TW201133512A - Paste composition for electrode and photovoltaic cell - Google Patents

Abstract

A paste composition for the electrode including metal particles having copper as main component, a flux, glass particles, a solvent, and a resin are provided. In addition, a photovoltaic cell having electrodes formed by using the paste composition for the electrode is provided.

Description

201133512 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a paste composition for an electrode and a photovoltaic cell. [Prior Art] A surface electrode is generally provided in a photovoltaic cell, and the wiring resistance or contact resistance of the surface electrode is related to a voltage loss associated with conversion efficiency, and 'the width or shape of the wiring affects the incident amount of sunlight ( For example, 'Recognition of Hiroshi Kawakawa's "The Latest Technology and System for Solar Power Generation," CMC Press, 2001, p26-p27). The surface electrodes of photovoltaic cells are typically formed in the following manner. In other words, the conductive composition is applied to the n-type semiconductor layer formed by thermally diffusing phosphorus or the like on the light-receiving surface side of the p-type germanium substrate at a high temperature, and then applied to the surface by screen printing or the like. C~900. (The surface electrode is formed by calcination, and the conductive composition forming the surface electrode contains conductive metal powder, glass particles, various additives, etc. As the conductive metal powder, silver powder is generally used. However, for various reasons, the industry has studied the use of metal powders other than powders. For example, it has revealed that there are conductive groups that can form electrodes for silver and photovoltaic cells (for example, see Japanese Patent Laid-Open No. 2-6-313744). Interesting another:,

The current publication J 〇 is a precious metal due to the resource problem, and silver which is used for electrode formation instead of silver. Since the raw material metal itself is expensive, it is desirable to propose a 2 3 201133512 composition (silver containing paste). Paste material. As a promising, steel used in a semiconductor wiring material can be cited. Copper is not only rich in resources, but also the cost of raw metal is also silver. However, copper is a material which is easily oxidized at the above-mentioned high temperature. For example, the composition for forming an electrode described in the above-mentioned item 2 is an electrode, and it is necessary to be calcined in an atmosphere such as nitrogen gas. An object of the invention is to provide a paste composition for an electrode which suppresses formation of an oxide film of copper during firing, and which can form an electrode having a low specific resistance, and a photovoltaic cell having a t-pole formed by (10) an electrode material composition. . The first embodiment of the present invention is a paste composition for an electrode, which comprises metal particles containing copper as a main component, a flux, glass particles, a solvent, and a resin. The paste composition for an electrode preferably further contains silver particles. The metal particles mainly composed of copper are preferably selected from the group consisting of phosphorus-containing copper alloy particles, coated with silver particles, and _ selected from the group consisting of triweis, saturated fatty acids, unsaturated fatty acids, inorganic metal compound salts, and organic Metallization = at least one of copper particles obtained by surface treatment of a group consisting of a salt of a salt, a polyaniline resin, and a metal alkoxide. The flux is preferably at least one selected from the group consisting of a fatty acid, a boric acid compound, a fluoride, and a borofluoride. The above glass particles preferably contain an oxide containing phosphorus. A second aspect of the present invention is a photovoltaic cell having the above-mentioned electrode for the electrode on the Dream substrate which is imparted with the composition of the 4 201133512-.•Tai paste composition. The above and other purposes, features and gamma of the invention are more obvious and difficult to _, and in conjunction with the closed type, the tempering is also inhibited in detail:::: by the addition of flux Calcination = £? ===: The following is a description of the embodiments of the present invention. Further, the most T 2: i "~" indicates a range including the numerical values described before and after the minimum value and the dare value. <Paste composition for electrode> The paste composition for an electrode of the present invention comprises: at least one metal particle containing steel as a main component, at least a seed agent, at least one type of glass particle, at least one solvent, and at least A resin. According to the above configuration, the formation of an oxide film of copper is suppressed during firing, and an electrode having a low specific resistance can be formed. (Metal particles containing copper as a main component) The metal particles containing copper as a main component in the present invention (hereinafter sometimes referred to as "particles containing copper") mean that the content of the copper component in one metal particle is 50 mass. More than % of metal particles. 201133512 The copper constituting the copper particles may be a metal other than pure copper, or may be a metal particle composed substantially of steel, and a metal containing copper and a component of oxidizing (4) to copper may be used as the above substance. Metal made of copper

Au, etc. S, T Bu V, %, Ba Bu Xin, W, M〇, Ti, Co, Ni, ^ Gui is Ϊ; Α 1 细 氧 氧 、, dissolved 'material 喊 shouting point, rate example = up = The content of the other atoms contained in the middle may be 3% by mass or less, and from the viewpoint of the low resistivity of the liquid, it is (4) or less by mass%. It is better to use metal particles with a component that imparts oxidation resistance to steel.

Themd A 1 . Simultaneously measuring (in the case of 1 ^ennd Analysis 'TG_DTA), the electrode containing the maximum oxidization at the time of oxidization of M can suppress the formation of a low resistivity electrode.设定#署:敎;' The second time is left in the normal atmosphere, using the heat D (four) set as the test = device (SII Nan, TG / DTA-6200 type). The gy A J system is called the upper-f-shirt; the TGDTA towel indicates the peak temperature of the heat peak of the area. Specific examples of the above-mentioned copper-containing particles 6 201133512 include phosphorus-containing copper alloy particles, silver-coated copper particles, and surface-treated copper particles. The steel-containing particles may be used singly or in combination of two or more. The particle diameter of the steel-containing particles is not particularly limited, and the particle diameter when the cumulative value is 50% (hereinafter, it may be abbreviated as "〇5〇% 〇.4 qing~10 qing" is preferably 1哗~7 division. By setting it to 〇4 μηι or more, the oxidation resistance is more effectively improved. In addition, the contact area of the copper-containing particles of the 2' electrode t becomes larger, and the resistance is increased.

St:: In addition, the particle size of the particles containing copper is squeaked by particle size (manufactured by 曰 Machine Co., Ltd., (4) _ type) (4) The other shape of the above-mentioned granules is scaly, and can be Any of the flat, block, plate, and scaly shapes, in terms of raw and low resistivity, is preferably spherical or flat: copper; the above-mentioned inclusions included in the paste have The total content of copper particles and silver particles is ^1^!^ 7 7 2 contains 72 f *〇/o^9〇t4〇/o, ?4 - copper alloy particles containing lining - quality / 〇. 2 is a phosphorus-containing copper alloy, and a soldering material called a right-handed right is known. • Dip can also be used as steel: degree 201133512 =. Qi] # By using phosphorus-containing copper alloy particles: the shape of the copper-containing particles contained in the shape can form an electrode with oxygen resistance = Γ & Further, the low-temperature calcination of the electrode can be obtained as the monthly b, and the effect of the process cost can be reduced. The content ratio of the filling ratio included in the phosphorus-containing copper alloy in the present invention is the ratio of the heat loss to the peak area of the maximum area. Specifically, the total mass of the copper alloy in (4) is preferably set to °· as the _ content ratio contained in the copper alloy. 1% by mass to 8 mass%, more preferably set. The amount / 〇 ~ 7.8 mass%, and more preferably set to 1 mass. /. ~ 7.5 mass%. The content of the scale contained in the copper alloy containing the dish is 8 mass% or less, and the lower resistivity can be achieved, and the productivity of the copper-containing alloy is excellent. Further, by having a W content of 〇 〇 1% by mass or more, more excellent acid resistance can be achieved. The above-mentioned copper alloy particles contain copper and alloy, but may also be more than 3 other atoms. Examples of the other atom include, for example, %, Si, K Na, Li, Ba, Sr, Ca, Mg, Be, Zn, Pb, Cd, Ή, V, =, A, Zr, W, Mo, Ti, Co. , Ni, Au, etc. In addition, from the viewpoint of adjusting characteristics such as oxidation resistance and melting point, it is preferable to include. Further, the S ratio of other atoms contained in the scale-containing copper alloy particles is, for example, the phosphorus-containing alloy particle towel. The amount can be set to 3% by mass or less, and from the viewpoint of oxidation resistance and low electrical resistivity, the amount is preferably 5% or less. 8 201133512 The particle size of the above-mentioned copper-containing alloy particles is not particularly limited, and the particle diameter is 50% (hereinafter, it is abbreviated as "(10)/, ', preferably 0.4 μιη to 10 qing". _~5(4). The oxidation resistance is more effectively improved by _0.4 (four) or more. In addition, the resistivity is more effectively lowered by the contact of the copper-containing alloy particles in the 'electrode below'. The amount of the phosphorus-containing conjugate is not particularly limited, and may be any of spherical, flat, massive, plate-like, and scaly, etc., from the viewpoint of oxidation resistance and low electrical resistivity. Preferably, the spherical seed is flat or plate-shaped. The filled copper alloy can be produced by a commonly used method = the filled copper alloy particles can be used to achieve the desired dish content = preparation Phosphorus-containing copper alloy, the usual method for preparing metal powder = preparation, for example, 'water atomization method rib money method in metal handbook (Maruzen (stock) publishing division has specific 'for example, phosphorus-containing copper alloy Dissolved, dried by nozzle spray 2, 'drying the obtained powder The classification condition can produce a content ratio of the above-mentioned dish-containing i: gold particles contained in the composition containing the desired particle diameter, and the inclusion of the silver particles included in the present invention. The total content of the copper alloy particles and the silver particles may be, for example, from 0.01% to 94% by mass, from the viewpoint of oxidation resistance and low electrical resistivity. 9 201133512, preferably 72% by mass to 90% by mass, More preferably, it is 74 mass% / 8 mass%. ° 8 In the present invention, the phosphorus-containing copper alloy particles may be used singly or in combination of two or more. In addition, it may be combined with a phosphorus-containing steel alloy. Further, in the present invention, in the present invention, it is preferable that the phosphorus content of the paste composition for an electrode is 0.01 mass in terms of oxidation resistance and low resistivity of the electrode. % to 8 mass% of the phosphorus-containing copper alloy particles, 7 〇 mass%, two pi mass%, more preferably the phosphorus content in the paste composition for an electrode, containing phosphorus, and having a phosphorus content of 5% by mass to 7.5 mass% Copper alloy particles 74% by mass. The coated copper particles _ as the silver-coated copper particles in the present invention may be copper particles coated with a small amount of copper particles, and silver silver particles are used as the present invention. The 2 = sub- included in the compositional towel can form an electrode having excellent oxidation resistance and low electrical resistivity. Particles: 'The interface resistance between the copper particles and the silver particles is 4% in the resistivity of the composition. By using the silver package = L: effect _· can suppress the oxidation of copper at room temperature, and the extraction rate), the _ coating amount (silver content) in the coated copper particles is preferably For example, the thermogravimetry-heat difference is simultaneously measured by the peak of the wave crest (3) cut and covered 201133512

The L body is on the total of the copper particles coated with silver, but the oxidation resistance and the electric_low resistance mass are, for example, 3% by mass to 80% by mass, and more preferably, the mass of the bismuth L is The particle size of the silver-coated copper particles is not particularly limited, and is Ϊ: [4; Γ particle size (hereinafter sometimes abbreviated as "D5 〇 %"), preferably 〇. 4 μιη to 10 μιη, more preferably —~— Above 0.4 μ^η, the oxidation resistance is improved more effectively. Further, the contact area between the copper particles coated with the second rate == becomes a large shape, and the oxidation resistance and the low resistivity are flattened in a flat shape or a plate shape. The phase is preferably spherical, and the copper particles coated with silver can also contain other atoms in the range of the loss = the range of other atoms, such as wealth.

Cd τ; λ Ll, such as, Sr, Ca, 岣, Be, Zn, Pb, = Tl, V, Sn, A1, Zr, w, M〇, Ti, c〇, NiA4. From the viewpoint of adjusting characteristics such as oxidation resistance and melting point, it is preferable that the copper particles coated with silver, which are 0/, and two other atoms contained, can be set to 3 mass/〇 or less. From the viewpoint of oxidation resistance and low electrical resistivity, it is preferably mascara 201133512 or less. Further, it is also preferable that the copper particles coated with silver are a copper alloy coated with phosphorus by silver. Thereby, the oxidation resistance is further improved = the resistivity of the formed electrode is further lowered. The details of the copper alloy containing bismuth in the copper particles coated with silver are the same as those of the scaly copper alloy described above, and the preferred form is also used as the preparation of the silver-coated copper particles. Method, the method for preparing copper-coated copper particles (preferably phosphorus-containing steel: two: = points, there is no particular limitation (or containing copper alloy powder) dispersed in sulfur:: two in the 'then Adding "=== generation:: added copper powder slurry to the copper powder dispersion to form a silver layer on the surface of the copper powder. The acid salt triethyl sulphate and the system can be used as follows: The amine tetraethyl is used as a silver ion solution, pentaacetic acid, imine diacetic acid, etc. Further, for example, a silver nitrate solution or the like can be used for the liquid. Coating ==;; Another paste: Group: Silver coated steel particles and silver particles The total content of 3 after = particle mass ° / °, in terms of oxidation resistance and low resistivity of 2 mass%, more preferably; in the present invention, the above-mentioned silver coated copper particles can be used alone 12 2011335 - The species may be used in combination of two or more kinds of copper particles, and copper-containing particles other than copper particles may be used in combination. ΐ::: The silver in the total mass from the viewpoint of the two low resistivity contains yttrium. The copper particles coated with silver-coated copper particles are 74% by mass to 88%, and the yttrium is coated with silver. In the case of the silver particles of the total ==:4 of the silver particles, it is preferable that the content of the silver contained in the paste composition for the electrode is 1% by mass to 88% by mass, and the phosphorus content is 〇〇1 by mass. The amount of 7g f of the gamma-containing alloy particles coated with silver of % to 8% by mass is ～% by mass to 94% by mass (including the total content of the phosphorus-containing synthons and silver particles of the filaments described below) It is more preferable that the paste composition for an electrode contains silver-containing phosphorus-containing copper having a silver content of 5 mass%, 〇 to 75 mass%, and a phosphorus content of i mass% to 7.5 mass%. The alloy particles are 74% by mass to 88% by mass (the total content of the silver-coated disk-containing copper alloy particles and silver particles when silver particles are described later). • Surface-treated copper particles _ In the present invention The copper-containing particles are selected from the group consisting of triazole compounds, saturated fatty acids, unsaturated fatty acids, inorganic metal compound salts, and organic metals. At least one of a group consisting of a salt composed of a salt of a salt, a polystyrene-based resin, and a metal alkoxide (hereinafter sometimes referred to as a "surface treatment agent") is subjected to a surface treatment of 13 201133512, and the steel particles are excellent. More preferably, copper particles obtained by at least one surface treatment selected from the group consisting of triterpenoids, saturated linoleic acid, unsaturated linonic acid, and inorganic metal compound salts are used by using a surface treating agent. At least the copper particles which have been subjected to the surface treatment can form an electrode having excellent oxidation resistance and low electrical resistivity as the copper-containing particles contained in the hair stylus composition towel. Further, when the moisture is mixed to the electrode When a paste composition towel is used, by using the surface-treated copper particles, the following effects can be obtained: oxidation of copper at room temperature can be suppressed, and the lifespan can be improved. In the present invention, the above surface treatment agents may be used singly or in combination of two or more. In the present invention, the surface-treated steel particles are selected from the group consisting of triazole compounds, saturated fatty acids, unsaturated fatty acids, inorganic metal compound salts, metallization & salts, polyaniline resins, and metal oxide oxides. At least one of the groups of the groups is subjected to surface treatment and other surface treatment agents are used. In the above-mentioned surface treatment agent, for example, benzo-soxadiazole, etc., and as a saturated fatty acid in the above surface treatment agent, for example, can be listed. Work is also lacking and _ j magical. Heptanoic acid, octanoic acid, citric acid, citric acid, undecanoic acid, acid, t triacid, tetradecanoic acid, pentadecanoic acid, stearic acid, nineteen acid, floral acid, etc. Further, as the above-mentioned surface treatment shot, there may be mentioned, for example, acrylic acid, methacrylic acid, crotonic acid, methacrylic acid, oleic acid, oleic acid, whale oleic acid, oleic acid, 201133512 sinapic acid, sorbic acid, linoleic acid, linoleic acid, peanut oleic acid, etc. Further, as the inorganic metal compound salt in the above surface treatment agent, for example, sodium citrate, sodium stannate, tin sulfate, sulfuric acid may be mentioned. Zinc, sodium zincate, cerium nitrate, sodium zirconate, zirconium oxychloride, titanium sulphate, titanium chloride, potassium oxalate, etc. Further, examples of the organometallic compound salt in the surface treatment agent include hard fat. The difference between lead acid, lead acetate and tetraalkoxy zirconium Further, as the metal alkoxide in the surface treatment agent, for example, titanium alkoxide and zirconium alkoxide are exemplified. Examples, lead alkoxides, decane oxides, stannous oxides, indium alkoxides, etc. 々 As other surface treatment agents, for example, dodecylbenzenesulfonic acid, etc., when stearic acid or hard is used, When lead oleate is used as a surface treatment agent, at least a combination of stearic acid and stearic acid (4) and acetic acid (4) as a surface treatment agent can form an electrode having further improved oxidation resistance and lower resistivity. The surface-treated copper particles may be coated with at least one of the surface treatment agents of at least one of the surface of the copper particles. The surface treatment content contained in the surface-treated trainer is preferably 2 thermal masses. In the thermal phase difference, the wave of the heat generation peak having the largest area is at a level of 28 CTC or more. Specifically, it is preferable that the mass of the copper particles treated by the surface is more than or equal to the mass%, and the degree of the chemical property is high. View In particular, it is preferably from 0. 01% by mass to 1% by mass in the surface-treated copper particles, more preferably from 0.05% by mass to 8% by mass based on the mass of the surface-treated copper particles. Copper of surface treated copper particles can also be used without destructive invention 15

201133512 L $effect model _ contains other primitives as other atoms, :sb, Si, K, Na, Li, Ba, Sr, Ca, Mg, BeZnpb:

OiH, Sn, Ab Zr, w, M〇, Ti, c〇, see, and

Au et al. In addition, it is preferable to adjust the oxidation resistance, and it is preferable to include A A and J. In addition, the content of the surface-treated copper particles contained therein is, for example, the surface-treated copper particle towel or mass. In the case of 〇/〇, the oxidation resistance and the low resistivity are 3 to 31% by mass or less. 1 It is also preferred that the gold surface-treated copper particles are also preferably surface treated with the phosphorus-containing copper. Thereby, the oxidation resistance is increased, and the resistivity of the formed electrode is further lowered. The details of the phosphorus-containing alloy in the surface-treated copper particles are the same as those described above, and the preferred type of copper particles are not particularly limited to "D50%". "), preferably 〇.4 叫~下=4 or more 'oxidation resistance is more effectively improved. Further, the contact area of the surface-treated copper particles of the above-mentioned electric (four) is increased, and the specific resistance is more effectively lowered. 2', the shape of the above-mentioned surface-treated copper particles is not particularly limited to a spherical shape, a flat shape, a block shape, a plate shape, and a scale shape, etc., and is resistant to oxidation and low resistance. From the viewpoint of the rate, it is preferable that 201133512 is substantially spherical, flat, or plate-shaped. The surface treatment method of the copper particles to be applied to the agent can be suitably selected by dissolving the agent. For example, the preparation is such that at least a portion of the surface that can be dried by the surface can be dried by the surface. Suitable choice. For example, it is possible to correspond to the surface of the & solvate, the solvent, the acetaminophen, the alcohol, the isopropyl alcohol, and the like, and the like, such as a wide diol solvent or a card reagent such as diethylene glycol monobutyl ether. - Alcohol monoethyl acetate, such as carbitol acetate, specifically, 'for example, #using stupid and saliva, Sansao Yao as a surface treatment _, can make _ system dissolve & Lok, then Surface treatment of copper particles. Table of preparation of surface treatment ===== The second degree of agriculture can be appropriately selected according to the surface treatment amount which can be set to, for example, i has 10/0. 85 mass ^ page %~% f The amount %, preferably 2 mass. /. ~ Surface ==== Combined::: The above-mentioned surface-treated copper particles and silver particles are included in the above-mentioned surface. %, in terms of oxygen resistance: 2 leather = 17 20113351}, it is preferably 72 mass% to 90% by mass, more preferably 74% by mass to 88% by mass. Further, in the present invention, the above surface is The steel particles to be treated may be used singly or in combination of two or more. In addition, they may be used in combination with copper-containing particles other than the surface-treated copper particles. In the present invention, from the viewpoint of oxidation resistance and low electrical resistivity of the electrode, it is preferable that the paste composition for an electrode contains a compound selected from the group consisting of a quinone compound, a saturated fatty acid, an unsaturated fatty acid, and an inorganic metal. Surface-treated copper particles 7 〇 mass%, at least one of 组1% by mass to 1% by mass of the compound salt, the organometallic compound salt, the polyaniline resin, and the metal alkoxide ～94% by mass (when the silver particles described later are contained, the total content of the surface-treated copper particles and the silver particles) is more preferably contained in the paste composition for an electrode to contain a compound selected from the group consisting of three bite compounds and saturated fatty acids. When at least one of the group consisting of the unsaturated fatty acid and the inorganic metal compound salt is 5% by mass to 8% by mass, the surface-treated copper particles are 74% by mass to 88% by mass (including silver particles to be described later) The total content of the surface-treated copper particles and the silver particles). Further, it is preferably contained in the paste composition for an electrode to contain a compound selected from the group consisting of diazoles. At least one of a group consisting of a saturated fatty acid, an unsaturated fatty acid, an inorganic metal compound salt, an organometallic compound salt, a polyaniline resin, and a metal alkoxide is 1% by mass to 1% by mass 0/〇 The surface-treated phosphorus-containing copper alloy particles having a phosphorus content of 8 mass% or less are 7% by mass to 94% by mass (when the package 201133512 contains silver particles described later, the surface-treated phosphorus is contained. The total content of the copper alloy particles and the silver particles is more preferably included in the electrode paste composition to contain a group selected from the group consisting of triterpenoids, saturated fatty acids, unsaturated fatty acids, and inorganic metal compound salts. The surface-treated copper alloy particles having a phosphorus content of at least one of 0. 05% by mass to 8% by mass and having a phosphorus content of 1% by mass to 7.5% by mass or less are % by mass to 88% by mass ( The total content of the surface-treated phosphorus-containing copper alloy particles and silver particles in the case of containing silver particles described later). (Glass Particles) The paste composition for an electrode of the present invention contains at least one kind of glass particles. The paste composition for an electrode contains glass particles, and at a temperature at which the electrode is formed, a tantalum nitride film as an anti-reflection film is removed by a fire-through of the stomach, and an ohmic electrode is formed on the electrode and the substrate. contact. The glass particles are softened and melted at the electrode formation temperature, and the contacted tantalum nitride film is oxidized, and the oxidized cerium oxide is inserted, whereby the glass particles of the antireflection film can be removed, and the glass particles can be removed without particular limitation. Glass particles commonly used in the art are used. In the present invention, from the viewpoint of oxidation resistance and low resistivity of the electrode, glass particles containing glass having a glass softening point of 600 〇 c or less and a crystallization initiation temperature exceeding 600 C are preferable. Further, the glass softening point is measured by a usual method using a thermomechanical analyzer (TMA), and the crystallization starting temperature is a thermogravimetric-thermal difference analyzing device (Thermal)

The Gravimetry-Differential Thermal Analyzer (TG-DTA) was measured by the usual method of 201133512. The glass particles generally contained in the electrode composition may also be composed of glass containing the wrong glass. As such a glass containing the error, for example, the glass described in Japanese Patent Laid-Open No. Hei-5-4, and the like can be preferably used. Further, in the present invention, it is preferable to use a substantially uncut glass without considering the influence on the environment. For example, the error-free glass described in paragraph number 〇〇24 to Duanluo number 0025 of Japanese Patent Laid-Open Publication No. 2006-313744, or the Japanese Patent Publication No. 2009-188281, and the like. The error-free glass is also preferably used in the present invention since it is suitably selected from the glass. Further, in order to insert the silica dioxide efficiently, the glass particles preferably contain a glass containing an _oxide, and more preferably a glass (10) acid glass ρ2〇5-based glass containing a pentoxide. Further, it is more preferable to include a glass containing bismuth pentoxide in addition to the pentoxide oxide (Ρ2〇5_ν system glass). By further containing antimony pentoxide, the oxidizing property is further improved, and the resistivity of the electrode is further lowered. It is considered to be caused, for example, by the fact that by further containing vanadium pentoxide, the softening point of the glass is lowered. When the glass particles include phosphorus pentoxide and pentoxide oxide glass (P2〇5-V205 glass), the content of the bismuth pentoxide is preferably 1% by mass or more based on the total mass of the glass. More preferably, i mass% ~ 70 mass%. Further, the above-mentioned five-oxide five-filled pentoxide-based glass may further contain other components as needed. As other components, 'barium oxide (Ba〇), 201133512 = oxidized (Mn 〇 2), oxidized key (Mg 〇 3), oxynitride (Na 2 〇), oxidized _ (K 2 〇), dioxide 2 3, crane (W〇3), yttrium oxide (10)). By more. Contains ^ into 丨 ^ temperature into - step down. Further, it is possible to suppress the reaction with the silver particles contained in the copper-containing particles. The content of the glass particles of the second weave = upper f glass, the mass of the paste composition for the electrode, preferably 0% by mass to 1% by mass, more preferably 〇ϋΐίτ and even more preferably 1% by mass. 7% by mass. The oxidation resistance, the low resistivity of the electrode, and the low contact resistance are more effectively achieved by including the glass particles described above. In the present invention, it is preferable to contain glass particles (U mass% to 1% by mass) of glass as _+@1·ν2〇5-based glass, and it is more preferable that the content of the glass particles is from 01 to 01% by mass. The glass particles of the above p2〇5_v2o5-based glass 〇J% by mass (solvent and resin). The paste composition for an electrode of the present invention contains at least one solvent, thereby being compatible with the transfer of the base (4) (10). The liquid physical properties (for example, viscosity surface tension, etc.) of the electrode paste composition are adjusted to the desired liquid physical properties.

There is no special restriction on a smile. For example, it may be exemplified by calcined, cyclohexane, and j-based solvents; gasified hydrocarbons such as diethylene glycol, Erqiyiyuan, and digasbenzene, and diterpene: tetraterpene, henan, tetrahydropyridinium "cyclic ether solvent such as butyl, diterpene, H-pentane, dioxane; hydrazine, hydrazine-dimercaptocarbamide, 21 201133512 N,N-dimercaptoacetamide Solvent; sulfoxide solvent such as disulfone; ketone solvent such as acetone or alumina; ethanol, 2^ethyl_, diethyl ketone, cyclohexanone; 2 2^- ^ ^ alcohol, dipropyl _, etc. Alcoholized pentanediol monopropane r2m ^ monoethyl _, 2, 2, 4 - trimethyl W- = methyl η 丄, 2, 4 dimethyl diol diol monobutyrate, 2, 2, 4-anthracenyl-1,3-pentanediol monoglycidylacetate, acetic acid §, 2,2,4·triethyl-1,3·pentanediol monool An oxime solvent such as acetate, diethylene glycol monobutyl ether acetate or the like; an ether solvent of butyl alcohol; 01 red. Said Qi J-Ethyl Alcohol-Ethyl ether 4 more rarity, lemon _, private Π / / alcohol, laurel olefin, belles diterpene α_ lingene, P-pinene, rosin, fragrant celery , Zhuangzi solvent of water buds, etc. 'and mixtures of these. The above-mentioned solvent in the present invention is preferably a s-based solvent or a terpene system selected from at least two, from the viewpoint of coating properties and printability of the electrode for forming an electrode on the substrate. The seed in the ether solvent of the solvent or the polyol is more preferably at least one selected from the group consisting of an ester solvent of a polyhydric alcohol and a terpene solvent. In the present invention, the above solvents may be used singly or in combination of two or more. In addition, as the above-mentioned resin, any one which can be thermally decomposed by calcination can be used without any particular limitation, and the commonly used ones in the technical field are used. "Yaohe & 'For example, cellulose-based resins such as mercapto cellulose, ethyl cellulose, slow-acting methyl cellulose, and nitrocellulose; polyvinyl alcohol t, 'polyvinyl pyrrolidone; acrylic resin Vinyl acetate-acrylic acid ruthenium copolymer; butyral resin such as polyvinyl butyral; phenol-modified alkyd resin; alkyd resin such as 2011 f 13 13 13 13 13 13 13 13 13 13 13 13 Tree 爿 a; rosin ester resin, etc. The viewpoint of the disappearance of the upper body fat of the invention towel in the case of calcination is preferably selected from the group consisting of cellulose resin and propylene resin, and is preferably selected from cellulose resin. At least one of them. In the present invention, the above resins may be used alone or in combination of two or more. In the paste composition for an electrode of the present invention, the content of the resin in the solvent disk may be appropriately selected in accordance with the desired liquid difficulty and the type of the solvent and resin to be used. For example, the content of the resin is preferably 0.01% by mass to 5% by mass based on the total mass of the paste composition for an electrode, more preferably 5% by mass to 4% by mass, and even more preferably (Uf amount) %〜3质量%, and more preferably 〇15% by mass to 2.5% by mass. Further, the total content of the solvent and the resin is preferably 3 mass 〇/〇 in the total mass I of the paste composition for an electrode. 29.8 mass 0 / 〇, more preferably 5 mass 〇 / 0 〜 25 mass / /, and more preferably 7 mass % ~ 2 〇 mass %. By using the solvent and resin content within the above range, the electrode paste The composition of the composition is excellent in imparting flexibility to the substrate, and an electrode having a desired width and height can be formed more easily. (Cosolvent) The electrode-depleted composition contains at least one flux. The flux, the oxidation resistance is further improved, and the resistivity of the formed electrode is further decreased. Further, the adhesion between the electrode material and the tantalum substrate can be obtained. 23 201133512 Effect ^ As the flux in the present invention, as long as Is a surface that can be suppressed to the copper-containing particles f The flux for forming the oxide film is not particularly limited. Specifically, for example, a fatty acid, a boric acid compound, a fluoride, and a borofluoride oxime are preferred cosolvents. More specifically, ten Diacid, tetradecanoic acid, eight small $ thousand y acid, stearic acid, sorbic acid, only mouth-small acid, boron oxide, potassium borate, borax long-lasting acid clock, boron fluorination, sodium borofluoride , fluorination clock, acid gasification unloading 'acidic sodium fluoride, acid fluorination clock, fluorination unloading, sodium fluoride, fluorination, etc.. Among them, the heat resistance of the electrode material during calcination (the flux is calcined) The non-volatile property at low temperature) and the anti-oxidation enthalpy of the copper-containing particles can be listed as "excellent aids". In the present invention, the fluxes can be used separately. One type is used in combination of two or more. In addition, 'the amount of s of the solvent of the electric recording composition of the present invention' effectively exhibits the oxidation resistance of the particles containing copper, and the viewpoint of lowering the end of the electrode material. Depending on the aspect of the removed portion In the total amount of f of the electrode composition for the electrode, it is oi mass% to 5% by mass, more preferably μf amount% to 4 mass%, preferably G.5 mass% to 3.5 mass%, especially Preferably, the Q 7 mass (silver particles) of the electrode composition of the present invention further comprises at least one silver 24 201133512 particle. By containing silver particles, the oxidation resistance is further improved, and the electric conductivity of the electrode is further lowered. Further, the effect of improving the weldability in the production of the photovoltaic cell module can be obtained. For example, it can be considered as follows. Generally, it is 6 〇〇 as the electrode forming temperature region. 〇 to 9 〇〇 its temperature = domain In the middle, a small amount of solid solution of silver in copper and a small amount of solid solution of copper in silver are formed, and the interface between copper and silver is dissolved. _> The correction can contain _ particles and filaments to the same temperature. 'When slowly cooling to room temperature, no area is generated, but since the formation of the electrode is cooled from the high temperature range to normal temperature, it can be considered that the layer of the high temperature lower body acts as a non-equilibrium solid solution phase or a eutectic of copper and silver. The surface of the tissue particles and the particles containing copper. It is considered that such a copper-silver solid layer contributes to the oxidation resistant silver solid solution layer of the copper-containing particles at the electrode formation temperature at 300 〇c to . When the temperature is higher than c, the shape 2 = ' is the peak of the peak indicated by the simultaneous measurement of the thermal mass and the thermal difference, and the peak temperature of the peak is the copper-containing particle* on the α, and the content can be more effectively enhanced. The oxidation resistance of the copper eclipse further decreases the resistivity of the formed electrode. Other atoms that are inevitably mixed in, such as m, Ba, sr, ca, Mg, Be, znpbcd, Ή, V, Sn , Ba Bu Zr, w, M〇, Ti, c〇, secret, Au, etc. The particle diameter of the silver particles in the present invention is not particularly limited, and the particle diameter (D50%) at 50 Å/〇 is preferably 〇', greedy μΓη~1〇μηη, more preferably 25 201133512 1 μπι~7 Ιιη. By setting it to 0.4 or more, oxidation resistance is more effectively improved. When the material is 10 μm or less, the contact area between the metal particles such as silver particles and copper particles in the electrode is increased, and the specific resistance is more effectively lowered. In the paste composition for an electrode of the present invention, the relationship between the particles containing copper and the particle diameter ((10%%) of the silver particles is not particularly limited, and it is preferable that the particle diameter (D5G%) of the chi-square is smaller than that of the other. The diameter (five) G%), more preferably the ratio of the particle diameter to the particle diameter of the other side is 1 to 10. Thereby, the electric side of the electrode is more effectively lowered. The reason for the following is that the contact area between the copper-containing "metal particles in the electrode and the silver particles and the metal particles becomes larger. The outer portion of the silver particles of the composition of the present invention (4) is oxidized and resistant to the electrode. From the viewpoint of low resistivity, it is preferably 8.4 f % % to 85 5 f % by weight, more preferably 8.9 mass ❶ /. ~ 80.1 mass 〇 / 〇 in the paste composition. In the present invention, the content of the copper-containing particles in which the total amount of the silver particles and the silver particles are set is preferably 9% by mass in terms of the oxidation resistance and the low resistivity of the electrode. ^ phase ° to mass% ~ 77% by mass. By the above, if the above glass particles == is, more than % of the example photovoltaic power: =! further decline. In addition, in the lift to make a hydrofluoric acid aqueous solution = turn t The electrode for efficiency is formed into a hydrofluoric acid aqueous solution of the hydrogen electrode material of the Shih-hss substrate (the property of the electrode 26 201133512 aqueous solution of hydrofluoric acid and peeled off from the silk plate) is obtained. The content of the copper-containing particles is 88%. 〇 〇 〇 卩 卩 卩 含有 含有 含有 含有 含有 含有 含有 含有The contact resistance between the copper and the plate contact electrode is further lowered. In view of the oxidation resistance, the right phase resistivity, and the coating property of the stone substrate, the above-mentioned electrode composition of the present invention is the above. The total content of the second silver particles and the above silver particles is preferably 7Q% by mass to 4% by mass; 8 f is 72% by mass to 92% by mass, and more preferably 74% by weight of A to 88% by mass. The content of the composition containing the _ particles and the above-mentioned trainer is %, and the content of the composition for the electrode can be easily achieved. The ratio of the particles containing the steel and the silver particles can be easily achieved. Further, it is preferable that the above-mentioned copper-containing particles ==total content, from the viewpoint of oxidation resistance resistivity in the paste composition for an electrode of the present invention. The content rate is 7〇 mass%, mass%, and the content ratio of the above glassy substance is Πf amount%~(1)f%%, and the total content of the solvent and the above-mentioned secret fat is 3% by mass to 29%.里 / 〇 'Upper speed cosolvent is (U mass / ~ ~ 5 mass%, more preferably the above copper containing particles ^ and the above silver particles The total content is 74 f % % to 88 f % %, the above ratio is 1 f 4% to 7 f % by weight, the solvent and the above-mentioned brake = 2% by mass to 20% by mass, and the content of the above flux is 0.7 篁% to 3% by mass. 27 201133512 (compound-containing compound) The paste composition for an electrode preferably further contains at least one compound containing a dish. Thereby, oxidation resistance is more effectively improved, and resistance of the electrode Further, the effect is further obtained: an element in the compound containing carbon is diffused as an n-type dopant in the ruthenium substrate, and the power generation efficiency is improved when the photovoltaic cell is fabricated. From the viewpoint of oxidizability and low resistivity of the electrode, a compound having a large content of phosphorus atoms in the molecule and not evaporating or decomposing at a temperature of about 200 ° C is preferable. ▲ Specific examples of the phosphorus-containing compound include a phosphate such as phosphoric acid, a phosphate such as ammonium phosphate, an alkyl phosphate, and an aryl phosphate.

Sa is an acid such as a cyanoic acid, a cyclic cyanohydrin such as a hexaoxy oxonitrile, and derivatives thereof. The phosphorus-containing compound in the present invention has a oxidation resistance and a low P yield of the electrode, and δ' is preferably selected from the group consisting of acid filling, acid filling, acid vinegar, and cyclic phosphazene. At least one of the group, more preferably at least one selected from the group consisting of and a ring-shaped nitrile. The content of the above-mentioned compound containing a compound of the present invention is preferably a5fi% to 1G% by mass, more preferably 1%, from the viewpoint of the low resistivity of the oxygen resistance in the paste composition for the electrode. Quality® /. ~ 7 mass%. Zhewu is in the fortune of the present invention. Preferably, the total de 13 of the f-shaped composition is selected from the group consisting of phosphoric acid, ammonium phosphate, phosphorus 1-germanium, anthracene and cyclic phosphazene as a phosphorus-containing compound. At least one of the 〇5 质 28 201133512 : ^ 2 is preferably at least one of the group consisting of nitriles in the total mass of the paste composition for the electrode, and 'when the present invention has a composition containing 0 It is preferable from the viewpoint of the chemical resistance and the low resistivity of the electrode. In the above, the total content of the particles and the above-mentioned filaments is % mass 4 liters/〇, and the content of the glass particles is 0.1% by mass to 10 = /°. The above-mentioned agent, the above resin, and the above-mentioned tree-containing The total content of the compound is from 5% by mass to 20% by mass, and the content of the co-solvent is (U mass / 〇 5 mass /.) More preferably, the total content of the copper-containing particles and the silver particles is 74. The mass % to 88 f is %, the content of the glass particles is 1% by mass to 7% by mass, and the solvent, the resin, and the above-mentioned J-containing compound are contained in an amount of % by amount to 7 f %, and a flux The content of the composition is from 0.7% by mass to 3% by mass. (Other components), and further, in addition to the above components, the paste composition for an electrode of the present invention may further include other components generally used in the technical field of the technical field. Examples of the other component include a plasticizer, a dispersant, a surfactant, an inorganic binder, a metal oxide, a ceramic, an organometallic compound, etc. The method for producing the paste composition for an electrode of the present invention is not particularly limited. Restriction. Available it often The above-mentioned copper-containing particles, glass particles, a solvent, a resin, and optionally silver particles are dispersed and mixed to produce the paste composition for an electrode of the present invention, 〇29 201133512 (Manufacturing method of electrode using paste composition for electrode) = (IV) The electric fine f-shaped composition of the present invention is used to produce an electrode 烨 烨 ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ 解 解 解 解 解 解 , , , The paste composition for an electrode can form an electrode having a low specific resistance even in the presence of oxygen (for example, cal' calcination treatment). For example, using the above-mentioned electrode paste composition to form a photoelectrode combination The material is formed into a desired shape, and then dried, and then calcined, whereby the electrode of the electric battery can be formed into a desired shape. Further, by using the paste composition for the electrode, even in the case of oxygen In the presence of (for example, large milk), it is also possible to form an electrode with a low electrical resistivity. For example, a method of applying a paste composition for an electrode to a stone substrate is described. law , the distribution method, etc., in terms of the production of the concept of 5, preferably by screen printing. Using the screen printing cloth to send the hair _ electric paste composition, 1 ΐί ii80Pa.s~10oopa The viscosity of the range of .s. In addition, the electrode is tempered); the viscosity of the material is the viscosity at 25t. The amount of the paste composition for the electrode can correspond to the electricity to be formed. For example, 'the electrode can be given a paste composition. Further, it is 2 g/m~1〇g/m2, preferably 4 coffee 2 to 8 coffee 2. a# ίίί, as the use of the present invention The paste composition for an electrode is used to form an electrode, ', ', and a miscellaneous member (City condition). The heat treatment conditions generally used in the technical field of 201133512 can be applied. Generally, the heat treatment temperature (heating temperature) is _. 〇~9〇(rc, ί When the electrode composition of the present invention is used, lower temperature and lower heat treatment conditions can be applied, for example, it can be used at a heat treatment temperature of _. 8 耽 8 具有Further, the 'heat treatment time can be appropriately selected in accordance with the heat treatment temperature and the like, and can be set, for example, to 1 second to 20 seconds. <Photovoltaic cell> The photocell of the present invention is given to the presence of oxygen in the presence of oxygen. An electrode formed by calcining a paste or a composition on a stone substrate, whereby a photovoltaic cell having excellent characteristics can be obtained, and the photovoltaic productivity is excellent. A specific example of the photovoltaic cell of the present invention will be described, but the present invention is not limited thereto. A cross-sectional view, an example of a light-receiving surface and a back surface of an exemplary photovoltaic cell element are shown in Figs. 1, 2, and 3. In the semiconductor substrate 130 of the photovoltaic cell element, a single crystal or a S1 or the like is used. The semiconductor substrate 130 contains boron or the like to form a p-type semiconductor. The light-receiving surface side suppresses the reflection of sunlight. by a concave-convex shape (texture, not shown) is doped with phosphorus or the like on the light-receiving surface side, and a diffusion layer n3ι of an n-type semiconductor is disposed with a thickness of a submicron order, and at a boundary with the P ^ block portion Further, a pn junction portion is formed. Further, on the light-receiving surface side, an anti-reflection layer 31 132 having a thickness of 10 Å nm & right ytterbium nitride is provided on the diffusion layer 131 by a vapor deposition method or the like. The light-receiving surface electrode 133 on the light-receiving surface side and the current-collecting electrode 134 and the power-extracting electrode 135 formed on the back surface will be described. The light-receiving surface electrode 133 and the power extraction electrode 135 are formed of the paste composition for the electrode. The electrode 134 is made of a glass paste containing a glass powder, and the above-mentioned composition is applied to a desired pattern, and then dried, and the atmosphere is _°C~ In this case, the glass particles contained in the electrode paste composition for forming the light-receiving surface electrode 133 are reacted (calcined through) with the anti-reflection layer m on the light-receiving surface side. Light-receiving electrode 133 and expansion The layer 131 is electrically connected (ohmic contact). In the present invention, the light-receiving surface electric S 133 is formed by using the paste composition for an electrode, and the copper is used as a conductive metal on the surface to suppress oxidation of copper. The yoke is formed into a low-resistivity light-receiving electrode 133. In addition, when the sinter is performed on the back side, the collector electrode 134_electrode composition sheet _ is dispersed to the back surface of the semiconductor substrate 130 to form an electrode component. The diffusion layer 136 can thereby obtain an ohmic contact between the semiconductor substrate and the collector electrode 134 and the power extraction electrode 135. Further, as an example of another type of photovoltaic cell element of the present invention, A perspective view (a) of the AA cross-sectional structure and a plan view (b) of the back side electrode structure are shown in FIG. If the number is not 4, the through-holes are formed on the unit wafer of the Shishi substrate including the p-type semiconductor by the laser drill paste or the like, and the both sides of the light-receiving surface side and the back surface 32 201133512 l ^ are formed. Further, in addition to the wire receiving, an n-type semiconductor layer 3 formed by n-type formation is formed on the light-receiving surface side, and an anti-reflection film (not shown) is formed on the n-type semiconductor layer 3. This is the same step as the si-type photovoltaic cell unit to form the crystallization of the precursor, and then the electrode of the present invention is transferred to the inside of the through hole formed by the printing method or the ink jet method, and further, on the side of the light receiving surface. The f-shaped composition for the hair-electrode was printed in a grid shape to form a composition layer of 'the composition layer' to form the via electrode 4 and the collector thumb 2 for current collection. % Here, it is preferable that the paste for filling and printing is a paste which is characterized by a viscosity-based property which is most suitable for each process, and can be filled and printed at one time using a paste of the same composition. On the other hand, a high-concentration doping layer 5 for preventing recombination of carriers is formed on the opposite side (back side) of the light receiving surface. Here, boron (B) or aluminum = (1) is used as an impurity element forming the high concentration doping layer 5 to form a p+ layer. The still doped layer 5 can be, for example, due to the formation of the antireflection film described above. The single-step process t is performed by using B as a diffusion diffusion treatment, or when A1 is used, which can be formed by printing the A1 paste on the opposite side in the above printing step. Thereafter, at 050 Ό to 8503⁄4 Calcination is carried out, and the paste composition for the electrode which is filled and printed on the antireflection film formed on the inside of the through hole and the light receiving surface side is ohmically contacted with the lower n-type layer by the effect of firing through. 33 201133512 Further, on the opposite side, as shown in the plan view of Fig. 4 (b), the electrode-like composition of the present invention is printed on the n-side, and is uniformly printed, whereby the back electrodes 6 and 7 are formed. In the present invention, the paste composition electrode 4 for the electrode, the gate electrode 2 for current collection 2, the back electrode 6 and the back electrode = copper is used as the conductive metal, and (4) oxidation is suppressed, and the yield is excellent. Low-resistivity via electrode 4, collector gate electrode 2 Arctic 6 and back electrode 7. In addition, the electrode paste composition for photovoltaic cells of the present invention does not correspond to the electrode of the photovoltaic cell as described above, for example, the electrode of the village is preferably used for a plasma display. Wires and shielded wires, ceramic capacitors, antenna circuits, various sensor circuits, heat-dissipating materials for semiconductor components, etc.: In addition, all the Japanese disclosures of 2010-013516 and Japan, Yusuke 2〇10-2222〇5 The content is quoted as a reference = in the specification. 'All documents, Japanese patent application, and technical specifications described in the specification are cited in the form of a reference to the specific and individual reference, the Japanese patent application. The same extent as in the technical specifications is referred to in the present specification as a reference. [Examples] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples. Unless otherwise stated, "parts" and "%" are the mass 1 basis. <Example 1A> 34 201133512. (a) Preparation of paste composition for electrode contains 1% by mass Filling the phosphorus-containing steel alloy, dissolving it and then pulverizing it by water atomization method, then drying, classifying and mixing the classified powder, and performing deoxidation and dehydration treatment to obtain a mass of 1 / 〇 Phosphorus containing copper alloy particles. Furthermore, the particle size (D50%) of the steel containing the dish is 1.5 μιη. Preparation contains 32 parts of oxidative hunger (V205), phosphorus oxide (ρ2〇5) % injury, barium oxide (BaO) 10 parts, strontium oxide (w〇3) 1 part, sodium oxide (Na20) 1 part, oxidized (K20) 3 parts, oxidized (Zn〇) 1 part, manganese oxide (ZnO) 8 parts of glass (hereinafter, abbreviated as "G19"). The obtained glass G19 had a softening point of 447. . The crystallization temperature is 6 〇" 叱 or more. Glass particles having a particle diameter (d5〇q/.) of 17 were obtained using the obtained glass G19'. 39 parts of the phosphorus-containing copper alloy particles obtained above, 45.9 parts of silver particles (particle diameter (D50%) of 3 μm, high purity chemicals manufactured by Aldrich Co., Ltd.), 17 parts of glass particles, and boron as a flux Potassium fluoride t ^, and contains 4. A mixture of 13.2 parts of butyl carbitol (BCA) solution of ethylcellulose (EC) was mixed, and then stirred in an agate mortar for 20 minutes to prepare a paste composition for electrodes ία. (b) Photovoltaic cell fabrication The p-type semiconductor substrate with a thickness of 190 μm formed of an n-type semiconductor layer, a texture and an anti-reflection film (tantalum nitride film) was formed on the party's surface and cut into 125 mm×l25 mm. size. The paste composition 1 for an electrode obtained in the above-mentioned 35 201133512 was printed on the light-receiving surface so as to have an electrode pattern as shown in Fig. 2 by a screen printing method. The pattern of the electrode is composed of a finger line of 15 〇 μηι width and a bus bar of U mm width, and the printing condition is appropriately adjusted so that the film thickness after calcination reaches 2 ( (screen sieve sieve) Hole, Printing Speed, Printing Pressure> The obtained person was placed in an oven heated to 150 Torr for 15 minutes, and the solvent was removed by evapotranspiration. Then, the aluminum electrode paste was printed on the entire back surface by screen printing. It is suitable to adjust the printing strip in such a way that the thickness of the satin is 40 μm

Pieces. The winner was placed in a heat of 15 〇. (In the oven: remove the solvent by evapotranspiration for 15 minutes. S Then, in the infrared rapid heating furnace, heat treatment at 850 ° C for 2 seconds in the atmosphere, to form a photovoltaic cell Unit 1A. <Example 2A> In the case of Example 1A, the heat treatment temperature at the time of electrode formation was changed to 75 〇t instead of 〇, 隹- instead of 85 〇C and the heat treatment for 10 seconds was repeated. This is the same as that of the example 1A. The electro-photovoltaic cell unit 2A is the same as that of the example 1A. [Example 3A> In the example 1A, the addition of the phosphoric acid diameter (D50%) to the grain of the AΛ elbow particle is changed. (4) Array 'In addition to this, the same example 4A> is the same as the example 1A> (4) simple photovoltaic cell unit 3A. In the example 1A, the amount of the depleted gasification as the current y" is from 36 201133512 A l is 2 In addition to the addition amount of the alcohol B (tetra) (B) solution containing 4% of ethyl cellulose (EC), in order to avoid every bit of damage, the light of the pole is also formed to form a desired Electricity (Example 5A, Example 7A, Example 8A) In Example 1A, the flux was replaced with Table 1. In addition, Lai (4) 丨 1Δ 4, a refining agent,

The light-made fine electrode of the electrode is expected to be the first battery unit 5Α, the photovoltaic battery unit 7-8, the photovoltaic power J < example 6Α> (4) tr, MA 'using the following prepared glass particles (ΑΥ1) SSI4: (G19), other than that, in the same manner as in Example 5, a photovoltaic cell 6α^ was formed to form a desired electrode, and the glass particles (ΑΥ1) contained oxygen (V2〇5) 45 parts, and an oxidation disk (, 2〇5) 24.2 parts, bismuth oxide (Ba〇) 2 () 8 parts, oxidation record (sb2〇3) injury, oxidized crane (W03) 5 parts, and particle size (D5〇%) is i 7 (four). Further, the glass had a softening point of 492 t and a crystallization temperature of 6 Å. 〇 Above. <Comparative Example 1A> A photovoltaic cell 1A for comparison with a sample having a desired electrode was formed in the same manner as in Example 1A except that the flux composition for the electrode was prepared without adding a flux. 37 201133512 J-aSI inch ε [1<]

Processing temperature / processing time 850 ° C / 2 750 ° C / l sec 850 ° C / 2 850 ° C / 2 850 ° C / 2 850 ° C / 2 850 ° C / 2 850 ° C/2 seconds 850 ° C / 2 sec &lt; 0 ¥ Rong content (parts) 〇Ο oooooo solvent type borofluoride potassium borofluoride potassium borofluoride potassium borofluoride potassium dodecanoic acid borofluoride Potassium sodium borate 1 content (parts) (N o BCA solution containing 4% EC (parts) CN rn CN rn CN &lt;N 〇(S CO (N rn cs rn &lt;N ΓΟ &lt;s rn glass particle type〇 \ Ο 〇 \ O On 5 On 3 〇 \ o ON 〇〇 \ 〇 Os o Content (parts) r-; r-; Bubu silver particle size (D50%) (μπι) mmm CO cn m Content (parts) 〇\ 〇\ jri Os On JO 〇\ jo Os Os On »〇00 particle size of copper-containing particles (D50%) (μπι) in l〇 content (parts) &lt;Ν σ; CO cs cK fS O'; m m CO m m m m m m m m m m 1 contains p 1 instance instance 实例 instance 2A instance 3A instance 4A instance 5A instance 6A Example 7A Example 8A Comparative Example 1A °°ε201133512 _ . —r*i &lt;Evaluation&gt; The fabricated photovoltaic cell unit was evaluated as WXS-155S-10 manufactured by Wacom Electric (share) which simulates sunlight. The measurement device of [_v CURVE TRACER MP-160 (manufactured by EKO INSTRUMENT Co., Ltd.) as a current-voltage (IV) evaluation device is combined and set. The respective measurement values as the photovoltaic power generation performance are set to be compared. The measured value of the example 1A is shown in Table 2 as a relative value of 1000. Further, Eff (conversion efficiency), FF (filling factor), Voc (open circuit voltage), and jsc (short circuit current) which are power generation performance of the photovoltaic cell are shown. The measured values obtained by measurement according to JIS-C-8912, JIS-C-8913, and JIS-C-8914, respectively. [Table 2] Example Example 1 Α Eff (phase * f value) Conversion efficiency 102.5 as photovoltaic cell power generation performance FF (relative value) Fill factor 103 0 Voc (relative value) Open circuit voltage 99 3 Jsc (relative value) Short circuit current 2Α Example 3Α 104) 92.0 103.3 91.1 101.3 93.2 Example 4Α 99.6 103.2 101.1 102.0 98.9 Example 5Α ----- 90S-- 100.0 Example 6Α 991 100.5 97.8 100,2 Example 7Α -- 100.2 98.1 99.8 103.5 101.2 98.4 Example 8A -- 102.3 Comparative Example 1A 1 ππ λ — 100.5 98.2 i〇i 7 — [-ο "100,0 _ 100.0 &lt;Example 1B> In 'Use a silver bag prepared by Japanese Patent Laid-Open No. 14_100191 Cover:: Quality II Copper-clad particles (manufactured by our company, silver package, and lining. 'particle size is 5·8 M^m) prepared by silver-coated copper 39 201133512, except for the same example. _ pool unit 1B. Temperature: 7: Medium J heat treatment (calcination) at the time of electrode formation (calcining instead of assignment, and performing heat treatment for 10 seconds outside the desired electric H) to be compared with Example 18 The photovoltaic cell 2B in which the electrode of m is formed is formed in a manner. &lt;Example 3B&gt; (=: Further adding: 1 part of phosphoric acid' and changing the size of the silver particles to 1 μηι, except for the same method as in Example 1B, the silk battery unit 3Β was fabricated. Example 4Β&gt; 1 heart: 2, 'will be, y X X _ potassium fluoride is added in an amount of 2 & and will contain 4% ethyl cellulose (other than ^ ,, the same as in Example 1B) The method was to form a photovoltaic cell 4B which was formed to be extremely polarized. 3 Electrical power to be seen &lt;Example 5B, Example 7B&gt; In Example 1B, the flux was replaced with a table to form a film in the same manner as the electrode. Photovoltaic f cell unit 5B, cell unit 1 'Exposure of the month> Example 6B> In Example 1B, the above glass particles (Αγι) sub ((10)) were used, except that in the same manner as Example 5, 201133512 Photovoltaic cell 6B of the desired electrode. <Comparative Example 1B> A desired electrode was formed in the same manner as in Example 1B except that the flux composition for the electrode in the preparation of Example 1B was not used. Photovoltaic cell 1B for comparison. 41 201133512 J-a5l Inch ε ε &lt;]

Processing temperature / processing time 850 ° C / 2 750 ° C / l sec 850 ° C / 2 850 ° C / 2 850 ° C / 2 850 ° C / 2 850 ° C / 2 850 ° C/2 seconds &lt;0 ¥ Rongdi content (parts) 〇o 〇〇Ο Ο 助 Flux type potassium borofluoride potassium fluoride potassium borofluoride potassium borofluoride potassium | dodecanoic acid | Sodium borofluoride 1 content (parts) (N w-^ Ο cup CQ CS η ΓΊ ΓΠ 〇 &lt;N fO CN CO CA fO (Ν cn glass particle type 0\ Ο σ&gt; ο 〇\ 〇〇\ Ο On o 〇\ ·—h O Os ϋ Content (parts) Bu BuΓ-; Silver particle size (D50%) (μτη) mmm cn m CO m Content (parts) ON 〇\ ON jrj 〇\ »〇On JO Os ON 00 Particle size of copper (D50%) (μηι) 00 00 ui 00 ... 00 00 to 00 in 00 uS 00 Content (parts) CN 〇\ m CM On m (N 〇\ cn (N 〇\ m (N Os m (S ON cs αί m I type is coated with Ag, covered with Ag, coated with Ag, coated with Ag, coated with Ag, covered with Ag, coated with Ag, covered with Ag, IB 1 Example 2B 1 Example 3B Example 4B Example 5B Example 6B Example 7B Comparative Example IB 201133512 &lt;Evaluation&gt; The measurement of the battery unit was carried out by using WXS-155S-10 manufactured by Wacom Electric Co., Ltd., which is a simulated sunlight, and pv CURVE TRACER MP-160 (manufactured by EKO INSTRUMENT Co., Ltd.) as a current_voltage (IV) evaluation tester. The measured values of the photovoltaic power generation performance are set as the relative values of the comparative example 1B as 1 而 and are shown in Table 4. The performance Eff (conversion efficiency), FF (, charge factor), V0C (open circuit voltage), and Jsc (short circuit current) are respectively performed by JIS-C-8912, JIS-C-8913, and JIS-C-8914. The measured value obtained by the measurement. [Table 4]

Eff (relative value) Conversion efficiency 102.3 Power generation performance as photovoltaic cell FF (relative value) Fill factor Voc (relative value) Open circuit voltage JSC (relative value) Short-circuit current

Instance

Example 1B Example 2B Example 3B Example 4B Example 5B Example 6B Example 7B Comparative Example 1B <Example 1C> The formula was formed to form a desired electric enthalpy. The stupid three-child 'phosphorus-containing hydrazine which will be used as a surface treating agent: 吏The surface-treated copper particles prepared as described below were used to replace the three-side copper alloy 'the same square 1C except 1 - 1A. Dissolve in Solvent B 43 201133512 Alcohol to prepare a 50% surface treatment solution. Copper powder (manufactured by Fukuda Metal Foil Co., Ltd., having a purity of 99.9% and a particle size of 5 μπ〇) was immersed in the surface treatment solution for 5 G minutes, and then dried to prepare surface-treated copper particles. The content of the surface treatment agent in the surface-treated copper particles was 1% in the total mass of the surface-treated copper particles. Further, the particle diameter (〇5〇%) was 5 μηη. <Example 2C> In Example 1C In the heat treatment at the time of electrode formation (the temperature is changed to 75 G ° C instead of the heat, and the heat treatment is performed for 1 G seconds), the power is expected to be the same as the example. Feeding element 2C. Formed with <Example 3C> in Example 1C + 'and then adding linic acid i part' and diameter (D50%) changed f A ! a melon in the pile square dog m is Qing's except for example 1C is the same photovoltaic cell 3C with 70% of the desired electrode. <Example 4C> i The 'round, V? long-term _ is added from 77 and will contain 4% ethyl cellulose (£ c) Ding Ding must: the addition of alcohol acetate (BCA) 3 liquid, the formation of the same type of photovoltaic cell ^4C The desired electricity was obtained in the same manner as in Example 1C except that the H(tetra) refining agent was replaced with the H (four) refining agent in the same manner as in Example 1C. The photovoltaic cell unit 6C of the 201133512 electrode photovoltaic cell 5C, photovoltaic 6〇-f com' spear, in the same manner as the example 5C to form a desired photovoltaic cell 6C. Example 1C &gt; Photovoltaic cell lc for comparison was formed in the same manner as in the preparation of the paste composition for an electrode in Example 1C by reading the example 1C (4). ' 45 201133512 J-aSI e

Processing temperature / processing time 850 ° C / 2 750 ° C / 10 sec 850 ° C / 2 850 ° C / 2 850 ° C / 2 850 ° C / 2 850 ° C / 2 850 ° C /2 seconds &lt;0 replacement content (parts) 〇〇Ο Ο Ο Ο 〇 flux type borofluoride potassium borofluoride potassium borofluoride potassium borofluoride potassium dodecanoic acid 1 1 12 acid il boron fluorination Sodium 1 content (parts) »·Η CN 〇^ c . Τ' 4^ ΕΏ Vw^ &lt;N CO ΓΠ CN rn CN Ο cs rn CN rn (Ν ΓΛ &lt;s glass particle type σ\ Ο 〇ON Ο 〇 \ Ο ON a 〇\ 〇ON Ο Content (parts) Bub&&quot;Ν ο *&gt; Bub·1 Silver particle size (D50%) (μηι) ΓΟ m CO CO m ΓΛ Content (parts) Os Tri 〇\ Ον jn On at 〇\ON iri 〇\ •Η ir! 00 1 particle size of copper-containing particles (D50%) (μιη) W-) in m U-) content (parts) (S σί CN On CN Os ΓΛ (N Os Μ ON m CN 〇\ CN OS m 1 Type 1 Surface Treatment | 1 Surface Treatment | Surface Treatment 1 Surface Treatment, Surface Treatment Surface Treatment Surface Treatment Surface Treatment 1 Example 1C 1 I Example 2C 1 Example 3C Factory Example 4C 1 Example 5C "Example 6C 1 I Example 7C 1 Comparative Example 1C 9 inch 201133512 &lt;Evaluation&gt; The photovoltaic cell produced was evaluated by using WXS-155S-10 manufactured by Wacom Electric (share) which simulates sunlight as a current-voltage (IV) evaluation tester. The measurement device of the LV CURVE TRACER MP-160 (manufactured by EKO INSTRUMENT Co., Ltd.) was combined and set. The measured value of the power generation performance of the photovoltaic cell was set to the relative value of the comparative example 1C as 100.0. 6. In addition, Eff (conversion efficiency), FF (fill factor), Voc (open circuit voltage), and jsc (short circuit current) which are power generation performances of photovoltaic cells are respectively based on JIS-C-8912 and JIS-C. -8913, and JIS_C_8914 The measured value obtained by measurement. [Table 6] Example

Example 1C

Example 2C

Example 3C

Example 5C

Example 6C

Example 7C

Comparative Example 1C

Eff (relative value) Conversion efficiency 101.2 84.6 102.3 100.3 100.1 101.8 103.5 Ίοοό&quot; Deduction for photovoltaic cell FF (relative value) Fill factor 100.2 92.2 101.2 100.0 99.9 99.3 102.7 100.0 v〇c (relative value) Open circuit _97.6 Jsc (relative value) Short circuit current

Although the present invention has been disclosed in the preferred embodiments as defined above, it is intended that the present invention may be used in the context of the present invention. u Bao Bao [Simple Description of the Drawings] 47 201133512 FIG. 1 is a cross-sectional view of a photovoltaic cell of the present invention. Fig. 2 is a plan view showing the light-receiving surface side of the photovoltaic cell of the present invention. Figure 3 is a plan view showing the back side of the photovoltaic cell of the present invention. Fig. 4a is a perspective view showing a cross-sectional structure of a seven-dimensional avυ &gt; photovoltaic cell unit of the present invention. Fig. 4b is a plan view showing the structure of the back side electrode of the seven yl/ / A, 'J " 37 photovoltaic cell of the present invention. [Description of main components] 1 : Unit wafer 2 including a P-type germanium substrate: current collection Gate electrode 3: n-type semiconductor layer 4: via electrode 5: high-concentration doped layer 6, 7: back surface electrode 130: semiconductor substrate 131: diffusion layer 132: anti-reflection layer 133: light-receiving surface electrode 134: collector electrode 135: power take-out electrode 136: electrode component diffusion layer 48

Claims (1)

201133512 VII. Patent application scope 1. Metal particle conjugates include: copper-based particles, solvent, and resin. The electric paste composition according to the item (4), which further comprises silver particles. 3. For the electrode composition according to the above-mentioned item, the copper-based metal particles are selected from the group consisting of copper alloy particles containing lining, copper particles coated with silver, and utilization. Copper particles obtained by surface treatment of at least one of free triterpenoids, saturated fatty acids, unsaturated fatty acids, inorganic metal compound salts, organometallic compound salts, polyphenylene (IV), and metal oxides At least one of them. 4. The paste composition for an electrode according to claim 1, wherein the flux is at least one selected from the group consisting of a fatty acid, a boric acid compound, a fluoride, and a fluoride. The paste composition for an electrode according to claim 1, wherein the glass particles contain an oxide containing scales. 6. A photovoltaic cell having a paste composition for electrode coating according to any one of items 1 to 5 of the Japanese Patent Application Laid-Open No. Hei. Electrode. 49