CN103474128B - A kind of method of preparing copper-indium-galliun-selenium film solar cell - Google Patents
A kind of method of preparing copper-indium-galliun-selenium film solar cell Download PDFInfo
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- CN103474128B CN103474128B CN201310418784.5A CN201310418784A CN103474128B CN 103474128 B CN103474128 B CN 103474128B CN 201310418784 A CN201310418784 A CN 201310418784A CN 103474128 B CN103474128 B CN 103474128B
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Abstract
The invention discloses a kind of method of preparing copper-indium-galliun-selenium film solar cell, comprise: (1) starches composite conducting molybdenum by serigraphy, blade coating or is sprayed on ceramic substrate, then through 150-250 DEG C of oven dry, 450-1150 DEG C heat treatment and 150-250 DEG C of annealing, make back electrode, this composite conducting molybdenum slurry comprises the component of following weight portion: molybdenum powder 50-80 weight portion, lead-free glass powder 5-15 weight portion, organic carrier 10-25 weight portion and the additive 5-10 weight portion of particle diameter 0.01-50 μ m; Wherein organic carrier comprises that mass ratio is epoxy resin and the organic solvent of 1-5:9-20, and additive comprises appropriate NaOH, thickener, plasticizer and surfactant; (2) on the basis of above-mentioned back electrode, prepare copper-indium-galliun-selenium film solar cell. The composite conducting molybdenum slurry that method of the present invention is used can adopt antivacuum technology of preparing to prepare the back electrode of copper-indium-galliun-selenium film solar cell, and technique is simple, reduces manufacturing cost.
Description
Technical field
The invention belongs to electrode of solar battery preparation field, be specifically related to one and prepare copper-indium-galliun-selenium film solar cellMethod.
Background technology
In energy crisis day by day serious today, the research of new forms of energy and application seem and become more and more important. Solar energy is as new energyImportant a member in the industry of source, has cleanliness without any pollution, the advantage such as inexhaustible, safe and harmless. CIGS solar cellThere is stable performance, the feature such as capability of resistance to radiation is strong, production cost is low, environment-friendly high-efficiency, may become follow-on commercializationThin-film solar cells. But solar energy industry still exists the inferior positions such as expensive, unstable, in China, the sunThe application of energy also substantially also rests on large-scale power station, and large-scale power station is distributed in the ground that the density of population such as the Northwest are low substantiallyDistrict, in China other areas, particularly big city, application also seldom. One as current solar energy industry development hasThe important directions of prospect, BIPV can well solve the application of solar energy in urban area. Current photovoltaic is builtBuilding integrated is mainly that the silica-based solar panel that waits is integrated in to the building surfaces such as roof, and this mode both can increase additionallyCost, affect again attractive in appearance.
Summary of the invention
The object of the invention is to overcome prior art defect, a kind of side of preparing copper-indium-galliun-selenium film solar cell is providedMethod.
Technical scheme of the present invention is as follows:
A method of preparing copper-indium-galliun-selenium film solar cell, comprising:
(1) composite conducting molybdenum is starched by serigraphy, blade coating or is sprayed on ceramic substrate, then through 150-250 DEG COven dry, 450-1150 DEG C heat treatment and (150-250 DEG C) annealing, make back electrode, and this composite conducting molybdenum slurry comprises following weightThe component of part:
Wherein organic carrier comprises that mass ratio is epoxy resin and the organic solvent of 1-5:9-20, and additive comprises in right amountNaOH, thickener, plasticizer and surfactant, epoxy resin is a kind of or mixing in E44 and E51 epoxy resin,Organic solvent comprises Macrogol 200, and organic solvent is made up of Macrogol 200, PEG400 and terpinol, itsThe mass ratio of middle terpinol and Macrogol 200 is 0-30:55-100, the quality of PEG400 and Macrogol 200Than being 0-15:55-100;
(2) on the basis of above-mentioned back electrode, prepare copper-indium-galliun-selenium film solar cell.
NaOH is mainly used in providing sodium element to promote the grain growth of CIGS thin-film, favourable raising solar cell effectRate; Thickener is a kind of auxiliary rheological agents, and its Main Function is viscosity and the plasticity for regulating electrocondution slurry, improves stickyKnot property.
The molybdenum powder of described particle diameter 0.01-50 μ m: in the time that the molybdenum powder particle using is excessive, in the process of molybdenum slurry sintering, molybdenumThe defective tightness of combination between particle, rete is coarse, and sintering defect is many, and the properties of electrode can decline; And when molybdenum powder particle diameterToo small, because surface can be excessive, between particle, more easily reunite and be not easy to disperse, more than a certain constant concentration, be just not easy printingAnd levelling, electrode preparation difficulty, cost is corresponding also to be increased greatly.
Described lead-free glass powder makes molybdenum slurry in heat treatment process, connect, strain, fix conductive phase molybdenum particle, and formation causesClose conductive film is also bonded together whole rete and substrate securely. In addition the adding to improve and lead of this glass dust,Electricity slurries system various aspects of performance, disperses more even such as making to conduct electricity the each composition of slurries; The difference that glass dust percentage composition is chosenCan also adjust the heat treatment temperature that regulates molybdenum slurry, the molybdenum slurry using at 400～1200 DEG C of preparation heat treatment temperatures.
Described epoxy resin is a kind of or mixing in E44 and E51 epoxy resin. It has good cohesive force, antioxygenChange, corrosion resistant characteristic, can also regulate slurries viscosity, can add in addition trace polyurethane-modified, makes it easierSolidify.
Organic solvent comprises Macrogol 200, and organic solvent is made up of Macrogol 200, PEG400 and terpinol,Wherein the mass ratio of terpinol and Macrogol 200 is 0-30:55-100, the matter of PEG400 and Macrogol 200Amount is than being 0-15:55-100. Above-mentioned these organic solvents are nontoxic, relatively good to the wellability of molybdenum powder, can be by molybdenum powder particleEvenly wrap up and be beneficial to the dispersed of molybdenum powder particle, make electrocondution slurry be not easy to produce and reunite and precipitation, wherein terpinolFor colourless thick liquid, boiling point is 220.85 DEG C, contains oxygen atom in structure, can reduce the reunion of molybdenum nano-scale particle,Can also in the time of slurry drying, control evaporation rate, prevent from applying the local rete that causes because solvent evaporates is too fast of rete simultaneouslyShrink the uneven cracking that produces; The polyethylene glycol that relative molecular weight is lower has the extensive compatibility with various solvents, is goodSolvent and solubilizer, mix whole slurries system more even, and rate of drying and the thickener etc. of control slurry addAdd the solubility of agent. In addition PEG-4000 or defoamer can play and avoid liquid level to occur in the process stirringBubble, polyethylene glycol-200 are also as NMF, and viscosity diluent, can add poly-second two if slurries viscosity is too highAlcohol-200 regulate. In sintering process, these solvents can progressively volatilize or decompose, and avoid film surface and inner generationCavity, volatilizees while arriving certain temperature clean, noresidue ash content.
In a preferred embodiment of the invention, described thickener is ethyl cellulose, butyl cellulose, ethoxyA kind of or mixing in cellulose and methyl hydroxyethylcellulose; Not only can make slurry thickening, after slurry sintering, have oneDetermine mechanical strength, can also make slurry be not easy oxidation and precipitation, improve slurry rheological property, give the machinery of electrocondution slurry excellencePerformance and bin stability, form tough film, (more than approximately 300 DEG C) energy under high temperature after organic solvent volatilization at a certain temperatureReach thermal decomposition effusion and noresidue ash content.
Described plasticizer is the organic polymer plasticizer with flexible group;
Described surfactant comprises a kind of or mixing in ethanol, toluene, SPAN85, lecithin. ItsMiddle SPAN85 has good intermiscibility in organic media, improves the wetability of organic solvent, higher in additionHydroxyl value and molecular weight can ensure that in the more metallic particles of absorption it suspends, and has facilitation to the stability of slurry;Ethanol is good to the wetability of molybdenum powder particle, and to other additives such as solubility of ethylcellulose is good.
In a preferred embodiment of the invention, described plasticizer comprises dibutyl phthalate, polyesters plasticisingAgent or polyalcohol ester plasticizer. Above-mentioned plasticizer can increase polymer plasticity and electrocondution slurry viscosity, reaches and optimizes conductionThe object of slurry levelability and thixotropy and processing characteristics.
Finally can also be according to different application conditions, such as different substrates, add other flow control agents, gelling agent,The auxiliary agents such as thixotropic agent, change the performance such as rheological characteristic and thixotropy of electrocondution slurry.
The invention has the beneficial effects as follows:
1, compared with prior art, the composite conducting molybdenum slurry that method of the present invention is used can adopt antivacuum technology of preparingPrepare the back electrode of copper-indium-galliun-selenium film solar cell, adopt silk screen print method, spraying process or knife coating, technique letterSingle, reduce manufacturing cost.
2, the solar cell that prepared by the present invention can directly be integrated on construction material, is conducive to realize photovoltaic building oneChange.
3, it is high temperature resistant that the composite conducting molybdenum that prepared by the present invention is starched the molybdenum film forming on pottery, preparing other layers of CIGSTime facilitate high-temperature process.
Brief description of the drawings
Fig. 1 is composite conducting molybdenum slurry scanning after 1100 DEG C of heat treatment on ceramic substrate prepared by the embodiment of the present invention 1One of electromicroscopic photograph;
Fig. 2 is composite conducting molybdenum slurry scanning after 1100 DEG C of heat treatment on ceramic substrate prepared by the embodiment of the present invention 1Two of electromicroscopic photograph;
Fig. 3 is composite conducting molybdenum slurry scanning electricity after 900 DEG C of heat treatment on ceramic substrate prepared by the embodiment of the present invention 2One of mirror photo;
Fig. 4 is composite conducting molybdenum slurry scanning electricity after 900 DEG C of heat treatment on ceramic substrate prepared by the embodiment of the present invention 2Two of mirror photo.
Detailed description of the invention
By detailed description of the invention, technical scheme of the present invention is further detailed and is described below.
Embodiment 1
By 7g molybdenum powder (particle diameter 0.01-50 μ m), the poly-second two of 0.5g glass dust (lead-free glass powder), 0.5g terpinol, 1gAlcohol-200,0.25g PEG-4000,0.1g epoxy resin E44 (or E51), 0.005gNaOH, 0.1g ethyl fibreDimension element, 0.01g dibutyl phthalate, class of 0.03g department 85 (SPAN85s), 0.5g ethanol, 0.005gOrganic silicone oil is put together and is mixed, and makes composite conducting molybdenum slurry.
Molybdenum is starched to serigraphy or blade coating on ceramic substrate, 200 DEG C of oven dry, then heat treatment 0.5 at 1100 DEG CHour, be incubated 2 hours at 200 DEG C, prepare conduction molybdenum film electrode (being described back electrode). By using scanning electronMicroscope (SEM) is observed their surface and cross section (as depicted in figs. 1 and 2), uses four point probe resistance meterMeasure film rectangular resistance and characterize, and calculated resistance rate. Adopt (the AmericanSociety of American Society Testing and MaterialsForTestingMaterials, ASTM) standard test method ASTM-D3359-08, StandardTestMethodsforThe caking property test that MeasuringAdhesionbyTapeTest carries out film characterizes, and test result is as shown in table 1 below:
Table 1 sample resistivity and caking property test result
Continue to prepare copper-indium-galliun-selenium film solar cell on this conduction molybdenum film electrode.
Embodiment 2
By 7g molybdenum powder (particle diameter 0.01-50 μ m), the poly-second two of 0.5g glass dust (lead-free glass powder), 0.5g terpinol, 1gAlcohol-200,0.25g PEG-4000,0.1g epoxy resin E44 (or E51), 0.005gNaOH, 0.1g ethyl fibreDimension element, 0.01g dibutyl phthalate, class of 0.03g department 85 (SPAN85s), 0.5g ethanol, 0.005gOrganic silicone oil is put together and is mixed, and makes composite conducting molybdenum slurry.
Molybdenum is starched to serigraphy or blade coating on ceramic substrate, 200 DEG C of oven dry, then heat treatment 0.5 at 900 DEG CHour, be incubated 2 hours at 200 DEG C, prepare conduction molybdenum film electrode. By using SEM (SEM)Observe their surface and cross section (as shown in Figure 3 and Figure 4), use four point probe resistance meter to measure film square electricityResistance characterizes, and calculated resistance rate. Adopt (the AmericanSocietyforTesting of American Society Testing and MaterialsMaterials, ASTM) standard test method ASTM-D3359-08, StandardTestMethodsforMeasuringThe caking property test that AdhesionbyTapeTest carries out film characterizes, and test result is as shown in table 2 below:
Table 2 sample resistivity and caking property test result
Continue to prepare copper-indium-galliun-selenium film solar cell on this conduction molybdenum film electrode.
Those skilled in the art can adjust in following process conditions, and obtain same as the previously described embodiments or close skillArt effect:
Annealing temperature 150-250 DEG C;
Described organic solvent also comprises terpinol and/or PEG400, and the mass ratio of terpinol and Macrogol 200 is0-30:55-100, the mass ratio of PEG400 and Macrogol 200 is 0-15:55-100.
Described thickener is one in ethyl cellulose, butyl cellulose, hydroxyethylcellulose and methyl hydroxyethylcellulosePlant or mix;
Described plasticizer is the organic polymer plasticizer with flexible group, preferably includes dibutyl phthalate, poly-Ester plasticizer or polyalcohol ester plasticizer;
Described surfactant comprises a kind of or mixing in ethanol, toluene, SPAN85, lecithin.
The above, be only preferred embodiment of the present invention, therefore can not limit according to this scope of the invention process, complies withEquivalence that the scope of the claims of the present invention and description are done changes and modifies, and all should still belong in the scope that the present invention contains.
Claims (3)
1. a method of preparing copper-indium-galliun-selenium film solar cell, is characterized in that: comprising:
(1) composite conducting molybdenum is starched by serigraphy, blade coating or is sprayed on ceramic substrate, then through 150-250 DEG COven dry, 450-1150 DEG C heat treatment and 150-250 DEG C of annealing, make back electrode, and this composite conducting molybdenum is starched by following weight portionComponent composition:
Wherein organic carrier comprises that mass ratio is epoxy resin and the organic solvent of 1-5:9-20, and additive comprises in right amountNaOH, thickener, plasticizer and surfactant, epoxy resin is a kind of or mixing in E44 and E51 epoxy resin,Organic solvent comprises Macrogol 200, and organic solvent is made up of Macrogol 200, PEG400 and terpinol, itsThe mass ratio of middle terpinol and Macrogol 200 is 0-30:55-100, the quality of PEG400 and Macrogol 200Than being 0-15:55-100;
(2) on the basis of above-mentioned back electrode, prepare copper-indium-galliun-selenium film solar cell.
2. a kind of method of preparing copper-indium-galliun-selenium film solar cell as claimed in claim 1, is characterized in that: instituteStating thickener is a kind of or mixing in ethyl cellulose, butyl cellulose, hydroxyethylcellulose and methyl hydroxyethylcellulose;Described plasticizer is the organic polymer plasticizer with flexible group; Described surfactant comprises ethanol, toluene, sorbA kind of or mixing in alcohol acid anhydride trioleate, lecithin.
3. a kind of method of preparing copper-indium-galliun-selenium film solar cell as claimed in claim 2, is characterized in that: instituteState plasticizer and comprise dibutyl phthalate, polyesters plasticizer or polyalcohol ester plasticizer.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107634146A (en) * | 2015-12-22 | 2018-01-26 | 成都新柯力化工科技有限公司 | Prepare forerunner's precursor emulsion of the photovoltaic material of flexible perovskite structure and preparation method thereof |
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| CN109887641A (en) * | 2019-02-18 | 2019-06-14 | 邓建明 | It is a kind of to effectively improve and CuInSe2The Mo layer of layer ohm contact performance |
| CN110148639B (en) * | 2019-05-15 | 2021-05-14 | 安徽正熹标王新能源有限公司 | Preparation method of Mo back electrode for CIGS thin-film solar cell |
| CN112786232B (en) * | 2019-11-11 | 2023-01-03 | 江西佳银科技有限公司 | N-type solar cell silver paste doped with organic gallium and preparation method thereof |
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| US4576735A (en) * | 1983-10-14 | 1986-03-18 | Hitachi, Ltd. | Electroconductive molybdenum paste |
| JP2005243500A (en) * | 2004-02-27 | 2005-09-08 | Kyocera Chemical Corp | Conductive paste, solar cell and manufacturing method of solar cell |
| CN101820002A (en) * | 2009-02-27 | 2010-09-01 | 比亚迪股份有限公司 | Conductive paste for solar cell and preparation method thereof |
| CN102439716A (en) * | 2008-11-14 | 2012-05-02 | 应用纳米技术控股股份有限公司 | Inks and pastes for solar cell fabrication |
| JP2012092438A (en) * | 2010-09-27 | 2012-05-17 | Hitachi Metals Ltd | Mo-based sputtering target and method of manufacturing the same, and cigs-based thin-film solar cell using the same |
| CN103077764A (en) * | 2013-02-01 | 2013-05-01 | 李春生 | Electrocondution slurry for front side electrode of solar cell |
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- 2013-09-13 CN CN201310418784.5A patent/CN103474128B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4576735A (en) * | 1983-10-14 | 1986-03-18 | Hitachi, Ltd. | Electroconductive molybdenum paste |
| JP2005243500A (en) * | 2004-02-27 | 2005-09-08 | Kyocera Chemical Corp | Conductive paste, solar cell and manufacturing method of solar cell |
| CN102439716A (en) * | 2008-11-14 | 2012-05-02 | 应用纳米技术控股股份有限公司 | Inks and pastes for solar cell fabrication |
| CN101820002A (en) * | 2009-02-27 | 2010-09-01 | 比亚迪股份有限公司 | Conductive paste for solar cell and preparation method thereof |
| JP2012092438A (en) * | 2010-09-27 | 2012-05-17 | Hitachi Metals Ltd | Mo-based sputtering target and method of manufacturing the same, and cigs-based thin-film solar cell using the same |
| CN103077764A (en) * | 2013-02-01 | 2013-05-01 | 李春生 | Electrocondution slurry for front side electrode of solar cell |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107634146A (en) * | 2015-12-22 | 2018-01-26 | 成都新柯力化工科技有限公司 | Prepare forerunner's precursor emulsion of the photovoltaic material of flexible perovskite structure and preparation method thereof |
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