embodiment 3, the long crystalline substance current value that light-absorption layer (CIGS:Sb) measures more completely is about 30mA/cm 2, and the current value that in comparative example 2, long brilliant poor light-absorption layer (CIGS) measures is about 22mA/cm 2.From relatively above-mentioned, doping Sb to CIGS can promote the electric current of solar cell really.
Comparative example 3
Stoichiometry according to table 3 weigh copper powder, indium powder, selenium powder, with containing the gallium nitrate of the crystallization water, put into 1L high-pressure reactor.600mL ethylenediamine solution is added in high-pressure reactor and stirs.After complete sealed high pressure reactor, with air in nitrogen replacement high-pressure reactor, high-pressure reactor is placed in heater, by temperature increase to 200 DEG C, reacts and be cooled to room temperature after 24 hours.Separate solvent and alloy powder with filter type, after oven dry, verify that alloy powder composition is as table 3 with ICP-MS.
Table 3
Then above-mentioned CIGS powder 10g and Sb is got 2se 3powder 0.5g carries out the ball milling processing procedure of embodiment 3, forms slurry.Except the alloy powder difference of ball milling, other ball milling parameter, wet on molybdenum glass, dry and high-temperature heat treatment makes the long processing procedure such as brilliant of predecessor film then identical.The CIGS+Sb after long crystalline substance is observed with SEM 2se 3film, finds that the length crystalline substance of film obviously has the phenomenon of layering, shows the melting phenomenon of its nano-powder not as expected.(please refer to after above-mentioned film is made assembly solid-StateElectronics, vol.56, Iss.1, Feb.2011, Pages175-178), the light-absorption layer (CIGS+Sb of layering in comparative example 3 2se 3) current value that measures is about 10mA/cm 2.Can find that the method directly mixed by Sb and CIGS can not increase photoelectric conversion efficiency by electrical result.
Although the present invention discloses as above with several preferred embodiment; so itself and be not used to limit the present invention; anyly have the knack of this those skilled in the art; without departing from the spirit and scope of the invention; when doing any change and retouching, the protection range of therefore the present invention when depending on after the attached claim person of defining be as the criterion.

Claims (10)

1. a slurry, comprising:
The copper-indium-gallium-selenium nanoparticles of the antimony dopant of 1 weight portion;
The dispersant of 0.05 to 0.15 weight portion; And
The organic solvent of 4 to 7 weight portions,
Wherein the copper-indium-gallium-selenium nanoparticles of this antimony dopant is suspended in this organic solvent by this dispersant.
2. slurry as claimed in claim 1, wherein this organic solvent system C 1-6monohydric alcohol.
3. slurry as claimed in claim 2, wherein this monohydric alcohol system methyl alcohol, normal propyl alcohol or above-mentioned combination.
4., as the slurry of claim 1, wherein this dispersant comprises anionic dispersing agent, cationic dispersing agent, electric neutrality type dispersant, multifunctional group dispersant or non-ionic polar dispersant.
5. slurry as claimed in claim 4, wherein this dispersant system monoethanolamine.
6. slurry as claimed in claim 1, wherein the average grain diameter of the copper-indium-gallium-selenium nanoparticles of this antimony dopant is 10 to 50nm.
7. slurry as claimed in claim 1, wherein this antimony dopant copper-indium-gallium-selenium nanoparticles consist of Cu 1-x(In 1-yga y) Se 2 ± z: Sb w, wherein 0≤x≤0.2,0.1≤y≤0.9,0≤z≤0.2, and 0<w≤0.2.
8. a formation method for the light-absorption layer of solar cell, comprising:
Substrate is provided,
Form back electrode layer on this substrate;
Slurry described in claim 1 is put on this back electrode layer;
Heat this slurry, to form precursor layer; And
Heat this precursor layer to form light-absorption layer.
9. the formation method of the light-absorption layer of solar cell as claimed in claim 8, wherein heats under this precursor layer is carried out at the environment of selenium steam or sulfur vapor with the step system forming this light-absorption layer.
10. the formation method of the light-absorption layer of solar cell as claimed in claim 8, wherein heating this precursor layer to form the temperature of the step of this light-absorption layer is 500 DEG C to 600 DEG C.
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