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WO2015115565A1 - Composition de formation d'électrode, électrode, élément de cellule solaire, leur procédé de fabrication, et cellule solaire - Google Patents

Composition de formation d'électrode, électrode, élément de cellule solaire, leur procédé de fabrication, et cellule solaire Download PDF

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Publication number
WO2015115565A1
WO2015115565A1 PCT/JP2015/052572 JP2015052572W WO2015115565A1 WO 2015115565 A1 WO2015115565 A1 WO 2015115565A1 JP 2015052572 W JP2015052572 W JP 2015052572W WO 2015115565 A1 WO2015115565 A1 WO 2015115565A1
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Prior art keywords
electrode
particles
mass
tin
nickel
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English (en)
Japanese (ja)
Inventor
修一郎 足立
吉田　誠人
野尻　剛
倉田　靖
祥晃 栗原
聡美 根本
隆彦 加藤
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Resonac Corp
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Hitachi Chemical Co Ltd
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Priority claimed from JP2014017939A external-priority patent/JP2015146357A/ja
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Priority to CN201580006053.7A priority Critical patent/CN105934830B/zh
Publication of WO2015115565A1 publication Critical patent/WO2015115565A1/fr
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/20—Electrodes
    • H10F77/206—Electrodes for devices having potential barriers
    • H10F77/211—Electrodes for devices having potential barriers for photovoltaic cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to an electrode forming composition, an electrode, a solar cell element, a manufacturing method thereof, and a solar cell.
  • electrodes are formed on the light receiving surface and the back surface of the solar cell.
  • the electrode In order to efficiently extract the electric energy converted in the solar cell by the incidence of light to the outside, the electrode has a sufficiently low volume resistivity (hereinafter also simply referred to as “resistivity”), and the electrode It is necessary to form a good ohmic contact with the semiconductor substrate and to be in close contact with the semiconductor substrate with high strength.
  • resistivity a sufficiently low volume resistivity
  • the electrode it is necessary to form a good ohmic contact with the semiconductor substrate and to be in close contact with the semiconductor substrate with high strength.
  • the electrode on the light receiving surface from the viewpoint of minimizing the loss of incident sunlight, the wiring width tends to be reduced and the aspect ratio of the electrode tends to be increased.
  • a silicon-based solar cell using a silicon substrate is generally used, and the electrode on the light receiving surface of the silicon-based solar cell is usually formed as follows. That is, a texture (unevenness) is formed on the light receiving surface side of the p-type silicon substrate. Next, a conductive composition is applied by screen printing or the like on the n-type diffusion layer formed by thermally diffusing phosphorus or the like on the surface of the p-type silicon substrate at a high temperature, and this is applied in the atmosphere at 800 ° C. to 900 ° C. The electrode on the light receiving surface is formed by heat treatment (baking) at 0 ° C.
  • the back electrode is formed in the same manner as the electrode on the light receiving surface except that it is formed on the surface opposite to the light receiving surface.
  • the conductive composition forming the electrode on the light receiving surface and the electrode on the back surface contains conductive metal particles, glass particles, various additives, and the like.
  • silver particles are generally used as the conductive metal particles for the electrodes for taking out the output among the electrodes on the light receiving surface and the electrodes on the back surface.
  • the resistivity of the silver particles is as low as 1.6 ⁇ 10 ⁇ 6 ⁇ ⁇ cm, the silver particles are self-reduced and sintered under the above heat treatment (firing) conditions, and good ohmic contact with the silicon substrate.
  • the electrode formed from the silver particles is excellent in the wettability of the solder material, and can be suitably bonded to a wiring material (such as a tab wire) that electrically connects the solar cell elements. .
  • an electrode formed from a conductive composition containing silver particles exhibits excellent characteristics as an electrode of a solar cell.
  • silver is a noble metal, and the bullion itself is expensive.
  • a conductive material that replaces silver is desired.
  • An example of a promising conductive material that can replace silver is copper that is applied to semiconductor wiring materials. Copper is abundant in terms of resources, and the price of bullion is as low as about 1/100 of silver.
  • copper is a material that is easily oxidized at a high temperature of 200 ° C. or higher in the atmosphere, and it is difficult to form an electrode in the above process.
  • JP 2005-314755 A and JP 2004-217952 A in order to solve the above-mentioned problems of copper, oxidation resistance is imparted to copper using various methods, and high-temperature heat treatment (firing) is performed.
  • high-temperature heat treatment firing
  • copper particles that are difficult to oxidize have been reported.
  • Another problem for applying copper to a solar cell electrode is ohmic contact with a semiconductor substrate. That is, even if the copper-containing electrode can be formed without being oxidized during the high-temperature heat treatment (firing), the copper contacts the semiconductor substrate, thereby causing mutual diffusion between the copper and the semiconductor substrate. In some cases, a reactant phase of copper and a semiconductor substrate is formed at the interface between the two. For example, when a silicon substrate is used, copper is in contact with the silicon substrate, thereby causing mutual diffusion between copper and silicon, and a reaction phase of copper and silicon at the interface between the electrode and the silicon substrate. Cu 3 Si may be formed.
  • Such a reactant phase such as Cu 3 Si may reach a depth of several ⁇ m from the interface of the semiconductor substrate, which may cause cracks in the semiconductor substrate.
  • the reactant phase may penetrate an n-type diffusion layer formed in advance on the semiconductor substrate and deteriorate the semiconductor performance (pn junction characteristics) of the solar cell.
  • the formed reactant phase may raise the copper-containing electrode, thereby hindering the adhesion between the electrode and the semiconductor substrate, resulting in a decrease in the mechanical strength of the electrode.
  • the present invention has been made in view of the above problems, and has an electrode formation that can form a copper-containing electrode having a low resistivity, a good ohmic contact with a semiconductor substrate, and an excellent adhesion to the semiconductor substrate. It aims at providing the electrode formed using the composition for this and this electrode formation composition, the solar cell element which has this electrode, its manufacturing method, and a solar cell.
  • the present invention is as follows.
  • An electrode-forming composition comprising metal particles containing phosphorus-tin-nickel-containing copper alloy particles and glass particles.
  • ⁇ 4> The electrode formation according to any one of ⁇ 1> to ⁇ 3>, wherein the phosphorus-tin-nickel-containing copper alloy particles have a nickel content of 3.0% by mass to 30.0% by mass. Composition.
  • ⁇ 5> In the particle size distribution of the phosphorus-tin-nickel-containing copper alloy particles, the particle diameter (D50%) when the volume integrated from the small diameter side is 50% is 0.4 ⁇ m to 10.0 ⁇ m ⁇ 1> to ⁇ 4>
  • ⁇ 6> The composition for forming an electrode according to any one of ⁇ 1> to ⁇ 5>, wherein the glass particles have a softening point of 650 ° C.
  • Electrode forming composition according to ⁇ 6>, wherein the glass particles have a softening point of 583 ° C. or lower.
  • the metal particles further include at least one selected from the group consisting of phosphorus-containing copper alloy particles, tin-containing particles, and nickel-containing particles. Electrode forming composition.
  • tin-containing particles are at least one selected from the group consisting of tin particles and tin alloy particles having a tin content of 1.0% by mass or more.
  • the nickel-containing particles are at least one selected from the group consisting of nickel particles and nickel alloy particles having a nickel content of 1.0% by mass or more. Any one of ⁇ 9> to ⁇ 11> The composition for electrode formation as described in the item.
  • a solar cell element comprising a semiconductor substrate and an electrode that is a heat-treated product of the electrode forming composition according to any one of ⁇ 1> to ⁇ 18> provided on the semiconductor substrate.
  • the said electrode is a solar cell element as described in ⁇ 20> containing the alloy phase containing copper, tin, and nickel and the glass phase containing tin, phosphorus, and oxygen.
  • a solar cell element comprising a step of applying the electrode forming composition according to any one of ⁇ 1> to ⁇ 18> on a semiconductor substrate, and a step of heat-treating the electrode forming composition Manufacturing method.
  • a solar cell comprising the solar cell element according to ⁇ 20> or ⁇ 21> and a wiring material disposed on an electrode of the solar cell element.
  • the composition for electrode formation which has a low resistivity, has a favorable ohmic contact with a semiconductor substrate, and can form the copper containing electrode which was further excellent in the adhesive force with a semiconductor substrate, and this composition for electrode formation
  • the electrode formed using the thing, the solar cell element which has this electrode, its manufacturing method, and a solar cell can be provided.
  • the term “process” is not only an independent process, but is included in this term if the purpose of the process is achieved even if it cannot be clearly distinguished from other processes.
  • a numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the content of each component in the composition is such that when there are a plurality of substances corresponding to each component in the composition, the plurality of substances present in the composition unless otherwise specified. Means the total amount.
  • the particle diameter of each component in the composition is such that when there are a plurality of particles corresponding to each component in the composition, the plurality of particles present in the composition unless otherwise specified.
  • the term “layer” includes a configuration of a shape formed in part in addition to a configuration of a shape formed on the entire surface when observed as a plan view.
  • the electrode-forming composition of the present invention contains metal particles containing at least one type of phosphorus-tin-nickel-containing copper alloy particles and at least one type of glass particles.
  • the structure which the composition for electrode formation concerns the oxidation of copper in the heat processing (baking) in air
  • an electrode forming composition is applied to a semiconductor substrate to form an electrode, a good ohmic contact can be formed between the formed electrode and the semiconductor substrate. Furthermore, an electrode having excellent adhesion to the semiconductor substrate can be formed.
  • the composition for forming an electrode of the present invention contains at least one of phosphorus-tin-nickel-containing copper alloy particles as metal particles.
  • the electrode forming composition of the present invention contains, as necessary, at least one selected from the group consisting of phosphorus-containing copper alloy particles, tin-containing particles, and nickel-containing particles as metal particles, silver particles, and the like. Also good.
  • the total content of metal particles in the electrode forming composition is not particularly limited.
  • the total content of the metal particles in the electrode forming composition is preferably, for example, 65.0% by mass to 94.0% by mass, more preferably 68.0% by mass to 92.0% by mass. More preferably, it is 70.0% by mass to 90.0% by mass.
  • the total content of the metal particles is 65.0% by mass or more, it tends to be adjusted to a suitable viscosity when the electrode forming composition is applied.
  • the composition for forming an electrode of the present invention contains at least one of phosphorus-tin-nickel-containing copper alloy particles as metal particles.
  • a brazing material called phosphorus copper brazing (phosphorus concentration: about 7% by mass or less) is known.
  • Phosphor copper brazing is also used as a bonding material between copper and copper.
  • the phosphorus-tin-nickel-containing copper alloy particles used in the present invention are copper alloy particles further containing tin and nickel in addition to phosphorus.
  • tin and nickel in the copper alloy particles it is possible to form an electrode having a low resistivity and excellent adhesion in a heat treatment (firing) step described later, and to further improve the oxidation resistance of the electrode. it can.
  • the copper alloy particles contain phosphorus and tin, phosphorus, tin, and copper in the phosphorus-tin-nickel-containing copper alloy particles react with each other in a heat treatment (firing) step, which will be described later, and a Cu—Sn alloy phase and Sn— A PO glass phase is formed.
  • a low resistivity electrode can be formed.
  • the Cu—Sn alloy phase is generated at a relatively low temperature of about 500 ° C. It is considered that when the copper alloy particles used in the present invention contain nickel, the Cu—Sn alloy phase formed above reacts further with nickel to form a Cu—Sn—Ni alloy phase.
  • This Cu—Sn—Ni alloy phase may be formed even at a high temperature of 500 ° C. or higher (for example, 800 ° C.). As a result, an electrode having a low resistivity can be formed while maintaining oxidation resistance even in a heat treatment (firing) step at a high temperature.
  • the Cu—Sn—Ni alloy phase is a Cu—Sn—Ni alloy phase and forms a dense bulk body in the electrode.
  • the bulk body functions as a conductive portion, so that the resistivity of the electrode can be reduced.
  • the term “dense bulk body” as used herein means that a massive Cu—Sn—Ni alloy phase is in close contact with each other to form a three-dimensionally continuous structure.
  • the formation of such a structure means that a scanning electron microscope (eg, Hitachi High-Technologies Corporation, TM-1000 scanning) can be used to scan an arbitrary cross section perpendicular to the electrode forming surface of the substrate on which the electrodes are formed. This can be confirmed by observing at a magnification of 100 to 10,000 times using a scanning electron microscope.
  • the cross section for observation is a cross section obtained by cutting with an RCO-961 type diamond cutter manufactured by Refine Tech Co., Ltd.
  • the cross section for observation after cutting may still have cutting flaws or the like due to a cutting machine, it is preferable to polish it with abrasive paper or the like to remove surface irregularities on the observation cross section, and then buff, etc. More preferably, mirror polishing is used.
  • an electrode when an electrode is formed on a semiconductor substrate using the electrode forming composition of the present invention, an electrode having high adhesion to the semiconductor substrate can be formed, and the ohmic contact between the electrode and the semiconductor substrate is good.
  • This can be considered as follows by taking a semiconductor substrate containing silicon (hereinafter also simply referred to as “silicon substrate”) as an example.
  • the Sn—PO glass phase formed by the reaction of phosphorus and tin in the phosphorus-tin-nickel-containing copper alloy particles in the heat treatment (firing) step is the three-dimensional of the Cu—Sn—Ni alloy phase in the electrode. It exists between the bulk bodies (voids) and between the Cu—Sn—Ni alloy phase and the silicon substrate. Since the Cu—Sn—Ni alloy phase and the Sn—PO glass phase are three-dimensionally continuous with each other and are not mixed after being formed by heat treatment (firing), the strength of the electrode itself is kept high. . In addition, since the Sn—PO glass phase is present at the interface between the silicon substrate and the electrode, the adhesion between the electrode and the silicon substrate is improved.
  • the Sn—PO glass phase functions as a barrier layer for preventing mutual diffusion between copper and silicon, so that an ohmic contact between the electrode formed by heat treatment (firing) and the silicon substrate is achieved. It can be considered that the contact becomes good. That is, by using the composition for forming an electrode of the present invention, the reaction between copper and silicon is suppressed, the formation of a reactant phase (Cu 3 Si) is suppressed, and the semiconductor performance (for example, pn junction characteristics) is reduced. Therefore, it is considered that a good ohmic contact between the electrode and the silicon substrate can be exhibited while maintaining the adhesion of the formed electrode to the silicon substrate.
  • Such an effect is generally manifested when an electrode is formed on a silicon-containing substrate using the electrode forming composition of the present invention. Similar effects can be expected, and the type of semiconductor substrate is not particularly limited.
  • Semiconductor substrates include silicon substrates, gallium phosphide substrates, gallium nitride substrates, diamond substrates, aluminum nitride substrates, indium nitride substrates, gallium arsenide substrates, germanium substrates, zinc selenide substrates, zinc telluride substrates, cadmium telluride substrates.
  • the composition for electrode formation of this invention is not limited to the application to the semiconductor substrate for solar cell formation, It can use also for the semiconductor substrate etc. which are used for manufacture of semiconductor devices other than a solar cell.
  • the present invention by containing phosphorus-tin-nickel-containing copper alloy particles as metal particles in the electrode forming composition, first, the copper oxide of phosphorus atoms in the phosphorus-tin-nickel-containing copper alloy particles An electrode having excellent oxidation resistance and low resistivity is formed by utilizing the reducing property against the above. Next, since the alloy particles contain tin and nickel, the Cu—Sn alloy phase, or the Cu—Sn—Ni alloy phase and the Sn—PO glass phase are contained in the electrode while keeping the resistivity of the electrode low. It is formed.
  • the Sn—P—O glass phase is formed in a three-dimensional continuous structure of a Cu—Sn alloy phase or a Cu—Sn—Ni alloy phase, so that the electrode itself has a dense structure, and as a result, the electrode An improvement in strength is obtained.
  • the Sn—PO glass phase functions as a barrier layer for preventing mutual diffusion of copper and silicon, a good ohmic contact is formed between the electrode containing copper and the silicon substrate. It can be considered that such a characteristic mechanism can be realized by a heat treatment (firing) step.
  • the above-described effects can be obtained even when, for example, phosphorus-containing copper alloy particles, tin-containing particles, and nickel-containing particles are combined without using phosphorus-tin-nickel-containing copper alloy particles in the electrode forming composition. Can be done. However, by using phosphorus-tin-nickel-containing copper alloy particles in the electrode-forming composition, for example, the obtained electrode is compared to the case where phosphorus-containing copper alloy particles, tin-containing particles and nickel-containing particles are used in combination. There is a tendency that the resistivity is further reduced and the adhesion with the silicon substrate is improved.
  • the element that forms the electrode is contained in the same alloy particle, so that the Cu-Sn-Ni alloy Phase network formation tends to occur uniformly, and the resistivity of the electrode decreases.
  • the Sn—PO glass phase is produced from the individual phosphorus-tin-nickel-containing copper alloy particles, the Sn—PO glass phase is easily distributed uniformly in the electrode. Thereby, the space
  • the locally thick Sn—PO glass phase is suppressed, and the generation of cracks due to the Sn—PO glass phase is suppressed. As a result, the strength in the electrode can be improved.
  • the phosphorus content contained in the phosphorus-tin-nickel-containing copper alloy constituting the phosphorus-tin-nickel-containing copper alloy particles in the present invention is not particularly limited. From the viewpoint of improving the oxidation resistance (lowering the resistivity of the electrode) and forming ability of the Sn—PO glass phase, the phosphorus content is, for example, 2.0% by mass to 15.0% by mass. It is preferably 2.5% by mass to 12.0% by mass, more preferably 3.0% by mass to 10.0% by mass. Since the phosphorus content in the phosphorus-tin-nickel-containing copper alloy is 15.0% by mass or less, the resistivity of the electrode can be reduced, and the production of phosphorus-tin-nickel-containing copper alloy particles Excellent in properties.
  • the Sn—PO glass phase can be effectively formed and the adhesion to the silicon substrate is improved.
  • An electrode excellent in ohmic contact can be formed.
  • Phosphorus-tin-nickel-containing copper alloy particles satisfying the above content can be suitably used as electrode-forming alloy particles.
  • the tin content contained in the phosphorus-tin-nickel-containing copper alloy constituting the phosphorus-tin-nickel-containing copper alloy particles is not particularly limited.
  • the tin content contained in the phosphorus-tin-nickel-containing copper alloy is, for example, It is preferably 3.0% by mass to 30.0% by mass, more preferably 4.0% by mass to 25.0% by mass, and more preferably 5.0% by mass to 20.0% by mass. Further preferred.
  • the tin content in the phosphorus-tin-nickel-containing copper alloy is 30.0% by mass or less, a low resistivity Cu—Sn—Ni alloy phase can be formed. Also, by setting the tin content in the phosphorus-tin-nickel-containing copper alloy to 3.0% by mass or more, the reactivity with copper and nickel during heat treatment (firing) and the reactivity with phosphorus are improved. In addition, the Cu—Sn—Ni alloy phase and the Sn—P—O glass phase can be effectively formed.
  • the nickel content contained in the phosphorus-tin-nickel-containing copper alloy constituting the phosphorus-tin-nickel-containing copper alloy particles is not particularly limited.
  • the nickel content contained in the phosphorus-tin-nickel-containing copper alloy is preferably 3.0% by mass to 30.0% by mass, for example, and 3.5% by mass to 25.%.
  • the content is more preferably 0% by mass, and further preferably 4.0% by mass to 20.0% by mass.
  • the nickel content in the phosphorus-tin-nickel-containing copper alloy is 30.0% by mass or less, a low resistivity Cu—Sn—Ni alloy phase can be effectively formed.
  • oxidation resistance particularly in a high temperature region of 500 ° C. or more can be improved.
  • the combination of phosphorus content, tin content, and nickel content contained in the phosphorus-tin-nickel-containing copper alloy constituting the phosphorus-tin-nickel-containing copper alloy particles includes oxidation resistance and electrode resistivity.
  • the phosphorus content is, for example, 2 0.0 mass% to 15.0 mass%
  • the tin content is, for example, 3.0 mass% to 30.0 mass%
  • the nickel content is, for example, 3.0 mass%.
  • the phosphorus content is 2.5% to 12.0% by mass, and the tin content is 4.0% to 25.0% by mass.
  • the nickel content is 3.5 mass% to 25.0 mass% More preferably, the phosphorus content is 3.0% by mass to 10.0% by mass, the tin content is 5.0% by mass to 20.0% by mass, and the nickel content is 4.0%. More preferably, it is from 2% by mass to 20.0% by mass.
  • the phosphorus-tin-nickel-containing copper alloy particles are copper alloy particles containing phosphorus, tin, and nickel, but may further contain other atoms inevitably mixed therein. Examples of other atoms inevitably mixed include Ag, Mn, Sb, Si, K, Na, Li, Ba, Sr, Ca, Mg, Be, Zn, Pb, Cd, Tl, V, Al, and Zr. , W, Mo, Ti, Co, Au and Bi.
  • the content of other atoms inevitably mixed in the phosphorus-tin-nickel-containing copper alloy particles can be, for example, 3% by mass or less in the phosphorus-tin-nickel-containing copper alloy particles, From the viewpoint of reducing the resistivity and the electrode resistivity, it is preferably 1% by mass or less.
  • the content of each element in the phosphorus-tin-nickel-containing copper alloy constituting the phosphorus-tin-nickel-containing copper alloy particles can be measured by quantitative analysis using an inductively coupled plasma mass spectrometry (ICP-MS) method. .
  • ICP-MS inductively coupled plasma mass spectrometry
  • the content of each element in the phosphorus-tin-nickel-containing copper alloy constituting the phosphorus-tin-nickel-containing copper alloy particles can also be measured by a quantitative analysis by an energy dispersive X-ray spectroscopy (EDX) method.
  • EDX energy dispersive X-ray spectroscopy
  • phosphorus-tin-nickel-containing copper alloy particles were embedded in a resin, cured, then cut with a diamond cutter or the like, and polished with water-resistant abrasive paper, polishing liquid, or the like as needed. It is preferable to analyze the cross section of the phosphorus-tin-nickel-containing copper alloy particles in the cross section. The reason can be considered as follows, for example.
  • the phosphorus-tin-nickel-containing copper alloy particles of the present invention contain phosphorus, moisture absorption of the phosphorus-tin-nickel-containing copper alloy particles occurs depending on the handling environment, and as a result, the surface of the particles is oxidized. There is a possibility. It is considered that the film formed by this oxidation exists on the very surface and hardly affects the quality of the phosphorus-tin-nickel-containing copper alloy particles. On the other hand, there may be a difference in the content of each element between the particle surface and the inside of the particle due to an increase in the oxygen content on the particle surface. Therefore, when measuring the content of each element in the phosphorus-tin-nickel-containing copper alloy particles, it is considered preferable to measure the particle cross section instead of the particle surface.
  • Phosphorus-tin-nickel-containing copper alloy particles may be used singly or in combination of two or more.
  • “use in combination of two or more types of phosphorus-tin-nickel-containing copper alloy particles” means two or more types of phosphorus having the same particle shape such as the particle size and particle size distribution described later, although the component ratio is different. -When tin-nickel-containing copper alloy particles are used in combination, when the component ratio is the same, but two or more types of phosphorus-tin-nickel-containing copper alloy particles having different particle shapes are used in combination, the component ratio and particle shape are A case where two or more types of phosphorus-tin-nickel-containing copper alloy particles different from each other are used in combination.
  • the particle diameter of the phosphorus-tin-nickel-containing copper alloy particles is not particularly limited.
  • the particle diameter (hereinafter sometimes abbreviated as “D50%”) when the volume accumulated from the small diameter side is 50% is preferably 0.4 ⁇ m to 10 ⁇ m, for example, and preferably 1 ⁇ m to 7 ⁇ m. More preferably.
  • the particle diameter of the phosphorus-tin-nickel-containing copper alloy particles is measured by a laser diffraction particle size distribution analyzer (for example, Beckman Coulter, Inc., LS 13, 320 type laser scattering diffraction particle size distribution analyzer). Specifically, phosphorus-tin-nickel-containing copper alloy particles are added in a range of 0.01% by mass to 0.3% by mass to 125 g of a solvent (terpineol) to prepare a dispersion. About 100 ml of this dispersion is poured into a cell and measured at 25 ° C. The particle size distribution is measured with the refractive index of the solvent being 1.48.
  • a laser diffraction particle size distribution analyzer for example, Beckman Coulter, Inc., LS 13, 320 type laser scattering diffraction particle size distribution analyzer.
  • the shape of the phosphorus-tin-nickel-containing copper alloy particles is not particularly limited, and may be any of a substantially spherical shape, a flat shape, a block shape, a plate shape, a scale shape, and the like. From the viewpoint of oxidation resistance and lowering of the resistivity of the electrode, the shape of the phosphorus-tin-nickel-containing copper alloy particles is preferably substantially spherical, flat or plate-like.
  • the electrode forming composition of the present invention contains, as metal particles, phosphorus-containing copper alloy particles, tin-containing particles, nickel-containing particles, silver particles, etc. in addition to phosphorus-tin-nickel-containing copper alloy particles
  • the content of the phosphorus-tin-nickel-containing copper alloy particles when the content is 100.0% by mass may be, for example, 10.0% by mass to 100.0% by mass, and 10.0% by mass It is preferably ⁇ 98.0% by mass, more preferably 15.0% by mass to 96.0% by mass, further preferably 20.0% by mass to 95.0% by mass, and 25. It is particularly preferably 0 to 92.0% by mass.
  • the voids in the electrode tend to be effectively reduced and the electrode can be densified. Further, by setting the content of the phosphorus-tin-nickel-containing copper alloy particles to 98.0% by mass or less, the resistivity of the electrode is reduced by including other metal particles, and the adhesion of the electrode to the silicon substrate is reduced. There exists a tendency which can express effects, such as improvement.
  • the phosphorus-tin-nickel-containing copper alloy can be produced by a commonly used method.
  • the phosphorus-tin-nickel-containing copper alloy particles are prepared using a phosphorus-tin-nickel-containing copper alloy prepared to have a desired phosphorus content, tin content, and nickel content. It can be prepared using conventional methods.
  • phosphorus-tin-nickel-containing copper alloy particles can be produced by a conventional method using a water atomizing method. For details of the water atomization method, the description of Metal Handbook (Maruzen Co., Ltd. Publishing Division) can be referred to.
  • a desired phosphorus-tin-nickel-containing copper alloy particle is obtained by melting a phosphorus-tin-nickel-containing copper alloy, pulverizing this by nozzle spraying, and drying and classifying the obtained powder. Can be manufactured.
  • phosphorus-tin-nickel-containing copper alloy particles having a desired particle size can be produced by appropriately selecting classification conditions.
  • the composition for electrode formation of the present invention may further contain at least one kind of phosphorus-containing copper alloy particles as metal particles.
  • phosphorus-containing copper alloy particles By including phosphorus-containing copper alloy particles, the resistivity of the electrode is lowered and the adhesion of the electrode to the semiconductor substrate tends to be improved. This can be considered, for example, as follows. That is, depending on the combination of the composition of the phosphorus-tin-nickel-containing copper alloy particles and the composition of the phosphorus-containing copper alloy particles, the phosphorus-containing copper alloy particles have a lower temperature and higher heat generation during heat treatment (firing). Reaction may start.
  • the electrode-forming composition during the heat treatment (firing) is heated from a relatively low temperature, so that the reaction of the phosphorus-tin-nickel-containing copper alloy particles (formation of Cu—Sn—Ni alloy phase, And the formation of the Sn—PO glass phase).
  • the phosphorus-containing copper alloy particles themselves may generate copper by reduction with phosphorus in the heat treatment (firing) step, and it is considered that the resistivity of the entire electrode can be lowered.
  • the phosphorus-containing copper alloy particles participate in a network composed of a Cu—Sn—Ni alloy phase and a Sn—PO glass phase derived from the phosphorus-tin-nickel-containing copper alloy particles by heat treatment (firing), so that the entire electrode It is considered that the resistivity of the electrode is reduced and the structure of the electrode is densified, and as a result, the strength in the electrode and the adhesion to the semiconductor substrate are improved.
  • the phosphorus content contained in the phosphorus-containing copper alloy particles in the case where the electrode-forming composition of the present invention contains phosphorus-containing copper alloy particles is, for example, from the viewpoint of oxidation resistance and heat generation effect during heat treatment (firing), for example It is preferably 0.1% by mass to 8.0% by mass, more preferably 0.2% by mass to 8.0% by mass, and 0.5% by mass to 7.7% by mass. Is more preferable.
  • the phosphorus-containing copper alloy particles are an alloy containing copper and phosphorus, but may further contain other atoms inevitably mixed therein.
  • Examples of other atoms inevitably mixed include Ag, Mn, Sb, Si, K, Na, Li, Ba, Sr, Ca, Mg, Be, Zn, Pb, Cd, Tl, V, Sn, and Al. , Zr, W, Mo, Ti, Co, Ni, and Au.
  • the content rate of the other atoms inevitably mixed in the phosphorus-containing copper alloy particles can be, for example, 3% by mass or less in the phosphorus-containing copper alloy particles, and the oxidation resistance and the resistivity of the electrode. In view of the above, the content is preferably 1% by mass or less.
  • the phosphorus-containing copper alloy particles may be used alone or in combination of two or more.
  • “use in combination of two or more types of phosphorus-containing copper alloy particles” means that two or more types of phosphorus-containing copper alloy particles having the same particle shape such as particle diameter and particle size distribution described later, although the component ratios are different. Are used in combination, but when two or more types of phosphorus-containing copper alloy particles having the same component ratio but different particle shapes are used in combination, two or more types of phosphorus-containing copper alloy particles having different component ratios and particle shapes are used. The case where it uses in combination is mentioned.
  • the particle diameter of the phosphorus-containing copper alloy particles in the present invention is not particularly limited, and D50% is, for example, preferably 0.4 ⁇ m to 10 ⁇ m, and more preferably 1 ⁇ m to 7 ⁇ m.
  • D50% is, for example, preferably 0.4 ⁇ m to 10 ⁇ m, and more preferably 1 ⁇ m to 7 ⁇ m.
  • the method for measuring the particle size (D50%) of the phosphorus-containing copper alloy particles is the same as the method for measuring the particle size of the phosphorus-tin-nickel-containing copper alloy particles.
  • the shape of the phosphorus-containing copper alloy particles is not particularly limited, and may be any of a substantially spherical shape, a flat shape, a block shape, a plate shape, a scale shape, and the like. From the viewpoint of oxidation resistance and reduction in the resistivity of the electrode, the shape of the phosphorus-containing copper alloy particles is preferably substantially spherical, flat or plate-like.
  • the phosphorus-containing copper alloy particle content is phosphorus when the total content of metal particles is 100.0% by mass.
  • the content of the containing copper alloy particles is preferably, for example, 0.1% by mass to 50.0% by mass, and more preferably 0.5% by mass to 45.0% by mass.
  • the phosphorus and copper contents in the phosphorus-containing copper alloy particles are the same as those of the phosphorus-tin-nickel-containing copper alloy particles, either by inductively coupled plasma mass spectrometry (ICP-MS), or by energy dispersive X-rays. It can be measured by spectroscopic (EDX) quantitative analysis.
  • ICP-MS inductively coupled plasma mass spectrometry
  • EDX energy dispersive X-rays
  • composition for electrode formation of the present invention may further contain at least one kind of tin-containing particles as metal particles.
  • tin-containing particles By including the tin-containing particles, the strength in the electrode is improved, and the adhesion of the electrode to the semiconductor substrate tends to be improved.
  • This can be considered, for example, as follows. That is, depending on the combination of the phosphorus-tin-nickel-containing copper alloy particles and the tin-containing particles, the formation of the Sn—PO glass phase can be promoted, and the voids in the electrode are reduced (the electrode structure is densified). Can). As a result, it is considered that the strength in the electrode is improved and the adhesion of the electrode to the semiconductor substrate is improved.
  • the tin-containing particles are not particularly limited as long as they contain tin. Among these, at least one selected from the group consisting of tin particles and tin alloy particles is preferable, and at least selected from the group consisting of tin alloy particles having a tin content of 1.0% by mass or more. One type is more preferable.
  • the purity of tin in the tin particles is not particularly limited. For example, the purity of the tin particles can be 95.0% by mass or more, preferably 97.0% by mass or more, and more preferably 99.0% by mass or more.
  • the type of alloy is not limited as long as the tin alloy particles are alloy particles containing tin.
  • the tin alloy particles are alloy particles containing tin.
  • the tin alloy particles having a tin content of, for example, 1.0% by mass or more
  • the tin content is more preferably 3.0 mass% or more, and the tin content is more preferably 10.0 mass% or more.
  • the alloys constituting the tin alloy particles include Sn—Ag alloy, Sn—Cu alloy, Sn—Ag—Cu alloy, Sn—Ag—Sb alloy, Sn—Ag—Sb—Zn alloy, Sn—Ag—Cu—Zn.
  • Tin alloys such as 8Cu-0.5Sb, Sn-2Ag-7.5Bi, Sn-3Bi-8Zn, Sn-9Zn, Sn-52In, Sn-40Pb have the same melting point as Sn (232 ° C). Or have a lower melting point.
  • the tin alloy particles composed of these tin alloys are melted at the initial stage of heat treatment (firing) to cover the surface of the phosphorus-tin-nickel-containing copper alloy particles, and the phosphorus-tin-nickel-containing copper alloy particles It can be preferably used in that it can react uniformly.
  • the tin alloy particles include Sn-AX-BY-CZ, in which the element X contains A mass%, the element Y contains B mass%, and the element Z contains C mass%. Indicates that In the present invention, these tin-containing particles may be used alone or in combination of two or more.
  • “use in combination of two or more kinds of tin-containing particles” means that two or more kinds of tin-containing particles having the same particle shape such as the particle diameter and particle size distribution described below are used in combination although the component ratio is different. In this case, when two or more types of tin-containing particles having the same component ratio but different particle shapes are used in combination, two or more types of tin-containing particles having different component ratios and particle shapes may be used in combination. .
  • the tin-containing particles may further contain other atoms that are inevitably mixed.
  • Other atoms inevitably mixed include, for example, Ag, Mn, Sb, Si, K, Na, Li, Ba, Sr, Ca, Mg, Be, Zn, Pb, Cd, Tl, V, Al, Zr, W, Mo, Ti, Co, Ni and Au can be mentioned.
  • the content of other atoms inevitably mixed in the tin-containing particles can be, for example, 3.0% by mass or less in the tin-containing particles, and the melting point and the phosphorus-tin-nickel-containing copper alloy From the viewpoint of reactivity with particles, it is preferably 1.0% by mass or less.
  • the D50% of the tin-containing particles is, for example, preferably 0.5 ⁇ m to 20 ⁇ m, more preferably 1 ⁇ m to 15 ⁇ m, and even more preferably 5 ⁇ m to 15 ⁇ m.
  • the D50% of the tin-containing particles is 0.5 ⁇ m or more, the oxidation resistance of the tin-containing particles themselves tends to be improved.
  • the tin-containing particles in the electrode by setting the D50% of the tin-containing particles to 20 ⁇ m or less, the tin-containing particles in the electrode, the phosphorus-tin-nickel-containing copper alloy particles, and the phosphorus-containing copper alloy particles, silver particles, and nickel contained as necessary
  • the contact area with the contained particles increases, and the reaction during the heat treatment (firing) tends to proceed effectively.
  • the method for measuring the particle size (D50%) of the tin-containing particles is the same as the method for measuring the particle size of the phosphorus-tin-nickel-containing copper alloy particles.
  • the shape of the tin-containing particles is not particularly limited, and may be any of a substantially spherical shape, a flat shape, a block shape, a plate shape, a scale shape, and the like. From the viewpoint of oxidation resistance and lowering the resistivity of the electrode, the shape of the tin-containing particles is preferably substantially spherical, flat or plate-like.
  • the content of tin-containing particles is the content of tin-containing particles when the total content of metal particles is 100.0% by mass.
  • the rate is preferably, for example, from 0.1% by mass to 50.0% by mass, and more preferably from 0.5% by mass to 45.0% by mass.
  • composition for forming an electrode of the present invention may further contain at least one kind of nickel-containing particles as metal particles.
  • nickel-containing particles By including the nickel-containing particles, oxidation resistance at high temperature tends to be exhibited in the heat treatment (firing) step.
  • the nickel-containing particles are not particularly limited as long as the particles contain nickel.
  • at least one selected from the group consisting of nickel particles and nickel alloy particles is preferable, and selected from the group consisting of nickel alloy particles whose nickel particles and nickel content are, for example, 1.0% by mass or more. It is more preferable that it is at least one kind.
  • the purity of nickel in the nickel particles is not particularly limited.
  • the purity of the nickel particles can be 95.0% by mass or more, preferably 97.0% by mass or more, and more preferably 99.0% by mass or more.
  • the type of alloy is not limited as long as the nickel alloy particles are alloy particles containing nickel.
  • the nickel alloy particles having a nickel content of, for example, 1.0% by mass or more More preferably, nickel alloy particles having a nickel content of 3.0% by mass or more, more preferably nickel alloy particles having a nickel content of 5.0% by mass or more, nickel It is particularly preferable that the nickel alloy particles have a content of 10.0 mass% or more.
  • the alloy constituting the nickel alloy particles examples include a Ni—Fe alloy, a Ni—Cu alloy, a Ni—Cu—Zn alloy, a Ni—Cr alloy, and a Ni—Cr—Ag alloy.
  • nickel alloy particles composed of Ni-58Fe, Ni-75Cu, Ni-6Cu-20Zn, and the like can react uniformly with phosphorus-tin-nickel-containing copper alloy particles during heat treatment (firing). Therefore, it can be suitably used.
  • the notation for nickel alloy particles is, for example, Ni-AX-BY-CZ, in which the element X contains A mass%, the element Y contains B mass%, and the element Z contains C mass%.
  • these nickel-containing particles may be used alone or in combination of two or more.
  • “use in combination of two or more kinds of nickel-containing particles” means that two or more kinds of nickel-containing particles having the same particle shape such as particle diameter and particle size distribution described later are used in combination although the component ratio is different. In this case, when two or more kinds of nickel-containing particles having the same component ratio but different particle shapes are used in combination, two or more kinds of nickel-containing particles having different component ratios and particle shapes are used in combination. .
  • the nickel-containing particles may further contain other atoms that are inevitably mixed.
  • other atoms inevitably mixed include Ag, Mn, Sb, Si, K, Na, Li, Ba, Sr, Ca, Mg, Be, Zn, Pb, Cd, Tl, V, Al, and Zr. , W, Mo, Ti, Co, Sn, and Au.
  • the content of other atoms inevitably mixed in the nickel-containing particles can be, for example, 3.0% by mass or less in the nickel-containing particles, and the phosphorus-tin-nickel-containing copper alloy particles From the viewpoint of the reactivity, it is preferably 1.0% by mass or less.
  • the particle diameter of the nickel-containing particles is not particularly limited. D50% is, for example, preferably 0.5 ⁇ m to 20 ⁇ m, more preferably 1 ⁇ m to 15 ⁇ m, and even more preferably 5 ⁇ m to 15 ⁇ m.
  • D50% is, for example, preferably 0.5 ⁇ m to 20 ⁇ m, more preferably 1 ⁇ m to 15 ⁇ m, and even more preferably 5 ⁇ m to 15 ⁇ m.
  • D50% of the nickel-containing particles By setting D50% of the nickel-containing particles to 0.5 ⁇ m or more, the oxidation resistance of the nickel-containing particles themselves tends to be improved. Further, by setting the D50% of the nickel-containing particles to 20 ⁇ m or less, the contact area with the phosphorus-tin-nickel-containing copper alloy particles in the electrode is increased, and heat treatment (firing) with the phosphorus-tin-nickel-containing copper alloy particles. The reaction of time tends to advance effectively.
  • the method for measuring the particle size (D50%) of the nickel-containing particles is the same as the method for measuring the particle size of the phosphorus-tin-nickel-containing copper alloy particles.
  • the shape of the nickel-containing particles is not particularly limited, and may be any of a substantially spherical shape, a flat shape, a block shape, a plate shape, a scale shape, and the like. From the viewpoint of oxidation resistance and reduction in the resistivity of the electrode, the shape of the nickel-containing particles is preferably substantially spherical, flat or plate-like.
  • the content of nickel-containing particles is the content of nickel-containing particles when the total content of metal particles is 100.0% by mass.
  • the rate is preferably, for example, from 0.1% by mass to 50.0% by mass, and more preferably from 0.5% by mass to 45.0% by mass.
  • composition for electrode formation of the present invention may further contain at least one kind of silver particles as metal particles.
  • silver particles By containing silver particles, the oxidation resistance is improved and the resistivity as an electrode tends to be lowered. Further, the Ag particles are precipitated in the Sn—PO glass phase formed by the reaction of the phosphorus-tin-nickel-containing copper alloy particles, so that the ohmic contact between the Cu—Sn—Ni alloy phase in the electrode and the semiconductor substrate is achieved. Tend to improve. Furthermore, when it is set as a solar cell module, it exists in the tendency for the solder connectivity to improve.
  • Silver constituting the silver particles may contain other atoms inevitably mixed therein.
  • other atoms inevitably mixed include Mn, Sb, Si, K, Na, Li, Ba, Sr, Ca, Mg, Be, Zn, Pb, Cd, Tl, V, Sn, Al, and Zr. , W, Mo, Ti, Co, Ni, and Au.
  • the content of other atoms inevitably mixed in the silver particles can be, for example, 3% by mass or less in the silver particles, and 1 mass from the viewpoint of the melting point and the low resistivity of the electrode. % Or less is preferable.
  • D50% is, for example, preferably 0.4 ⁇ m to 10 ⁇ m, and more preferably 1 ⁇ m to 7 ⁇ m.
  • the oxidation resistance tends to be effectively improved.
  • the silver particles in the electrode, the phosphorus-tin-nickel-containing copper alloy particles, and the phosphorus-containing copper alloy particles, tin-containing particles and nickel contained as necessary The contact area with the contained particles increases, and the resistivity of the electrode tends to decrease effectively.
  • the method for measuring the particle size (D50%) of the silver particles is the same as the method for measuring the particle size of the phosphorus-tin-nickel-containing copper alloy particles. Moreover, there is no restriction
  • the content of silver particles is as follows: The content of silver particles when the total content of metal particles is 100.0% by mass, For example, the content is preferably 0.1% by mass to 10.0% by mass, and more preferably 0.5% by mass to 8.0% by mass.
  • the electrode forming composition contains at least one kind of glass particles.
  • the adhesion between the formed electrode and the semiconductor substrate is improved during heat treatment (firing).
  • silicon nitride constituting the antireflection layer is removed by so-called fire-through during heat treatment (firing), and an ohmic contact between the electrode and the semiconductor substrate is formed.
  • the glass particles preferably have a softening point of 650 ° C. or lower and a crystallization start temperature exceeding 650 ° C., for example, from the viewpoint of lowering the resistivity of the formed electrode and the adhesion between the electrode and the semiconductor substrate.
  • the softening point and the crystallization start temperature are measured by a usual method using a differential thermal-thermogravimetric analyzer (TG-DTA).
  • the glass particles are softened or melted at the electrode-forming temperature and come into contact with an antireflection layer composed of silicon nitride to oxidize silicon nitride.
  • an antireflection layer composed of silicon nitride to oxidize silicon nitride.
  • the glass particles contained in the electrode forming composition preferably contain lead from the viewpoint that silicon dioxide can be efficiently taken up.
  • glass containing lead examples include those described in Japanese Patent No. 3050064, and these can also be suitably used in the present invention.
  • lead-free glass examples include lead-free glass described in paragraphs 0024 to 0025 of JP-A-2006-313744, lead-free glass described in JP-A-2009-188281, and the like. It is also preferable to select the glass appropriately and apply it to the present invention.
  • the glass particles are
  • the softening point is preferably 650 ° C. or lower, and the crystallization start temperature is preferably higher than 650 ° C. If it is such a glass particle, the glass particle which does not contain the component required for fire through like lead can be used.
  • the softening point of the glass particles is more preferably 583 ° C. or lower.
  • glass component constituting the glass particles examples include silicon oxide (SiO or SiO 2 ), phosphorus oxide (P 2 O 5 ), aluminum oxide (Al 2 O 3 ), boron oxide (B 2 O 3 ), and vanadium oxide.
  • V 2 O 5 potassium oxide (K 2 O), bismuth oxide (Bi 2 O 3 ), sodium oxide (Na 2 O), lithium oxide (Li 2 O), barium oxide (BaO), strontium oxide (SrO) ), Calcium oxide (CaO), magnesium oxide (MgO), beryllium oxide (BeO), zinc oxide (ZnO), lead oxide (PbO), cadmium oxide (CdO), tin oxide (SnO), zirconium oxide (ZrO 2 ) , tungsten oxide (WO 3), molybdenum oxide (MoO 3), lanthanum oxide (La 2 O 3), niobium oxide (N 2 O 5), tantalum oxide (Ta 2 O 5), yttrium oxide (Y 2
  • glass particles containing at least one selected from the group consisting of SiO 2 , P 2 O 5 , Al 2 O 3 , B 2 O 3 , V 2 O 5 , Bi 2 O 3 , ZnO and PbO are used. It is preferable to use glass particles containing at least one selected from the group consisting of SiO 2 , PbO, B 2 O 3 , Bi 2 O 3 , and Al 2 O 3 . In the case of such glass particles, the softening point tends to be effectively reduced. Furthermore, since such glass particles have improved wettability with phosphorus-tin-nickel-containing copper alloy particles, sintering between the particles proceeds in a heat treatment (firing) step, and an electrode with low resistivity is formed. Tend to be able to.
  • glass particles containing phosphorous pentoxide are preferable, and in addition to diphosphorus pentoxide, dipentapentoxide. More preferably, the glass particles further contain vanadium (P 2 O 5 —V 2 O 5 glass particles).
  • divanadium pentoxide the oxidation resistance is improved and the resistivity of the electrode tends to decrease. This can be attributed to, for example, that the softening point of the glass is lowered by further containing divanadium pentoxide.
  • the content of divanadium pentoxide is, for example, 1% by mass or more in the total mass of the glass It is preferably 1% by mass to 70% by mass.
  • the D50% of the glass particles is preferably 0.5 ⁇ m to 10 ⁇ m, for example, and more preferably 0.8 ⁇ m to 8 ⁇ m.
  • the workability in the preparation of the electrode forming composition tends to be improved.
  • the method for measuring D50% of the glass particles is the same as the method for measuring the particle diameter of the phosphorus-tin-nickel-containing copper alloy particles.
  • the shape of the glass particles is not particularly limited, and may be any of a substantially spherical shape, a flat shape, a block shape, a plate shape, a scale shape, and the like. From the viewpoint of oxidation resistance and a reduction in the resistivity of the electrode, the shape of the glass particles is preferably substantially spherical, flat or plate-like.
  • the content of the glass particles is, for example, preferably 0.1% by mass to 15.0% by mass, and preferably 0.5% by mass to 12.0% by mass in the total mass of the electrode forming composition. More preferably, the content is 1.0% by mass to 10.0% by mass.
  • glass particles with a content in such a range oxidation resistance, low electrode resistivity, and low contact resistivity can be achieved effectively. Furthermore, the contact and reaction between the phosphorus-tin-nickel-containing copper alloy particles tend to be promoted.
  • the mass ratio of glass particles to the mass of metal particles is preferably 0.01 to 0.20, for example, 0.03 to 0.15. More preferably.
  • glass particles with a content in such a range oxidation resistance, lower electrode resistivity, and lower contact resistivity tend to be achieved effectively. Furthermore, it exists in the tendency which can promote the contact between metal particles and reaction.
  • the ratio of the particle size (D50%) of the glass particles to the particle size (D50%) of the metal particles (glass particles / metal particles) is preferably 0.05 to 100, for example, 0.1 to 20 It is more preferable that By setting such a particle size ratio, there is a tendency to effectively achieve oxidation resistance, lower electrode resistivity, and lower contact resistivity. Furthermore, it exists in the tendency which can promote the contact between metal particles and reaction.
  • the particle diameter (D50%) of all metal particles refers to a particle diameter corresponding to 50% of volume accumulation from the small diameter side in the particle size distribution.
  • the electrode forming composition of the present invention may contain at least one kind of resin. Moreover, the composition for electrode formation of this invention may contain at least 1 type of the solvent. Thereby, the liquid physical properties (viscosity, surface tension, etc.) of the electrode-forming composition can be adjusted within a range suitable for the application method when applying to a semiconductor substrate or the like.
  • Solvents include hydrocarbon solvents such as hexane, cyclohexane and toluene, halogenated hydrocarbon solvents such as dichloroethylene, dichloroethane and dichlorobenzene, and cyclics such as tetrahydrofuran, furan, tetrahydropyran, pyran, dioxane, 1,3-dioxolane and trioxane.
  • hydrocarbon solvents such as hexane, cyclohexane and toluene
  • halogenated hydrocarbon solvents such as dichloroethylene, dichloroethane and dichlorobenzene
  • cyclics such as tetrahydrofuran, furan, tetrahydropyran, pyran, dioxane, 1,3-dioxolane and trioxane.
  • Ether solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, sulfoxide solvents such as dimethyl sulfoxide, diethyl sulfoxide, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, cyclohexanone, ethanol, 2-propanol, Alcohol solvents such as 1-butanol and diacetone alcohol, 2,2,4-trimethyl-1,3-pentanediol monoacetate, 2,2,4-trimethyl-1,3 Ester solvents of polyhydric alcohols such as tandiol monopropionate, 2,2,4-trimethyl-1,3-pentanediol monobutyrate, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, butyl cellosolve, diethylene glycol mono Examples include ether solvents of polyhydric alcohols such as but
  • a polyhydric alcohol ester solvent from the viewpoint of applicability (coatability and printability) when applying the electrode-forming composition to the semiconductor substrate. It is preferably at least one selected, and more preferably at least one selected from the group consisting of polyhydric alcohol ester solvents and terpene solvents.
  • any resin usually used in the technical field can be used without particular limitation as long as it can be thermally decomposed by heat treatment (firing), and even a natural polymer compound is a synthetic polymer compound. May be.
  • the resin include cellulose resins such as methylcellulose, ethylcellulose, carboxymethylcellulose, and nitrocellulose; acrylic resins such as polyvinyl alcohol compounds, polyvinylpyrrolidone compounds, and polyethyl acrylate; vinyl acetate-acrylate copolymers;
  • examples include butyral resins such as polyvinyl butyral, phenol-modified alkyd resins, alkyd resins such as castor oil fatty acid-modified alkyd resins, epoxy resins, phenol resins, and rosin ester resins. Resin may be used individually by 1 type or may combine 2 or more types.
  • the resin is preferably at least one selected from the group consisting of a cellulose resin and an acrylic resin from the viewpoint of disappearance in heat treatment (firing).
  • the weight average molecular weight of the resin is not particularly limited.
  • the weight average molecular weight of the resin is preferably, for example, 5000 to 500,000, and more preferably 10,000 to 300,000.
  • an increase in the viscosity of the electrode forming composition tends to be suppressed. This can be considered, for example, because the three-dimensional repulsion when the resin is adsorbed on the metal particles is sufficient, and aggregation of these resins is suppressed.
  • the weight average molecular weight of the resin is 500000 or less, aggregation of the resins in the solvent is suppressed, and an increase in the viscosity of the electrode forming composition tends to be suppressed.
  • the weight average molecular weight of the resin is 500000 or less, it is suppressed that the combustion temperature of the resin becomes high, and when the electrode forming composition is heat-treated (baked), the resin is not burned but remains as a foreign substance. There is a tendency that an electrode having a low resistivity can be formed.
  • the weight average molecular weight is obtained by conversion from a molecular weight distribution measured using GPC (gel permeation chromatography) using a standard polystyrene calibration curve.
  • the calibration curve is approximated in three dimensions using five standard polystyrene sample sets (PStQuick MP-H, PStQuick B, Tosoh Corporation).
  • PStQuick MP-H gel permeation chromatography
  • PStQuick B Tosoh Corporation
  • the content of the solvent and the resin is appropriately determined according to the type of the solvent and the resin used so that the electrode forming composition has desired liquid properties.
  • the total content of the solvent and the resin is preferably 3.0% by mass to 50.0% by mass, for example, 5.0% by mass to 45.0% by mass in the total mass of the electrode forming composition. %, More preferably 7.0% by mass to 40.0% by mass.
  • the total content of the solvent and the resin is within the above range, the application suitability when applying the electrode-forming composition to the semiconductor substrate is improved, and an electrode having a desired width and height is easily formed. Tend to be able to.
  • the electrode forming composition of the present invention includes a solvent and a resin, the content ratio of the solvent and the resin is appropriately determined depending on the type of the solvent and the resin used so that the electrode forming composition has desired liquid properties. You can choose.
  • the composition for forming an electrode of the present invention has a total content of metal particles of, for example, 65.0 mass% to 94.0 from the viewpoints of oxidation resistance, electrode resistivity reduction, and adhesion to a semiconductor substrate.
  • the glass particle content is, for example, 0.1% by mass to 15.0% by mass, and the total content of metal particles is 68.0% by mass to 92.0% by mass. More preferably, the glass particle content is 0.5% by mass to 12.0% by mass, the total content of the metal particles is 70.0% by mass to 90.0% by mass, The content is more preferably 1.0% by mass to 10.0% by mass.
  • the composition for forming an electrode of the present invention contains a solvent and a resin
  • the composition for forming an electrode of the present invention contains metal particles from the viewpoint of oxidation resistance, low resistivity of the electrode, and adhesion to a semiconductor substrate.
  • the total content is, for example, 65.0 mass% to 94.0 mass%
  • the glass particle content is, for example, 0.1 mass% to 15.0 mass%
  • the total content of solvent and resin The ratio is preferably, for example, 3.0% by mass to 50.0% by mass
  • the total content of metal particles is 68.0% by mass to 92.0% by mass
  • the content of glass particles is 0%.
  • the total content of the solvent and the resin is 5.0% by mass to 45.0% by mass, and the total content of the metal particles is 70.0% by mass. % To 90.0% by mass, the glass particle content is 1.0% to 10.0% by mass, And it is more preferable that the total content of the resin is 7.0 wt% to 40.0 wt%.
  • the composition for electrode formation may further contain at least one kind of flux.
  • the flux when an oxide film is formed on the surface of the metal particles, the oxide film is removed, and the reaction of the phosphorus-tin-nickel-containing copper alloy particles during the heat treatment (firing) can be promoted. It is in. Moreover, it exists in the tendency for the adhesiveness of an electrode and a semiconductor substrate to improve by containing a flux.
  • the flux is not particularly limited as long as the oxide film formed on the surface of the metal particles can be removed.
  • fatty acids, boric acid compounds, fluorinated compounds, and borofluorinated compounds can be mentioned as preferred fluxes.
  • a flux may be used individually by 1 type or may be used in combination of 2 or more type.
  • the flux include lauric acid, myristic acid, palmitic acid, stearic acid, sorbic acid, stearic acid, propionic acid, boron oxide, potassium borate, sodium borate, lithium borate, potassium borofluoride, borofluoride Sodium, lithium borofluoride, acidic potassium fluoride, acidic sodium fluoride, acidic lithium fluoride, potassium fluoride, sodium fluoride, lithium fluoride and the like can be mentioned.
  • potassium borate and potassium borofluoride are preferable fluxes from the viewpoint of complementation of heat resistance during heat treatment (firing) (property that flux does not volatilize at low temperatures during heat treatment (firing)) and oxidation resistance of metal particles. It is done.
  • the content of the flux includes the viewpoint of effectively expressing the oxidation resistance of the metal particles and the void formed by removing the flux when the heat treatment (firing) is completed.
  • the total mass of the electrode forming composition is, for example, preferably 0.1% by mass to 5.0% by mass, and more preferably 0.3% by mass to 4.0% by mass. Is more preferably 0.5% by mass to 3.5% by mass, particularly preferably 0.7% by mass to 3.0% by mass, and 1.0% by mass to 2.5% by mass. % Is very preferred.
  • the electrode-forming composition can further contain other components that are usually used in the technical field, if necessary.
  • other components include plasticizers, dispersants, surfactants, inorganic binders, metal oxides, ceramics, and organometallic compounds.
  • ⁇ Method for producing electrode forming composition> There is no restriction
  • the dispersion method and the mixing method are not particularly limited, and can be appropriately selected and applied from commonly used dispersion methods and mixing methods.
  • the electrode of the present invention is a heat-treated product of the electrode forming composition of the present invention.
  • the electrode of the present invention is produced using the electrode forming composition of the present invention.
  • the electrode forming composition is applied to the region where the electrode is to be formed, dried as necessary, and then subjected to heat treatment (firing) to obtain a desired region.
  • heat treatment firing
  • a method of forming an electrode By using the electrode forming composition of the present invention, an electrode having a low resistivity can be formed even when heat treatment (firing) is performed in the presence of oxygen (for example, in the air).
  • the composition for forming an electrode is applied on a semiconductor substrate so as to have a desired shape, and is dried as necessary. After that, an electrode having a low resistivity can be formed into a desired shape by heat treatment (firing). Further, by using the electrode forming composition of the present invention, an electrode having a low resistivity can be formed even when heat treatment (firing) is performed in the presence of oxygen (for example, in the air). Furthermore, the electrode formed on the semiconductor substrate using the electrode forming composition of the present invention has excellent adhesion to the semiconductor substrate and can achieve good ohmic contact.
  • Examples of the method for applying the electrode forming composition include a screen printing method, an ink jet method, a dispenser method, and the like, and the screen printing method is preferable from the viewpoint of productivity.
  • the electrode forming composition When applying the electrode forming composition to a semiconductor substrate or the like by a screen printing method, the electrode forming composition is preferably pasty.
  • the paste-like electrode forming composition preferably has a viscosity in the range of 20 Pa ⁇ s to 1000 Pa ⁇ s, for example.
  • the viscosity of the electrode forming composition is measured at 25 ° C. using a Brookfield HBT viscometer.
  • the amount of the electrode forming composition applied to the semiconductor substrate can be appropriately selected according to the size of the electrode to be formed.
  • the application amount of the electrode forming composition may be, for example, 2 g / m 2 to 10 g / m 2, and preferably 4 g / m 2 to 8 g / m 2 .
  • heat treatment (firing) conditions for forming an electrode using the electrode forming composition heat treatment conditions usually used in the technical field can be applied.
  • the heat treatment (firing) temperature is 800 ° C. to 900 ° C., but when the electrode forming composition of the present invention is used, it is used in a wide range from low temperature heat treatment conditions to general heat treatment conditions. be able to.
  • an electrode having good characteristics can be formed at a wide range of heat treatment temperatures of 450 ° C. to 900 ° C.
  • the heat treatment time can be appropriately selected according to the heat treatment temperature and the like, and can be, for example, 1 second to 20 seconds.
  • any apparatus that can be heated to the above temperature can be used as appropriate, and examples thereof include an infrared heating furnace and a tunnel furnace.
  • the infrared heating furnace is highly efficient because electric energy is input into a heating material in the form of electromagnetic waves and converted into thermal energy, and rapid heating is possible in a short time. Furthermore, since there are few products by combustion and non-contact heating, it is possible to suppress contamination of the generated electrodes.
  • the tunnel furnace automatically and continuously conveys the sample from the entrance to the exit and performs heat treatment (firing), it can be uniformly heat treated (fired) by controlling the division of the furnace body and the conveying speed. From the viewpoint of the power generation performance of the solar cell element, it is preferable to perform heat treatment with a tunnel furnace.
  • the solar cell element of the present invention includes at least a semiconductor substrate and an electrode that is a heat-treated product (baked product) of the composition for forming an electrode of the present invention provided on the semiconductor substrate.
  • the solar cell element which has a favorable characteristic is obtained, and it is excellent in productivity of this solar cell element.
  • the solar cell element means one having a semiconductor substrate on which a pn junction is formed and an electrode formed on the semiconductor substrate.
  • the manufacturing method of the solar cell element of this invention has the process of providing the composition for electrode formation of this invention on a semiconductor substrate, and the process of heat-processing the said composition for electrode formation.
  • FIG. 1, FIG. 2 and FIG. 3 show a schematic sectional view, a schematic plan view of a light receiving surface, and a schematic plan view of a back surface, respectively.
  • an n + -type diffusion layer 2 is formed near the surface of one surface of the semiconductor substrate 1, and the output extraction electrode 4 and the antireflection layer 3 are formed on the n + -type diffusion layer 2. Is formed. Further, a p + type diffusion layer 7 is formed in the vicinity of the surface of the other surface, and a back surface output extraction electrode 6 and a back surface current collecting electrode 5 are formed on the p + type diffusion layer 7.
  • a single crystal or polycrystalline silicon substrate is used for the semiconductor substrate 1 of the solar cell element. This semiconductor substrate 1 contains boron or the like and constitutes a p-type semiconductor.
  • the light receiving surface side is formed with unevenness (also referred to as texture, not shown) using an etching solution containing NaOH and IPA (isopropyl alcohol). Phosphorus or the like is doped on the light receiving surface side, the n + -type diffusion layer 2 is formed with a thickness of the order of submicron, and a pn junction is formed at the boundary with the p-type bulk portion. Further, on the light receiving surface side, an antireflection layer 3 such as silicon nitride is provided on the n + -type diffusion layer 2 with a thickness of about 90 nm by PECVD (plasma enhanced chemical vapor deposition) or the like.
  • PECVD plasma enhanced chemical vapor deposition
  • the light receiving surface electrode 4 provided on the light receiving surface side schematically shown in FIG. 2, and the back surface collecting electrode 5 and the back surface output extraction electrode 6 formed on the back surface schematically shown in FIG. To do.
  • the light-receiving surface electrode 4 and the back surface output extraction electrode 6 are formed from the electrode forming composition of the present invention.
  • the electrode 5 for back surface current collection is formed from the composition for aluminum electrode formation containing a glass particle.
  • the electrode forming composition and the aluminum electrode forming composition of the present invention are formed in a desired pattern by screen printing or the like.
  • the electrode forming composition of the present invention the light-receiving surface electrode 4 and the back surface output extraction electrode 6 having excellent resistivity and contact resistivity can be formed even if heat treatment (firing) is performed at a relatively low temperature.
  • the glass particles contained in the electrode-forming composition of the present invention for forming the light-receiving surface electrode 4 react with the antireflection layer 3 (fire-through) to receive light.
  • the surface electrode 4 and the n + -type diffusion layer 2 are electrically connected (ohmic contact).
  • the light-receiving surface electrode 4 is formed using the electrode-forming composition of the present invention, so that copper is suppressed as a conductive metal, and the oxidation of copper is suppressed. 4 is formed with good productivity.
  • the formed electrode contains a Cu—Sn—Ni alloy phase (alloy phase containing copper, tin and nickel) and a Sn—PO glass phase (tin, phosphorus and oxygen). It is preferable that the Sn—PO glass phase (not shown) is disposed between the light receiving surface electrode 4 or the back surface output extraction electrode 6 and the semiconductor substrate 1. preferable. Thereby, reaction with copper and a semiconductor substrate is suppressed, and the electrode which is excellent in adhesiveness with low resistivity can be formed.
  • aluminum in the aluminum electrode forming composition for forming the back surface collecting electrode 5 diffuses into the back surface of the semiconductor substrate 1, and the p + -type diffusion layer 7 is formed. By forming, an ohmic contact can be obtained between the semiconductor substrate 1 and the back surface collecting electrode 5.
  • the aluminum electrode forming composition for forming the back surface collecting electrode 5 is printed first, and after drying, the atmosphere After forming the back surface collecting electrode 5 by heat treatment (baking) at about 750 ° C. to 900 ° C., the electrode forming composition of the present invention is printed on the light receiving surface side and the back surface side, and after drying, 450 ° C. in the atmosphere.
  • a method of forming the light-receiving surface electrode 4 and the back surface output extraction electrode 6 by heat treatment (firing) at about ⁇ 650 ° C. can be mentioned.
  • This method is effective in the following cases, for example. That is, when the aluminum electrode forming composition for forming the back surface collecting electrode 5 is heat-treated (fired), depending on the composition of the aluminum electrode-forming composition, the aluminum particles may be used at a heat treatment (firing) temperature of 650 ° C. or lower. In some cases, the p + -type diffusion layer 7 cannot be sufficiently formed due to insufficient sintering and the amount of aluminum diffusion into the semiconductor substrate 1. In this state, an ohmic contact cannot be sufficiently formed between the semiconductor substrate 1 on the back surface, the back surface collecting electrode 5 and the back surface output extraction electrode 6, and the power generation performance as a solar cell element may be lowered.
  • the electrode forming composition of the present invention is printed,
  • the light-receiving surface electrode 4 and the back surface output extraction electrode 6 are preferably formed by heat treatment (firing) at a low temperature (450 ° C. to 650 ° C.).
  • FIG. 4 is a schematic plan view of a back-side electrode structure common to a so-called back contact solar cell element according to another embodiment of the present invention, and FIG. 4 shows an outline of a solar cell element which is a back contact solar cell element according to another embodiment.
  • the perspective view which shows a structure is shown in FIG.5, FIG6 and FIG.7, respectively. 5, 6, and 7 are perspective views taken along a section AA in FIG. 4.
  • through holes that penetrate both the light receiving surface side and the back surface side are formed by laser drilling, etching, or the like. Further, a texture (not shown) for improving the light incident efficiency is formed on the light receiving surface side. Further, an n + -type diffusion layer 2 by n-type diffusion treatment is formed on the light-receiving surface side, and an antireflection layer (not shown) is formed on the n + -type diffusion layer 2. These are manufactured by the same process as the conventional silicon solar cell element. The n + type diffusion layer 2 is also formed around the surface of the through hole and the opening on the back surface side of the through hole.
  • the electrode forming composition of the present invention is filled in the previously formed through hole by a printing method, an ink jet method or the like, and the electrode forming composition of the present invention is also formed in a grid on the light receiving surface side.
  • the composition layer which is provided and forms the through-hole electrode 9 and the light-receiving-surface current collecting electrode 8 is formed.
  • the electrode forming composition used for filling and application is preferably one having an optimum composition for each process such as physical properties such as viscosity, but the electrode forming composition having the same composition is used.
  • the filling and application may be performed in a lump.
  • an n + -type diffusion layer 2 and a p + -type diffusion layer 7 for preventing carrier recombination are formed on the back surface side.
  • boron (B), aluminum (Al), or the like is used as an impurity element for forming the p + -type diffusion layer 7.
  • the p + -type diffusion layer 7 may be formed by performing a thermal diffusion process using, for example, B as a diffusion source in a step before the formation of the antireflection layer.
  • Al is used as the impurity element
  • the aluminum electrode forming composition may be applied to the opposite side and heat-treated (fired).
  • the electrode forming composition of the present invention is applied to the n + -type diffusion layer 2 and the p + -type diffusion layer 7 in stripes, thereby forming the back electrode. 10 and the back electrode 11 are formed.
  • the back electrode is formed using the electrode forming composition of the present invention only on the n + type diffusion layer 2. Good.
  • the solar cell element having the structure shown in the perspective view of FIG. 6 is manufactured in the same manner as the solar cell element having the structure shown in the perspective view of FIG. 5 except that the light receiving surface collecting electrode is not formed. Can do. That is, in the solar cell element having the structure shown in the perspective view of FIG. 6, the electrode forming composition of the present invention can be used for forming the through-hole electrode 9, the back electrode 10, and the back electrode 11.
  • the solar cell element having the structure shown in the perspective view of FIG. 7 is shown in the perspective view of FIG. 5 except that the n-type silicon substrate 12 is used as the base semiconductor substrate and no through hole is formed. It can be manufactured in the same manner as the solar cell element having the structure. That is, in the solar cell element having the structure shown in the perspective view of FIG. 7, the electrode forming composition of the present invention can be used for forming the back electrode 10 and the back electrode 11.
  • the electrode-forming composition of the present invention is not limited to the use of the above-described solar cell electrode, but is used for electrode wiring, shield wiring, ceramic capacitors, antenna circuits, various sensor circuits, and semiconductor devices of plasma displays. It can also be suitably used for applications such as heat dissipation materials. Among these, it can be suitably used particularly when an electrode is formed on a substrate containing silicon.
  • the solar cell is configured by providing a wiring material such as a tab wire on the electrode of the solar cell element, and connecting a plurality of solar cell elements via the wiring material as necessary, and sealing resin It means a state sealed with, for example.
  • the solar cell of this invention has the solar cell element of this invention, and the wiring material arrange
  • the solar cell of this invention should just be comprised by arrange
  • the solar cell may be constituted by connecting a plurality of solar cell elements via a wiring material and further sealing with a sealing material.
  • the wiring material and the sealing material are not particularly limited, and can be appropriately selected from those usually used in the industry.
  • the wiring material is not particularly limited, and a solder-coated copper wire (tab wire) for a solar cell can be suitably used.
  • solder composition examples include Sn—Pb, Sn—Pb—Ag, Sn—Ag—Cu, etc.
  • Sn—Ag—Cu based which does not substantially contain lead. It is preferable to use solder.
  • the thickness of the copper wire of the tab wire is not particularly limited, and 0.05 mm to 0 in view of the difference in thermal expansion coefficient or connection reliability with the solar cell element during the heating and pressing treatment and the resistivity of the tab wire itself. 0.5 mm, preferably 0.1 mm to 0.5 mm.
  • the cross-sectional shape of the tab line is not particularly limited, and any of a rectangular shape (flat tab) and an elliptical shape (round tab) can be applied, and a rectangular shape (flat tab) is preferably used.
  • the total thickness of the tab wire is not particularly limited, but is preferably 0.1 mm to 0.7 mm, and more preferably 0.15 mm to 0.5 mm.
  • the classified powder is blended with an inert gas, subjected to deoxidation and dehydration treatment, and phosphorus containing 5.0% by mass of phosphorus, 17.5% by mass of tin, and 20.0% by mass of nickel Tin-nickel-containing copper alloy particles were prepared.
  • the particle diameter (D50%) of the phosphorus-tin-nickel-containing copper alloy particles was 5.0 ⁇ m, and the shape thereof was substantially spherical.
  • a glass composed of 5.0% by mass of aluminum oxide (Al 2 O 3 ) and 9.0% by mass of zinc oxide (ZnO) (hereinafter sometimes abbreviated as “G01”) was prepared.
  • the obtained glass G01 had a softening point of 420 ° C. and a crystallization start temperature of over 650 ° C.
  • glass G01 particles having a particle diameter (D50%) of 2.5 ⁇ m were obtained.
  • the shape was substantially spherical.
  • the shapes of the phosphorus-tin-nickel-containing copper alloy particles and glass particles were determined by observing with Hitachi High-Technologies Corporation TM-1000 scanning electron microscope.
  • the particle diameter (D50%) of the phosphorus-tin-nickel-containing copper alloy particles and glass particles was calculated using a Beckman Coulter Co., Ltd., LS 13, 320 type laser scattering diffraction particle size distribution analyzer (measurement wavelength: 632 nm). .
  • the softening point and the crystallization start temperature of the glass particles were obtained from a differential heat (DTA) curve using a Shimadzu Corporation, DTG-60H type differential thermal-thermogravimetric simultaneous measuring device. Specifically, in the DTA curve, the softening point can be estimated from the endothermic part, and the crystallization start temperature can be estimated from the heat generating part.
  • DTA differential heat
  • FIG. 1 A p-type semiconductor substrate having a thickness of 190 ⁇ m having an n + -type diffusion layer, a texture, and an antireflection layer (silicon nitride layer) formed on the light receiving surface is prepared, and the size is 125 mm ⁇ 125 mm. Cut out.
  • the electrode-forming composition 1 obtained above was printed using a screen printing method so as to form an electrode pattern as shown in FIG.
  • the electrode pattern is composed of 150 ⁇ m wide finger lines and 1.5 mm wide bus bars, and the printing conditions (screen plate mesh, printing speed and printing pressure) are appropriately set so that the thickness after heat treatment (firing) is 20 ⁇ m. It was adjusted. This was placed in an oven heated to 150 ° C. for 15 minutes, and the solvent was removed by evaporation.
  • the electrode forming composition 1 and the aluminum electrode forming composition are placed on the surface opposite to the light receiving surface (hereinafter also referred to as “back surface”).
  • back surface the surface opposite to the light receiving surface
  • screen printing was performed so that an electrode pattern as shown in FIG. 3 was obtained.
  • the pattern of the back surface output extraction electrode 6 formed using the electrode forming composition 1 was composed of two lines, and was printed so that the size of one line was 123 mm ⁇ 5 mm.
  • the printing conditions (screen plate mesh, printing speed and printing pressure) were appropriately adjusted so that the thickness of the back surface output extraction electrode 6 after heat treatment (firing) was 20 ⁇ m.
  • the aluminum electrode forming composition was printed on the entire surface other than the back surface output extraction electrode 6 to form a pattern of the back surface collecting electrode 5. Moreover, the printing conditions of the composition for forming an aluminum electrode were appropriately adjusted so that the thickness of the back surface collecting electrode 5 after heat treatment (firing) was 30 ⁇ m. This was placed in an oven heated to 150 ° C. for 15 minutes, and the solvent was removed by evaporation.
  • heat treatment is performed using a tunnel furnace (Noritake Co., Ltd., Limited, one-row transport W / B tunnel furnace) in an air atmosphere at a maximum temperature of 800 ° C. and a holding time of 10 seconds.
  • the formed solar cell element 1 was produced.
  • Example 2 the solar cell element 2 was formed in the same manner as in Example 1 except that the heat treatment (firing) conditions during electrode formation were changed from the maximum temperature of 800 ° C. for 10 seconds to the maximum temperature of 850 ° C. for 8 seconds. Produced.
  • Example 3 In Example 1, the phosphorus content of the phosphorus-tin-nickel-containing copper alloy particles was changed from 5.0% by mass to 5.6% by mass, and the tin content was changed from 17.5% by mass to 12.3% by mass.
  • the composition for electrode formation 3 was prepared in the same manner as in Example 1 except that the nickel content was changed from 20.0% by mass to 14.0% by mass, and the solar cell element 3 was produced. .
  • Example 4 In Example 1, the phosphorus content of the phosphorus-tin-nickel-containing copper alloy particles was changed from 5.0% by mass to 6.0% by mass, and the tin content was changed from 17.5% by mass to 8.8% by mass.
  • the composition 4 for electrode formation was prepared similarly to Example 1 except having changed and changing nickel content from 20.0 mass% to 10.0 mass%, and the solar cell element 4 was produced. .
  • Example 5 In Example 1, the content of the phosphorus-tin-nickel-containing copper alloy particles was changed from 67.0 parts to 74.5 parts, and the content of the glass G01 particles was changed from 8.0 parts to 5.5 parts. The content of diethylene glycol monobutyl ether (BC) was changed from 20.0 parts to 16.5 parts, and the content of polyethyl acrylate (EPA) was changed from 5.0 parts to 3.5 parts. Prepared the electrode forming composition 5 in the same manner as in Example 1 to produce a solar cell element 5.
  • BC diethylene glycol monobutyl ether
  • EPA polyethyl acrylate
  • Example 6 phosphorus-containing copper alloy particles containing 7.0% by mass of phosphorus were added to the electrode forming composition.
  • the phosphorus-containing copper alloy particles were prepared by classification, deoxygenation, and dehydration after water atomization in the same manner as the phosphorus-tin-nickel-containing copper alloy particles of Example 1.
  • the phosphorus-containing copper alloy particles had a particle size (D50%) of 5.0 ⁇ m and a substantially spherical shape.
  • the content of each component in the electrode-forming composition is 46.9 parts of phosphorus-tin-nickel-containing copper alloy particles, 20.1 parts of phosphorus-containing copper alloy particles, and 8 of glass G01 particles. 0.06 parts, diethylene glycol monobutyl ether (BC) 20.0 parts, and polyethyl acrylate (EPA) 5.0 parts in the same manner as in Example 1 except that the electrode-forming composition 6
  • the solar cell element 6 was prepared.
  • Example 7 In Example 6, the content of the phosphorus-tin-nickel-containing copper alloy particles was changed from 46.9 parts to 53.6 parts, and the content of the phosphorus-containing copper alloy particles was changed from 20.1 parts to 13.4 parts. Except having changed, it carried out similarly to Example 6, and prepared the composition 7 for electrode formation, and produced the solar cell element 7.
  • FIG. 7 In Example 6, the content of the phosphorus-tin-nickel-containing copper alloy particles was changed from 46.9 parts to 53.6 parts, and the content of the phosphorus-containing copper alloy particles was changed from 20.1 parts to 13.4 parts. Except having changed, it carried out similarly to Example 6, and prepared the composition 7 for electrode formation, and produced the solar cell element 7.
  • Example 8 tin particles (Sn; particle diameter (D50%) is 5.0 ⁇ m; purity is 99.9% by mass) were added to the electrode forming composition. Specifically, the content of each component in the electrode-forming composition is 57.5 parts of phosphorus-tin-nickel-containing copper alloy particles, 9.5 parts of tin particles, and 8.0 parts of glass G01 particles.
  • an electrode-forming composition 8 was prepared, A solar cell element 8 was produced.
  • Example 9 In Example 1, nickel particles (Ni; particle diameter (D50%) is 5.0 ⁇ m; purity is 99.9% by mass) were added to the electrode forming composition. Specifically, the content of each component in the electrode-forming composition is 59.5 parts of phosphorus-tin-nickel-containing copper alloy particles, 7.5 parts of nickel particles, and 8.0 parts of glass G01 particles. In the same manner as in Example 1 except that 20.0 parts of diethylene glycol monobutyl ether (BC) and 5.0 parts of polyethyl acrylate (EPA) were prepared, an electrode-forming composition 9 was prepared, A solar cell element 9 was produced.
  • BC diethylene glycol monobutyl ether
  • EPA polyethyl acrylate
  • Example 10 In Example 1, silver particles (Ag; particle diameter (D50%) is 3.0 ⁇ m; purity is 99.5% by mass) were added to the electrode forming composition. Specifically, the content of each component is 62.5 parts of phosphorus-tin-nickel-containing copper alloy particles, 4.5 parts of silver particles, 8.0 parts of glass G01 particles, diethylene glycol monobutyl ether (BC). Except having made 20.0 parts and 5.0 parts of polyethyl acrylate (EPA) into 5.0 parts, the electrode formation composition 10 was prepared and the solar cell element 10 was produced.
  • EPA polyethyl acrylate
  • Example 11 In Example 10, the content of the phosphorus-tin-nickel-containing copper alloy particles was changed from 62.5 parts to 60.3 parts, and the content of silver particles was changed from 4.5 parts to 6.7 parts, Furthermore, a composition 11 for electrode formation was prepared in the same manner as in Example 10 except that the heat treatment (firing) conditions during electrode formation were changed from a maximum temperature of 800 ° C. for 10 seconds to a maximum temperature of 850 ° C. for 8 seconds. And the solar cell element 11 was produced.
  • Examples 12 to 20> the phosphorus content, the tin content and the nickel content of the phosphorus-tin-nickel-containing copper alloy particles, the particle diameter (D50%) and the content thereof, the phosphorus content of the phosphorus-containing copper alloy particles, the particle diameter (D50%) and its content, composition of tin-containing particles, particle size (D50%) and its content, composition of nickel-containing particles, particle size (D50%) and its content, silver particle content, glass
  • the electrode was prepared in the same manner as in the above example except that the type of particle and its content, the type and content of solvent, and the type and content of resin were changed as shown in Tables 1 to 3. Forming compositions 12-20 were prepared respectively.
  • Glass G02 particles were obtained. The softening point of the glass G02 was 492 ° C., and the crystallization start temperature exceeded 650 ° C. Furthermore, the shape of the glass G02 particles was substantially spherical.
  • the solvent “Ter” represents terpineol
  • the resin “EC” represents ethyl cellulose (Dow Chemical Japan Co., Ltd., weight average molecular weight: 190000).
  • a desired electrode was formed in the same manner as in the above example except that each of the obtained electrode forming compositions 12 to 20 was used and the heat treatment (firing) conditions were changed as shown in Table 4. Solar cell elements 12 to 20 were produced.
  • a solar cell element 21 having a structure as shown in FIG. 5 was produced.
  • a specific manufacturing method is described below.
  • the electrode forming composition 1 was filled in the previously formed through hole by an ink jet method, and further printed on the light receiving surface side in a grid.
  • the electrode forming composition 1 and the aluminum electrode forming composition were printed in stripes in a pattern as shown in FIG. 4, and the electrode forming composition 1 was placed under the through holes. Formed to be printed. Using a tunnel furnace (Noritake Co., Ltd., single-line transport W / B tunnel furnace), this is heat-treated at a maximum firing temperature of 800 ° C. and a holding time of 10 seconds to form a desired electrode. The produced solar cell element 21 was produced. At this time, about the part which printed the composition for aluminum electrode formation, the p ⁇ +> type
  • Example 22 In Example 21, except that the electrode-forming composition 1 was changed from the electrode-forming composition 1 to the electrode-forming composition 15 obtained above, and a light-receiving surface collecting electrode, a through-hole electrode, and a back electrode were formed. In the same manner as in Example 21, a solar cell element 22 was produced.
  • Example 23 Using the electrode forming composition 1 obtained above, a solar cell element 23 having a structure as shown in FIG. 6 was produced.
  • the solar cell element 23 was manufactured in the same manner as in Example 21 and Example 22 except that the light receiving surface electrode was not formed.
  • the firing conditions were a maximum temperature of 800 ° C. and a holding time of 10 seconds.
  • Example 24 A solar cell element 24 was produced in the same manner as in Example 23 except that the composition for electrode formation 1 was changed to the composition for electrode formation 24 in Example 23. Specifically, the phosphorus content in the phosphorus-tin-nickel-containing copper alloy particles contained in the electrode forming composition was changed from 5.0% by mass to 5.6% by mass, and the tin content was 17.5% by mass. % Was changed to 12.3% by mass, and the nickel content was changed from 20.0% by mass to 14.0% by mass. Further, the glass particles were changed from G01 particles to glass G03 particles.
  • Glass G03 is composed of silicon dioxide (SiO 2 ) 13.0% by mass, boron oxide (B 2 O 3 ) 25.0% by mass, zinc oxide (ZnO) 38.0% by mass, aluminum oxide (Al 2 O 3). ) 12.0% by mass and 12.0% by mass of barium oxide (BaO) were prepared and pulverized to obtain glass G03 particles having a particle size (D50%) of 2.0 ⁇ m.
  • the softening point of the glass G03 was 583 ° C., and the crystallization start temperature exceeded 650 ° C. Furthermore, the shape of the glass G03 particles was substantially spherical.
  • Example 25 Using the electrode forming composition 1 obtained above, a solar cell element 25 having a structure as shown in FIG. 7 was produced.
  • the manufacturing method is the same as in Example 21 and Example 22, except that an n-type silicon substrate is used as the base substrate and that the light-receiving surface electrode, the through hole, and the through hole electrode are not formed.
  • the firing conditions were a maximum temperature of 800 ° C. and a holding time of 10 seconds.
  • Example 26 A solar cell element 26 was produced in the same manner as in Example 25 except that the composition for electrode formation 1 was changed to the composition for electrode formation 24 in Example 25.
  • Example 27 In the above examples, the phosphorus content, the tin content and the nickel content of the phosphorus-tin-nickel-containing copper alloy particles, the particle diameter (D50%) and the content thereof, the type and content of glass particles, and the type of solvent And the composition 27 for electrode formation was prepared like the said Example except having changed the kind of resin, and its content, as shown in Table 1-Table 3, and its content. Next, a solar cell element in which a desired electrode was formed in the same manner as in the above example except that the obtained electrode forming composition 27 was used and the heat treatment (firing) conditions were changed as shown in Table 4. 27 was produced.
  • Example 1 The preparation of the electrode-forming composition in Example 1 was carried out except that the respective components were changed so that the compositions shown in Tables 1 to 3 were obtained without using phosphorus-tin-nickel-containing copper alloy particles.
  • an electrode forming composition C1 was prepared.
  • a solar cell element C1 was produced in the same manner as in Example 1 except that the electrode-forming composition C1 containing no phosphorus-tin-nickel-containing copper alloy particles was used.
  • Electrode forming compositions C2 having the compositions shown in Tables 1 to 3.
  • a solar cell element C2 was produced in the same manner as in Comparative Example 1 except that the electrode forming composition C2 was used.
  • An electrode-forming composition C4 having the composition shown in Tables 1 to 3 was prepared using only copper alloy particles containing phosphorus and nickel as metal particles without using the phosphorus-tin-nickel-containing copper alloy particles.
  • a solar cell element C4 was produced in the same manner as in Comparative Example 1 except that the electrode forming composition C4 was used.
  • An electrode-forming composition C5 having the composition shown in Tables 1 to 3 was prepared using only copper alloy particles containing tin and nickel as metal particles without using the phosphorus-tin-nickel-containing copper alloy particles.
  • a solar cell element C5 was produced in the same manner as in Comparative Example 1 except that the electrode forming composition C5 was used.
  • Example 21 ⁇ Comparative Example 7> In Example 21, except that the electrode-forming composition 1 was changed to the electrode-forming composition C1 obtained above, and a light-receiving surface collecting electrode, a through-hole electrode, and a back electrode were formed. In the same manner as in Example 21, a solar cell element C7 was produced.
  • Example 23 a solar cell element C8 was produced in the same manner as in Example 23 except that the composition 1 for electrode formation was changed to the composition C1 for electrode formation obtained above.
  • Example 9 a solar cell element C9 was produced in the same manner as in Example 25 except that the electrode forming composition 1 was changed to the electrode forming composition C1 obtained above.
  • each measurement value obtained is shown in Table 5 converted into a relative value with the measurement value of Comparative Example 1 (solar cell element C1) as 100.0.
  • Comparative Example 2 the resistivity of the formed electrode increased, and evaluation was impossible. The reason is considered to be due to oxidation of copper particles.
  • Examples 21 to 26 and 27 and Comparative Examples 1 to 6 were the back output electrodes, and Examples 21 to 26 As for the back electrodes of Comparative Examples 7 to 9, the cross section of each electrode was observed with a scanning electron microscope Miniscope TM-1000 (Hitachi Ltd.) at an acceleration voltage of 15 kV, and Cu— The presence or absence of Sn—Ni alloy phase and Sn—PO glass phase was investigated. The results are also shown in Tables 5 to 8.
  • the backside output extraction electrodes of Examples 1 to 20 and 27 and Comparative Examples 1 to 6 were adhered to the silicon substrate.
  • a stud pin pin diameter: ⁇ 4.1 mm
  • a tensile load was applied to the stud pin using a thin film adhesion strength measuring apparatus (Romulus, QUAD GROUP), and the load at break was evaluated. At this time, the broken part was also observed.
  • Comparative Examples 3 to 5 the power generation performance deteriorated as compared with Comparative Example 1. This is considered as follows, for example.
  • Comparative Example 3 and Comparative Example 4 since Sn was not contained in the alloy particles used, the Sn—PO glass phase was not formed, and copper and silicon in the silicon substrate were not subjected to heat treatment (firing). It is considered that interdiffusion of the pn junction has occurred and the pn junction characteristics in the substrate have deteriorated.
  • Comparative Example 5 since the alloy particles used did not contain phosphorus, the Sn—PO glass phase was not formed as in Comparative Examples 3 and 4, and during the heat treatment (firing).
  • the power generation performance of the solar cell elements produced in Examples 1 to 20 and 27 was almost the same as the measured value of the solar cell element of Comparative Example 1.
  • a Cu—Sn—Ni alloy phase and a Sn—PO glass phase were present in the light receiving surface electrode.
  • the adhesion strength of the back surface output extraction electrodes of the solar cells produced in Examples 1 to 20 and 27 to the silicon substrate was almost the same as that of Comparative Example 1.
  • the formed electrode is in close contact with the silicon substrate with high strength because the broken portion was in the silicon substrate.
  • Comparative Example 2 it is considered that the inside of the electrode is occupied by a melt of copper oxide and glass frit and is in close contact with the silicon substrate with a certain degree of strength.
  • Comparative Examples 3 to 5 as described above, mutual diffusion of copper and silicon occurs between the electrode after heat treatment (firing) and the silicon substrate, and a reactant phase (Cu 3 Si) is formed. It is considered that the adhesion force of the electrode is greatly reduced by lifting a part of the electrode from the substrate.
  • Comparative Example 6 no phosphorus-tin-nickel-containing copper alloy particles were used, but the power generation performance of the produced solar cell element was almost the same as the measured value of the solar cell element of Comparative Example 1. Further, from the results of the structure observation, even when a combination of phosphorus-containing copper alloy particles, tin-containing particles and nickel-containing particles was used, a Cu—Sn—Ni alloy phase and a Sn—PO glass phase were formed. As in 1 to 20 and 27, it is considered that an electrode having a low resistivity is formed. On the other hand, in Comparative Example 6, the adhesion to the silicon substrate was reduced, but this can be considered as follows, for example.
  • Example 21 and Example 22 exhibited almost the same power generation performance as the solar cell element of Comparative Example 7.
  • a Cu—Sn—Ni alloy phase and a Sn—PO glass phase were present in the light receiving surface electrode.
  • the presence or absence of the Cu—Sn—Ni alloy phase and the Sn—P—O glass phase in the electrode of the electrode according to Comparative Example 7 was because only silver particles were used as metal particles in the electrode forming composition C1. I did not investigate.
  • Example 23 and Example 24 exhibited almost the same power generation performance as the solar cell element of Comparative Example 8.
  • a Cu—Sn—Ni alloy phase and a Sn—PO glass phase were present in the light receiving surface electrode.
  • the presence or absence of the Cu—Sn—Ni alloy phase and the Sn—P—O glass phase in the electrode of the electrode according to Comparative Example 8 was because only silver particles were used as metal particles in the electrode forming composition C1. I did not investigate.
  • Example 25 and Example 26 exhibited almost the same power generation performance as the solar cell element of Comparative Example 9.
  • a Cu—Sn—Ni alloy phase and a Sn—PO glass phase were present in the light receiving surface electrode.
  • the presence or absence of the Cu—Sn—Ni alloy phase and the Sn—P—O glass phase in the electrode of the electrode according to Comparative Example 9 was because only silver particles were used as metal particles in the electrode forming composition C1. I did not investigate.

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Photovoltaic Devices (AREA)
  • Conductive Materials (AREA)

Abstract

L'invention concerne une composition de formation d'électrode contenant des particules de verre et des particules métalliques, dont des particules d'alliage de cuivre contenant du phosphore, de l'étain et du nickel; une électrode formée au moyen de la composition de formation d'électrode; un élément de cellule solaire comportant l'électrode; un procédé pour sa production de ceux-ci; et une cellule solaire.
PCT/JP2015/052572 2014-01-31 2015-01-29 Composition de formation d'électrode, électrode, élément de cellule solaire, leur procédé de fabrication, et cellule solaire Ceased WO2015115565A1 (fr)

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