TW201242038A - Substrate for photoelectric conversion element with molybdenum electrode, photoelectric conversion element and solar cell - Google Patents

Abstract

A substrate for a photoelectric conversion element is provided, in which a plurality of alkali metal ions can be efficiently diffused in a photoelectric conversion semiconductor layer, and a photoelectric conversion efficiency of the photoelectric conversion element can be elevated. The substrate for the photoelectric conversion element of the disclosure has an alkali metal silicate layer (30) on a substrate (10). The alkali metal silicate layer (30) includes sodium silicate, and lithium silicate or potassium silicate. Or, the substrate for the photoelectric conversion element of the disclosure has an alkali metal silicate layer (while alkaline earth metals are excluded) (30) on a substrate (10). The alkali metal silicate layer (30) includes silicon, alkali metals, and at least one of group 13 elements except aluminum or group 15 elements except nitrogen. The alkali metal silicate layer (30) is formed by a liquid-phase method.

Description

201242038, 厶厶〇 / 6. Description of the Invention: [Technical Field] The present invention relates to a substrate for a photoelectric conversion element having a molybdenum electrode, and a photoelectric conversion element suitable for use in a solar cell or the like, and a solar cell [Prior Art]

A photoelectric conversion element having a laminated structure of a lower electrode (back surface electrode) and a photoelectric conversion layer and an upper electrode (transparent electrode) for generating a current by absorbing light on a substrate is used for a solar cell or the like. Previously, a solar cell in which bulk single crystal Si or polycrystalline Si or thin film j was used was used as a wire, but in recent years, it has been studied that the semi-conductive (four) solar f pool does not depend on si. As a compound semi-conducting and solar cell, it is known that a light of a film such as a CIS (Cu-In-Se) system or a CIGS (c; u _Ga Se) system containing a group lb element, a group IIIb element, and a group VIb element High absorption rate and high photoelectric conversion efficiency. It is known that a photoelectric conversion element such as a CIS system or a CIGS system is known, and the photoelectric conversion efficiency of the photoelectric conversion layer is improved by the diffusion of the metal, preferably Na, in the photoelectric conversion layer (Patent Document 1 and Patent Document 2). First, a soda lime glass substrate containing Na is being used to diffuse Na in the photoelectric conversion layer. However, when a metal substrate, a polymer substrate, a substrate, or the like is used as the solar cell substrate, it is not possible to supply the substrate, so there is a problem that the conversion efficiency is not mentioned. Therefore, in the case of using a substrate containing no sodium, the following operation is performed: the supply layer is set by the liquid phase method, or by borrowing 4 201242038

IWI, a co-steaming clock with CIGS to introduce sodium, or a Mo-Na as an electrode, etc., for example, Patent Document 3 discloses that a metal oxide coating is applied by liquid phase coating, in detail, coating Buna stone acid salt. Further, Patent Document 4 discloses that an anodized substrate is brought into contact with an aqueous sodium hydroxide solution to be doped. Further, Patent Document 5 discloses that an oxidized stone film is formed on a steel substrate by a sol-gel method, and further, an insulating layer is formed by using the material containing (6). However, it is known that an alkali metal other than sodium, that is, lithium or potassium, cesium or cesium, can be added to CIGS in a smaller amount, and the effect of improving electric conversion efficiency is low even if it is added (Non-Patent Literature) i and non-patent document 2). [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Publication No. 2922465 [Patent Document 2] Japanese Patent Laid-Open Publication No. Hei No. Hei. No. Hei. [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei. No. 2-158511 [Non-Patent Document] [Non-Patent Document 1] Thin film (Thin S〇lid Fiims), Volume 36, ρ.9-ρ.16 (2000)

[Non-Patent Document 2] M. A. contreras et al., "The 26th IEEE Photovoltaic Specialized Conference δ 义 义 义 义 录 录 (c〇nference Rec〇r (j

Twenty Sixth IEEE Ph〇t〇v〇ltaic Specialists Conference)", 20124203 8f 2000, p.359-p.362 'Title' on the role of Na and the improvement of CIGS absorption materials using MF 刖 drive layer (〇 n the role of Na and modifications to CIGS absorber materials using high MF precursor layers )" as described above. 'Previously the most common insight is as follows: when forming a photoelectric conversion semiconductor layer, sodium diffuses from the sodium supply layer into the photoelectric conversion semiconductor layer, Thereby, the power generation efficiency is improved, but it is known that even if the sodium supply layer is provided, the power generation efficiency is not improved higher than expected. The reason for this is that impurities are generated by the reaction of sodium with the molybdenum of the electrode, and after the etching of the electrode film formation in the manufacturing step of the integrated solar cell, water washing is necessary, but it is confirmed by the water washing. Sodium is dissolved to cause loss. Further, it is presumed that in the reaction of sodium and molybdenum, the sputtering energy is a driving force for the reaction mainly generated when the molybdenum is sputtered on the alkali metal silicate layer. The present invention has been made in view of the above circumstances, and it is an object of the invention to provide a substrate for a photoelectric conversion element, a photoelectric conversion element, and a solar cell, wherein the substrate for the photoelectric conversion element can efficiently use the metal ions in the photoelectric conversion semiconductor layer. The ground diffusion, and the photoelectric conversion efficiency of the photoelectric conversion element can be improved. A substrate for a photoelectric conversion element with a flip electrode according to a first aspect of the present invention includes a substrate for a photoelectric conversion element, and a lithium niobate or potassium niobate and sodium citrate are accumulated on the substrate. An alkali metal ruthenate layer; and a molybdenum electrode laminated on the alkali metal ruthenate layer. Lonely 曰 The first aspect of the metal citrate layer of lithium or potassium relative to the stone oxime 6 201242038 ---- 丨 j · Preferably 0.001 or more and 1 or less. The sum of lithium or potassium in the first aspect relative to the molar ratio of cerium and the molar ratio with respect to sodium is preferably 1 or less. The first aspect of the alkali metal ruthenate layer preferably comprises boron or lanthanum. The thickness of the alkali metal ruthenate layer of the first aspect is preferably 2 μηη or less. The substrate of the first aspect is preferably a metal substrate. Che Yujia formed an anodized film on the surface of the metal substrate. The metal substrate is preferably a coating material obtained by integrating one side or both sides of aluminum, stainless steel or iron steel plate with an aluminum plate. The anodized aluminum film is preferably a porous anodized aluminum film, and the porous anodized aluminum film has a compressive stress. The photoelectric conversion element of the present invention can be formed on the substrate for a photoelectric conversion element according to the first aspect described above. A substrate for a photoelectric conversion element according to a second aspect of the present invention is characterized in that the substrate has an alkali metal tellurite layer (but does not contain an alkaline earth metal), and the alkali metal tellurite layer contains the thirteenth except aluminum. a group element or at least an anthracene, an anthracene, and an alkali metal of a Group 15 element other than nitrogen, and formed by a liquid phase method; and the substrate for a photoelectric conversion element includes a layer deposited on the metallosilicate layer Indium electrode. The Group 13 element other than the one or the Group 15 element other than the nitrogen is preferably boron or phosphorus. The metal of the second aspect is preferably nano. The first aspect of the metal test is preferably two types including a clock or potassium, and sodium. The total molar ratio of the Group 13 element other than aluminum or the Group 15 201242038 element other than nitrogen to 矽 is preferably 15 or less. The thickness of the alkali metal ruthenate layer of the second aspect is preferably 2 pm. The substrate of the second aspect is more preferably a metal substrate. ° It is especially preferable to form an anodized film on the surface of a metal substrate. The metal substrate is more preferably a covering material obtained by integrating one side and two sides of a steel, a non-mineral steel or an iron steel plate with an aluminum plate. The electric conversion element of the present invention can be formed on the substrate in another order. The electrode, the photoelectric conversion semiconductor layer, and the upper electrode conversion element' are characterized in that the composition of the four-conversion-conducting semiconductor layer is a compound semiconductor including at least a brass structure of a group lb element, a group IIIb element, and a group VIb element. The conversion semiconductor layer contains a clock ion or a potassium ion and a sodium ion. The content of each of the ions, ions, and blood sodium ions contained in the photoelectric conversion semiconductor layer is preferably lxl〇i5 atms/cm3 or more. The clock ions or the clock ions and the sodium ions contained in the photoelectric conversion semiconductor layer are preferably supplied from the donor layer of the molybdenum electrode. The main component of the photoelectric conversion semiconductor layer is preferably a compound semiconductor containing at least one of the following elements: at least one lb group element selected from the group consisting of ^ and ^; selected from the group consisting of... f ; 1 , Illb alizarin; and at least one vib group element selected from the group consisting of s, know and Te. The substrate is preferably a metal substrate. 8 201242038 Preferably, an anodized film is formed on the surface of the metal substrate. The metal substrate is preferably a coating material obtained by integrating aluminum sheets, aluminum sheets, or iron steel sheets on one surface and an aluminum plate. An anodized aluminum film is preferably a porous anodized aluminum film, and the smectic anodized aluminum film has a compressive stress. The solar cell of the present invention can be provided with the above-mentioned photoelectric conversion element. [Effects of the Invention] The substrate for a photoelectric conversion element according to the first aspect of the present invention has an alkali metal ruthenate layer containing an alkali metal ruthenate (other than an alkali metal other than sodium) and sodium citrate, even by Sodium is used in combination with other alkali metals to form an electrode containing molybdenum on the alkali metal ruthenate layer, and also inhibits the reaction of sodium with molybdenum to form impurities, and suppresses the dissolution of sodium by water washing, thereby allowing alkali metal citrate The sodium of the layer is efficiently diffused in the photoelectric conversion semiconductor layer, and the power generation efficiency of the photoelectric conversion element can be improved. The mechanism of action for obtaining the above effects by using sodium in combination with other metals is not necessarily clear, but it is presumed that other alkali metals (especially lithium or potassium) have lower hygroscopicity than sodium, due to the alkali metal tannic acid. Lithium or potassium is contained in the salt layer, and the moisture contained in the alkali metal silicate layer is absolutely reduced. As a result, the oxidation reaction due to moisture is less likely to occur, so that generation of impurities is suppressed, and sodium elution due to water washing is reduced. The substrate for a photoelectric conversion element according to the second aspect of the present invention includes at least one of a group 13 element other than aluminum or a group 15 element other than aluminum in the metal silicate layer. The formation of the electrode containing the key on the alkali metal ruthenate layer also inhibits the reaction of sodium with molybdenum to form a foreign matter, or the 201242038 t pif inhibits the elution of the alkali metal by water washing, thereby allowing the alkali metal citrate layer to be alkali The metal is efficiently diffused in the photoelectric conversion semiconductor layer, and the power generation efficiency of the photoelectric conversion element can be improved. The mechanism of action for obtaining the above-described effects by the alkali metal silicate layer containing at least one of the Group 13 element other than aluminum or the Group 15 element other than nitrogen is not necessarily a dish, but is presumed to be as follows. In the case of an alkali metal ruthenate layer containing only Shi Xi, metal and oxygen, the alkali metal ions are solid-solubilized in the glass t, but since the alkali metal ions are monovalent, the glass containing the sulphur-oxygen is not formed. Glass network. Therefore, the interaction between the alkali metal and oxygen is insufficient, and it is easy to be segregated from the glass and segregated on the surface. If the gold-collecting ions are segregated on the surface, there arises a problem that a high-energy splash: a key is reacted to form a foreign matter when the electrode is disposed. On the other hand, it is known that an oxide of a Group 13 element other than aluminum or a Group 15 element other than nitrogen is solid-dissolved in a phthalic acid glass to form a single phase glass, which is in the alkali metal ruthenate layer of the present invention. Also, by adding a Group 13 element other than aluminum or a Group 15 element other than nitrogen, ions of the elements enter into a glass network containing xenon-oxygen to form a uniform glass. The details are not necessarily clear, but it is presumed that the microstructure of the glass changes, and the stability of the metal ions in the glass is improved. Therefore, the release of the alkali metal ions is suppressed, and the segregation of the alkali metal ions to the surface is not caused, and the prevention can be prevented. Foreign matter generation when the key is turned over. Further, it is presumed that since the segregation of alkali metal ions to the surface is suppressed, the elution of the metal ions by the water washing is also alleviated. In the photoelectric conversion element of the present invention, in addition to the 201242038-X-- or potassium ion in the photoelectric conversion semiconductor layer, it is possible to improve the formation of the lithium-ion-converting semiconductor layer in addition to the scales. The amount of _ contained in the photoelectron 5 λ light (four) photoconductor containing nano ions is roughly measured. Although the physical properties and characteristics of the photoelectric conversion semiconductor layer are sub- ing, the presence of the ion ions contributes to the photoelectric high. This situation was first discovered by the inventors. The substrate for a photoelectric conversion element according to the first aspect of the present invention will be described in detail. The metal oxide layer in the substrate for the photoelectric conversion element of the first aspect includes potassium ascorbate and Weiner. It can also be used to cut both acid and potassium. The lithium or potassium of the alkali metal ruthenate layer is 0.001 or more and 1 or less, more preferably 0.01 or more and i or less, and particularly preferably 1 〇 • 2 or more and i or less, particularly preferably G.05 or more and 0.5 or less. (4) The total dream contained in the metal silicate layer (including strontium from sodium citrate), in the case of both oxalic acid and potassium sulphate, 'refers to lithium and potassium Mohrby from lithium oleate, potassium citrate and bismuth from sodium citrate. If the molar ratio of the ri" or the clock to the stone eve becomes greater than 1 ', the lithium or potassium becomes too much, and it is solidified as a sulphate. On the other hand, if the molar ratio of chain or potassium to shixi is less than 0.001, lithium or potassium is too small, and an additive effect cannot be obtained, and the photoelectric conversion efficiency of the photoelectric 201242038 conversion element is not improved. Preferably, the molar ratio of lithium or potassium to the total sulphate contained in the alkali metal ruthenate layer, and the molar ratio of sodium to the total radix contained in the metal silicate layer The sum is preferably 1 or less, more preferably 0.8 or less. If the bell or potassium is not contained, the insulating property is lowered, and when the platinum which is usually used for the back electrode is formed into a film, the impurity power generation efficiency is lowered. The reason is presumed to be that the water absorption of sodium is high. On the other hand, in the case of only bell or potassium, power generation efficiency cannot be improved. Further, if the molar ratio of lithium to potassium to cerium and the molar ratio of sodium to cerium are greater than cerium, it is difficult to cure as ceric acid salt, and since the amount of cerium is small, adhesion to the substrate is small. Sexual decline. A method of producing sodium citrate, lithium niobate or potassium citrate is known as a wet method or a dry method, and can be produced by dissolving cerium oxide with sodium hydroxide, lithium hydroxide or potassium hydroxide, respectively. . Further, various metal molars of the molar ratio of the molar ratio are commercially available, and the metal oxide salts can also be used. As sodium sulphate, aspartic acid, and potassium oxalate, various sodium molar ratios of sodium citrate, lithium niobate, and potassium citrate are commercially available. As an index indicating the ratio of bismuth to alkali metal, the molar ratio of Si 〇 2 / A 2 〇 (A: alkali metal) is often used. For example, lithium niobate has lithium niobate 35, lithium niobate 45, lithium niobate 75, and the like. Potassium citrate is commercially available as No. 1 potassium citrate, No. 2 potassium citrate, and the like. Sodium citrate is known to have sodium decanoate, sodium metasilicate, sodium citrate No. 1, sodium sulphate No. 2, sodium citrate No. 3, sodium sulphate No. 4, etc. The molar ratio of moorium increased to tens of thousands of sodium morbid. A solution of any concentration can be obtained by mixing the above sodium citrate, lithium niobate, and potassium citrate with water at a ratio of 12 201242038. The ratio of the bell or potassium to the shovel can be varied by the mixing of the alkali metal silicates, and can be varied by mixing various sodium citrates at any ratio. By changing the amount of water added, the viscosity of the coating liquid can be adjusted to determine appropriate coating conditions. The method of applying the coating liquid onto the substrate is not particularly limited, and examples thereof include a knife-to-knife method, a wire bar method, a gravure method, a spray method, a dipping coating method, a spin coating method, and a capillary coating method. And other methods. Further, the supply of lithium niobate, potassium niobate and sodium citrate in the alkali metal ruthenate layer is not necessarily required to be a source of linal acid, potassium oxalate or sodium silicate. For example, in the case where the alkali metal citrate layer contains lithium niobate and sodium citrate, the cerium acid clock and sodium hydroxide, or lithium hydroxide and sodium citrate are mixed with water at an arbitrary ratio, respectively. In the case where the sulphuric acid layer contains the sulphuric acid and the sodium sulphate, 'the potassium hydroxide and sodium citrate, or the potassium citrate and the sodium hydroxide are mixed with water at an arbitrary ratio, and the stone may be made. An alkali metal citrate layer of an acid clock and sodium sulphate or potassium citrate and sodium citrate. Further, as a supply source, a lithium salt, a potassium salt, or a sodium salt may be added, respectively. For example, nitrates, sulfates, acetates, phosphates, chlorides, bromides, iodides, and the like are used. A coating solution of an alkali metal ruthenate other than lithium niobate, potassium citrate or sodium citrate can be added to a sodium citrate solution by adding a desired alkali metal nitrate, sulfate, acetate, acidate, It is easily obtained by chloride, desertification, iodide or the like. A compound containing boron or a compound containing phosphorus may also be added to the aqueous alkali metal citrate solution. By adding these compounds, Mo film forming suitability and power generation efficiency can be further improved. The details may not be clear, but 13 201242038 • w · especially ^ ▲ * Presumed as: by adding boron or phosphorus to the alkali metal citrate 'the microstructure change of the glass, the stability of the alkali metal ions in the glass is improved' Therefore, the release of alkali metal ions is suppressed, and the film forming suitability of Mo is improved, and the power generation efficiency is improved. The Si Peng source is preferably a borate such as z-p-acid or sodium tetraborate. Phosphorus sources are: phosphoric acid, peroxyphosphoric acid, phosphonic acid, phosphinic acid, diphosphoric acid, triphosphoric acid, polyphosphoric acid, cyclo-triphosphate, cyclo-tetraphosphonic acid, diphosphonic acid, and salts of such acids, etc. Listed by: lithium phosphate, sodium phosphate, potassium phosphate, lithium hydrogen phosphate, ammonium phosphate, sodium hydrogen phosphate, calcium hydrogen phosphate, ammonium hydrogen phosphate, lithium dihydrogen phosphate, sodium dihydrogen phosphate, calcium dihydrogen phosphate, dihydrogen phosphate Ammonium, sodium pyrophosphate, tribasic acid, and the like. The alkali metal tellurite layer can be produced by applying a coating liquid onto a substrate and then performing heat treatment. The inventors of the present invention measured the dehydration temperature by a method using thermogravimetric analysis and temperature rise degassing analysis, and as a result, it was found that the dehydration was 2 Torr. 〇 ～300°C or so. At a temperature lower than 200 °C, the coating liquid cannot be sufficiently dried, and a metal oxide layer having high water resistance cannot be formed, which is not preferable. In addition, in the heat treatment at 300 ° C or lower, the alkali metal citrate layer has a large amount of residual water, reacts with carbon dioxide in the atmosphere, and forms impurities such as carbonate on the surface, or generates molybdic acid when the Mo electrode is sputtered. Sodium and so on. Therefore, the heat treatment temperature is preferably 200 ° C or more, and more preferably 3 〇 (rCW, particularly preferably 400 ° C or more. Since the above heat treatment at a higher temperature is carried out, the substrate used in the first aspect is more It is preferable to use a coated substrate in which an anodic oxide film is formed on the surface of the sinter and a dissimilar metal. The following description of the coated substrate is described in 201242038, which is known as a crack that does not occur at a high temperature or higher. It is also known that by heat-treating the substrate at 30 CTC or more in advance, compression/force can be imparted to the anodic oxide film, and the heat can be improved, and long-term reliability of insulation can be ensured. After the application of the metal salt layer, the treatment is carried out, and the dehydration of the g sulphate layer must be (4) heat treatment and heat treatment necessary for anodic oxidative stress. In addition, at a temperature exceeding 60 ,, Exceeding the glass transition temperature of the citrate is not good. The thickness of the metal oxide layer after the heat treatment of the stomach is 〇〇1 qing~2 μπι, preferably 0.05 μπι~1.5 (4), especially good 〇] ..._. If The thickness of the crucible becomes thicker than 2 pottery, and the amount of shrinkage of the metal-like stone in the treatment is increased, and cracking is likely to occur, so that it is not preferable. The substrate for the photoelectric conversion element of the second aspect of the invention is: acid The alkali metal t Ϊ in the substrate for a photoelectric conversion element according to the second aspect includes a group 13 element other than the group or a group 15 element (hereinafter, simply referred to as a group 13 element or '兀, 、). At least one of hydrazine and an alkali metal is formed by a liquid phase method. The Group 13 element or the Group 15 element is preferably boron or phosphorus. The base metal is preferably sodium, more preferably lithium. As with sodium or potassium strontium, there are two kinds of sodium, lithium or potassium. The outer salt layer is better than the potassium machine. (4) Moore is better than 〇·1 or less 'more preferably 〇.01 or more and 1 or less'. Preferably, it is 0.02 15 201242038 'Hu / pif or more and 1 or less, particularly preferably 0.05 or more and 0.5 or less. 矽 is the total 矽 contained in the alkali metal silicate layer (including bismuth from sodium citrate), including stone In the case of both lithium niobate and potassium citrate, it refers to the relationship between lithium and potassium and from lithium niobate. Potassium and molar ratio of bismuth from strontium citrate. If the molar ratio of lithium or potassium to strontium is greater than 1, lithium or potassium is too much to be solidified as citrate. On the other hand, if lithium or potassium When the molar ratio with respect to ruthenium is less than 0·(8), the lithium or potassium is too small to obtain an additive effect, and the photoelectric conversion efficiency of the photoelectric conversion element is not improved. Preferably, lithium or potassium is relative to the alkali metal ruthenate layer. The molar ratio of the molar ratio of the total enthalpy contained in the sodium to the total enthalpy contained in the alkali metal silicate layer is preferably 丨 or less, more preferably 〇 8 or less. In the case of potassium or potassium, the insulating property is lowered. Further, when the film is normally used for turning the back electrode, T becomes an impurity, and thus the power generation efficiency is lowered. The reason is estimated to be nano, and water is south. On the other hand, when the chain or potassium is only contained, the power generation efficiency cannot be improved. Further, if the molar ratio of lithium or potassium to cerium, the molar ratio of sodium to cerium to cerium, and the amount of cerium relative to cerium, it is cured as a cerium salt, and the adhesion to the substrate is lowered. The second aspect of the alkali metal ruthenate layer comprises a Group 13 element or a portion of the element which enters into the glass network comprising helium-oxygen. From this, it is presumed that the microstructure of the surface changes, the stability of the glass ions is improved, and the segregation of the alkali metal ions to the surface is not caused by the release of the metal ions. Therefore, the layer, for example, does not include a layer containing a Group 13 element or a Group 15 element as formed on the surface of the alkali metal silicate layer 201242038 ----- £. Further, if the soil-like metal is contained in the metal oxide layer, it is easy to form a smear, and the stability of the coating liquid at the time of forming the metal silicate layer is deteriorated. Therefore, the second aspect of the alkali metal silicate layer does not contain an alkaline earth metal. The molar ratio of the third group element or the group 15 element to the base metal of the alkali metal silicate layer T (in the case of containing a plurality of group 13 elements or 15th element, a total of a plurality of elements) Mohr ratio is preferably 〇〇〇i or more 〇·15 or less, more preferably 0. (8) 2 or more and 0.10 or less, and particularly preferably 〇〇〇5 to death 〇.08 or less, particularly preferably 0.01 or more 〇·〇5 the following. When it is less than 〇〇〇1, at least one of the group 13 element or the group 15 element is not contained in the shell J, and the foreign matter is likely to be precipitated on the surface of the alkali metal silicate layer, and the insulation is lowered' or When the normal remaining back surface electrode is formed into a film, foreign matter is easily formed, and thus power generation efficiency is lowered. On the other hand, when the molar ratio of at least one of the group 13 element or the group 15 element is larger than 〇.15, a precipitate is formed and a uniform coating liquid cannot be obtained, and even if this is sufficient The coating is also difficult to cure as _, and the amount of God is small, so that the adhesion to the substrate is lowered. The source of the germanium source and the metal source can be the same as those of the source and the metal source described in the substrate for the photoelectric conversion element of the first aspect. The Group 13 element other than aluminum or the Group 15 element other than nitrogen is: collar, gallium, indium, antimony, phosphorus, arsenic, antimony, antimony. The source of the butterfly and the source of the lining may be the same as those of the boron source and the phosphorus source described in the substrate for the photoelectric conversion element of the first aspect. Gallium source, indium source, and lanthanum source include gallium, indium, bismuth nitrate, sulfur 17 201242038 /pif acid salt, acetate, chloride, and the like. Examples of the arsenic source, the antimony source, and the antimony source include an oxo acid or an oxo acid salt of arsenic, antimony or bismuth. Examples thereof include arsenious acid, sodium citrate, and sodium silicate. The second aspect of the metallographic layer can be obtained by mixing the above sodium citrate, lithium niobate or potassium niobate with a source of a Group 13 element or a source of a Group 15 element with water at any ratio. Coating solution. The viscosity of the coating liquid can be adjusted by changing the force of the water to determine the appropriate coating conditions. The method of applying the coating liquid onto the substrate is not particularly limited, and for example, a doctor blade method, a wire bar method, a gravure method, a spray method, a dipping coating method, a spin coating method, a capillary coating method, or the like can be used. . The temperature condition of the heat treatment after applying the coating liquid onto the substrate may be carried out under the same conditions as those of the substrate for a photoelectric conversion element of the first aspect. Further, the substrate to be used may be the same substrate as the substrate for the photoelectric conversion element of the first aspect. Further, it is preferable that the thickness of the metal silicate layer after the heat treatment is also the same as that of the substrate for a photoelectric conversion element of the first aspect. / The light conversion element using the substrate for a photoelectric conversion element according to the first aspect of the present invention will be described. Further, the configuration of any of the photoelectric conversion elements of the substrate for photoelectric conversion using the first aspect and the substrate for photoelectric conversion device of the second aspect is the same. Fig. 1 is a schematic cross-sectional view showing a form of a photoelectric conversion element. Further, the scale and the like for easily recognizing the constituent elements are different from those of the actual person. As shown in FIG. 1, the conversion is performed by sequentially depositing an anodized film 2G formed by polar oxidation, a gold hydroxide layer 30, and a flip-flop 201242038 pole 40 on the substrate 1G to generate electricity by light absorption. The electron-transformed semiconductor layer 50, the buffer layer 60, the light-transmitting conductive layer (transparent electrode) 7〇, and the upper electrode (gate electrode) 80 of the electron pair. Further, FIG. 1 shows a photoelectric conversion element in which an anodized film 2A formed by anodization and a metal oxide layer 30 are formed on a substrate 1A, which may be as shown in FIG. The alkali metal silicate layer 30 is formed on the crucible (in the same manner, in FIG. 2, the same constituent elements as those in FIG. j are denoted by the same reference numerals). The substrate 10 can be used as a ceramic substrate (alkali-free glass, quartz glass, alumina, etc.), a metal substrate (stainless steel, titanium foil, tantalum, etc.), or a polymer substrate (such as polyacrylonitrile). From the viewpoint of heat correction and lightweightness, it is particularly preferable to be a metal substrate. In particular, the metal oxide film formed on the surface of the metal substrate by anodization can be used as a material of the insulator. In other words, it preferably contains a selected one from the group consisting of Shao (A1), iron (Fe), and wrong (zn, abundance;

'-_______. 19 20124203 8f ηδδο /pif The anodic oxide film 20 formed by the ruthenium oxidization is an insulating oxide film having a plurality of pores by anodic oxygen insulation, thereby ensuring high reading (4)^ Oxidation can be carried out by applying a voltage between the anode and the cathode in the same manner as the cathode by using the substrate 10 as an anode. The cathode can be used as slave or sau. The anodizing conditions also depend on the kind of the electrolyte to be used, and are not particularly limited. As conditions, for example, the electrolyte concentration is 0.1 mol/L 2 mol/L, the liquid temperature is yc 8 (rc, the current density is 〇(9) 5 A/cm 2 〇-6^A/cm, and the voltage is 1 v to 200 V. The electrolysis time is 3 minutes to minutes. The electrolyte is not particularly limited. Preferably, it contains sulfuric acid, phosphoric acid, chromic acid, oxalic acid, malonic acid, sulfamic acid, and the like. One type or two or more kinds of acidic electrolytes are used. When the electrolyte is used, the electrolyte concentration is preferably 〇2 m〇l/^1 m〇l/L, and the liquid temperature is 10 °C to 80 〇. C, current density is 0.05 A / cm2 ~ 〇. 3 〇 A / cm2, and the voltage is 3 〇 v ~ 150 V. The anodized film preferably includes a barrier layer portion and a porous layer portion, and the porous layer portion is at room temperature Generally, the barrier layer has a compressive stress. The porous layer has a tensile stress. Therefore, in a thick film of several μm or more, the entire anodized film is known to be a tensile stress. On the other hand, the above-mentioned coated material is used. When a heat treatment such as described later is carried out, a porous layer having a compressive stress can be produced. The thick film of several μm or more can also be used as a compressive stress in the entire anodized film, and cracks are not generated by the difference in thermal expansion at the time of film formation, and the long-term reliability in the vicinity of room temperature can be excellent. Insulating film. 20 201242038 The size of the above-mentioned compressive strain is preferably 〇〇1% or more, particularly preferably 0.05〇/〇 or more, particularly preferably 〇1〇% or more, and 0.25% or less. If the compressive strain is less than 0.01%, there is a compressive strain, but it is insufficient. In the final product form, the temperature is circulated for a long period of time, or the anodic oxide film formed as an insulating layer is cracked due to external external conditions. On the other hand, if the compressive strain is too large, the anode oxygen is generated by applying a strong compressive strain to the anodized film to cause cracking, or the second == the film is raised, and the flatness is lowered or peeled off. The insulating property is degraded. Therefore, the compressive strain is preferably 0.25% or less. = 'The Young's modulus of the anodized film is known to be about 5 〜 15 〇 mpI. Therefore, the magnitude of the above-mentioned compressive stress is higher. After 5 MPa to 300 anodic oxidation treatment, heat treatment can be performed = the anodic oxide film is given a compressive stress, and the crack resistance is "high. Because the plate is absolutely improved, it can be more suitably used as a substrate with an insulating layer. Heating When the treatment temperature is preferably b ^, it is preferably 30 cents; row; = 2 heat treatment, which can reduce the 'knife can' and the insulation property contained in the porous anodization. 3〇〇. The substrate of 1^!^吕 has the following problems: If the heat treatment on the crucible is performed, the function of the wire plate is lost, 21 201242038 1 2, _pif or due to the difference in thermal expansion coefficient between aluminum and anodized film, Cracks are generated in the anodized film, and insulation is lost. However, by using a coating material of aluminum and a dissimilar metal, heating can be performed at a temperature of 300 ° C or higher. The anodized film is an oxide film formed in an aqueous solution and retains moisture inside the solid, and is known, for example, in Chemical Letters, Vol. 34, No. 9 (2〇〇5), page 1286 (Chemistry Letters Vol. 34, No. 9). , (2005)

Pl286)". By solid-state magnetic resonance (NMR) measurement of the anodized film similar to this document, it was confirmed that the moisture content (OH group) inside the solid of the anodized film when heat treatment was performed at 10 ° C or higher. Reduction, especially at 2 〇 (the rc or more is significantly reduced. Therefore, it is presumed that by heating, the bonding state of A1_〇 and A1_〇H changes, and stress relaxation (annealing effect) is generated. In addition, the anode of the inventor et al. It is known from the measurement of the amount of dehydration of the oxide film that most of the dehydration is generated at room temperature of ~3 〇〇<t. In the case where an anodized film is to be used as the insulating film, the amount of water contained is overnight. Since the insulation property is lowered, the step of heat-treating at 300 C or more is extremely effective from the viewpoint of improving the insulating property. By using a coating material of a dissimilar metal as a substrate, and heat treatment of 3 〇 or more The combination 'y effectively exhibits an annealing effect, which achieves a high compressive strain that cannot be achieved by the prior art, and a small water content. Thereby, it is possible to further provide high insulation reliability. The substrate for the photoelectric conversion element has a thickness of preferably 3 μm to 50 μm from the viewpoint of electrical insulating properties, and has a film thickness of 3 μm or more, which can achieve both insulation and temperature. The heat resistance at the time of film formation due to the compressive stress is 22,420,38, and the long-term reliability. The film thickness is preferably 5 or more and 20 μm or less. When the film thickness is 5 μm or more, the gas insulation is excellent. Operation day ^ . ^ Prevention of electricity lies in: due to the thin film thickness, the increase in the anode oxygen u 'becomes the starting point of the crack and is prone to cracking: == : metal precipitates in the anodized film from metal impurities: ;: 3, η metal oxide, _ _ effect is relatively increased, and the = ϊΞ ϊΞ 氧化 氧化 氧化 氧化 在 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化In the case where the film is used as a heat-resistant substrate, or by a roll pair, when the film thickness is too thick, the drawability is lowered, and the cost and time required for the film are lowered, which is not preferable. In addition, bending resistance = or heat should The decrease is due to the decrease in the bending (four) property. When the anodized film is bent, the tensile stress of the surface and the interface is increased. Therefore, the stress distribution in the cross-sectional direction is increased, and local stress concentration is likely to occur. Thermal strain resistance. The reason for the decrease is presumed to be due to the fact that when the tensile stress is applied to the anodized film by the thermal expansion of the material, the larger the interface between the two and the second is, the larger the stress distribution in the cross-sectional direction increases, and the ς is generated. Local stress concentration. As a result, if the anodized film exceeds 5, the strain or thermal strain resistance is lowered, so it is not suitable for use as a chargeable 23 201242038 ΗΖ.ΔΟ / pif financial substrate, or by comparison The manufacture of rolls. In addition, insulation reliability is also reduced. The film thickness of the key electrode 4〇 is not limited to about nm to 1 〇〇〇 nm. The photoelectric conversion semiconductor layer 50 is a compound semiconductor-based photoelectric conversion semiconductor layer as a main component (the main component means a component of 2 G% by mass or more), and is particularly limited in terms of obtaining high photoelectric conversion efficiency. Element (chalc〇gen) compound semiconductor, compound semiconductor of chalcopyrite structure, compound semiconductor of defective stannite type structure. The chalcogen compound (compound containing S, Se, Te) is preferably: II-VI compound: ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, etc.; Group I-III-VI2: CuInSe2, CuGaSe2, Cu (In, Ga) Se2, CuInS2, CuGaSe2, Cu(In, Ga)(S, Se)2, etc.; I-III3-VI5 group compound: CuIn3Se5, CuGa3Se5, Cu(In,Ga)3Se5 and the like. The chalcopyrite type structure and the compound semiconductor of the defective yellow tin type structure are preferably: I-III-VI2 group compound: CuInSe2, CuGaSe], Cu(In, Ga)Se2, CuInS2, CuGaSe2, Cu(In, Ga (S, Se) 2 and the like; I-IIIrVI5 compound: CuIn3Se5, CuGa3Se5, Cu(In, Ga)3Se5 and the like. 24 201242038 Wherein the above description, (In, Ga), (S, Se: ^1e* (InixGax:), (Sl-ySey) (where 'Χ=〇~1, y=〇~1). The film formation method for converting the semiconductor layer is not particularly limited. For example, in the film formation of a Cl (G) S-based photoelectric conversion semiconductor layer containing Cn, In, (Ga), or S, a deuteration method or a multi-distillation may be used. The film thickness of the photoelectric conversion semiconductor layer 50 is not particularly limited, but is preferably 1.0 μm to 3.0 μm, and particularly preferably 1.5 μm to 2.0 μm. The buffer layer 60 is not particularly limited. Cds, ZnS,

Zn(S,0;^^Zn(S,0,0H), SnS,Sn(S,0;^^Sn(S,0,0H),

InS, In(S,0) and/or ln(S,〇,〇H) and the like are selected from Cd, Zn, Sn,

The film thickness of the metal sulfide layer 40 of at least one of the metal elements in the group of In is preferably 1 〇ηηι 2 2 ηι, more preferably 15 Å to 2 透光 trace transparent conductive layer (transparent electrode) 70 It is a layer that functions to take in light and to function as an electrode through which the lower electrode 4G flows as a current for generating the photoelectric conversion layer 5Q. The composition of the conductive layer % of the translucent layer is not particularly limited, and k is preferably η·Ζη() such as ZnO: A1 or the like. The film thickness of the light-transmitting conductive layer 7 is not particularly limited, and is preferably 50 nm to 2 Å. The upper electrode (gate electrode) 8G is not particularly limited, and examples thereof include A1 and the like. The film thickness of the upper electrode 8G is not particularly limited, but is preferably q′′ to 3哗. Inventive Photoelectric Conversion Element In other respects, the main constituent t of the photoelectric conversion semiconductor is a compound semiconductor containing a group element, a group IIIb element and a group VIb conductor, and a photoelectric conversion half and a potassium ion-cutting material. With sodium ions. It can also contain the content of each of the lumps, potassium ions and nano ions contained in the photoelectric conversion semiconductor layer of 201224038. (4) The content of ions above lxl()i5 atms/em3 is preferably dip (10)-~lxl()2Q Atms/em3 & good is 2xl018 atms/cm3~lxl02〇atms/cm3, especially 5_18 atms/cm3~1 χ 1 〇2〇atms/cm3. The content of lithium ion or potassium ion is preferably lxl 〇 15 - sW 〜 5 x 1 〇 19 atms / cm 3 , more preferably 1 χΐ〇 16 _ know 3 〜 5 x l 〇 19 atms / cm 3 , especially preferably lxl 〇 17 atms / cm 3 ~ 5χΐ〇ΐ9 atms/cm3 钟 The photoelectric ions or potassium ions and nano-ions contained in the photoelectric conversion semiconductor layer can be shared by the photoelectric conversion semiconductor layer, or the NaF, LiF, KF can be vapor-deposited on the Mo electrode in advance. Such as fluoride and so on. Further, a photoelectric conversion semiconductor layer may be formed on the Mo film of a Na or Li or K, or a compound containing Na戋Li or κ may be deposited after the photoelectric conversion semiconductor layer is formed to perform post-annealing. Alternatively, the molybdenum electrode 4 may be penetrated from the alkali supply layer 3 by using the photoelectric conversion element substrate with the molybdenum electrode and the second embodiment of the photoelectric conversion element substrate with the molybdenum electrode in the first aspect. And spread. The substrate for a photoelectric conversion element of the present invention can be preferably used for a solar cell or the like. A solar cell can be fabricated by mounting a cover glass, a protective film, or the like on the photoelectric conversion element 1 as needed. Hereinafter, the substrate for a photoelectric conversion element of the present invention will be further described in detail by way of examples. Example of the first aspect (preparation of the substrate) 26 201242038. As a substrate, a 3 cm square non-glass substrate (used in Example i, Example 7 and Example 32) and a SUS43 substrate (thickness 1 〇〇 (4)) were prepared. Example 2, Example 5, Example 8, Example 25, Example 27, Comparative Example, Comparative Example 5, Comparative Example 6, and Comparative Example 8), anodized substrate (examples other than the above, and comparative example 2, t匕Example 3, Comparative Example 4, and Comparative Example 7 were used). The anodized aluminum substrate was produced by the following method. A coating material comprising aluminum having a thickness such as μηι and SUS43〇 having a thickness of 10〇4111 was anodized using a oxalic acid electrolyte under a constant voltage of 40 V to prepare a substrate on which an anodized aluminum having a surface of 1 μm was formed. . (Preparation, Examples, and Comparative Examples of Coating Liquid) A lithium supply source (manufactured by Nissan Chemical Co., Ltd., trade name: lithium niobate 45, lithium niobate 75, lithium hydroxide) and a potassium supply source (manufactured by Fuji Chemical Co., Ltd., trade name: 1 potassium citrate, potassium citrate), sodium supply source (manufactured by Showa Chemical, product name No. 1 sodium citrate, sodium citrate No. 3; and manufactured by Tosoh Industries, trade name ^ No. 4 Table 2 and the water are respectively added in the mass ratio shown in Table i and Table 3, and further, boron or sodium tetraborate as a boron supply source and phosphoric acid as a phosphoric acid source are added as shown in Table 2. The mass ratio is mixed to prepare a coating liquid. The coating liquid was dropped on the substrate, and an alkali metal silicate layer was formed by spin coating. Then, the substrate was knives and processed at 45 〇〇c. After the heat treatment, M 厚度 having a thickness of 8 〇〇 nm was formed on the substrate by direct current (dc) sputtering. (Mo filming property evaluation) ^ The amount of impurities on the surface of Mo on the alkali metal silicate layer formed above was observed with an optical microscope, and the amount of foreign matter was observed. The micrographs of Example 27 20124203 8f /pll 9 and Comparative Example 1 are shown in Fig. 3. In Example 9, no foreign matter was observed, but in Comparative Example 1, 1 丄 foreign matter was observed every i mm square. The microscope observation was carried out in the same manner as in the other examples and the comparative examples, and the price was shown in Tables 1 to 3 based on the number of foreign matters per square meter. AA: No foreign matter was observed. A: The foreign matter is one or more and less than one. B: The foreign matter is one or more and less than one. C: 10,000 or more foreign substances. (Production of Solar Cell) A CIGS solar cell was formed on the Mo electrode. Further, in the present example, a granular raw material of high-purity copper and indium (purity of 99.9999%), high-purity Ga (purity of 99.999%), and high-purity Se (purity of 99.999%) was used as a steam source. A thermocouple (chr〇mei_aiUmel thermocouple) was used as a substrate temperature monitor. The main vacuum chamber was vacuum-exhausted until l〇-6 Torr (1.3×10 −3 Pa), and then the evaporation rate from each evaporation source was controlled, and the film thickness was formed under the film forming conditions of the highest substrate temperature of 530 〇C. 1·8μηι CIGS film. Then, a solution growth method was used to deposit a CdS film of about 90 nm as a buffer layer, and a Zn〇: A1 film of a transparent conductive film was formed by DC 贱. Finally, an A1 gate electrode was formed by a steaming clock method to serve as an upper electrode, thereby fabricating a solar cell unit. (Measurement of power generation efficiency) The solar cell (area 0.5 cm2) produced is irradiated with air quality.

201242038 X-ray (Air Mass, AM) =1·5, 100 mW/cm2 of simulated sunlight, measuring energy conversion efficiency. For the photoelectric conversion elements of the examples and the comparative examples, eight samples were prepared. The photoelectric conversion efficiency was measured for each of the photoelectric conversion elements under the above conditions, and the most southmost value was used as the conversion efficiency of the photoelectric conversion elements of the respective examples and comparative examples. Further, the coefficient of variation (a value obtained by dividing the standard deviation of 8 cells by the average value) was evaluated as the efficiency unevenness of the cells. (Measurement of sodium concentration) The photoelectric conversion elements (CIGS layers) were measured for the photoelectric conversion elements of the examples and the comparative examples. The sodium concentration was measured using a secondary ion mass spectrometer (SIMS). The primary ion type used for the measurement was set to Cs+, and the acceleration voltage was set to 5.0 kV. The nano-length in the photoelectric conversion layer (CIGS layer) has a distribution in the thickness direction, and is integrated to derive an average value, which is used for the evaluation of the sodium concentration. The measurement results of the Mo film forming suitability, the sodium concentration, and the power generation efficiency are shown in Table 1, Table 2, and Table 3 together with the formulation of the coating liquid, and the sodium supply source and the supplied source used in the examples and the comparative examples. The mass ratio of the potassium supply source is not in Table 4, Table 5 and Table 6. The molar ratios of Table 1, Table 2, and Table 3 are values obtained by converting the mass ratio into a molar ratio (in addition, sodium hydroxide and lithium oxide are solids). Further, the sum of the molar ratios in Table 1 was calculated by numerically calculating the molar ratio of the clock or the unloading phase to the molar ratio of strontium and the molar ratio of sodium to strontium to the third decimal place. 29 201242038 JUZ-oo(N(N inch bucket Id variation coefficient (%) (Ν mv〇m ν-» VO ro P; v〇ΓΛ ON mo P; 00 m 〇\ m oo m 〇\ m ON m ON m 00 ΓΛ ON m ν〇m Power generation efficiency (%) rn 丨_H CO rn yri 9 ·Η CN CO CO <N rn CO (N Tf inch cn v〇CN oo ΓΟ 00 inch cn CO (N inch cn ΓΠ <n rn rH rn 寸 CO T·^ ^ IJ 4? J1 〇〇o X DO o XM o X 30 o X oo 〇X DO o X OO o X DO o X eo o X DO 〇X f— 00 o X 30 o X oo ο X OO 〇X 00 〇X OO 〇X OO Ο »—Η X 00 〇X ao o X 30 Ο X DO Ο T-* X 00 o X Na concentration [atms/cm3] 2χ1019 2xl019 | 2X1019 I 1 3xl019 J o X 3xl019 1 2xl019 IO' 〇X (N 2xl019 2χ1019 2xl019 2χ1019 2χ1019 9\ o X m 2xl019 I 2X1019 2xl〇19 2xl019 I 2xl019 2xl019 2χ1019 2xl019 〇智恕< 5 << 5 ί << lt 5 ί < Mo Erbi and d 00 〇o ο o VO v〇〇<n 〇VO CO oo CN 〇WJ fS VO o yn v〇ov〇VO ov〇(N Ο Γ〇i〇Ο VJ d Ο 〇\ d On fNj Na/Si o On m 〇d ο oo κη d ζι 〇O inch o 00 cs oogo κη 〇ο fS VO ov〇v〇o 〇m fN ο CN CN 〇On 〇沄ο g ο o Li/Si or K/Si (N 〇00 ogdg ο v〇o <N 〇o CM &lt ;N 〇oooo 〇cs o Ό CN soo JO d ο m O s 〇ο s ο (N <N ^ ΦΊ 3 On o | 3.333 CN inch ro CN m (N 卜 om ΓΟ CN CN CN rn clock supply source ^ ΦΊ S (N v〇(N d (Ν Ο 黩 黩 <N .CN 龆(N if.lJ <Ν 氢氧化 氢氧化 锂 供给 供给 供给 供给 o o o o o o o o o o 00 00 00 00 00 00 00 00 00 00 CN 〇JN d Lithium silicate lithium niobate 45 Lithium niobate 45 Lithium niobate 45 Lithium niobate 45 Lithium niobate 45 1 Lithium niobate 45 1 Lithium niobate 45 Lithium niobate 45 Lithium niobate 45 I Lithium niobate 45 Hydrogen Lithium oxide hydroxide chain lithium niobate 45 lithium niobate 45 lithium hydroxide sodium supply j ΦΙ μ oo 00 oo CN 00 00 (N ΓΛ O ο Ο oo ο in inch inch Ο 骚想mm inch inch iSs m inch hydride i Μ inch inch inch •hi«3 m 饀m inch inch inch inch inch ear ear|example 2 I 1 instance 3 1 1 instance 4 1 1 instance 5 1 | example 6 1 instance 7 | example 8 1 instance 9 1 1 instance i〇I 1 instance li instance 12 1 instance 13 I j instance 14 I | example 15 | example 16 1 instance 17 I instance 18 1 instance 19 I 1 instance 20 1 1 instance 21 1 instance 22 oe 201242038 [( Nd Ji^ooCNCN inch

v〇ΓΟ inch\〇 inch yr) m CN 〇\ CN οο l®1 ^ Co tri Ο) cs Ο) Ui rn <N CN inch·—— Η 寸 inch·inch· — cn 甸 转 I ^ g 00 〇 X ixio18 [χΙΟ18 Χίο18 Χίο18 χΙΟ18 xlO18 xlO18 XlO18 χΙΟ18 χΙΟ18 J ^ 1 t " 1 σ\ 3\ ο 〇\ Ο £ ο 〇Ν Ο r»·* Ο 9\ o 〇N o σ\ Ο Ον Ο 〇\ Ο 4 1 <-* Λ X <Ν X cs X (Ν X <Ν AX CN X cs X CN X <Ν <<<<<ζ<d<d< ς <ς <<〇<<<<< 00 ^Ti 00 m οο ΟΟ ιη 00 u-><N ι〇(NV〇00 l〇00 yn 00 ι〇00 € S ο d Ο Ο Ο Ο dod ο ο Moerby CO σ\ m On cn σ\ CO 〇\ ΓΟ Ον CO Qj rjj ON m 〇\ m σ\ ΓΟ 〇\ m 2 do Ο Ο Ο c> 〇〇ο ο 00 00 00 00 00 00 00 00 〇〇〇〇O »—H o tH ο Ο τ—^ ο ooo Ο ο Ο J ®HS oo ο Ο Ο W*J o 〇ο Ο Ο Phosphate ^ * Μ (Ν Ο S ο CN| o 0.001 ^―« Ο ο Si Sodium Sodium ^ ® w 2 r4 ci Boron Adding amount [g] inch dd CN d 0.001 0.006 φή -3⁄4 3 inch inch crowded window _ -§ 2 痪oo ^H ο Ο ο o VH ο 2 ο φ| Name S oo Ο ο ο v〇VO o » —H ο ο ο m cs iT) CN ν〇CN 00 CN 〇\ CN Pi m cn Military leather ζ ζ %ί m %: %: ίΚ IK IK 201242038 JUZ.O0CSCN inch [e崦] Coefficient of change (% ) ^T) I〇Qj 9 σ; Power generation efficiency (%) oom O On ο ο ο 00 〇 ο Li concentration or K concentration [atms/cm3] CO o X 〇〇"o X 〇〇Id X 00 "o X 1 1 > I Na concentration [atms/cm3] 1 1 1 1 2χ1019 〇\ "〇X 00 *〇X 00 00 "ο cough±i 1谳边ΐ ί u 〇U ffl M- The sum of the two is JO 〇〇00 On do Os 00 ο νο 〇tr> Ο Ο Na/Si 1 1 1 1 ON 〇〇ο \〇〇<η ο g ο Li/Si or K/Si JTi 〇〇〇 〇On 〇O 1 1 1 1 j S in cs o ΙΛί CN Potassium supply source j — s **N Push! ® <N lithium supply source φ| 33 皓JO o .im.t lithium niobate 45 lithium niobate 75 sodium supply j «w S in 鞔糇ψ^4 m Μ inch η y. Comparative example 1 Comparative example 2 |Comparative Example 3 Comparative Example 4 1 Comparative Example 5 Comparative Example 6 1 Comparative Example 7 Comparative Example 8 ζ ε 201242038 [Table 4] Kind of mass ratio of nano supply source Si〇2 Na20 Moisture No. 1 37.0% 17.0% 46.0% No. 3 29.0% 10.0% 61.0% No. 4 23.9% 6.3% 69.8% Gao Er Er 14.8% 0.6% 84.7% [Table 5] Lithium supply source type mass ratio Si02 Li20 Molybdate lithium niobate 45 20.1% 2.3% 77.7% Tannin 75 20.5% 1.4% 78.1% [Table 6] Kinds of mass ratio of potassium supply source Si〇2 K20 Moisture No. 1 28.7% 22.0% 49.3% No. 2 20.9% 9.0% 70.1% As shown in Table 1, there is a tannic acid Examples 1 to 10 of the alkali metal silicate layer of lithium or potassium citrate and sodium citrate were compared with Comparative Example 5 to Comparative Example 8 as a metal citrate layer containing only sodium citrate. Near double the power generation efficiency. In these examples, it is considered that the sodium concentration is approximately equal to that of sodium diffusion of CIGS sufficiently; however, the stealing ratio of the impurities of Comparative Example 5 to Comparative Example 8 is considered to be high, thereby causing low power generation efficiency. w ^ 2 ^ is the ratio of the metal (4) salt layer containing only the gift clock, the father's column 2, the alkali metal citrate layer 33 containing only potassium citrate, and the comparative example 3 and the comparative example of 201242038 - ΤΛΑυ / _pif In 4, although the film forming suitability of bismuth is good, since the sodium citrate is not contained, the power generation efficiency is as low as nearly 30% compared with the example. It is considered that since sodium is not present in the alkali metal ruthenate layer, sodium is not diffused in the CIGS, and the efficiency is not improved. From this, it is understood that the power generation efficiency can be greatly improved by using lithium niobate or potassium niobate in combination with sodium citrate. Example 11 used sodium hydroxide instead of sodium citrate as a sodium supply source, and lithium niobate was used in combination. Further, in Example 12 and Example 13, lithium hydroxide was used instead of Shixia I as the source of supply ‘and the use of sodium silicate. In this case, the metalloate salt to be treated also becomes a mixture of the sodium alginate and the acid clock of the present invention. Among them, the example 11 has a film forming suitability and a slightly lower power generation efficiency than the example 丨 to the example 10. The reason is considered to be that the sum of the molar ratio of lithium relative to lanthanum to the molar ratio of sodium to yt is greater than i. In addition, Example 13 was slightly inferior in power generation efficiency as compared with Example J to Example 10. The reason is considered to be that the molar ratio of the clock to the cymbal is greater than one. Fig. 2 is an electron micrograph of the CIGS crystal of Example 4, Comparative Example 1, and Comparative Example 5. In the example 4 of the substrate for a photoelectric conversion element of the present invention, the particle diameter of the CIGS crystal was larger than that of the comparative example 1, and the effect of alkali addition was confirmed. In Comparative Example 5, the particle size was large, and the effect of alkali addition was confirmed, but the conversion efficiency was low. The reason for this was that the Mo film-forming suitability was low, and impurities were formed at the Mo/CIGS interface. Examples 14 to 19 changed the amount of addition of the sodium supply source, the lithium supply source, and the potassium supply source. According to these examples, the range of the molar ratio of the clock or the discharge to the stone eve is 1 or less, and the range of lithium relative to the molar ratio of yttrium to yttrium relative to lanthanum 34 201242038 and the range below 丨, Shows better power generation efficiency. The power generation efficiency seems to be better than that of the case where no alkali phosphorus is contained. However, since the coefficient of variation is small, the power generation of the entire unit has 111 power generation efficiency, and the generated + main is known. — The power generation efficiency in Example 4 is low. On the other hand, as shown in Table 1, ι: '❺& contains 1 ^ ion or κ ion in addition to 1 ^ ion, and the power generation efficiency increases. When Li ion or κ is contained, Comparative Example 5 of Na ion is compared with an example having the same % ion concentration and = 3 Li ion or κ ion, it is understood that Li ion = ion is lower than Na ion. Even if the cesium ion or the κ ion is present, the presence of the 'Ll ion or the cesium ion greatly contributes to the improvement of the photoelectric conversion efficiency. Example of the second aspect (preparation of the substrate) As the substrate, a glass substrate of 3 cm square, a SUS43 substrate (thickness: 100 μm), and an anodized substrate were prepared. The anodized substrate is produced by the following method. The coating material of SUS430 having a thickness of 30 μm and a thickness of 5 Å was anodized using an oxalic acid electrolyte under a strange voltage of 4 〇ν to prepare an anodized aluminum having a surface formed with 1 G 哗. Substrate. (Formation of alkali metal silicate layer and Mo electrode) 35 201242038 HZZO /pif Lithium niobate (manufactured by Nissan Chemical Co., Ltd.: lithium niobate 45 (Si〇2: Li2〇: water = 20.1%: 2.3%: 77.7%) ), potassium citrate (made by Fuji Chemical Co., Ltd.): No. 2 potassium citrate (Si02: K2 〇: water = 20.9%: 9.0%: 7〇1%)), sodium sulphate (made by Showa Chemical: No. 3 citric acid) Sodium (SiO 2 : Na 2 〇: water = 29 〇 % : 10.0% : 61.0%)), boric acid, sodium tetraborate decahydrate, disc acid (85 〇 / 〇 solution), water shown in Table 7 and Table 8, respectively The mass ratio is mixed to prepare a coating liquid. The coating liquid was dropped on the substrate, and a metal silicate layer was formed by spin coating. Then, the substrate was heat-treated at 45 (TC) for 30 minutes. After the heat treatment, Mo was formed to a thickness of 8 Å on the substrate by DC sputtering. Further, Comparative Example 3 was not coated because the coating liquid was cured. (Evaluation of Surface Properties of Mo) The amount of foreign matter was observed on the surface of the M〇 surface on the alkali metal niobate layer formed as described above using an optical microscope, and the amount of foreign matter was observed. The micrographs of Example 9 and Comparative Example 1 are shown. In Fig. 4, no foreign matter was observed in Example 9 but 10,000 or more foreign bodies were observed per 1 mm square in Comparative Example 1. = Microscopic observation was performed on other examples and comparative examples (4) 'Based on every 1 mm square The number of the foreign matter was evaluated based on the following criteria and is shown in Tables 1 and 2. AA: No foreign matter was observed A. The foreign matter was one or more and less than one. B · The foreign matter was 10 or more and less than 100. C. Foreign matter is more than 10. (Production of solar cell) 36 201242038 A CIGS solar cell is formed on the Mo electrode. In addition, in this example, the purity to copper and indium (purity of 99.9999%) is used. Purity Ga (purity 99.999%), high purity A granular raw material of Se (purity 99 999%) is used as a steaming clock source. A chrome-nickel nickel thermocouple is used as a substrate temperature monitor. The main vacuum chamber is evacuated until 3xl 3.3Pa). From the evaporation rate of each evaporation source, an aGS film having a film thickness of about 18 μm was formed under the film formation conditions of the highest substrate temperature of 530C. Then, a Cds film of about 9 〇 nm is deposited as a buffer layer by a solution growth method, and a thickness of the ZnO: Α1 film is formed by a DC 贱 贱 method. Finally, an A1 is formed by vapor deposition. The solar cell is fabricated by using the gate electrode as the upper electrode. (Measurement of power generation efficiency) The solar cell (area G 5 em2) to be produced is irradiated with air mass (AM) = 1.5, 100 mW/cm2. Simulated sunlight, measurement, and mass conversion efficiency. For the solar power of the example and the comparative example, eight ## products were separately produced. For each solar cell unit, the electrical conversion efficiency, the standard deviation of the shirts of the service and (4) were divided by the average. The value obtained by the value) The conversion efficiency of the solar cell of the early solar cell and the measurement result of the enthalpy efficiency of the comparative example were taken as M. The surface evaluation is shown in Tables 7 and 8 together with the formulation of the coating liquid. The molar ratio is a value obtained by converting the mass ratio into a molar ratio*. 37 201242038 J-a Bu OOCNCN inch

LI unit efficiency wi r<i ΓΟ ΓΟ m ΓΛ inch rn rn cn cn to rn inch cn ΓΟ m Ο) inch · <N ♦μ 〇\ rn CO rM cs coefficient of variation (%) 〇〇\ 〇\ On CO Pi 00 (N CN CN m inch inch foreign object number 5 ί < CQ < m < ΐ 5 5 ί ί Moer than adding ion / Si 0.0667 0.0167 0.0109 0.0224 0.0045 0.0002 0.0017 0.0001 0.0018" 0.0788 0.0197 1 0.0128 | 0.0265 1 0.0053 0.0238 1 0.0468 Adding amount [g] o 〇ο 〇〇*—η o ο oo ο ο ο o ο o Boron and phosphorus supply source φΐ -3⁄4 3 咚 inch o 〇<Ν Ο JQ d S 〇0.001” Oo 0.001 so inch ο »-Η Ο CS ο (N 〇S ο cs o (N 〇乡草 f 四棚酸纳十hydrate锊湓锊齐荸盘 W 四棚酸纳十hydrate W potassium source added Quantity [g] inch d* $ S CN (N lithium supply source φή times ο ο ο Ο ο S throw 1 lithium niobate 45 1 lithium niobate 45 1 lithium niobate 45 lithium niobate 45 lithium niobate 45 sodium supply j ®w S ο ο ο Ο Ο νο v〇菜ΓΟ mm 糇ΓΟ CO CO CO m m Ss m if.lJ 5fe m ifltJ m 龋m remainder m if.* J age anodized aluminum anodized aluminum anodized anodized aluminum anodized aluminum anodized aluminum 00 P anodized aluminum C/5 DC/3 | 2 I Example 3 | Example 4 I Leather 1 Example 6 I 1 Example 7 I 00 | Example 9 I | Example 10 1 Example 11 Example 12 1 Example 13 Example 14 | Example 15 1 1 Example 16 se 201242038 J?re8z (N inch Unit efficiency| <N $ Ο — τ~Η q — >~·Η — ΓΟ 〇6 ΓΟ Coating solution solidification | Coefficient of variation (%) m CN 〇\ 00 Oj ν〇cn Number of foreign objects PQ PQ < 〇U Moerby added ion/Si | 0.0002 I 0.0012 | o.oooi | 0.0011 0.0000 1 o.oooo 1 0.1590 S 疫 o ο O 〇iT) Bu 〇〇 〇〇 boron · Phosphorus supply source φ| and S dark o .ooi | 0.006 | o.ooi | 〇〇use hot aoul w 荸 钾 钾 钾 缌 缌 缌 缌 缌 缌 缌 缌 缌 缌 缌 缌 缌 缌 缌 缌 缌 缌 缌 缌 45 45 矽 45 45 45 45 45 45 45 45 45 45 Lithium niobate 45 lithium niobate 45 lithium niobate 45 lithium niobate 45 sodium supply _ 矣2 痪o Ο Ο 〇Ο 〇m .Ifni! beam m if.tJ m if.O age mmmm anodizing in Lu anodized alumina anodizing Ming anodizing is If 1 1 instance π Example 18 1 Example 19 | Example 20 I Comparative Example 1 1 Comparative Example 2 1 Comparative Example 3 201242038 /pif As shown in Table 8, in Examples 1 to 20 to which boron or scale was added, 'compared with Comparative Example 1 and Comparative Example 2 to which no boron or phosphorus was added, foreign matter on the surface of Mo was greatly suppressed. In Comparative Example 比较 and Comparative Example 2, the foreign matter density on the surface of M〇 was high, and a partial short circuit between the lower electrode of Mo and the upper electrode was generated, or the interface resistance of the Mo electrode and the CIGS photoelectric conversion layer in the vicinity of the foreign matter was improved, and therefore it was considered that The power generation efficiency is low and not large. In the case of the example 10 to the example 5, the surface property of the crucible is improved, the power generation efficiency is higher, and the unevenness is also increased.

St in == to improve power generation efficiency by moving things or qing qing. In addition, the example: the ear ratio is reduced, the example two: Example 4 or Example 13 reduces boron or 疋 疋 11 11 11 11 11 , , , , , , , , , , , , , , 兔 兔 兔 兔 兔 兔 兔 兔 兔 兔 兔 兔 兔 兔 兔 兔 兔 兔 兔 兔 兔 兔The foreign body of the heart is more preferably the relative molar ratio of _2^ 闽 间 间 】 】 】 】 】 】 : : : : : : : : : : : : : : : 图 图 图 图 图 图 图 图 图 图 图 图 图 图 图 图 图 图 图Change the photoelectric conversion of the photoelectric conversion electrode of the substrate with a few pieces. (4) Outline profile of the form of the application

Figure 3 is an electron micrograph of Example 4, Comparative Example of the first aspect. And CIGS of Comparative Example 5 Fig. 4 is an example of the second aspect called 1 (four). Surface light 201242038 —...t—Learning a microscope photo. [Major component symbol description] 1 : Photoelectric conversion element 10 : Substrate 20 : Anodized film 30 : Metallurgy > 5 酸 酸 layer 40 : Molybdenum electrode 50 : Photoelectric conversion semiconductor layer 60 : Buffer layer 70 : Translucent conductive Layer 80: upper electrode 41

Claims (1)

201242038 *tz,^o iyif VII. Patent application scope: 1. A substrate with a (four) pole (four) electrical conversion element, characterized in that it comprises: a 2-electrode conversion substrate, and a packet-cut acid clock laminated on the substrate Or an alkali metal citrate layer of potassium I and sodium citrate; and a flip electrode laminated on the above metal oxide layer. 2. The substrate for a 0-piece electrode according to the above-mentioned patent application, wherein the alkali metal tellurite layer has a molar ratio of potassium to erbium of 0.001 or more.迚 3·If you apply for the base plate with the = in the second item of the special circumnavigation, the sum of the above-mentioned unloading relative to the above-mentioned two ratios and the above-mentioned nano relative to the above-mentioned shixi is the sum of the molar ratios! the following. The substrate with a replacement component according to the third aspect of the patent application, wherein the metallurgical substrate of the above-mentioned metallurgical compound=the substrate for the component is a rush=, as described in item 5 of the patent scope. A substrate for photoelectric conversion of a molybdenum electrode, wherein the substrate is a metal substrate. The photoelectric conversion substrate with the extraction electrode according to the rtf6 item, wherein the photoelectric conversion substrate 疋 (4), the single steel or the iron 42 201242038 steel plate having the anode oxygen-alternating electrode formed on the surface of the metal substrate is single-sided or ^ The coated material is made of a slab. A 9. The substrate for photoelectric conversion of the remaining electrode described in Item 8 of the patent scope, the anodic oxidation-reducing film of the towel is a porous anodized film, and the domain is well-polarized. Compressive stress. 10. A substrate for a photoelectric conversion element having a molybdenum electrode, comprising: an alkali metal tellurite layer (but not an alkali metal) on the substrate; the alkali metal tellurite layer containing aluminum a group 13 element or a group of elements other than nitrogen, at least one of which is formed by a liquid phase method; and the above-mentioned substrate having a (four) pole for photoelectric conversion unit contains a layer of The above-mentioned germanium electrode on the metal salt layer is examined. 11. The substrate for the replacement of the substrate with a molybdenum electrode as described in the first paragraph of the π patent scope, wherein the group 13 element other than the above or the group 15 element other than nitrogen is boron or phosphorus . </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; Turning the vibration to look at the 12th rhyme (4) (four) pole photoelectric = the substrate for the replacement of the workpiece, wherein the above metal includes the clock or potassium, and _ 2 14. Μ _13 Gu Sui with the extraction of the photoelectric &amp; With a substrate, the total of the group 13 element or the group 15 element other than the above, relative to the above-mentioned broken moir, "15. The substrate, wherein the thickness of the metallization layer of the above-mentioned metallurgical layer is 2, and the substrate for the conversion element of the pin electrode according to the fifteenth aspect of the invention, wherein the substrate is a metal substrate The substrate for a photoelectric conversion element with a * mesh electrode according to claim 16 of the invention, wherein the substrate of the above-mentioned metal substrate is formed in the above-mentioned &amp;&amp;&amp; There is an anode 18. The substrate with a conversion element as described in claim 17 of the patent application, wherein the metal substrate is missing or residual: the early surface of the steel plate or the coated material formed by integrating the aluminum plates on both sides. In the case of the __18 item, the substrate with the f-ary element is In the above-mentioned anodizing, the above-mentioned porous anodized film has a compressive stress. ==* to 9th, 13th to 19th-2, with a 1-mesh electrode On the substrate of photoelectric conversion element 21. 21. Kind of photoelectric conversion element, in the pole, photoelectric conversion semiconductor layer and upper electrode, the main component of the characteristic == contains the family element, the gamma element =, the halogen element to 乂1 a compound semiconductor of a yellow iron ore structure, and the photoelectric conversion semiconductor layer includes a _ sub or a _ sub, and a sodium ion. 22. The photoelectric conversion element according to the patent scope of 5 2! The content of each of the hetero- or the smear and the sodium ion in the half-layer is 1x(8)5/ey or more. 201242038 Λ. A. 23. The photoelectric conversion element according to claim 21 or 22, wherein The clock ions or potassium ions and sodium ions contained in the photoelectric conversion semiconductor layer are supplied from an inspection supply layer formed between the substrate and the molybdenum electrode. 24. For the scope of claim 21, item 22 Or the first magic item, the photoelectric conversion The main component of the photoelectric conversion semiconductor layer is a compound semiconductor containing at least one of the following elements: at least one of the group elements selected from the group consisting of Cu and Ag; and consisting of Al, Ga, and In At least one of the Group VIIIb elements in the group consisting of S, Se, and Te; and 25. The photoelectric conversion element according to claim 24, The substrate is a metal substrate. The photoelectric conversion element according to claim 25, wherein an anodized aluminum film is formed on a surface of the metal substrate. The photoelectric conversion element according to claim 26, wherein the metal substrate is a coating material obtained by integrating one side or both sides of aluminum, stainless steel or iron steel plate with an aluminum plate. The photoelectric conversion element according to claim 27, wherein the anodized aluminum film is a porous anodized aluminum film, and the porous anodized aluminum film has a compressive stress. A solar cell characterized by comprising the photoelectric conversion element according to any one of the items 25 to 28. 45