WO2016111299A1 - Composition conductrice, élément à semi-conducteur, et élément de batterie solaire - Google Patents
Composition conductrice, élément à semi-conducteur, et élément de batterie solaire Download PDFInfo
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- WO2016111299A1 WO2016111299A1 PCT/JP2016/050161 JP2016050161W WO2016111299A1 WO 2016111299 A1 WO2016111299 A1 WO 2016111299A1 JP 2016050161 W JP2016050161 W JP 2016050161W WO 2016111299 A1 WO2016111299 A1 WO 2016111299A1
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- electrode
- conductive composition
- mass
- silicone resin
- glass
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- 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 potential barriers
- 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 potential barriers 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
-
- 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
Definitions
- the present invention relates to a conductive composition.
- it is related with the electroconductive composition which can be used in order to form the electrode pattern of a solar cell.
- a finger (collecting current) electrode made of a thin wire formed of a conductor such as silver, and the finer electrode A bus bar electrode to be connected is provided.
- these electrodes are also collectively referred to as light receiving surface electrodes.
- a light receiving surface electrode includes a conductive powder such as silver as a conductor component, and an organic vehicle component composed of an organic binder and a solvent, and is prepared in a paste form (including a slurry form and an ink form).
- a material (hereinafter also referred to as “conductive composition”, simply “composition”) is printed 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 fired. It is formed with.
- conductive composition simply “composition”
- Patent Documents 1 to 3 are known as conventional techniques related to the conductive composition used for forming the light receiving surface electrode of such a solar cell.
- JP 2010-087251 A JP 2012-023095 A Special table 2012-508812
- the conductive composition for forming an electrode of a solar cell may contain glass frit in addition to the above constituent materials.
- the glass frit can function as an inorganic binder that softens or melts during firing to achieve a good bond between the substrate and the electrode.
- a favorable fire through characteristic is expressed because an electroconductive composition contains glass frit. That is, when manufacturing a solar cell, typically, an antireflection film is first formed on almost the entire light receiving surface of a silicon substrate, and a conductive composition for forming a light receiving surface electrode is formed on the antireflection film. Are supplied in a desired electrode pattern and fired.
- the glass frit in the conductive composition reacts with the antireflection film during firing and takes it into the glass.
- the conductive powder in the conductive composition passes through the antireflection film (fire-through), and realizes good electrical connection (ohmic contact) with the silicon substrate.
- the fire-through characteristics of the conductive composition are used in this way, it is not necessary to remove the antireflection film partially when forming a fine light-receiving surface electrode, and it is easy to use. This eliminates the risk of gaps or overlaps with the surface electrode formation position, which is preferable.
- the portion where the light receiving surface electrode is formed becomes a light shielding portion (non-light receiving portion).
- the light receiving surface electrode is made thinner (fine line) than before, the light receiving area per cell unit area can be expanded and the output per cell unit area can be improved.
- the electrode is not bulky (thickened) by the amount of thinning, the line resistance of the electrode increases and the output characteristics of the solar cell deteriorate. Therefore, for the fine line formation of the light-receiving surface electrode, it is simultaneously required to improve the electrode thickness, that is, to have a high aspect ratio (ratio of electrode thickness to line width: large thickness / line width; hereinafter the same). It is done.
- the conventional conductive composition is expected to be further improved from the viewpoint of achieving both good ohmic contact and fine line formation of the above-described electrode.
- the present invention has been made in view of such a situation, and its main purpose is to realize thinning of the electrode pattern and high aspect ratio, and to satisfactorily form a contact point between the electrode and the substrate. It is providing the electroconductive composition for electrode formation.
- Another object of the present invention is to provide a semiconductor element with improved function or performance, for example, a solar cell element, that can be realized by adopting the conductive composition.
- the present invention provides a conductive composition that can be suitably used for forming an electrode (electrode pattern).
- This conductive composition includes conductive powder, glass frit, silicone resin, organic binder, and dispersion medium, and the glass frit has a SiO 2 component ratio of 0 mass when converted to oxide. % Or more and 5% by mass or less.
- the conductive composition disclosed herein contains glass frit, it can form an electrode having good bonding properties with a substrate, and an antireflection film can be formed when forming a solar cell electrode. Even if it is a case where it supplies to the top, the contact of an electrode and a board
- the SiO 2 component derived from glass frit or silicone resin is not preferable in that it can increase the insulating resistance component in the electrode.
- the glass frit does not contain a SiO 2 component, or the ratio of the SiO 2 component in the glass frit is limited as described above, so that the electrode characteristics are not impaired. It achieves both high fire-through characteristics and electrode shape stability at a high level.
- the 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.
- the silicone resin has a weight average molecular weight of 3000 or more and 90000 or less. With such a configuration, electrical characteristics such as line resistance of the electrode can be further enhanced as compared with the case where no silicone resin is added.
- the metal species constituting the conductive powder is any one or two selected from the group consisting of nickel, platinum, palladium, silver, copper, and aluminum. It is characterized by containing more than seed elements. With such a configuration, an electrode having excellent conductivity can be configured.
- the present invention also provides a semiconductor device including an electrode formed using any one of the conductive compositions described above.
- This semiconductor element can typically be a solar cell element including a light-receiving surface electrode formed using the conductive composition.
- a finer electrode pattern and an electrode having a finer line width are bulky (higher (In aspect ratio). Therefore, for example, further fine lines can be realized in printing of electrode patterns of various semiconductor elements, and a high-performance semiconductor element in which the semiconductor element is further miniaturized and highly integrated is realized.
- the conductive composition disclosed herein is typically a conductive composition capable of forming an electrode by firing.
- the conductive composition is essentially the same as the conventional conductive composition of this type.
- the conductive powder, the glass frit, and the organic vehicle component for dispersing these components (described later, A mixture of an organic binder and a dispersant), and a silicone resin as an essential component.
- a mixture of an organic binder and a dispersant A mixture of an organic binder and a dispersant
- silicone resin as an essential component.
- the conductive powder that is the main component of the solid content of the paste it is possible to consider powders made of various metals or their alloys having desired conductivity and other physical properties according to the application.
- the material constituting the conductive powder include gold (Au), silver (Ag), copper (Cu), platinum (Pt), palladium (Pd), ruthenium (Ru), rhodium (Rh), iridium ( Ir), metals such as osmium (Os), nickel (Ni) and aluminum (Al) and their alloys, carbonaceous materials such as carbon black, LaSrCoFeO 3 -based oxides (for example, LaSrCoFeO 3 ), LaMnO 3 -based oxides ( Examples thereof include conductive ceramics represented by transition metal perovskite oxides represented by LaSrGaMgO 3 ), LaFeO 3 -based oxides (eg LaSrFeO 3 ), LaCoO 3 -based oxides (eg LaSrCoO 3
- particularly preferable conductive powders are composed of a simple substance of a noble metal such as platinum, palladium and silver and alloys thereof (Ag—Pd alloy, Pt—Pd alloy, etc.) and nickel, copper, aluminum and alloys thereof. It is mentioned as a material which comprises. From the viewpoint of relatively low cost and high electrical conductivity, a powder made of silver and its alloy (hereinafter also simply referred to as “Ag powder”) is particularly preferably used.
- Ag powder silver and its alloy
- the conductive composition of the present invention will be described using an example in which Ag powder is used as the conductive powder.
- the particle size of the Ag powder and other conductive powders is not particularly limited, and those having various particle sizes according to the application can be used. Typically, those having an average particle diameter of 5 ⁇ m or less based on the laser / scattering diffraction method are suitable, and those having an average particle diameter of 3 ⁇ m or less (typically 1 to 3 ⁇ m, for example 1 to 2 ⁇ m) are preferably used. It is done.
- the shape of the particles constituting the conductive powder is not particularly limited. Typically, a spherical shape, a flake shape (flake shape), a conical shape, a rod shape, or the like can be preferably used. Spherical or scaly particles are preferably used for reasons such as easy formation of a fine light-receiving surface electrode with good filling properties.
- the conductive powder to be used those having a sharp (narrow) particle size distribution are preferable.
- a conductive powder having a sharp particle size distribution that does not substantially contain particles having a particle diameter of 10 ⁇ m or more is preferably used.
- the ratio (D10 / D90) of the particle size (D10) when the cumulative volume is 10% and the particle size (D90) when the cumulative volume is 90% in the particle size distribution based on the laser scattering diffraction method can be adopted.
- the value of D10 / D90 is 1, and conversely, the value of D10 / D90 approaches 0 as the particle size distribution becomes wider.
- a conductive composition using a conductive powder having such an average particle size and particle shape has a good filling property of the conductive powder and can form a dense electrode. This is advantageous in forming a fine electrode pattern with high shape accuracy.
- the conductive powder such as Ag powder is not particularly limited by the manufacturing method thereof.
- conductive powder typically Ag powder
- a known wet reduction method, gas phase reaction method, gas reduction method or the like can be classified and used as necessary.
- classification can be performed using, for example, a classification device using a centrifugal separation method.
- the glass frit is a component that can function as an inorganic binder of the conductive powder, and improves the bonding between the conductive particles constituting the conductive powder and between the conductive particles and the substrate (object on which the electrode is formed). Work.
- this conductive composition when used, for example, for forming a light-receiving surface electrode of a solar cell, the presence of the glass frit may cause the conductive composition to penetrate an antireflection film as a lower layer during firing. This makes it possible to achieve good adhesion and electrical contact with the substrate.
- Such a glass frit is preferably adjusted to a size equal to or smaller than that of the conductive powder.
- the average particle diameter based on the laser / scattering diffraction method is preferably 4 ⁇ m or less, more preferably 2 ⁇ m or less, and more preferably about 0.1 ⁇ m or more and 3 ⁇ m or less.
- the composition of the glass frit can be used as the proportion of SiO 2 component when converted oxides 0 mass% to 5 mass% or less (e.g., less than 5 wt%).
- the SiO 2 component is preferably contained in the glass frit in that the stability of the system is improved and the erosion property at the time of fire-through can be adjusted.
- a silicone resin described later is included as an essential component, and this silicone resin forms a SiO 2 component during firing. Excess SiO 2 component can increase the softening point of the glass frit and reduce the erosion of the conductive composition during fire-through. In addition, if electrode formation by firing at a lower temperature becomes impossible, electrode performance may be adversely affected.
- the ratio of the SiO 2 component of the glass frit is limited to an extremely small amount as described above.
- the SiO 2 component in the glass frit is preferably 4% by mass or less, for example, 3% by mass or less.
- the SiO 2 component in the glass frit may be 0% by mass (that is, not including the SiO 2 component).
- Glass of various compositions can be used.
- a so-called lead-based glass, lead-lithium-based glass, zinc-based glass, borate-based glass, borosilicate-based glass (however, the amount of Si is a name that is conventionally expressed by those skilled in the art)
- the glass may be alkaline glass, lead-free glass, tellurium glass, glass containing barium oxide, bismuth oxide, or the like.
- these glasses include Si (but the amount of Si is limited), Pb, Zn, Ba, Bi, B, Al, Li, Na, K, in addition to the main glass constituent elements appearing in the above names.
- Such a glass frit may be, for example, a crystallized glass partially containing crystals in addition to a general amorphous glass. As for the glass frit, as long as the SiO 2 component as a whole is adjusted as described above, one kind of glass frit may be used alone, or two or more kinds of glass frit may be mixed. It may be used.
- the softening point of the glass constituting the glass frit is not particularly limited, but is preferably about 300 to 600 ° C. (for example, 400 to 500 ° C.). Specific examples of the glass whose softening point can be adjusted in the range of 300 ° C. or more and 600 ° C. or less include glass containing a combination of the following elements.
- the conductive composition containing glass frit having such a softening point when used, for example, when forming a light-receiving surface electrode of a solar cell element, it exhibits good fire-through characteristics and forms a high-performance electrode. Preferred to contribute.
- the silicone resin is characteristic as an essential constituent component contained in the conductive composition disclosed herein.
- a conductive composition can maintain a stable shape from printing to firing, for example, and can stably form a finer and higher aspect ratio electrode.
- the silicone resin may generate SiO 2 component in the electrode by firing.
- SiO 2 component is preferable in that the stability of the system and the binding property between the electrode and the substrate can be improved without directly increasing the softening point of the glass frit.
- An organic compound containing silicon (Si) can be used without particular limitation as the silicone resin (which may be simply referred to as silicone).
- the silicone resin is typically uniformly dispersed or dissolved in the conductive composition as a liquid or oily composition.
- an organic compound having a main skeleton based on a siloxane bond Si—O—Si
- it may be a linear silicone in which an alkyl group or a phenyl group is introduced into a dangling bond (side chain, terminal) in the main skeleton.
- it may be a linear modified silicone in which other substituents such as a polyether group, an epoxy group, an amine group, a carboxyl group, an aralkyl group, and a hydroxyl group are introduced into a side chain, a terminal, or both. It may be a linear block copolymer alternately bonded with silicone.
- Such a silicone resin is preferable because an electrode having a high aspect ratio can be formed as the weight average molecular weight (hereinafter sometimes simply referred to as “Mw”) increases.
- Mw is preferably 90,000 or less, more preferably 70,000 or less, and particularly preferably 60,000 or less.
- the lower limit of Mw is not particularly limited, but can be, for example, 1,000 or more, preferably 3,000 or more, more preferably 5,000 or more, and particularly 10,000 or more, for example 20,000 or more. preferable.
- the organic vehicle component for dispersing the constituent elements such as the above conductive powder various kinds of those conventionally used in this type of conductive composition are not particularly limited depending on the desired purpose. Can do.
- the vehicle is composed of organic binders and organic solvents of various compositions. In such an organic vehicle component, all of the organic binder may be dissolved in an organic solvent, or only a part thereof may be dissolved or dispersed (may be a so-called emulsion type organic vehicle).
- organic binder examples include cellulose polymers such as ethyl cellulose and hydroxyethyl cellulose, acrylic resins such as polybutyl methacrylate, polymethyl methacrylate, and polyethyl methacrylate, epoxy resins, phenol resins, alkyd resins, polyvinyl alcohol, polyvinyl butyral, etc.
- An organic binder based on is preferably used.
- a cellulosic polymer for example, ethyl cellulose
- a viscosity characteristic capable of performing particularly good screen printing can be realized.
- a preferable solvent constituting the organic vehicle is an organic solvent having a boiling point of about 200 ° C. or higher (typically about 200 to 260 ° C.).
- An organic solvent having a boiling point of about 230 ° C. or higher (typically about 230 to 260 ° C.) is more preferably used.
- organic solvents include 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), ethylene glycol and diethylene glycol.
- An organic solvent such as a derivative, toluene, xylene, mineral spirit, terpineol, mentanol, or texanol can be preferably used.
- Particularly preferred solvent components include butyl carbitol (BC), butyl carbitol acetate (BCA), 2,2,4-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 electrode formation method, typically the printing method, etc., but generally conforms to the conductive composition of the composition conventionally employed. It can be set as a mixture ratio.
- the ratio of each component can be determined using the following formulation as a guide. That is, the content of the conductive powder in the conductive composition is suitably about 70% by mass or more (typically 70% to 95% by mass) when the entire paste is 100% by mass. More preferably, it is preferably about 80 to 90% by mass, for example, about 85% by mass. Increasing the content of the conductive powder is preferable from the viewpoint of forming a dense electrode pattern with good shape accuracy. On the other hand, if the content is too high, the handleability of the paste and the suitability for various printability may be reduced.
- Silicone resin is preferable because an electrode can be formed with a higher aspect ratio by adding even a very small amount to the conductive powder.
- the addition amount of the silicone resin can typically be 0.005 parts by mass or more, preferably 0.01 parts by mass or more, and More preferably, it is 1 part by mass or more. Excessive addition is not preferable for increasing the resistance of the formed electrode. Therefore, the addition amount of the silicone resin can be typically 1.2 parts by mass or less, preferably 0.9 parts by mass or less when the conductive powder is 100 parts by mass, It is more preferable that the amount is not more than part by mass.
- the ratio of the glass frit to the conductive powder is unclear because of the relationship with the silicone resin, but in order to obtain good fire-through characteristics, typically when the conductive powder is 100 parts by mass,
- the amount can be 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more. Excessive addition is not preferable in order to increase the resistance of the electrode to be formed, and can be typically 12 parts by mass or less, preferably 10 parts by mass or less, and 8 parts by mass or less. Is more preferable.
- the above-mentioned silicone resin and the glass frit is a source of SiO 2 components contained in the electrode. And the content can be considered complementarily in that this SiO 2 component can suppress the fire-through characteristic or can become an insulating resistance component in the electrode. More specifically, since the electroconductive composition disclosed here contains a silicone resin, the SiO 2 component in the glass frit can be suppressed to a small amount. However, for example, when the amount of the silicone resin exceeds approximately 0.15 parts by mass (for example, 0.2 parts by mass or more), the conductive composition penetrates the antireflection film or forms a good contact with the substrate. It is preferable to secure a sufficient amount of glass frit corresponding to the amount of silicone resin.
- the mass ratio of glass frit to silicone resin is preferably 7.5 or more, more preferably 8 or more, 8.3 or more, for example 10 or more Is particularly preferred.
- the silicone resin and the glass frit can themselves be the resistance component of the electrode.
- the mass ratio of the glass frit to the silicone resin is preferably about 18 or less, more preferably 16.5 or less, for example, 15 or less, and further preferably 12 or less.
- the series resistance Rs can be effectively reduced by keeping the amount ratio of the glass frit to the silicone resin within a predetermined range.
- the organic binder may be contained in a proportion of about 15% by mass or less, typically about 1% by mass to 10% by mass when the mass of the conductive powder is 100% by mass. preferable. Particularly preferably, it is contained at a ratio of 2% by mass to 6% by mass with respect to 100% by mass of the conductive powder.
- this organic binder may contain the organic binder component which is melt
- the organic binder component dissolved in the organic solvent and the organic binder component not dissolved are included, the ratio thereof is not particularly limited, but for example, the organic binder component dissolved in the organic solvent is (40% to 100%) can be occupied.
- the content ratio of the organic vehicle as a whole is variable in accordance with the properties of the paste to be obtained.
- the total amount of the conductive composition is 100% by mass, for example, 5% by mass to 30% by mass. %, Is preferably 5% by mass to 20% by mass, more preferably 5% by mass to 15% by mass (particularly 7% by mass to 12% by mass).
- the conductive composition disclosed herein can contain various inorganic additives and / or organic additives other than those described above without departing from the object of the present invention.
- the inorganic additive ceramic powder other than the above (ZnO 2, Al 2 O 3, etc.), other various fillers and the like.
- additives such as surfactant, an antifoamer, antioxidant, a dispersing agent, a viscosity modifier, are mentioned, for example.
- the above conductive composition has shape stability, for example, it may be a printing composition applied to screen printing, gravure printing, offset printing, ink jet printing, etc. Is suitable). And it can employ
- FIG. 1 and FIG. 2 schematically show an example of a solar cell element (cell) 10 that can be suitably manufactured by implementing the present invention, and is made of single crystal, polycrystalline, or amorphous silicon (Si).
- This is a so-called silicon-type solar cell element 10 that uses the wafer as the semiconductor substrate 11.
- a cell 10 shown in FIG. 1 is a general single-sided light receiving solar cell element 10.
- this type of solar cell element 10 includes an n-Si layer 16 formed by forming a 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.
- an antireflection film 14 made of titanium oxide or silicon nitride formed by CVD or the like, and light receiving surface electrodes 12 and 13 made of a conductive composition mainly containing Ag powder or the like. .
- the back side of the p-Si layer 18 As with the light-receiving surface electrode 12, the back side outside formed by a predetermined conductive composition (typically a conductive paste whose conductive powder is Ag powder).
- a connection electrode 22 and a back surface aluminum electrode 20 having a so-called back surface field (BSF) effect are provided.
- the aluminum electrode 20 is formed on substantially the entire back surface by printing and baking a conductive composition mainly composed of aluminum powder.
- an Al—Si alloy layer (not shown) is formed, and aluminum diffuses into the p-Si layer 18 to form a p + layer 24.
- the p + layer 24 that is, the BSF layer, the photogenerated carriers are prevented from recombining in the vicinity of the back electrode, and for example, an improvement in short circuit current and open circuit voltage (Voc) is realized.
- the bus bar electrode 12 is a connection electrode for collecting carriers collected by the finger electrode 13. The portion where the light receiving surface electrodes 12 and 13 are formed forms a non-light receiving portion (light shielding portion) on the light receiving surface 11A of the solar cell element.
- the bus bar electrode 12 and the finger electrode 13 are made as fine lines as possible to reduce the corresponding non-light receiving portion (light shielding portion).
- the light receiving area per unit cell area is enlarged. This can extremely simply improve the output per unit area of the solar cell element 10.
- the height of the thinned electrode is high and uniform, but for example, when a sagging or a dent occurs in a part of the electrode, the sagging or the dent causes an increase in resistance, thereby collecting current. Loin is produced. Moreover, if even a part of the thinned electrode breaks, it is impossible to collect the generated current through the broken part (current collection is generated as a current flowing through the high resistance substrate). Current will be collected). Therefore, the formation of the light-receiving surface electrode of the solar cell element requires a conductive composition having excellent electrical stability and excellent shape stability by printing.
- Such a solar cell element 10 is generally manufactured through the following process. That is, an appropriate silicon wafer is prepared, and the p-Si layer 18 and the n-Si layer 16 are formed by doping a predetermined impurity by a general technique such as a thermal diffusion method or ion plantation. A substrate (semiconductor substrate) 11 is produced. Next, an antireflection film 14 made of silicon nitride or the like is formed by a technique such as plasma CVD. Thereafter, on the back surface 11B side of the silicon substrate 11, first, a predetermined pattern is screen-printed using a predetermined conductive composition (typically a conductive composition in which the conductive powder is Ag powder) and dried.
- a predetermined conductive composition typically a conductive composition in which the conductive powder is Ag powder
- a back side conductor coated material that becomes the back side external connection electrode 22 (see FIG. 1) after firing is formed.
- a conductive composition containing aluminum powder as a conductor component is applied (supplied) by a screen printing method or the like on the entire back surface, and dried to form an aluminum film.
- the conductive composition of the present invention is typically printed (supplied) on the antireflection film 14 formed on the surface side of the silicon substrate 11 with a wiring pattern as shown in FIG. 2 based on a screen printing method.
- the line width to be printed is not particularly limited, but by adopting the conductive composition of the present invention, the line width is about 70 ⁇ m or less (preferably in the range of about 50 ⁇ m to 60 ⁇ m, more preferably in the range of about 40 ⁇ m to 50 ⁇ m. ) Of the electrode pattern including the finger electrodes of () is formed.
- the substrate is dried in an appropriate temperature range (typically about 100 ° C. to 200 ° C., for example, about 120 ° C. to 150 ° C.). The contents of a suitable screen printing method will be described later.
- the silicon substrate 11 on which the paste application (dried film-like application) is formed on both sides is subjected to an appropriate baking temperature (for example, using a baking furnace such as a near-infrared high-speed baking furnace) in an air atmosphere. Baked at 700 to 900 ° C.).
- a fired aluminum electrode 20 is formed together with the light-receiving surface electrodes (typically Ag electrodes) 12 and 13 and the backside external connection electrode (typically Ag electrode) 22, and at the same time, Al (not shown)
- a -Si alloy layer is formed and aluminum is diffused into the p-Si layer 18 to form the p + layer (BSF layer) 24 described above, whereby the solar cell element 10 is manufactured.
- firing for forming the light receiving surface electrodes typically Ag electrodes 12 and 13 on the light receiving surface 11A side, the aluminum electrode 20 on the back surface 11B side, and external connection
- the firing for forming the electrode 22 may be performed separately.
- the conductive composition can be supplied (printed) on the silicon substrate 11 with a desired electrode pattern by screen printing. Since such a conductive composition is excellent in shape stability, for example, an electrode obtained after firing has a line width of 60 ⁇ m or less and a thickness of 20 ⁇ m or more (preferably a line width of 40 ⁇ m or more and 50 ⁇ m or less and a thickness of 20 ⁇ m or more. ) Of the finger electrode 13) can be formed with high quality in a state in which the occurrence of line thinning and disconnection is greatly reduced. The bus bar electrode is hardly affected by the thinning or disconnection of the wire, so that it is not necessary to use such a conductive composition.
- a bus bar electrode having a line width of about 1000 to 3000 ⁇ m can be formed with high quality.
- the output per unit area can be improved without increasing the resistance per finger electrode.
- the line resistance value of the entire electrode pattern can be kept low. Therefore, a solar cell element with high photoelectric conversion efficiency is provided by designing the width and number of finger electrodes 13 as an optimal combination.
- conductive composition for electrode formation was prepared by the following procedure. That is, as the conductive powder, silver (Ag) powder having an average particle diameter of 2 ⁇ m was used. As the glass frit, 12 types of glass powders (average particle size: 0.5 to 1.6 ⁇ m) shown in Table 1 below were used. As the silicone resin, polydimethylsiloxane having a weight average molecular weight Mw of 50,000 was used. Moreover, hydrogenated castor oil was used as the surfactant.
- the organic vehicle component a vehicle in which ethyl cellulose (EC) as an organic binder component was dispersed in texanol as a dispersion medium was used.
- EC ethyl cellulose
- Table 1 the symbol indicating the structure of the glass frit is “A” for leaded glass containing Pb, “B” for lead-free glass containing bismuth (Bi) or the like without containing Pb, and Pb.
- Other lead-free glass containing boron (B), silicon (Si), etc. without being included is represented by “C”, and a number indicating the content of the SiO 2 component in each glass composition is added.
- the softening point is changed in the range of 300 ° C. or more and 600 ° C. or less as shown in Table 1 by adjusting the composition.
- the glass frit is 2.50 parts by mass
- the silicone resin is 0 parts by mass, 0.0050 parts by mass, 0.30 parts by mass
- ethyl cellulose is 1 part by mass.
- the viscosity is adjusted to about 190 Pa ⁇ s with texanol. 21 conductive compositions were prepared. Table 2 below shows the types of glass frit used in the conductive compositions of the respective examples, the blending amount of the silicone resin, and the actually measured values of the viscosity of the obtained conductive compositions.
- the composition of the glass frit used in each example is represented by the symbols shown in Table 1.
- “-” in the column of the amount of silicone resin indicates that no silicone resin is blended (0 part by mass).
- the viscosity of the electrically conductive composition of each example is the value measured on condition of 20 rpm in 25 degreeC using the Brookfield type viscometer of HBT type.
- n-Si layer (n + layer) having a thickness of about 0.5 ⁇ m on the light receiving surface of the silicon substrate.
- a silicon nitride film having a thickness of about 80 nm was formed on the n-Si layer by plasma CVD (PECVD) to form an antireflection film.
- the back side electrode pattern was formed on the back side of the silicon substrate by using a predetermined silver electrode forming paste, followed by screen printing with a predetermined pattern to be a back side external connection electrode and drying. . Then, an aluminum electrode forming paste is screen-printed on the entire back surface side and dried to form an aluminum film.
- an electrode pattern for a light-receiving surface electrode (Ag electrode) was printed on the antireflection film by a screen printing method in an air atmosphere at room temperature. And dried at 120 ° C.
- an electrode pattern comprising three mutually parallel linear busbar electrodes and 90 finger electrodes parallel to each other so as to be orthogonal to the busbar electrodes. It was formed by screen printing.
- the target finger electrode pattern is such that the dimensions after firing are a line width of 45 ⁇ m to 55 ⁇ m and a film thickness of 15 ⁇ m to 25 ⁇ m.
- the bus bar electrode was set so that the line width after firing was approximately 1.5 mm.
- substrate which printed the electrode pattern on both surfaces was baked at the baking temperature of 700-800 degreeC in the atmospheric condition using the near-infrared high-speed baking furnace, and the solar cell for evaluation was produced.
- the series resistance Rs and energy conversion efficiency Eff of the electrode are defined in JIS C8913 from the IV curve obtained for the solar cell of each example using a solar simulator (Peg 10 manufactured by Beger). It was calculated based on the “output measurement method”. The result is shown in Table 2 as an average value of 100 data obtained by the solar simulator.
- Examples 5, 12 and 19 are examples in which a glass frit having a relatively high SiO 2 content of 7% by mass was used for the conductive composition, but no silicone resin was blended. is there. It was confirmed that the electrodes formed using these conductive compositions were significantly thinner than the electrodes of other examples, regardless of the composition of the glass frit. That is, it turned out that the printed body (coating film) of the electroconductive composition which does not contain a silicone resin sags, and its shape stability is low. On the other hand, the conductive compositions of Examples 1 to 4, 8 to 11 and 15 to 18 containing glassy frit having a SiO 2 ratio of 0, 3 and 5% by mass and containing a silicone resin are the same as those of Example 5 above.
- Example 5 does not contain a silicone resin. , 12 and 19, the thickness of the formed electrode is thicker, but on the other hand, it was confirmed that the series resistance and the conversion efficiency deteriorate. This is because a bulky electrode can be formed by the action of the silicone resin, but the glass frit and SiO 2 derived from the silicone resin are present in the electrode after firing, and this relatively large amount of SiO 2 serves as a resistance component. It is thought to be due to the action. Accordingly, it has been found that when a silicone resin is blended in the conductive composition, the proportion of SiO 2 in the glass frit is preferably less than 7% by mass, for example, 5% by mass or less.
- examples 1, 8 and 15 are examples using the glass frit that does not contain SiO 2 component. According to conventional common sense, these cannot be sufficiently reacted with the Si substrate at the time of firing, and it is expected that a good contact at the Si substrate / electrode interface is not formed. However, the series resistance and conversion efficiency of the solar cells of Examples 1, 8 and 15 were all equal or better than those using the glass frit containing the SiO 2 component. From this, it is considered that by adding a silicone resin to the conductive composition, this silicone resin exhibits the same action as SiO 2 in the glass frit during firing and functions as a substitute for SiO 2 .
- 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 with the addition of such a very small amount of silicone resin, a thick electrode can be formed as compared with Examples 5, 12 and 19 using a glass frit having a SiO 2 content of 7% by mass, The series resistance and conversion efficiency of solar cells were the same or better results. Therefore, by adding a silicone resin to the conductive composition even in a very small amount, the effect of improving the shape stability of the conductive composition (application) during printing or baking was obtained, and the aspect ratio was improved. It has been found that the electrode can be formed.
- Embodiment 2 Preparation of conductive composition
- A5 in Embodiment 1 was used as the glass frit.
- the weight average molecular weight Mw is (S1) 3000, (S2) 10,000, (S3) 20,000, (S4) 50,000, (S5) 70,000, (S6) 90,000 and (S7) 11 Seven kinds of polydimethylsiloxane were used.
- the number of disconnections was measured by the following procedure.
- the number of electrode disconnections was determined by specifying the number of electrode disconnections (cracks) for 100 substrates using a solar cell electroluminescence (EL) inspection device. The result is shown in FIG. 3 as an average value of the number of disconnection points per substrate.
- the aspect ratio of the electrode is calculated by measuring the width W and thickness (height) H of the light-receiving surface electrode of each example with a shape analysis laser microscope (manufactured by Keyence Corporation), and calculating the aspect ratio as (H / W). I asked for it.
- the results are shown in FIG. 3 as an average value of values measured for 100 light receiving surface electrodes.
- the line resistance value of the electrode was measured as a resistance value ( ⁇ ) at an arbitrary interval (24 mm) on the finger electrode surface using a resistance meter (manufactured by Hioki Electric Co., Ltd., Digital HiTester).
- the results are shown in FIG. 4 as an average value of values measured for 100 light receiving surface electrodes.
- the markers in the graphs of FIG. 3 and FIG. 4 indicate the results of S0 to S7 in order from the left side according to the X axis (ie, the weight average molecular weight Mw).
- the aspect ratio of the electrode can be significantly increased by adding a silicone resin to the conductive composition. Further, as the weight average molecular weight of the added silicone resin increases, it becomes possible to form an electrode with a high aspect ratio, and it is expected that Si contained in the silicone resin contributes to maintaining the shape of the electrode. Moreover, it has confirmed from FIG. 3 that the number of disconnection of an electrode changes with addition of a silicone resin in an electroconductive composition, and the weight average molecular weight of the added silicone resin.
- the number of disconnections of the electrode can be reduced by adding a silicone resin having a weight average molecular weight of, for example, 90,000 or less to the conductive composition as compared with the case where no silicone resin is added.
- a silicone resin having a weight average molecular weight of, for example, 90,000 or less to the conductive composition as compared with the case where no silicone resin is added.
- the weight average molecular weight exceeds 90,000, for example, 110,000 silicone resin is used, the number of disconnections tends to increase.
- the line resistance of the electrode was affected by the weight average molecular weight of the silicone resin in the conductive composition.
- This result shows a tendency similar to the result of the number of disconnections. That is, from the viewpoint of increasing the electrode shape to a high aspect ratio, it is preferable to add a silicone resin to the conductive composition.
- the inclusion of an excessive Si component can cause a disconnection of the electrode, and thus can be a resistance component. From these, it was found that it is preferable to use a silicone resin having an appropriate weight average molecular weight in order to achieve both high aspect ratio and low resistance characteristics of the electrode.
- the silicone resin added to the conductive composition is preferably, for example, one having a weight average molecular weight of less than 110,000, more preferably about 90,000 or less.
- a conductive composition was prepared by the following procedure, and the relationship between the silicone resin in the composition and the series resistance Rs was evaluated.
- the glass frit the content of SiO 2 component to a leaded glass is 5 mass% "A5"
- a lead-free glass 1 content of SiO 2 component is 5 wt% "B5
- the silicone resin polydimethylsiloxane having a weight average molecular weight Mw of 50,000 was used.
- the ratio of these glass frit and silicone resin with respect to 100 mass parts of silver powder was changed by the combination shown in following Table 3, and other conditions were carried out similarly to the said Embodiment 1, and prepared the electrically conductive composition.
- the solar cell element was produced by forming a light-receiving surface electrode using these electroconductive compositions.
- the series resistance Rs of the solar cell element thus prepared was measured and shown in Table 3.
- the conductive composition using the leaded glass frit A5 can form electrodes having higher characteristics such as the series resistance Rs than the conductive composition using the lead-free glass frit B5. Yes.
- Table 3 below, when glass frit A5 is used, it is determined that the resistance is low and good when Rs ⁇ 3.73, and when glass frit B5 is used, Rs ⁇ 3.91. The resistance was judged to be low and good. In Table 3, good results with low resistance are shown in bold. Further, the ratio of the glass frit to the silicone resin was calculated from the blending amount of the glass frit and the silicone resin shown in Table 3 and shown in Table 4. In Table 4, the results are shown in bold for the combinations of the glass frit and the silicone resin with good resistance in Table 3.
- the ratio of glass frit amount to silicone resin amount (glass frit mass / silicone) It can be seen that the series resistance Rs can be effectively reduced by keeping the resin mass) within a predetermined range. For example, regardless of the glass composition, the series resistance Rs can be effectively reduced by keeping the ratio of the glass frit amount within a range of about 7.5 to 18, preferably about 8.33 to 16.67. Recognize. This is considered to be because, for example, when the amount of the silicone resin contained in the conductive composition is increased, it is necessary to increase the amount of glass frit added in order to keep the series resistance Rs of the formed electrode low.
- a SiO 2 component can be generated from this silicone resin during electrode firing.
- This SiO 2 component has an effect of suppressing erosion at the interface between the electrode and the anti-reflection film or the substrate, like the SiO 2 component in the glass frit. Therefore, in order to achieve good contact between the electrode and the substrate while exhibiting good fire-through characteristics, the amount of glass frit added is adjusted to a value suitable for the amount of silicone resin added to the conductive composition. It is preferable to keep it.
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Abstract
L'invention concerne une composition conductrice qui peut être imprimée en un motif d'électrode plus étroit ayant un plus grand rapport de forme, et grâce à laquelle il devient possible de prévenir la rupture du motif d'électrode et l'augmentation non intentionnelle de la résistivité. Selon la présente invention, une composition conductrice destinée à former une électrode est décrite. La composition conductrice comprend une poudre conductrice, une fritte de verre, une résine de silicone, un liant organique et un milieu de dispersion. La fritte de verre contient un constituant SiO2 en une quantité de 0 à 5 % en masse inclus en termes de teneur en oxyde.
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CN110337726A (zh) * | 2016-10-31 | 2019-10-15 | LS-Nikko铜制炼株式会社 | 太阳能电池电极用导电性浆料以及使用上述浆料制造的太阳能电池 |
US10593439B2 (en) | 2016-10-21 | 2020-03-17 | Dupont Electronics, Inc. | Conductive paste composition and semiconductor devices made therewith |
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JP6762848B2 (ja) * | 2016-11-02 | 2020-09-30 | 東洋アルミニウム株式会社 | ペースト組成物 |
KR102152842B1 (ko) * | 2018-11-30 | 2020-09-07 | 엘에스니꼬동제련 주식회사 | 요변성 및 슬립성이 향상된 태양전지 전극용 도전성 페이스트 제조방법 |
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CN114538916A (zh) * | 2022-03-03 | 2022-05-27 | 太原理工大学 | 一种低温共烧陶瓷介质材料及其制备方法 |
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