CN113178495A - Conductive composition, semiconductor element, and solar cell element - Google Patents
Conductive composition, semiconductor element, and solar cell element Download PDFInfo
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- CN113178495A CN113178495A CN202110405333.2A CN202110405333A CN113178495A CN 113178495 A CN113178495 A CN 113178495A CN 202110405333 A CN202110405333 A CN 202110405333A CN 113178495 A CN113178495 A CN 113178495A
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Classifications
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- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
- H01L31/068—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
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- 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
- Y02E10/547—Monocrystalline silicon PV cells
Abstract
The present application relates to a conductive composition, a semiconductor element, and a solar cell element. The present application provides a method for making an electrode pattern possible to be thinned and have a high aspect ratio in printing, and capable of suppressing disconnection of the electrode patternConductive compositions with insignificant increase in electrical resistance. The present invention provides a conductive composition for forming an electrode. The conductive composition contains a conductive powder, a glass frit, a silicone resin, an organic binder, and a dispersion medium. SiO of the glass frit in terms of oxide2The proportion of the component (B) is 0 to 5 mass%.
Description
The present application is a divisional application filed on 2016 under the name of "conductive composition, semiconductor device and solar cell device" under the name of 201680005302.5.
Technical Field
The present invention relates to a conductive composition. And more particularly, to a conductive composition useful for forming an electrode pattern of a solar cell.
This application is based on the priority claim of Japanese patent application No. 2015-001855, filed on 7/1/2015, the entire contents of which are incorporated by reference in this specification.
Background
In view of recent increase in environmental awareness and energy saving, the popularization of solar cells has rapidly progressed, and accordingly, there is a demand for a solar cell having a higher performance than before, i.e., a cell structure having a high output power and a good photoelectric conversion efficiency. One of the means for achieving such a demand is to increase the light receiving area per unit area of the solar cell. For example, as one of the means for enlarging the light receiving area, thinning (fine line) of a linear electrode formed on the light receiving surface is expected.
On the light-receiving surface of the crystalline silicon solar cell, which has been the mainstream at present, typically, finger-shaped (current collecting) electrodes including thin wires formed of an electric conductor such as silver and bus bar electrodes connected to the finger-shaped electrodes are provided. Hereinafter, these electrodes are also collectively referred to as light-receiving surface electrodes. Such a light-receiving surface electrode contains a conductive powder such as silver as a conductive component and an organic binder (vehicle) component containing an organic binder and a solvent, and is formed by printing a material (hereinafter, also referred to as a "conductive composition", simply referred to as a "composition" or the like) prepared in a paste state (including a paste state or an ink state) on a light-receiving surface of a solar cell (cell) with a predetermined electrode pattern by a method such as a screen printing method and firing the material. As a conventional technique relating to a conductive composition used for forming a light-receiving surface electrode of such a solar cell, for example, patent documents 1 to 3 are cited.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent application No. 2010-087251
Patent document 2: japanese patent laid-open publication No. 2012 and 023095
Patent document 3: japanese Kohyo publication No. 2012-508812
Disclosure of Invention
Problems to be solved by the invention
However, the conductive composition for forming an electrode of a solar cell contains glass frit (glass frit) in addition to the above-described constituent materials. The glass frit can function as an inorganic binder that softens or melts during firing to achieve good bonding between the substrate and the electrode. In addition, in the manufacture of a solar cell, the conductive composition containing the glass frit exhibits good fire through (fire through) characteristics. That is, in the production of a solar cell, typically, an antireflection film is first formed on substantially the entire surface of the light-receiving surface of a silicon substrate, and a conductive composition for forming an electrode on the light-receiving surface is supplied onto the antireflection film in a desired electrode pattern and then baked. At this time, the glass frit in the conductive composition reacts with the antireflection film during firing, and is introduced into the glass. Thus, the conductive powder in the conductive composition passes (burns through) the antireflection film, thereby achieving good electrical connection (ohmic contact) with the silicon substrate. When the burnthrough property of the conductive composition is used as described above, it is not necessary to partially remove the antireflection film or the like in forming a fine light-receiving surface electrode, which is relatively simple, and there is no fear of a gap or overlap between the removed portion of the antireflection film and the formation position of the light-receiving surface electrode.
In addition, in the light-receiving surface of the solar cell, a portion where the light-receiving surface electrode is formed becomes a light-shielding portion (non-light-receiving portion). Therefore, if the light-receiving surface electrode is made thinner (thinner and more solid lines) than in the conventional art, the light-receiving area per unit area is increased, and the output per unit area can be increased. However, in this case, if the volume of the electrode is increased (thickened) only by the thinned portion, the line resistance (line resistance) of the electrode increases, resulting in a decrease in the output power characteristics of the solar cell. Therefore, in order to make the light-receiving surface electrode thin and solid, an improvement in the thickness of the electrode, that is, a high aspect ratio (the ratio of the thickness of the electrode to the line width: thickness/line width is large, the same applies hereinafter) is required.
However, further improvement is desired in the conventional conductive composition from the viewpoint of achieving both good ohmic contact of the electrode and thinning of the wiring.
The present invention has been made in view of the above circumstances, and a main object thereof is to provide a conductive composition for forming an electrode, which can realize a thinning of an electrode pattern and a high aspect ratio and can form a contact between the electrode and a substrate satisfactorily. In addition, another object is to provide a semiconductor element, such as a solar cell element, with improved functions or performances, which can be achieved by using the conductive composition.
Means for solving the problems
In order to achieve the above object, the present invention provides a conductive composition which can be suitably used for forming an electrode (electrode pattern). The conductive composition is characterized by containing conductive powder, glass powder, organic silicon resin, organic binder and dispersion medium, and SiO of the glass powder in terms of oxide2The proportion of the components is0 to 5 mass%.
The conductive composition disclosed herein can form an electrode having good adhesion to a substrate because it contains glass frit, and can form a contact between the electrode and the substrate by burning through even when the conductive composition is supplied onto an antireflection film when forming an electrode for a solar cell. And good ohmic contact can be achieved. Further, since the conductive composition contains a silicone resin, a fine electrode having a high aspect ratio can be stably formed. Here, SiO derived from glass frit or silicone resin2The component is not preferable because it increases an insulating resistance component in the electrode. Therefore, in the technique shown here, SiO is not contained by the glass frit2Composition, or SiO as in the above-mentioned glass frit2The ratio of the components can achieve both good burn-through characteristics and electrode shape stability at a high level without impairing the electrode characteristics.
In a preferred embodiment of the conductive composition disclosed herein, the silicone resin is contained in an amount of 0.005 to 0.9 parts by mass based on 100 parts by mass of the conductive powder. With this configuration, not only an electrode having a high aspect ratio but also an electrode having more excellent electrical characteristics can be formed.
In a preferred embodiment of the conductive composition disclosed herein, the silicone resin has a weight average molecular weight of 3000 or more and 90000 or less. With this configuration, electrical characteristics such as line resistance of the electrode can be further improved as compared with the case where no silicone resin is added.
In a preferred embodiment of the electrically conductive composition disclosed herein, the metal species constituting the electrically conductive powder contains one or more elements selected from the group consisting of nickel, platinum, palladium, silver, copper and aluminum. With this configuration, an electrode having excellent conductivity can be formed.
In order to achieve the above object, the present invention also provides a semiconductor device comprising an electrode formed using any one of the above conductive compositions. Typically, such a semiconductor element may be a solar cell element including a light-receiving surface electrode formed using the above-described conductive composition.
Specifically, the conductive composition of the present invention can form an electrode pattern and an electrode having a finer line width in a large volume (with a high aspect ratio) when supplied onto a light-receiving surface of a semiconductor substrate by, for example, a screen printing method. Therefore, for example, in printing of electrode patterns of various semiconductor elements, further thinning and wiring can be achieved, and a high-performance semiconductor element in which further miniaturization and high integration of the semiconductor element are achieved can be realized. Further, for example, application to a light-receiving surface electrode forming a solar cell element is particularly preferable because the amount of light received per unit area of the light-receiving surface can be increased and more electric power can be generated.
Drawings
FIG. 1 is a cross-sectional view schematically showing an example of the structure of a solar cell
Fig. 2 is a plan view schematically showing a pattern of an electrode formed on a light receiving surface of a solar cell.
Fig. 3 is a graph showing the relationship between the weight average molecular weight of the silicone resin in the conductive composition according to one embodiment and the number of disconnections and the aspect ratio of the formed electrode.
Fig. 4 is a graph showing a relationship between the weight average molecular weight of the silicone resin in the conductive composition and the line resistance of the formed electrode in one embodiment.
Detailed Description
Preferred embodiments of the present invention will be described below. Technical matters other than those specifically mentioned in the present specification and matters necessary for the implementation of the present invention can be grasped based on design matters of those skilled in the art in the related art. The present invention can be implemented based on the technical contents disclosed in the present specification and the technical common knowledge in the field.
The conductive composition disclosed herein is typically a conductive composition that can be formed into an electrode by firing. The conductive composition essentially contains, in the same manner as the conventional conductive composition, a conductive powder, a glass frit, and an organic binder component (a mixture of an organic binder and a dispersant, as described later) for dispersing these components, and further contains a silicone resin as an essential component. These components will be described below.
As the conductive powder forming the main body of the solid component of the paste, a powder containing various metals or alloys thereof having desired conductivity and other physical properties according to the application can be considered. Examples of the material constituting the conductive powder include: metals such as gold (Au), silver (Ag), copper (Cu), platinum (Pt), palladium (Pd), ruthenium (Ru), rhodium (Rh), iridium (Ir), osmium (Os), nickel (Ni), and aluminum (Al), and alloys thereof; carbonaceous materials such as carbon black; LaSrCoFeO3An oxide (e.g., LaSrCoFeO)3)、LaMnO3Oxide series (e.g. LaSrGaMgO)3)、LaFeO3An oxide (e.g., LaSrFeO)3)、LaCoO3Based on oxides (e.g. LaSrCoO)3) And conductive ceramics represented by transition metal perovskite oxides shown in the drawings. Among these, a powder containing a simple substance of a noble metal such as platinum, palladium, or silver, an alloy thereof (an Ag — Pd alloy, a Pt — Pd alloy, or the like), nickel, copper, aluminum, an alloy thereof, or the like is particularly preferable as a material constituting the conductive powder. In particular, from the viewpoints of relatively low cost, high electrical conductivity, and the like, it is preferable to use a powder containing silver or an alloy thereof (hereinafter also referred to as "Ag powder"). Hereinafter, the conductive composition of the present invention will be described by taking an example of the case of using Ag powder as the conductive powder.
The particle size of the conductive powder other than Ag powder is not particularly limited, and various particle sizes of the powder can be used according to the application. Typically, a powder having an average particle diameter of 5 μm or less by a laser scattering diffraction method is suitable, and a powder having an average particle diameter of 3 μm or less (typically 1 to 3 μm, for example, 1 to 2 μm) is preferably used.
The shape of the particles constituting the conductive powder is not particularly limited. Typically, spherical, scaly (flaky), conical, rod-shaped particles, and the like can be suitably used. Spherical or flaky particles are preferably used for the reason that a dense light-receiving surface electrode having good filling properties is easily formed. The conductive powder used is preferably a powder having a sharp (narrow) particle size distribution. For example, it is preferable to use a conductive powder having a sharp particle size distribution, which does not substantially contain particles having a particle size of 10 μm or more. As such an index, the ratio (D10/D90) of the particle diameter at 10% cumulative volume (D10) to the particle diameter at 90% cumulative volume (D90) in the particle size distribution by the laser scattering diffraction method can be used. When the particle diameters constituting the powder are all equal, the value of D10/D90 is 1, and conversely, the wider the particle size distribution, the closer the value of D10/D90 is to 0. It is preferable to use a powder having a relatively narrow particle size distribution with a D10/D90 value of 0.2 or more (for example, 0.2 or more and 0.5 or less).
The conductive composition using the conductive powder having such an average particle diameter and particle shape has good filling properties of the conductive powder, and can form a dense electrode. This is advantageous for forming a fine electrode pattern with good shape accuracy.
The method for producing the conductive powder such as Ag powder is not particularly limited. For example, conductive powder (typically Ag powder) produced by a well-known wet reduction method, gas phase reaction method, gas reduction method, or the like can be classified and used. The fractionation may be carried out using, for example, a fractionation device using a centrifugal separation method.
The glass frit can function as a component of the inorganic binder of the conductive powder, and also has an effect of improving adhesion between conductive particles constituting the conductive powder and between the conductive particles and a substrate (an object on which an electrode is formed). When the conductive composition is used for forming, for example, a light-receiving surface electrode of a solar cell, the presence of the glass frit enables the conductive composition to penetrate through an antireflection film as a lower layer during firing, and thus enables good adhesion and electrical contact with a substrate.
The glass frit is preferably adjusted to a size equal to or smaller than that of the conductive powder. For example, the average particle diameter by the laser scattering diffraction method is preferably 4 μm or less, preferably 2 μm or less, and typically more preferably 0.1 μm or more and 3 μm or less.
In addition, as for the composition of the glass frit, SiO in terms of oxide may be used2A glass frit having a component ratio of 0 mass% or more and 5 mass% or less (for example, less than 5 mass%). SiO is considered to improve the stability of the system and to adjust the erosiveness at burn-through2The component is preferably contained in glass frit. However, the technique disclosed here contains a silicone resin, which forms SiO during baking, as an essential constituent component, as described later2And (3) components. Excess SiO2The ingredients can increase the softening point of the glass frit and reduce the aggressiveness of the conductive composition during burn-through. In addition, if the electrode cannot be formed by firing at a lower temperature, the electrode performance may be adversely affected. Thus, in the techniques disclosed herein, the SiO of the glass frit is ground2The ratio of the components is limited to an extremely small amount as described above, for example. SiO in glass frit2The content is preferably 4% by mass or less, and may be 3% by mass or less, for example. In addition, SiO in the glass frit2The component (C) may be 0 mass% (i.e., SiO is not contained)2Ingredient(s).
Other components contained in the glass frit are not particularly limited, and glasses of various compositions can be used. For example, as the general glass composition, what is commonly referred to by those skilled in the art, that is, so-called lead-based glass, lead-lithium-based glass, zinc-based glass, borate-based glass, borosilicate-based glass (in which the amount of Si is limited), alkali-based glass, lead-free glass, tellurium-based glass, glass containing barium oxide, bismuth oxide, and the like can be used. It goes without saying that these glasses contain, In addition to the main constituent elements appearing In the above designations, one or more elements selected from the group consisting of Si (where the amount of Si is limited), Pb, Zn, Ba, Bi, B, Al, Li, Na, K, Rb, Te, Ag, Zr, Sn, Ti, W, Cs, Ge, Ga, In, Ni, Ca, Cu, Mg, Sr, Se, Mo, Y, As, La, Nd, C, Pr, Gd, Sm, Dy, Eu, Ho, Yb, Lu, Ta, V, Fe, Hf, Cr, Cd, Sb, F, Mn, P, Ce and Nb. Such glass frit is, for example, other than the generally amorphous stateIn addition to glass, crystallized glass partially containing crystals may be used. Further, the glass frit is adjusted to SiO as a whole as described above2The glass powder of one composition may be used alone or two or more compositions may be used in combination.
The softening point of the glass constituting the glass frit is not particularly limited, but is preferably about 300 ℃ to 600 ℃ (for example, 400 ℃ to 500 ℃). As the glass whose softening point is adjusted to be in the range of 300 ℃ to 600 ℃ as described above, specifically, for example, a glass containing elements shown below in combination is cited. B-Si-Al based glass, Pb-B-Si based glass, Si-Pb-Li based glass, Si-Al-Mg based glass, Ge-Zn-Li based glass, B-Si-Zn-Sn based glass, B-Si-Zn-Ta-Ce based glass, B-Zn-Pb based glass, B-Si-Zn-Pb-Cu based glass, B-Si-Zn-Al based glass, Pb-B-Si-Ti-Bi based glass, Pb-B-Si-Ti based glass, Pb-B-Si-Al-Zn-P based glass, Pb-Li-Bi-Te based glass, Pb-B-Si-Al-Zn-Te based glass, Pb-Si-Al-Li-Zn-Te glass, Pb-B-Si-Al-Li-Ti-Zn glass, Pb-B-Si-Al-Li-Ti-P-Te glass, Pb-Si-Li-Bi-Te-W glass, P-Pb-Zn glass, P-Al-Zn glass, P-Si-Al-Zn glass, P-B-Al-Si-Pb-Li glass, P-B-Al-Mg-F-K glass, Te-Pb glass, Tr-Pb-Li glass, V-P-Ba-Zn glass, V-B-Ti-B-Ti-W glass, and P-Si-Li-Ti-W glass, V-P-Na-Zn glass, AgI-Ag2O-B-P based glass, Zn-B-Si-Li based glass, Si-Li-Zn-Bi-Mg-W-Te based glass, Si-Li-Zn-Bi-Mg-Mo-Te based glass, Si-Li-Zn-Bi-Mg-Cr-Te based glass, etc. The conductive composition containing the glass frit having such a softening point is preferable because it exhibits good burn-through characteristics and contributes to the formation of a high-performance electrode when used for forming a light-receiving surface electrode of a solar cell element, for example.
The silicone resin is characterized as an essential constituent contained in the conductive composition disclosed herein. By containing the silicone resin, the conductive composition can stably maintain the shape from printing to baking, for example, and can stably form a finer electrode with a higher aspect ratio. In addition, the silicone resin can form SiO in the electrode by baking2And (3) components. SiO as described above2The components are not extracted directlyA high softening point of the glass frit is preferable in that the system stability and the adhesion between the electrode and the substrate can be improved.
As such a silicone resin (which may also be simply referred to as silicone), an organic compound containing silicon (Si) can be used without particular limitation. Typically, the silicone resin is uniformly dispersed or dissolved in the conductive composition as a liquid or oily composition. The silicone resin may preferably use, for example, an organic compound having a main skeleton based on a siloxane bond (Si-O-Si). For example, a linear silicone in which an alkyl group, a phenyl group, or the like is introduced into an unbonded bond (side chain, terminal) of the main skeleton may be used. Further, the silicone may be a linear modified silicone having a polyether group, an epoxy group, an amino group, a carboxyl group, an aralkyl group, a hydroxyl group, or other substituent introduced into a side chain, a terminal, or both of them, or may be a linear block copolymer in which a polyether and a silicone are alternately bonded.
Such a silicone resin is preferable because the higher the weight average molecular weight (hereinafter simply referred to as "Mw") is, the higher the aspect ratio of the electrode can be formed. However, when Mw is about 11 ten thousand, defects such as disconnection of the obtained electrode or increase in resistance are caused, which is not preferable. From this viewpoint, for example, Mw is preferably 9 ten thousand or less, more preferably 7 ten thousand or less, and particularly preferably 6 ten thousand or less. The lower limit of Mw is not particularly limited, and may be, for example, 1 thousand or more, preferably 3 thousand or more, more preferably 5 thousand or more, particularly preferably 1 ten thousand or more, for example 2 ten thousand or more.
As the organic binder component for dispersing the above-mentioned constituent elements such as the conductive powder, various binders used in the conductive composition can be used without particular limitation according to the intended purpose. Typically, the vehicle is comprised of an organic binder and an organic solvent of various compositions. In the organic binder component, the organic binder may be completely dissolved in the organic solvent or may be partially dissolved or dispersed (so-called emulsion type organic binder).
As the organic binder, for example, a cellulose-based polymer such as ethyl cellulose or hydroxyethyl cellulose, an acrylic resin such as polybutylmethacrylate, polymethylmethacrylate or polyethylmethacrylate, an epoxy resin, a phenol resin, an alkyd resin, polyvinyl alcohol or polyvinyl butyral is suitably used as a base. Particularly, a cellulose polymer (e.g., ethyl cellulose) is preferable, and viscosity characteristics that enable particularly good screen printing can be achieved.
The solvent constituting the organic vehicle is preferably an organic solvent having a boiling point of approximately 200 ℃ or higher (typically, approximately 200 to 260 ℃). More preferably, an organic solvent having a boiling point of about 230 ℃ or higher (typically, approximately 230 ℃ to 260 ℃) is used. As such an organic solvent, ester solvents such as butyl cellosolve acetate and butyl carbitol acetate (BCA: diethylene glycol monobutyl ether acetate), ether solvents such as butyl carbitol (BC: diethylene glycol monobutyl ether), organic solvents such as ethylene glycol and diethylene glycol derivatives, toluene, xylene, mineral spirits, terpineol, menthol, and esterol (Texanol) can be suitably used. Particularly preferred solvent components include Butyl Carbitol (BC), Butyl Carbitol Acetate (BCA), 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate, and the like.
The blending ratio of each constituent component contained in the conductive composition may vary depending on the method of forming the electrode, typically, the printing method, and the like, but the blending ratio of the conductive composition based on the composition adopted so far can be roughly formed. For example, the proportions of the respective constituent components may be determined based on the following compounding ratios.
That is, when the total paste is 100 mass%, the content of the conductive powder in the conductive composition is preferably about 70 mass% or more (typically, about 70 mass% to 95 mass%), more preferably about 80 mass% to 90 mass%, and for example, preferably about 85 mass%. From the viewpoint of forming a dense electrode pattern with good shape accuracy, it is preferable to increase the content ratio of the conductive powder. On the other hand, if the content ratio is too high, the workability of the paste, the suitability for various printing properties, and the like may be reduced.
Even if a very small amount of silicone resin is added to the conductive powder, the electrode can be formed with a higher aspect ratio, and therefore, this is preferable. For example, when the conductive powder is 100 parts by mass, the amount of the silicone resin added may be typically 0.005 parts by mass or more, preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more. The excessive addition is not preferable because the resistance of the formed electrode is increased. Therefore, the amount of the silicone resin added may be typically 1.2 parts by mass or less, preferably 0.9 parts by mass or less, and more preferably 0.8 parts by mass or less, based on 100 parts by mass of the conductive powder.
The ratio of the glass frit to the conductive powder is not generally defined because it is also related to the silicone resin, but in order to obtain good burn-through characteristics, the amount of the conductive powder is typically 0.1 part by mass or more, preferably 0.5 part by mass or more, and more preferably 1 part by mass or more, per 100 parts by mass of the conductive powder. The excessive addition is not preferable because it increases the resistance of the formed electrode, and may be typically 12 parts by mass or less, preferably 10 parts by mass or less, and more preferably 8 parts by mass or less.
The silicone resin and the glass frit are SiO contained in the electrode2The source of the ingredient. Furthermore, from this SiO2The content of the component can be complementarily considered in terms of suppressing the burn-through property or the resistance component which becomes insulating in the electrode. More specifically, the conductive composition disclosed herein can contain a silicone resin, and thus SiO in the glass frit can be reduced2The amount of the component is reduced to a small amount. However, for example, when the amount of the silicone resin is in the range of approximately more than 0.15 parts by mass (for example, 0.2 parts by mass or more), the conductive composition can penetrate the antireflection film or can be brought into good contact with the substrate, and therefore, it is preferable to secure a sufficient amount of the glass powder in accordance with the amount of the silicone resin. For example, the mass ratio of the glass frit to the silicone resin (mass of glass frit/mass of silicone resin) is preferably 7.5 or more, more preferably 8 or more, particularly preferably 8.3 or more, for example 10 or more. However, the silicone resin and the glass frit may themselves become electricity as described aboveThe resistance component of the pole. From the above viewpoint, the mass ratio of the glass frit to the silicone resin is preferably, for example, approximately 18 or less, more preferably 16.5 or less, and may be, for example, 15 or less, and further preferably 12 or less. For example, as described above, the series resistance Rs can be effectively reduced by limiting the mass ratio of the glass frit to the silicone resin to a predetermined range.
On the other hand, when the mass of the conductive powder is 100% by mass, the organic binder in the organic binder component is preferably contained in a proportion of about 15% by mass or less, typically about 1% by mass to 10% by mass. Particularly, it is preferably contained in a ratio of 2 to 6% by mass with respect to 100% by mass of the conductive powder. The organic binder may contain, for example, an organic binder component dissolved in an organic solvent and an organic binder component insoluble in an organic solvent. When the binder composition contains an organic binder component dissolved in an organic solvent and an organic binder component insoluble in an organic solvent, the ratio of these components is not particularly limited, but the organic binder component dissolved in an organic solvent may be 4 to 10, for example.
The content of the entire organic binder may vary depending on the properties of the paste to be obtained, and when the entire conductive composition is taken as 100 mass%, the content is preferably 5 to 30 mass%, more preferably 5 to 20 mass%, and still more preferably 5 to 15 mass% (particularly 7 to 12 mass%), for example.
The conductive composition disclosed herein contains various inorganic additives and/or organic additives other than those described above within a range not departing from the object of the present invention. Preferable examples of the inorganic additive include ceramic powders (ZnO) other than those described above2、Al2O3Etc.), other various fillers. Preferable examples of the organic additive include additives such as a surfactant, an antifoaming agent, an antioxidant, a dispersant, and a viscosity adjuster.
The above conductive composition is suitable as a printing composition (in some cases, paste, slurry, ink, or the like) suitable for screen printing, gravure printing, offset printing, inkjet printing, and the like because of its shape stability. In addition, when an electrode pattern requiring thinning and high aspect ratio is formed, such a general printing method can be particularly preferably used. Therefore, an example in which a comb-shaped electrode pattern including finer finger electrodes is formed on the light receiving surface by screen printing is shown with a solar cell element as an example of a semiconductor element, and a solar cell element as a semiconductor element disclosed herein will be described. The solar cell element may be the same as a conventional solar cell except for the configuration of the light-receiving surface electrode which is a feature of the present invention, and a portion having the same configuration and using the same material as those of the conventional solar cell is not a feature of the present invention, and thus, a detailed description thereof is omitted.
Fig. 1 and 2 schematically illustrate an example of a solar cell element (unit) 10 that can be suitably manufactured by the practice of the present invention, which is a so-called silicon-type solar cell element 10 using a wafer containing single-crystal, polycrystalline, or amorphous silicon (Si) as a semiconductor substrate 11. The cell 10 shown in fig. 1 is a typical single-sided light receiving type solar cell element 10. Specifically, this solar cell element 10 includes an n-Si layer 16 formed by pn junction on the light receiving surface side of a p-Si layer (p-type crystalline silicon) 18 of a silicon substrate (Si wafer) 11, and further includes an antireflection film 14 formed by Chemical Vapor Deposition (CVD) or the like on the surface thereof and containing titanium oxide or silicon nitride, and light receiving surface electrodes 12 and 13 formed of a conductive composition mainly containing Ag powder or the like.
On the other hand, the p-Si layer 18 includes, on the back surface side thereof: a Back-side external connection electrode 22 formed of a predetermined conductive composition (typically, a conductive paste in which the conductive powder is Ag powder) in the same manner as the light-receiving-Surface electrode 12, and a Back-side aluminum electrode 20 exhibiting a so-called Back Surface Field (BSF) effect. The aluminum electrode 20 is formed by printing and baking a conductive composition mainly containing aluminum powder on substantially the entire back surface. An Al-Si alloy layer, not shown, is formed during the firing, and aluminum diffuses into the p-Si layer 18 to form p+Layer 24. By forming the above-mentioned p+Layer 24, the BSF layer, prevents photogenerated carriers from recombining near the back electrode, for example, to achieve an increase in short circuit current (short circuit) and open circuit voltage (Voc).
As shown in fig. 2, on the light-receiving surface 11A side of the silicon substrate 11 of the solar cell element 10, a plurality of (for example, about 1 to 3) bus bar-shaped (connecting) electrodes 12 parallel to each other and a plurality of (for example, about 60 to 90) finger-shaped (current collecting) electrodes 13 parallel to each other and connected so as to intersect with the bus bar electrodes 12 are formed as the light-receiving surface electrodes 12 and 13.
The finger electrodes 13 are formed in many roots in order to collect photo carriers (holes and electrons) generated by receiving light. The bus bar electrode 12 is a connection electrode for collecting the carriers collected by the finger electrodes 13. The portions where the light-receiving- surface electrodes 12 and 13 are formed form non-light-receiving portions (light-shielding portions) on the light-receiving surface 11A of the solar cell element. Therefore, by making the bus bar electrodes 12 and the finger electrodes 13 (particularly the finger electrodes 13 having a large number) provided on the light receiving surface 11A as thin and solid as possible, the non-light receiving portions (light shielding portions) of the corresponding portions are reduced, and the light receiving area per unit area of the cell is enlarged. This makes it possible to increase the output per unit area of the solar cell element 10 extremely simply.
In this case, the height of the thinned electrode may be high and uniform, but if sagging or sagging occurs in a part of the electrode, for example, the sagging or sagging portion increases the resistance, resulting in a loss of current collection. Further, if a disconnection occurs in a part of the thinned electrode, the generated current cannot be collected through the disconnection portion (the generated current is collected as a current flowing through the high-resistance substrate in a state where a collection loss occurs). Therefore, in order to form a light-receiving surface electrode of a solar cell element, a conductive composition having high electrical characteristics and excellent shape stability by printing is required.
Such a solar cell element 10 is generally manufactured through the following process.
That is, the silicon substrate (semiconductor substrate) 11 is prepared by preparing an appropriate silicon wafer, doping a predetermined impurity by a general technique such as a thermal diffusion method or an ion implantation method, and forming the p-Si layer 18 and the n-Si layer 16. Next, the antireflection film 14 made of silicon nitride or the like is formed by a technique such as plasma CVD.
Then, on the back surface 11B side of the silicon substrate 11, a back surface side conductor-coated object to be the back surface side external connection electrode 22 (see fig. 1) is formed by first screen-printing a predetermined pattern using a predetermined conductive composition (typically, a conductive composition in which the conductive powder is Ag powder) and drying the same. Next, a conductive composition containing aluminum powder as a conductive component is applied (supplied) over the entire back surface side by screen printing or the like, and dried to form an aluminum film.
Next, the conductive composition of the present invention is printed (supplied) on the antireflection film 14 formed on the front surface side of the silicon substrate 11, typically, by a screen printing method, in a wiring pattern as shown in fig. 2. The line width to be printed is not particularly limited, and by using the conductive composition of the present invention, a coating film (print) having an electrode pattern of a finger electrode having a line width of about 70 μm or less (preferably, in the range of about 50 to 60 μm, and more preferably, in the range of about 40 to 50 μm) is formed. Next, the substrate is dried at a suitable temperature range (typically 100 ℃ to 200 ℃, for example, about 120 ℃ to 150 ℃). The contents regarding a suitable screen printing method are described later.
The silicon substrate 11 having the paste-coated material (dried film-shaped coated material) formed on each of both surfaces thereof is baked at an appropriate baking temperature (e.g., 700 to 900 ℃) in an atmospheric atmosphere using a baking furnace such as a near-infrared ray high-speed baking furnace.
By the above firing, the light receiving surface electrodes (typically, Ag electrodes) 12 and 13 and the rear surface external connection electrode (typically, Ag electrode) 22 are formed, the aluminum electrode 20 is fired, an Al-Si alloy layer (not shown) is formed, and aluminum is diffused into the p-Si layer 18 to form the p-Si electrode+Layer (BSF layer) 24, thereby producing the solar cell element 10.
Instead of simultaneous baking as described above, for example, baking for forming the light-receiving surface electrodes (typically Ag electrodes) 12 and 13 on the light-receiving surface 11A side, and baking for forming the aluminum electrode 20 and the external connection electrode 22 on the back surface 11B side may be performed separately.
According to the conductive composition disclosed herein, the conductive composition can be supplied (printed) on the silicon substrate 11 with a desired electrode pattern, for example, by screen printing. The conductive composition is excellent in shape stability, and thus, for example, with respect to an electrode obtained after firing, a finger electrode 12 having a line width of 60 μm or less and a thickness of 20 μm or more (preferably, a line width of 40 μm or more and 50 μm or less and a thickness of 20 μm or more) can be formed with high quality while the occurrence of thinning and breaking of the line is greatly reduced. Since the bus bar electrode is substantially free from influences caused by thinning, breaking, and the like of the line, the bus bar electrode having a line width of about 1000 μm to 3000 μm, for example, can be formed with high quality without using the above-described conductive composition. As described above, if thinning of the electrode lines and high aspect ratio can be achieved, for example, the output power per unit area can be increased without increasing the resistance of each finger electrode. Even when the resistance value of the electrode line slightly increases, the line resistance value of the entire electrode pattern can be suppressed to a low value. Therefore, by optimally combining the widths and the number of the finger electrodes 13, a solar cell element with high photoelectric conversion efficiency can be provided.
The following examples of the present invention are described, but the present invention is not intended to be limited to the examples.
(embodiment mode 1)
[ preparation of electroconductive composition ]
The conductive composition for forming an electrode was prepared by the following procedure. That is, as the conductive powder, silver (Ag) powder having an average particle diameter of 2 μm was used. Twelve kinds of glass powders (average particle size: 0.5 μm to 1.6 μm) shown in Table 1 below were used as the glass powder. As the silicone resin, polydimethylsiloxane having a weight average molecular weight Mw of 5 ten thousand was used. In addition, as the surfactant, hydrogenated castor oil was used. As the organic binder component, a binder in which Ethyl Cellulose (EC) as an organic binder component is dispersed in an ester alcohol as a dispersion medium is used.
In table 1, the symbols representing the structure of the glass frit are: the Pb-containing lead-based glass is denoted by "A", the Pb-free lead-based glass containing bismuth (Bi) and the like without containing Pb is denoted by "B", the other Pb-free glass containing boron (B), silicon (Si) and the like without containing Pb is denoted by "C", and the attached symbols represent SiO in each glass composition2Number of contents of ingredients. These glass frits usually have a softening point varying in the range of 300 ℃ to 600 ℃ as shown in table 1 by adjusting the composition.
[ Table 1]
TABLE 1
These materials were then compounded as follows: when the silver powder was taken as 100 parts by mass, the glass frit was taken as 2.50 parts by mass, the silicone resin was taken as any one of 0 part by mass, 0.0050 part by mass, and 0.30 part by mass, the ethyl cellulose was taken as 1.00 part by mass, and the hydrogenated castor oil was taken as 0.80 part by mass; while sufficiently kneading the mixture by using a three-roll mill, the viscosity was adjusted to approximately 190Pa · s by using an ester alcohol, thereby preparing conductive compositions of examples 1 to 21. Table 2 shows the kind of glass frit used in the conductive composition of each example, the compounding amount of the silicone resin, and the measured value of the viscosity of the obtained conductive composition. In table 2, the compositions of the glass frits used in the respective examples are shown by symbols shown in table 1. In addition, "-" in the column of the amount of the silicone resin means that no silicone resin (0 part by mass) is blended. The viscosity of each conductive composition was measured at 25 ℃ and 20rpm using a Brookfield viscometer of HBT type (Brookfield).
[ production of solar cell element (light-receiving surface electrode) for test ]
The light-receiving-surface electrodes (i.e., comb-shaped electrodes including finger electrodes and bus bar electrodes) were formed using the conductive compositions of examples 1 to 21 obtained above, thereby producing solar cell elements of examples 1 to 21.
Specifically, a commercially available p-type single crystal silicon substrate (thickness 180 μm) for solar cells having a size of 156mm four sides (6 inches square) was prepared, and the surface (light-receiving surface) thereof was etched with a mixed acid of hydrofluoric acid and nitric acid to remove the damaged layer and form a textured surface having irregularities. Next, a phosphorus-containing solution was applied to the textured surface, and a heat treatment was performed to form an n-Si layer (n) having a thickness of about 0.5 μm on the light-receiving surface of the silicon substrate+Layers). Next, a silicon nitride film having a thickness of about 80nm was formed as an antireflection film on the n-Si layer by a plasma cvd (pecvd) method.
Next, a predetermined silver electrode forming paste was used on the back surface side of the silicon substrate, and then screen-printed in a predetermined pattern so as to be an external connection electrode on the back surface side, and dried, thereby forming a back surface side electrode pattern. Subsequently, an aluminum electrode-forming paste was screen-printed on the entire back surface side, and dried to form an aluminum film.
Then, using the prepared conductive compositions of examples 1 to 21, an electrode pattern for a light-receiving surface electrode (Ag electrode) was printed on the antireflection film by a screen printing method under room temperature conditions in an atmospheric atmosphere, and dried at 120 ℃. Specifically, as shown in fig. 2, an electrode pattern including 3 mutually parallel linear bus bar electrodes and 90 finger electrodes orthogonal to and mutually parallel to the bus bar electrodes was formed by screen printing. The finger electrode pattern has a dimension after firing in the range of 45 to 55 μm in line width and 15 to 25 μm in film thickness. The bus bar electrode was set so that the line width after firing became approximately 1.5 mm.
The substrate having the electrode patterns printed on both surfaces thereof was baked at a baking temperature of 700 to 800 ℃ in an atmospheric atmosphere using a near-infrared high-speed baking furnace, thereby producing a solar cell for evaluation.
[ evaluation ]
The light-receiving surface electrode (finger electrode) of the solar cell fabricated as described above was measured for film thickness, line width, series resistance Rs, and energy conversion efficiency Eff by the following procedure.
The thickness (height) and the line width of the light-receiving surface electrode of each solar cell were measured at an arbitrary position by a shape analysis laser microscope (manufactured by keyence co. The results are shown in table 2 as an average of the values measured at 100.
The series resistance Rs and the energy conversion efficiency Eff of the electrode were calculated from an I-V curve obtained for each solar cell using a solar simulator (PSS 10 manufactured by Beger) based on the "crystal solar cell output power measurement method" specified in JIS C8913. The results are shown in table 2 as an average of 100 data obtained by the solar simulator.
[ Table 2]
As shown in Table 2, examples 5, 12 and 19 use SiO in the conductive composition2A relatively large amount of 7 mass% glass frit, but no silicone resin was added. It was confirmed that the electrode formed using these conductive compositions had a significantly reduced film thickness compared with the electrode of the other examples, regardless of the composition of the glass frit. That is, it was found that a printed material (coating film) of the conductive composition containing no silicone resin sags and has low shape stability.
On the other hand, it is known to use SiO2The conductive compositions of examples 1 to 4, 8 to 11, and 15 to 18, which contain the silicone resin in proportions of 0 mass%, 3 mass%, and 5 mass% of the glass frit, can form electrodes having a thicker film thickness than those of examples 5, 12, and 19 described above. That is, the shape during firing can be confirmedThe stability is improved, and an electrode with a high aspect ratio can be formed without depending on the composition of the glass frit. In addition, it was confirmed that the solar cell produced using the conductive composition had a substantially low series resistance Rs and a high conversion efficiency Eff, and the power generation performance was improved with an increase in the aspect ratio.
Note that SiO in the glass frit2The conductive compositions of examples 6, 7, 13, 14, 20 and 21, which contained the silicone resin at a ratio of 7 mass%, formed electrodes having a thicker film thickness than those of examples 5, 12 and 19, which did not contain the silicone resin, but were confirmed to have deteriorated series resistance and conversion efficiency. The reason is considered to be that: although a large-volume electrode can be formed by the action of the silicone resin, SiO derived from the glass frit and the silicone resin is present in the electrode after firing2The relatively large amount of SiO2And functions as a resistance component. Therefore, it is found that when a silicone resin is added to the conductive composition, SiO in the glass frit2The ratio of (b) is preferably less than 7% by mass, for example, 5% by mass or less.
In addition, in the conductive composition containing silicone resin, in example 1, 8 and 15, the use of SiO not contained2Examples of glass frits of the composition. These examples are expected to fail to react sufficiently with the Si substrate during firing and not to form a good contact at the Si substrate/electrode interface, according to conventional knowledge. However, with the use of SiO-containing materials2The solar cells of examples 1, 8 and 15 all had the same or better results in terms of series resistance and conversion efficiency as compared with the examples of the glass frit having the component(s). Therefore, it is considered that by compounding a silicone resin in the conductive composition, the silicone resin exhibits the effect of mixing with SiO in the glass frit in baking2Has the same effect. As SiO2The substitute of (2) plays a role. It was also confirmed that SiO in the glass frit can be made by blending a silicone resin in the conductive composition2The ratio of (a) is cut off or zero. Not containing SiO2The glass frit of (2) can greatly reduce the softening point, and it is considered that the use of a conductive composition containing such a glass frit can be utilizedAnd the firing temperature at the time of electrode formation is lowered.
Further, examples 3, 10 and 17 of the conductive composition containing a silicone resin are examples in which the silicone resin is suppressed to a very small amount. Even if such a very small amount of silicone resin is added, SiO is used2In examples 5 and 12 and example 19 in which the glass frit was contained in an amount of 7 mass%, the solar cell was able to form an electrode having a large film thickness and the series resistance and the conversion efficiency of the solar cell were equal to or better than each other. Therefore, it is found that even a very small amount of silicone resin is blended in the conductive composition, the effect of improving the shape stability of the conductive composition (coated material) during printing or firing can be obtained, and an electrode having an improved aspect ratio can be formed.
(embodiment mode 2)
[ preparation of electroconductive composition ]
The influence of the weight average molecular weight of the silicone resin on the properties of the conductive composition was evaluated in the following procedure. That is, a5 in embodiment 1 is used as the glass frit. Seven polydimethylsiloxanes having a weight average molecular weight Mw of (S1)3000, (S2)1 ten thousand, (S3)2 ten thousand, (S4)5 ten thousand, (S5)7 ten thousand, (S6)9 ten thousand and (S7)11 ten thousand are used as silicone resins. Further, 0.3 parts by mass of any of these silicone resins was added to 100 parts by mass of the silver powder, and under the same conditions as in embodiment 1, conductive compositions of S1 to S7 were prepared. For comparison, an electrically conductive composition of S0 was also prepared without blending a silicone resin.
Next, using the conductive compositions of S0 to S7 prepared as described above, solar cell elements of S0 to S7 were formed by a screen printing method in the same manner as in embodiment 1 described above.
[ evaluation ]
The light receiving surface electrode (finger electrode) formed as described above was measured for the number of disconnections, aspect ratio, and line resistance R by the following procedureL。
The number of broken lines of the electrodes was measured by specifying the broken line portions (crack portions) of the electrodes for 100 substrates using a solar cell Electroluminescence (EL) detector. The results are shown in fig. 3 as the average number of broken portions per 1 substrate.
The aspect ratio of the electrode was calculated as (H/W) by measuring the width W and thickness (height) H of the light-receiving surface electrode of each example using a shape analysis laser microscope (manufactured by keyence co. Fig. 3 shows the results as the average value of the values measured for the light-receiving surface electrode 100.
The line resistance of the electrode was measured as a resistance value (Ω) at an arbitrary interval (24mm) on the surface of the finger-shaped electrode using a resistance meter (digital multimeter, manufactured by Nissan electric Co., Ltd.). Fig. 4 shows the results as the average value of the values measured for the light-receiving surface electrode 100.
The symbols in the graphs of fig. 3 and 4 show the results of S0 to S7 in the order from the left side in terms of the X axis (i.e., the weight average molecular weight Mw).
As shown in fig. 3, it was confirmed that the aspect ratio of the electrode was significantly improved by adding the silicone resin to the conductive composition. In addition, the larger the weight average molecular weight of the added silicone resin becomes, the higher the aspect ratio of the electrode can be formed, and Si contained in the silicone resin is expected to contribute to maintaining the shape of the electrode.
In addition, as can be seen from fig. 3, the number of disconnections of the electrode was changed by adding a silicone resin to the conductive composition and by the weight average molecular weight of the added silicone resin. That is, in the present embodiment, by adding a silicone resin having a weight average molecular weight of, for example, 9 ten thousand or less to the conductive composition, the number of disconnections of the electrode can be reduced as compared with the case where no silicone resin is added. However, it is found that when a silicone resin having a weight average molecular weight of more than 9 ten thousand, for example, 11 ten thousand is used, the number of disconnections tends to increase.
As shown in fig. 4, it is understood that the line resistance of the electrode is affected by the weight average molecular weight of the silicone resin in the conductive composition. The results showed similar tendency to those of the number of broken lines. That is, from the viewpoint of increasing the aspect ratio of the electrode shape, it is preferable to add a silicone resin to the conductive composition. However, if the Si component is contained excessively, the electrode may be broken, and thus, the resistance component may be obtained. From these facts, it is found that in order to achieve both high aspect ratio and low resistance characteristics of the electrode, it is preferable to use a silicone resin having an appropriate weight average molecular weight. In the present embodiment, it is also preferable to use a silicone resin having a weight average molecular weight of less than 11 ten thousand, more preferably about 9 ten thousand or less, for example, as the silicone resin to be added to the conductive composition.
(embodiment mode 3)
[ preparation of electroconductive composition ]
The conductive composition was prepared by the following procedure, and the relationship between the silicone resin and the series resistance Rs in the composition was evaluated. Here, as the glass frit, a lead-based glass and SiO are used2"A5" having a component content of 5 mass%, and SiO as the lead-free glass 12The content of component (c) was 5% by mass of "B5". In addition, polydimethylsiloxane having a weight average molecular weight Mw of 5 ten thousand was used as the silicone resin. Then, the proportions of these glass frit and silicone resin relative to 100 parts by mass of silver powder were changed in the combination shown in table 3 below, and other conditions were the same as in embodiment 1 above, to prepare conductive compositions. Further, a light-receiving surface electrode is formed using these conductive compositions to produce a solar cell element.
The series resistance Rs of the solar cell elements prepared as described above was measured and shown in table 3. It is found that the conductive composition using the lead-based glass frit a5 can form an electrode having higher characteristics such as series resistance Rs, as compared with the conductive composition using the lead-free glass frit B5. Therefore, in Table 3 below, when glass frit A5 was used, it was judged that the resistance was low and good when Rs was not more than 3.73, and when glass frit B5 was used, it was judged that the resistance was low and good when Rs was not more than 3.91. The results of table 3 showing good results with low resistance are shown in bold.
The ratio of the glass frit to the silicone resin was calculated from the amounts of glass frit and silicone resin shown in table 3 and is shown in table 4. In table 4, the results of combinations of the amounts of glass frit and silicone resin in which the electrical resistance was improved in table 3 are shown in bold.
[ Table 3]
TABLE 3
Rs[mΩ]
[ Table 4]
TABLE 4
Glass powder/silicone resin mass ratio [ mass/mass ]
[ evaluation ]
As shown in table 3, in the present embodiment, when the amount of the silicone resin contained in the conductive composition is in the range of approximately 0.2 parts by mass or less, the series resistance Rs can be effectively reduced by limiting the amount of the glass frit added to a predetermined range. For example, it is known that the series resistance Rs can be effectively reduced by limiting the addition amount of the glass frit to 1.875 parts by mass to 3.125 parts by mass, regardless of the glass composition.
On the other hand, it is found that when the amount of the silicone resin contained in the conductive composition is in a range of approximately more than 0.15 parts by mass (for example, 0.2 parts by mass or more), the series resistance Rs can be effectively reduced by limiting the ratio of the amount of the glass frit to the amount of the silicone resin (glass frit mass/silicone resin mass) to a predetermined range. For example, it is found that the series resistance Rs can be effectively reduced by limiting the ratio of the amounts of the glass frit to a range of approximately 7.5 to 18, preferably approximately 8.33 to 16.67, regardless of the glass composition. This is considered to be because, for example, if the amount of silicone resin contained in the conductive composition is increased, the amount of glass frit added is required to be increased in order to keep the series resistance Rs of the electrode to be formed low. That is, if the conductive composition contains a silicone resin, it can be produced from the silicone resin during electrode bakingRaw SiO2And (3) components. The SiO2Composition and SiO in glass frit2The components similarly exhibit an action of suppressing erosion of the interface between the electrode and the antireflection film or the substrate. Therefore, it can be said that in order to exhibit good burn-through characteristics and to achieve good contact between the electrode and the substrate, it is preferable to adjust the amount of glass frit added in advance to a value suitable for the amount of silicone resin added to the conductive composition.
While the present invention has been described above with reference to preferred embodiments, the description is not intended to be limiting, and various changes may be made.
Description of the reference numerals
10 solar cell element (unit)
11 semiconductor substrate (silicon substrate)
11A light-receiving surface
11B back surface
12 bus electrode (light receiving surface electrode)
13 finger electrode (light receiving surface electrode)
14 anti-reflection film
16 n-Si layer
18 p-Si layer
20 back side aluminum electrode
22 electrode for external connection on back side
24 p+Layer(s)
Claims (5)
1. A conductive composition for forming a linear electrode on a light-receiving surface of a solar cell element,
which comprises a conductive powder,
Glass powder,
Organic silicon resin,
An organic binder, and
the dispersion medium is a mixture of a dispersion medium,
the metal species constituting the conductive powder contains any one or two or more elements selected from the group consisting of nickel, platinum, palladium, silver, copper and aluminum,
SiO of the glass powder in terms of oxide2The proportion of the component (B) is 0 to 5 mass%,
the silicone resin has a weight average molecular weight of 1000 or more and 90000 or less, and is dispersed or dissolved in the conductive composition as a liquid or oily composition.
2. The conductive composition according to claim 1, wherein a ratio of the silicone resin to 100 parts by mass of the conductive powder is 0.005 parts by mass or more and 0.9 parts by mass or less.
3. The conductive composition according to claim 1 or 2, wherein the silicone resin has a weight average molecular weight of 3000 or more and 90000 or less.
4. A semiconductor device comprising an electrode formed using the conductive composition according to any one of claims 1 to 3.
5. A solar cell element comprising a light-receiving surface electrode formed using the conductive composition according to any one of claims 1 to 3.
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| CN114538916A (en) * | 2022-03-03 | 2022-05-27 | 太原理工大学 | Low-temperature co-fired ceramic dielectric material and preparation method thereof |
Also Published As
| Publication number | Publication date |
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| TWI673726B (en) | 2019-10-01 |
| WO2016111299A1 (en) | 2016-07-14 |
| TW201626404A (en) | 2016-07-16 |
| JP2016127212A (en) | 2016-07-11 |
| CN107210325A (en) | 2017-09-26 |
| JP5957546B2 (en) | 2016-07-27 |
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