Title of Invention

METHOD FOR PRODUCING A THIN-FILM CHALCOPYRITE COMPOUND

Abstract

The invention is for a method for producing a thin film of chalcopyrite on a substrate, in particular for use in photovoltaic cells, this substrate consisting, for example, of molybdenum deposited in a thin layer on glass or a polymer, in which at least a thin liquid film of a solution is deposited on the substrate, said liquid film is dried in order to obtain a solid layer covering the substrate, and the chalcopyrite is formed by thermal reaction by placing said solid layer in contact with an atmosphere containing at least one element from the list comprising oxygen, sulphur, selenium and tellurium, characterized in that said solution consists of at least one mineral salt of a metal entering into the chalcopyrite composition and of an organic binder, dissolved in a polar solvent, and in that said solution is deposited on the substrate by an impression method selected from serigraphy, stencilling, spraying, spin-coating, tampography, flexography, and methods for spreading a liquid film, such as "doctor-blade" or "cup-coating", in order to obtain a solid layer of the mineral salt of said metal.

Full Text

[1] Chalcopyrite compounds, particularly deselinized copper and indium CulnSe2, also called CIS, and its alloys with gallium ("CIGS") and sulphur , (CIGSS) are promising candidates when used as a light-absorbing layer in photovoltaic cells in thin films. US Patent No. 4,335,266 is one example that describes the technology of CIS cells. Because of their high coefficient of absorption, a 1 to 2 mm thickness of CIGS chalcopyrite is sufficient to absorb all incident light. By changing the ratio of In/Ga and Se/S, a large range of values (1 to 2.4 eV) for the energy gap ("band-gap") can be obtained, and structures with a gradual band-gap are used in high output photovoltaic cells. Solar cells possessing a layer of polycrystalline CIGS have demonstrated conversion outputs exceeding 19%, as described by K. Ramanathan et al., Photovoltaics, 2003, 11, p. 225. The first industries have emerged and their production of solar cells with thin CIGS films is based on co-evaporation and selenization methods requiring a high vacuum, as described by Powalla et al., Proceedings of the 3rd WCPEC, Osaka, Japan, 2003, in publication, and by Kushiya et al. Proceedings of the 3* WCPEC, Osaka, Japan, 2003. Current CIGS solar modules have average outputs of 10 to 13%, with the goal being to obtain 13 to 15% with lower production costs than with crystalline silicon. These high output CIGS modules are obtained with expensive vacuumized equipment and sophisticated method controls; furthermore, from 20 to 40% of the primary materials are inevitably wasted. In order to reduce manufacturing costs, alternative deposition methods based on methods that do not rely on high vacuums have been proposed and studied. In general, these methods should allow the CIGS chalcopyrite layer to be quickly and simply deposited while completely using up the primary materials such as indium and gallium, which are relatively rare and expensive elements. Aside from the well-known methods such as electrochemical procedures, see for example U.S. Patent No. 5,871,630 and pyrolysis by spraying, for example, as in U.S. Patents 4,242,374 or 6,379,635, methods based on deposition of a paste have attracted attention these last few years, since outputs in excess of 13% have been obtained. As described in U.S. Patent No. 6,127,202, Kapur et al. have developed a procedure where a paste containing nanocrystalline metal oxide powder is first deposited on a substrate by spreading it ("doctor-blade"), then a treatment in a hydrogen atmosphere allows the oxides to be reduced to a metal layer which is then heated in a diluted H2Se atmosphere. This method requires, first, the elaboration of nanometric metal oxide powders in the appropriate Cu/ln and Cu/Ga ratio, and second, reduction in a hydrogenated atmosphere, followed by "selenization," requiring at least two heated vacuum environments for safety, since the gas used, H2Se, is highly toxic, making the procedure costly. Furthermore, the fact that the deposition of metal oxide paste must be treated in two stages considerably lengthens the time required for the cycle to produce the thin film of chalcopyrite substrate. [2] In another procedure described in U.S. Patent No. 5,910,336, organometallic compounds are dissolved in an organic solvent, then deposited on a substrate by spinning ("spin-coating") or by plunging ("dip-coating"), and after pyrolysis in an inert or reductive atmosphere, the resulting metal alloy is selenized in an oven and the chalcopyrite layer thus formed is completed into solar cells with an output of up to 9%. This method also requires fairly toxic and expensive metal-organic precursors, and the two-step procedure (reduction and then selenization) adversely affects deposition speed and adds to the cost. [3] The present invention relates to a rapid method that is economical in its use of primary materials and requires only simple equipment to produce a thin film of chalcopyrite on a substrate. The invention is characterized by the use of a solution containing metal mineral salts and an organic binder dissolved in a polar solvent. [4] These mineral salts may be halogens, nitrates, cyanides, cyanates or even thiocyanates or seleno-cyanates that may be either anhydrous or hydrated. [5] This solution is deposited on the substrate using an impression process such as serigraphy, stenciling, tampography, flexography, spin-coating, or methods for spreading liquid film ("doctor-blade" or "cup-coating"), or using a combination of several impression methods. Actually any method allowing a liquid to be transferred to a surface can be used, so long as the solution of metal mineral salts also contains an organic binder allowing the viscosity and rheology of said solution to be adjusted so as to be compatible with the impression or deposition method selected. The organic binder is typically selected from among celluloses, cellulose substitutes, polyvinyl alcohols, polyethlyenoxides, polyacrylonitriles, polysaccharides and nitrocelluloses soluble in the appropriate solvent. This solvent may be either water or an organic compound selected from aliphatic alcohols, polyglycols, polyethers, polyols, esters, ethers, ketones, nitrites, or alkoxy alcohols. This is not an exhaustive list; any organic solvent may be used so long as it ensures that the metal mineral salts and organic binders are soluble. The mineral salts solution, described herein above, contains at least one mineral salt of a metal selected from the list comprising copper, silver, gold, zinc, cadmium and mercury, and at least one mineral salt of a metal selected from the list comprising boron, aluminium, gallium, indium, thallium, carbon, silicon, germanium, tin and lead., It is also possible to have a mixture of water and one or more of the previously cited organic compounds. In order to obtain a thin layer of chalcopyrite according to the invention, the solution containing the metal mineral salts is deposited on the substrate, then dried to obtain a solid layer containing metal salts. The substrate thus treated is placed into contact with an atmosphere containing one or more of the elements typically selected from the list comprising oxygen, selenium, sulphur, or tellurium, and heated, causing a reaction that transforms the layer containing the metal salts into a thin and compact film of chalcopyrite. In a case where the salts contain copper, indium, and possibly also gallium in the appropriate atomic proportions and the thermal treatment atmosphere contains selenium, a Cu(lnGa)Se2 type chalcopyrite is obtained with physical and electrical properties favourable for the manufacture of photovoltaic solar cells. The substrate is not limited to molybdenum deposited on glass such as that is used in CIGS photovoltaic cells. Any substrate offering the required chemical resistance during thermal treatment in an atmosphere containing the one or more elements selected from the list comprising oxygen, sulfur, selenium and tellurium may be covered with a thin coating of chalcopyrite according to the invention. [6] The present invention is not limited to CIGS type chalcopyrite, but may extend to compounds such as CdTe, HgCdTe or Cu2ZnSnSe4, for example. It is also possible to use mixed oxides such as CuAI02, or even AglnS2 type sulphides when using corresponding metal salts. [7] The applications for chalcopyrites obtained according to the invention are not limited to photovoltaic cells, clearly, other applications are possible. For example, the chalcopyrites may be used as infrared detectors such as with HgCdTe, transparent electrically conductive coatings such as CuAI02, photovoltaic sensors such as CdTe, or even light emitters in luminous diode structures, or as semi-conductive material in electrical resistors or even transistors by using suitable doping. If metals such as Fe, Ni, Co, Cr enter into the composition of the chalcopyrite, it is also possible for it to have magnetic properties. [8] All of the following examples have been prepared from plates of sodo-calcic glass coated with a layer of molybdenum deposited by cathode pulverization. The thin films of chalcopyrite obtained using the method of the invention have served in photovoltaic cells, given that the chalcopyrite coatings have been optimized and customized for this application. [9] The general procedure according to the invention for producing chalcopyrite is divided into four steps: [10] Step 1: Preparation of a solution containing the metal mineral salt or salts and the organic binder or binders in a polar solvent. [11] Step 2: Deposition of this solution onto the substrate using a suitable method of impression to ensure a constant, defined thickness of liquid film on the substrate. [12] Step 3: Drying the substrate with its liquid film in air or in an inert atmosphere in order to obtain a compact and solid film containing the metal salt or salts. [13] Step 4: Thermal treatment in an atmosphere containing at least one element from the list comprising oxygen, sulphur, selenium and tellurium in order to form chalcopyrite. [14] Example 1. [15] In 25 ml of methanol (Fluka 99.5%) 1.106 g of anhydrous indium chloride (III) lnCI3 (Aldrich, 99.999%) are dissolved, followed by 0.938 g of hemi- pentahdyrate copper nitrate (II) Cu(NO3)2 2.5 H2O (Aldrich, 99.99%), then 3g of ethylcellulose "Ethocel®" (Fluka) with a standard 5-15 mPas viscosity are added to the solution in order to adjust consistency. [16] This solution is deposited on the molybdenum coated glass by spreading the solution with a glass stick that serves as a blade and by using 100 mm spacers which define the thickness of the liquid film thus obtained. A volume of approximately 1 ml of solution is sufficient to cover 10 cm2 of substrate. The substrate with the liquid film is immediately dried at 100-120° C for 2 to 3 minutes, then it is heated to 250° C in the air for 1 to 2 minutes. [17] Finally, the substrate thus treated is placed in a heated graphite environment containing 0.5 grams of sulphur (99.5%, Fluka) and after 10 minutes at 500° C, the substrate is covered with a thin film (approximately 1 mm) of polycrystalline chalcopyrite CulnS2. [18] Analysis using an EDX sweeping electronic microscope and X-ray diffraction permits identification of the chalcopyrite obtained in this manner. [19] Example 2 [20] 0.256 g of hydrated gallium nitrate (III) (99.999% Aldrich) are dissolved in 25 ml of methanol (Fluka, 99.5%), followed by 0.886 g of anhydrous indium chloride (III) lnCI3 (Aldrich, 99.999%), which permits an atomic ratio of In/Ga of 4, followed by 0.938 g of hemi-pentahydrate copper nitrate (II) Cu(NO3)2 2.5 H2O (Aldrich, 99.99%), which permits an atomic ratio of Cu/(ln + Ga) of 1, then 3 g of ethylcellulose "Ethocel®" (Fluka) with a standard viscosity of 5-15 mPas is added to the solution in order to adjust the consistency. [21] As in the preceding example, this solution is deposited on the molybdenum coated glass by spreading the solution with a glass stick which serves as a blade and by using 100 mm spacers which define the thickness of the liquid film thus obtained. The substrate with the liquid film is immediately air-dried by passing it through an ambient temperature of 120° C for 2 minutes, then it is heated by passing it in open air at 120° C to 300° C for 3 minutes. Finally, the substrate thus treated is placed in a nitrogen-filled glass tube and maintained at 10 mbar. This tube comprises two temperature zones. The substrate is placed in one and in the other, a cupel containing 0.2 g of selenium (99.9%, Aldrich). The zone with the selenium is maintained at 300° C and the substrate is heated to 560° C for 10 minutes. After this thermal treatment, also called "selenization" the substrate is covered with a thin layer (about 1 mm ) of polycrystalline chalcopyrite Culn0.5Ga0.2Se2 with favourable photovoltaic properties. 122] Example 3 [23] A first solution of 5 ml of methanol (Fluka, 99.5%) containing 0.767 g of hydrated gallium nitrate (III) (99.999%, Aldrich), 0.885 g of anhydrous indium chloride (III) lnCI3 (Aldrich, 99.999%) and 0.938 g of hemipentahydrate copper nitrate (II) Cu(No3)2 2.5 H2O (Aldrich, 99.99%) is prepared. A second solution is prepared with 5 ml. of 1-pentanol (99%, Fluka) containing the same quantities of metal salts as the first solution and additionally containing 0.5 g of ethylcellulose "Ethocel®" (Fluka) with a standard viscosity of 5-15 mPas. [24] The solution to be deposited is formulated by mixing in a ratio of 1:2 the first and second solutions, in order to obtain the desired viscosity and rheology. [25] Deposition on the molybdenum-coated glass, drying and selenization take place as described in Example 2. The resulting chalcopyrite possesses favourable photovoltaic properties once a thin 50 mm film of CdS has been applied to it using the well-known "chemical bath" method, followed by a transparent ZnO-based transparent contact doped with aluminum deposited by cathode pulverization. Such a photovoltaic cell has demonstrated a conversion output of 6.7% under standard 1000 W/m2 (92.94 W/ft2) lighting. CLAIMS: 1. A method for producing a thin film of chalcopyrite on a substrate, in particular for use in photovoltaic cells, this substrate consisting, for example, of molybdenum deposited in a thin layer on glass or a polymer, in which at least a thin liquid film of a solution is deposited on the substrate, said liquid film is dried in order to obtain a solid layer covering the substrate, and the chalcopyrite is formed by thermal reaction by placing said solid layer in contact with an atmosphere containing at least one element from the list comprising oxygen, sulphur, selenium and tellurium, characterized in that said solution consists of at least one mineral salt of a metal entering into the chalcopyrite composition and of an organic binder, dissolved in a polar solvent, and in that said solution is deposited on the substrate by an impression method selected from serigraphy, stencilling, spraying, spin-coating, tampography, flexography, and methods for spreading a liquid film, such as "doctor-blade" or "cup-coating", in order to obtain a solid layer of the mineral salt of said metal. 2. A method as claimed in claim 1, wherein at least one dissolved mineral salt is a salt of a metal selected from copper, silver, iron, zinc, tin, cadmium, aluminium, gallium, indium, antimony and bismuth. 3. A method as claimed in claim 1, wherein said solution contains at least one mineral salt of a metal selected from the list comprising copper, silver, gold, zinc, cadmium and mercury, and at least one mineral salt of a metal selected from the list comprising boron, aluminium, gallium, indium, thallium, carbon, silicon, germanium, tin and lead 4. A method as claimed in claim 3, wherein said solution contains at least one mineral salt of a metal selected from copper, silver, zinc, cadmium and at least one or more metals selected from aluminium, gallium, indium and tin in the form of mineral salts. 5. A method as claimed in claim 1, wherein said mineral salt contains at least one anion selected from halogens, nitrate, cyanide, cyanate, thiocyanate, selenocyanate, chloride and nitrate. 6. A method as claimed in claim 3, wherein said solution contains at least nitrate or anhydrous or hydrated copper chloride and at least one or more metals selected from aluminium, gallium, and indium, either in the form of nitrate, or in the form of anhydrous or hydrated chloride. 7. A method as claimed in claim 6, wherein said solution contains at least anhydrous or hydrated copper nitrate (II), anhydrous or hydrated indium chloride (III), and anhydrous or hydrated gallium nitrate (III). 8. A method as claimed in claim 1, wherein the organic binder is a mixture formed of at least two organic compounds selected from celluloses, cellulose substitutes, alkylcelluloses, polyvinyl alcohols, polyethylene oxides, polyacrylonitriles, polysaccharides, and nitrocelluloses. 9. A method as claimed in claim 1, wherein the polar solvent for said solution is selected from water and organic compounds such as aliphatic alcohols, nitriles, polyglycols, polyethers, polyols, esters, ethers, ketones, diols, and alkoxyalcohols and, in particular, methanol, ethanol, 1-propanol, 2-propanol, 1-pentanol, 1.2-propanediol, 1.3-propanediol, glycerin, diglyme, tetraglyme, acetonitrile, propionitrile and 3- methoxypropionitrile. 10. A method as claimed in claim 1, wherein the polar solvent for said solution is a mixture of water and one or more organic compounds selected from aliphatic alcohols, nitriles, polyglycols, polyethers, polyols, esters, ethers, ketones, diols, and alkoxyalcohols. 11. A method as claimed in claim 1, wherein the polar solvent for said solution is a mixture formed of water and at least two organic compounds selected from aliphatic alcohols, nitriles, polyglycols, polyethers, polyols, esters, ethers, ketones, diols, and alkoxyalcohols. 12. A method as claimed in claim 1, wherein said solution contains at least anhydrous or hydrated copper nitrate (II) in a 0.05 to 3 molar concentration, preferably in a 0.2 to 1 molar concentration, anhydrous or hydrated indium chloride (HI) in a 0.03 to 3 molar concentration, preferably in a 0.2 to 1 molar concentration, and anhydrous or hydrated gallium nitrate (III) in a 0 to 1 molar concentration, preferably in a 0 to 0.4 molar concentration, and as organic binder, at least one type of ethylcellulose in a 2 to 200 g/ 1 concentration, preferably in a 50 to 150 g/1 concentration, dissolved in methanol or dissolved in a mixture of methanol and 1-pentanol. 13. A method as claimed in claim 1, wherein said film of solution deposited on the substrate is dried by progressively heating it to a temperature ranging from 150 to 300° C in a neutral atmosphere or in open air in order to obtain a solid layer. 14. A method as claimed in claim 1, wherein said solid layer covering the substrate is transformed into chalcopyrite by a thermal reaction effected at a temperature ranging from 300 to 650° C, preferably between 500 and 600° C, by placing said solid layer in contact with an atmosphere containing at least one element such as selenium, sulfur or tellurium, or a mixture of these three elements, in the elementary state, for a period of time ranging from 1 and 30 minutes, preferably between 5 to 20 minutes. 15. A method as claimed in claims 1 and 2, wherein the chalcopyrite obtained is cadmium telluride (CdTe). 16. A method as claimed in claims 1 and 12, wherein the chalcopyrite obtained is CuIn8GaySe2, with the sum x+y being between 0.8 and 1.5 and with y being between 0 and 0.6. ABSTRACT METHOD FOR PRODUCING A THIN-FILM CHALCOPYRITE COMPOUND The invention is for a method for producing a thin film of chalcopyrite on a substrate, in particular for use in photovoltaic cells, this substrate consisting, for example, of molybdenum deposited in a thin layer on glass or a polymer, in which at least a thin liquid film of a solution is deposited on the substrate, said liquid film is dried in order to obtain a solid layer covering the substrate, and the chalcopyrite is formed by thermal reaction by placing said solid layer in contact with an atmosphere containing at least one element from the list comprising oxygen, sulphur, selenium and tellurium, characterized in that said solution consists of at least one mineral salt of a metal entering into the chalcopyrite composition and of an organic binder, dissolved in a polar solvent, and in that said solution is deposited on the substrate by an impression method selected from serigraphy, stencilling, spraying, spin-coating, tampography, flexography, and methods for spreading a liquid film, such as "doctor-blade" or "cup-coating", in order to obtain a solid layer of the mineral salt of said metal.

Documents:

03529-kolnp-2006 abstract.pdf

03529-kolnp-2006 claims.pdf

03529-kolnp-2006 correspondence others.pdf

03529-kolnp-2006 description (complete).pdf

03529-kolnp-2006 form-1.pdf

03529-kolnp-2006 form-3.pdf

03529-kolnp-2006 form-5.pdf

03529-kolnp-2006 international publication.pdf

03529-kolnp-2006 international search report.pdf

03529-kolnp-2006-assignment.pdf

03529-kolnp-2006-correspondence-1.1.pdf

03529-kolnp-2006-priority document.pdf

3529-KOLNP-2006-ABSTRACT.pdf

3529-KOLNP-2006-AMANDED CLAIMS.pdf

3529-KOLNP-2006-ASSIGNMENT.pdf

3529-KOLNP-2006-CANCELLED PAGES-1.1.pdf

3529-KOLNP-2006-CANCELLED PAGES.pdf

3529-KOLNP-2006-CORRESPONDENCE 1.2.pdf

3529-KOLNP-2006-CORRESPONDENCE.pdf

3529-KOLNP-2006-DESCRIPTION (COMPLETE).pdf

3529-KOLNP-2006-EXAMINATION REPORT.pdf

3529-KOLNP-2006-FORM 1.pdf

3529-kolnp-2006-form 18.pdf

3529-KOLNP-2006-FORM 2.pdf

3529-KOLNP-2006-FORM 3.pdf

3529-KOLNP-2006-GPA.pdf

3529-KOLNP-2006-GRANTED-ABSTRACT.pdf

3529-KOLNP-2006-GRANTED-CLAIMS.pdf

3529-KOLNP-2006-GRANTED-DESCRIPTION (COMPLETE).pdf

3529-KOLNP-2006-GRANTED-FORM 1.pdf

3529-KOLNP-2006-GRANTED-FORM 2.pdf

3529-KOLNP-2006-GRANTED-FORM 3.pdf

3529-KOLNP-2006-GRANTED-FORM 5.pdf

3529-KOLNP-2006-GRANTED-SPECIFICATION-COMPLETE.pdf

3529-KOLNP-2006-INTERNATIONAL PUBLICATION.pdf

3529-KOLNP-2006-INTERNATIONAL SEARCH REPORT & OTHERS.pdf

3529-KOLNP-2006-OTHERS.pdf

3529-KOLNP-2006-PA.pdf

3529-KOLNP-2006-PETITION UNDER RULE 137-1.1.pdf

3529-KOLNP-2006-PETITION UNDER RULE 137.pdf

3529-KOLNP-2006-PRIORITY DOCUMENT 1.1.pdf

3529-KOLNP-2006-REPLY TO EXAMINATION REPORT-1.1.pdf

3529-KOLNP-2006-REPLY TO EXAMINATION REPORT.pdf

3529-KOLNP-2006-TRANSLATED COPY OF PRIORITY DOCUMENT.pdf