CN108022672B - Paste composition - Google Patents

Paste composition Download PDF

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Publication number
CN108022672B
CN108022672B CN201711057979.6A CN201711057979A CN108022672B CN 108022672 B CN108022672 B CN 108022672B CN 201711057979 A CN201711057979 A CN 201711057979A CN 108022672 B CN108022672 B CN 108022672B
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aluminum
particles
paste composition
size distribution
particle diameter
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CN108022672A (en
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马尔万·达姆林
中原正博
铃木绍太
森下直哉
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Toyo Aluminum KK
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Toyo Aluminum KK
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20Conductive material dispersed in non-conductive organic material
    • H01B1/22Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/02Details
    • H01L31/0224Electrodes
    • H01L31/022408Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H01L31/022441Electrode arrangements specially adapted for back-contact solar cells
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/04Semiconductor 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
    • H01L31/06Semiconductor 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
    • H01L31/068Semiconductor 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
    • H01L31/0682Semiconductor 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 back-junction, i.e. rearside emitter, solar cells, e.g. interdigitated base-emitter regions back-junction cells
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/547Monocrystalline silicon PV cells

Abstract

The invention provides a paste composition which can form an electrode which brings high conversion efficiency and high short-circuit current value to a solar cell such as a PERC type solar cell. The paste composition contains at least one metal particle selected from aluminum particles and aluminum-silicon alloy particles, a glass powder and an organic vehicle, wherein the minimum particle diameter Dmin of the metal particle is 1.5 [ mu ] m or more and 2.0 [ mu ] m or less in a volume-based particle size distribution curve measured by a laser diffraction scattering method, the median particle diameter (D50) corresponding to a 50% point in the particle size distribution curve is 4.0 [ mu ] m or more and 8.0 [ mu ] m or less, the value of D represented by formula (1) is 0.7 or more, D50/(D90-D10) (1) in formula (1), D50 is the median particle diameter, D90 is the particle diameter corresponding to a 90% point in the particle size distribution curve, and D10 is the particle diameter corresponding to a 10% point in the particle size distribution curve.

Description

Paste composition
Technical Field
The present invention relates to a paste composition.
Background
In recent years, various studies and developments have been made for the purpose of improving the conversion efficiency (power generation efficiency) and reliability of a crystalline solar cell. As one of them, a PERC (passivated emitter and rear cell) type high conversion efficiency cell is attracting attention. The PERC type high conversion efficiency cell has a structure including an electrode mainly composed of aluminum, for example. It is known that the conversion efficiency of the PER C-type high conversion efficiency cell can be improved by appropriately designing the structure of the electrode layer. For example, patent document 1 discloses an aluminum paste composition containing a glass frit (glass frit) composed of 30 to 70 mol% of Pb2+1-40 mol% of Si4+10-65 mol% of B3+1-25 mol% of Al3+And (4) forming.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2013-145865
Disclosure of Invention
Technical problem to be solved by the invention
However, the conversion efficiency of a solar cell having an electrode formed using a conventional paste composition still has room for improvement as compared with the theoretical conversion efficiency, and a sufficiently high conversion efficiency has not yet been obtained. In particular, when a conventional paste composition is used, there is a problem that it is difficult to obtain a high short-circuit current value.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a paste composition capable of forming an electrode that provides a high conversion efficiency and a high short-circuit current value to a solar cell such as a PERC type solar cell.
Means for solving the problems
The present inventors have made extensive studies to achieve the above object, and as a result, have found that the above object can be achieved by using aluminum particles and/or aluminum-silicon alloy particles having a specific particle size distribution as an essential constituent component, and have completed the present invention.
That is, the present invention includes, for example, the subject matters described in the following items.
An ointment composition comprising at least: at least one metal particle selected from the group consisting of aluminum particles and aluminum-silicon alloy particles, a glass powder, and an organic vehicle (vehicle),
a volume-based particle size distribution curve measured by a laser diffraction scattering method, wherein the minimum particle diameter Dmin of the metal particles is 1.5 to 2.0 [ mu ] m, the median particle diameter (D50) corresponding to 50% of the points in the particle size distribution curve is 4.0 to 8.0 [ mu ] m, and the value of D represented by the following formula (1) is 0.7 or more,
D=D50/(D90-D10)(1)
in formula (1), D50 is the median particle diameter, D90 is the particle diameter corresponding to the 90% point in the particle size distribution curve, and D10 is the particle diameter corresponding to the 10% point in the particle size distribution curve.
Item 2. the paste composition of item 1, wherein the glass powder contains one or more elements selected from the group consisting of lead (Pb), bismuth (Bi), vanadium (V), boron (B), silicon (Si), tin (Sn), phosphorus (P), and zinc (Zn).
Item 3. the paste composition according to item 1 or item 2, wherein a content of the glass powder is 1 part by mass or more and 8 parts by mass or less, and a content of the organic vehicle is 20 parts by mass or more and 45 parts by mass or less, with respect to 100 parts by mass of the metal particles.
Effects of the invention
According to the paste composition of the present invention, an electrode capable of imparting high conversion efficiency and high short-circuit current value to a solar cell such as a PERC type solar cell can be formed.
Drawings
Fig. 1 is a schematic diagram showing an example of a cross-sectional structure of a PERC type solar cell, fig. 1(a) is an example of an embodiment thereof, and fig. 1(b) is another example of an embodiment thereof.
Fig. 2 is a schematic cross-sectional view of electrode structures fabricated in examples and comparative examples.
Description of the reference numerals
1: a silicon semiconductor substrate; 2: an n-type impurity layer; 3: an antireflection film (passivation film); 4: a gate electrode; 5: an electrode layer; 6: an alloy layer; 7: a p + layer; 8: a back electrode; 9: a contact hole; 10: a paste composition.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail.
The paste composition according to the present invention is a material used for forming an electrode of a solar cell, for example. The solar cell is not particularly limited, and examples thereof include a PERC (passivated emitter and rear) type high conversion efficiency cell (hereinafter, referred to as a "PERC type solar cell"). The paste composition according to the present invention can be used, for example, for forming a back electrode of a PERC type solar cell. Hereinafter, the paste composition according to the present invention may be abbreviated as "paste composition".
First, an example of the structure of the PERC type solar cell will be described.
PERC type solar cell unit
Fig. 1(a) and (b) are schematic views of general cross-sectional structures of PERC type solar cells. The PERC type solar cell may have a silicon semiconductor substrate 1, an n-type impurity layer 2, an antireflection film 3, a gate electrode 4, an electrode layer 5, an alloy layer 6, and a p + layer 7 as constituent elements.
The silicon semiconductor substrate 1 can be a p-type silicon substrate having a thickness of 180 to 250 μm, for example.
The n-type impurity layer 2 is provided on the light-receiving surface side of the silicon semiconductor substrate 1. The thickness of the n-type impurity layer 2 is, for example, 0.3 to 0.6. mu.m.
The antireflection film 3 and the gate electrode 4 are provided on the surface of the n-type impurity layer 2. The antireflection film 3 is formed of, for example, a silicon nitride film, and is also called a passivation film. The anti-reflection film 3 functions as a so-called passivation film, and thereby can suppress recombination of electrons on the surface of the silicon semiconductor substrate 1, and as a result, the recombination rate of generated carriers can be reduced. Thereby, the conversion efficiency of the PERC type solar cell unit is improved.
The antireflection film 3 is provided on the back surface side of the silicon semiconductor substrate 1, that is, on the surface opposite to the light receiving surface. A contact hole formed so as to penetrate through the antireflection film 3 on the back surface side and cut a part of the back surface of the silicon semiconductor substrate 1 is formed on the back surface side of the silicon semiconductor substrate 1.
The electrode layer 5 is formed so as to be in contact with the silicon semiconductor substrate 1 through the contact hole. The electrode layer 5 is formed of the paste composition of the present invention, and is formed in a predetermined pattern shape, and as shown in fig. 1(a), the electrode layer 5 may be formed so as to cover the entire back surface of the PERC type solar cell, or may be formed so as to cover the contact hole and its vicinity. Since the electrode layer 5 is mainly composed of aluminum, the electrode layer 5 is an aluminum electrode layer.
The electrode layer 5 can be formed by applying a paste composition in a predetermined pattern shape, for example. The coating method is not particularly limited, and examples thereof include known methods such as screen printing. After the paste composition is applied, it is dried as necessary, and then fired at a temperature exceeding the melting point of aluminum, for example, 660 ℃ for a short time to form the electrode layer 5.
When the baking is performed in this manner, aluminum contained in the paste composition diffuses into the silicon semiconductor substrate 1. Thereby, an aluminum-silicon (Al — Si) alloy layer (alloy layer 6) is formed between the electrode layer 5 and the silicon semiconductor substrate 1, and at the same time, a p + layer 7 as an impurity layer is formed by diffusion of aluminum atoms.
The p + layer 7 can provide an effect of preventing recombination of electrons and improving collection efficiency of generated carriers, that is, a so-called BSF (Back Surface Field) effect.
The electrode formed by the electrode layer 5 and the alloy layer 6 is a back surface electrode 8 shown in fig. 1. Therefore, the back electrode 8 is formed using a paste composition, and the back electrode 8 can be formed by applying the paste composition to the antireflection film 3 (passivation film 3) on the back surface, for example. In particular, when the back electrode 8 is formed using the paste composition according to the present invention, the formation of voids at the interface between the electrode layer 5 and the silicon semiconductor substrate 1 can be easily suppressed, and a favorable BSF effect can be obtained.
2. Paste composition
Next, the paste composition of the present embodiment will be described in detail.
The paste composition contains at least: at least one metal particle selected from aluminum particles and aluminum-silicon alloy particles, a glass powder, and an organic vehicle, wherein the minimum particle diameter Dmin of the metal particle is 1.5 μm or more and 2.0 μm or less in a volume-based particle size distribution curve measured by a laser diffraction scattering method, the median particle diameter (D50) at a 50% point in the particle size distribution curve is 4.0 μm or more and 8.0 μm or less, and the value of D represented by the following formula (1) is 0.7 or more,
D=D50/(D90-D10)(1)
in formula (1), D50 is the median particle diameter, D90 is the particle diameter corresponding to the 90% point in the particle size distribution curve, and D10 is the particle diameter corresponding to the 10% point in the particle size distribution curve.
According to the paste composition of the present invention, an electrode capable of imparting high conversion efficiency and high short-circuit current value to a solar cell such as a PERC type solar cell can be formed.
As described above, by using the paste composition, a back electrode of a solar cell such as a PERC type solar cell can be formed. That is, the paste composition of the present invention can be used for forming a back electrode for a solar cell, which is electrically contacted with a silicon substrate through a hole of a passivation film formed on the silicon substrate.
The paste composition contains at least one metal particle selected from the group consisting of aluminum particles and aluminum-silicon alloy particles as a constituent component. By containing the metal particles in the paste composition, a sintered body formed by firing the paste composition can exhibit electrical conductivity.
The paste composition may contain only one of the aluminum particles and the aluminum-silicon alloy particles as a constituent component, or may contain both of the aluminum particles and the aluminum-silicon alloy particles as a constituent component.
The shape of the metal particles is not particularly limited. For example, the shape of the metal particles may be any of spherical, elliptical, irregular, flaky, fibrous, and the like. If the metal particles are spherical in shape, the electrode layer 5 formed of the paste composition has an increased filling ability of the metal particles, and the resistance can be effectively reduced. In addition, when the shape of the metal particles is spherical, in the electrode layer 5 formed of the paste composition, the contact points of the silicon semiconductor substrate 1 and the metal particles (aluminum particles and/or aluminum-silicon alloy particles) increase, and thus a good BSF layer is easily formed.
When the paste composition contains aluminum particles, the alloy layer 6 and the p + layer 7 containing an aluminum-silicon alloy are formed between the paste composition and the silicon semiconductor substrate 1 when the paste composition is fired to form a sintered body, and therefore the BSF effect can be further improved.
On the other hand, if the paste composition contains aluminum-silicon alloy particles, the silicon component contained in the aluminum-silicon alloy particles can play a role of controlling an excessive reaction of aluminum in the paste composition with silicon in the silicon semiconductor substrate 1. This makes it easy to suppress the formation of voids at the interface between the electrode layer 5 and the silicon semiconductor substrate 1.
The purity of the aluminum particles and the aluminum-silicon alloy particles is not particularly limited, and the aluminum particles and the aluminum-silicon alloy particles may contain a metal that is inevitably contained.
The ratio of the aluminum-silicon alloy particles is not particularly limited as long as the particles are an alloy of aluminum and silicon. For example, when the aluminum-silicon alloy particles contain 5 mass% to 40 mass% of silicon, the resistance value of the electrode layer formed from the paste composition can be kept low.
In a volume-based particle size distribution curve measured by a laser diffraction scattering method, the minimum particle diameter Dmin of the metal particles is 1.5 μm or more and 2.0 μm or less. Dmin in this range means that the amount of the fine powder of the metal particles in the paste composition is small. When Dmin is less than 1.5 μm, the short-circuit current decreases, and when Dmin exceeds 2.0 μm, the open-circuit voltage decreases, and the conversion efficiency of the solar cell deteriorates. Dmin is particularly preferably 1.5 to 1.8 μm.
In the particle size distribution curve, the median diameter (D50) of the metal particles corresponding to the 50% point is 4.0 μm or more and 8.0 μm or less. If D50 is less than 4.0 μm, the conversion efficiency of the solar cell decreases, and if D50 exceeds 8.0 μm, the open circuit voltage decreases. Further, by setting D50 to 4.0 μm or more and 8.0 μm or less, the metal particles are less likely to agglomerate with each other, and the reactivity at the time of firing is also good, so that aluminum is likely to form an alloy with silicon or the like.
The value of D of the metal particles represented by formula (1) is 0.7 or more.
D=D50/(D90-D10)(1)
In formula (1), D50 is the median particle diameter, D90 is the particle diameter corresponding to the 90% point in the particle size distribution curve, and D10 is the particle diameter corresponding to the 10% point in the particle size distribution curve.
A value of D within this range means that the ratio of fine powder to coarse powder is small, the particle size distribution is small, and the metal particles have a more uniform particle size. If the value of D is less than 0.7, the resistance is less likely to decrease, and the conversion efficiency is insufficient. The upper limit of the value of D may be set to 2.0, for example, in which case the productivity is less likely to be lowered. The upper limit of the value of D is preferably 1.4. The value of D is particularly preferably 0.7 to 1.0.
The particle size distribution curve can be measured by a method described in JIS Z8825: 2013, and measuring the metal particles by a laser diffraction scattering method. Dmin refers to the value of the smallest particle diameter in the particle size distribution curve. D50 represents a particle diameter corresponding to a 50% point in the particle size distribution curve, in other words, a particle diameter at which the cumulative value of particle diameters in the particle size distribution curve is 50%. Similarly, D90 indicates the particle size at the cumulative value of 90%, and D10 indicates the particle size at the cumulative value of 10%.
In the present invention, the particle size distribution curve can be obtained using, for example, a laser diffraction scattering particle size distribution measuring apparatus "Microtrac MT3000II series" manufactured by Microtrac BEL corp, and Dmin, D10, D50 and D90 can be measured.
By setting the three parameters Dmin, D50 and D in the specific ranges, the solar cell having the electrode layer formed of the paste composition has a high short-circuit current (I) and the metal particles have a high short-circuit current (I)SC) And open circuit voltage (V)OC) And also increased, and can exhibit excellent conversion efficiency.
In particular, since the amount of the fine powder is controlled in the paste composition as described above, aluminum is easily alloyed with silicon or the like when the paste composition is fired, and a good BSF effect is easily obtained, and as a result, the conversion efficiency of the solar cell can be further improved as compared with the conventional one. As described above, the inventors of the present application have found that the fine powder of the metal particles in the paste composition, which has not been noticed conventionally, has a great influence on the conversion efficiency of the solar cell, and have adjusted the three parameters in order to prevent the mixing of the fine powder of the metal particles. This can improve the conversion efficiency of the solar battery cell.
The metal particles contained in the paste composition may be both aluminum particles and aluminum-silicon alloy particles. Further, the paste composition may contain other metal particles than the aluminum particles and the aluminum-silicon alloy particles as long as the effects of the present invention are not impaired.
When the paste composition contains both aluminum particles and aluminum-silicon alloy particles, the mixing ratio of the aluminum particles and the aluminum-silicon alloy particles is not particularly limited. For example, if the aluminum-silicon alloy particles are 100 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the aluminum particles, excessive reaction between aluminum and silicon in the silicon semiconductor substrate 1 can be more effectively controlled when the paste composition is fired, and excellent BSF effect can be easily obtained.
The aluminum particles and the aluminum-silicon alloy particles can be produced by a known method.
The adjustment of values of Dmin, D50, and D of the aluminum particles and the aluminum-silicon alloy particles can be performed by a conventional method for controlling the particle size distribution. In particular, from the viewpoint of ease of adjustment of these values, it is preferable to produce aluminum particles and aluminum-silicon alloy particles by a gas atomization method.
It is believed that the glass powder has an effect of assisting the reaction of the metal particles with silicon and the sintering of the metal particles themselves.
The glass powder is not particularly limited, and may be, for example, a known glass component contained in a paste composition for forming an electrode layer of a solar cell. Specific examples of the glass powder may include one or more elements selected from the group consisting of lead (Pb), bismuth (Bi), vanadium (V), boron (B), silicon (Si), tin (Sn), phosphorus (P), and zinc (Zn). In addition, lead-containing glass powder or lead-free glass powder such as bismuth-based, vanadium-based, tin-phosphorus-based, zinc borosilicate-based, and alkali borosilicate-based glass powder can be used. In particular, in consideration of the influence on the human body, it is preferable to use a lead-free glass powder. .
Specifically, the glass powder may contain a compound selected from the group consisting of B2O3、Bi2O3、ZnO、SiO2、Al2O3、BaO、CaO、SrO、V2O5、Sb2O3、WO3、P2O5And TeO2At least one component of the group. For example, in the glass powder, B may be combined2O3Component (B) and Bi2O3Molar ratio of component (B)2O3/Bi2O3) A glass frit of 0.8 to 4.0 inclusive, and V2O5Molar ratio of component (V) to BaO component2O5a/BaO) of 1.0 to 2.5.
The softening point of the glass powder may be 750 ℃ or lower, for example. The average particle diameter of the particles contained in the glass powder may be, for example, 1 μm or more and 3 μm or less.
The content of the glass powder contained in the paste composition is preferably 0.5 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the metal particles, for example. In this case, the silicon semiconductor substrate 1 and the antireflection film 3 (passivation film) have good adhesion and are less likely to increase in resistance. The content of the glass powder contained in the paste composition is particularly preferably 1 part by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the metal particles.
As the organic vehicle, a material in which various additives and resins are dissolved in a solvent as necessary can be used. Alternatively, the resin may be used directly as an organic vehicle without a solvent.
The solvent may be a known solvent, and specific examples thereof include diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether, and the like.
Examples of the various additives include antioxidants, preservatives, antifoaming agents, thickeners, tackifiers, coupling agents, static electricity imparting agents, polymerization inhibitors, thixotropic agents, and anti-settling agents. Specifically, for example, a polyethylene glycol ester compound, a polyethylene glycol ether compound, a polyoxyethylene sorbitan ester compound, a sorbitan alkyl ester compound, an aliphatic polycarboxylic acid compound, a phosphate ester compound, an amidoamine (amidoamine) salt of a polyester acid, an oxidized polyethylene compound, a fatty acid amide wax, or the like can be used.
As the resin, known types can be used, and two or more of heat-curable resins such as ethyl cellulose, cellulose nitrate, polyvinyl butyral, phenol resin, melamine resin, urea resin, xylene resin, alkyd resin, unsaturated polyester resin, acrylic resin, polyimide resin, furan resin, polyurethane resin, isocyanate compound, cyanate ester compound, polyethylene, polypropylene, polystyrene, ABS resin, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyvinyl alcohol, polyacetal, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyphenylene oxide, polysulfone, polyimide, polyether sulfone, polyarylate, polyether ether ketone, polytetrafluoroethylene, silicone resin, and the like can be used in combination.
The proportions of the resin, the solvent and the various additives contained in the organic vehicle can be arbitrarily adjusted, and for example, the same component ratios as those of known organic vehicles can be set.
The content ratio of the organic vehicle is not particularly limited, but is preferably 10 parts by mass or more and 500 parts by mass or less, and particularly preferably 20 parts by mass or more and 45 parts by mass or less, with respect to 100 parts by mass of the metal particles, for example, from the viewpoint of good printability.
The paste composition of the present invention is suitable for forming an electrode layer of a solar cell (particularly, a back electrode 8 of a PERC type solar cell as shown in fig. 1), for example. Therefore, the paste composition of the present invention can also be used as a solar cell back electrode forming agent.
Examples
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples.
(example 1)
100 parts by mass of aluminum particles produced by a gas atomization method, 1.5 parts by mass of particles having B, were mixed using a known dispersing apparatus (disperser)2O3-Bi2O3-SrO-BaO-Sb2O340/40/10/5/5 (mol%) ratio of glass powder,35 parts by mass of a resin solution (organic vehicle) in which ethyl cellulose was dissolved in diethylene glycol butyl ether was mixed to obtain a paste composition. Dmin, D10, D50 and D90 of the aluminum particles used are shown in table 1 below.
(example 2)
A paste composition was obtained in the same manner as in example 1, except that the aluminum particles were changed to aluminum-silicon alloy particles having Dmin, D10, D50, and D90 shown in table 1.
(example 3)
A paste composition was obtained in the same manner as in example 1, except that the aluminum particles were changed to aluminum particles having Dmin, D10, D50, and D90 shown in table 1.
(example 4)
A paste composition was obtained in the same manner as in example 1, except that the aluminum particles were changed to aluminum-silicon alloy particles having Dmin, D10, D50, and D90 shown in table 1.
(example 5)
A paste composition was obtained in the same manner as in example 1, except that the aluminum particles were changed to mixed particles of aluminum particles and aluminum-silicon alloy particles having Dmin, D10, D50, and D90 shown in table 1. In the mixed particles, the mass ratio of the aluminum particles to the aluminum-silicon alloy particles is 1: 1.
(example 6)
A paste composition was obtained in the same manner as in example 1, except that the aluminum particles were changed to mixed particles of aluminum particles and aluminum-silicon alloy particles having Dmin, D10, D50, and D90 shown in table 1. In the mixed particles, the mass ratio of the aluminum particles to the aluminum-silicon alloy particles is 1: 1.
comparative example 1
A paste composition was obtained in the same manner as in example 1, except that the aluminum particles were changed to aluminum particles having Dmin, D10, D50, and D90 shown in table 1.
Comparative example 2
A paste composition was obtained in the same manner as in example 1, except that the aluminum particles were changed to aluminum-silicon alloy particles having Dmin, D10, D50, and D90 shown in table 1.
Comparative example 3
A paste composition was obtained in the same manner as in example 1, except that the aluminum particles were changed to aluminum particles having Dmin, D10, D50, and D90 shown in table 1.
Comparative example 4
A paste composition was obtained in the same manner as in example 1, except that the aluminum particles were changed to aluminum particles having Dmin, D10, D50, and D90 shown in table 1.
Comparative example 5
A paste composition was obtained in the same manner as in example 1, except that the aluminum particles were changed to aluminum-silicon alloy particles having Dmin, D10, D50, and D90 shown in table 1.
Comparative example 6
A paste composition was obtained in the same manner as in example 1, except that the aluminum particles were changed to mixed particles of aluminum particles and aluminum-silicon alloy particles having Dmin, D10, D50, and D90 shown in table 1. The mass ratio of the aluminum particles to the aluminum-silicon alloy particles in the mixed particles is 1: 1.
comparative example 7
A paste composition was obtained in the same manner as in example 1, except that the aluminum particles were changed to aluminum particles having Dmin, D10, D50, and D90 shown in table 1.
Comparative example 8
A paste composition was obtained in the same manner as in example 1, except that the aluminum particles were changed to aluminum particles having Dmin, D10, D50, and D90 shown in table 1.
Comparative example 9
A paste composition was obtained in the same manner as in example 1, except that the aluminum particles were changed to aluminum particles having Dmin, D10, D50, and D90 shown in table 1.
Comparative example 10
A paste composition was obtained in the same manner as in example 1, except that the aluminum particles were changed to aluminum particles having Dmin, D10, D50, and D90 shown in table 1.
(evaluation method)
A fired substrate as a solar cell for evaluation was produced as follows. First, as shown in FIG. 2(A), a silicon semiconductor substrate 1 having a thickness of 180 μm was prepared. Then, as shown in FIG. 2B, a YAG laser having a wavelength of 532nm was used as a laser oscillator to form a contact hole 9 having a diameter D of 100 μm and a depth of 1 μm on the surface of the silicon semiconductor substrate 1. The silicon semiconductor substrate 1 had a resistance value of 3 Ω · cm and was a back surface passivation type single crystal.
Then, as shown in fig. 2C, each of the paste compositions 10 obtained in the above examples and comparative examples was printed on the surface of the silicon semiconductor substrate 1 so as to cover the entire rear surface (the surface on the side where the contact holes 9 were formed) with a screen printer so as to be 1.0 to 1.1 g/pc. Then, although not shown, Ag paste produced by a known technique is printed on the light-receiving surface. Then, firing was performed using an infrared band furnace (an infrared ベルト furnace) set to 800 ℃, and by this firing, as shown in fig. 2(D), an electrode layer 5 was formed, and aluminum diffused into the silicon semiconductor substrate 1 at the time of firing, whereby an Al — Si alloy layer 6 was formed between the electrode layer 5 and the silicon semiconductor substrate 1, and a p + layer (BSF layer) 7 was formed as an impurity layer formed by diffusion of aluminum atoms. A fired substrate for evaluation was produced in the manner described above.
Solar simulator (solar simulator) using the WACOM ELECTRIC CO., LTD.: WXS-156S-10, I-V measurement apparatus IV15040-10, I-V measurement was performed on the solar cell obtained as described above. Thus, the short-circuit current (I) is measuredSC) And open circuit voltage (V)OC) And a curve factor (FF) and a conversion efficiency Eff are calculated. The curve factor (FF) was performed using a commercially available solar simulator.
In the evaluation of voids (void), the presence or absence of voids at the interface between the substrate and the electrode layer was observed by observing the cross section of each sample of the obtained fired substrate using an optical microscope (200 times), and the number of contact holes in the observation field of the optical microscope was ◎ when no voids were formed in all the contact holes, ○ when the number of contact holes having voids formed was less than 20% of the total number, and △ when the number of contact holes having voids formed was 20 to 50% of the total number.
The evaluation results are shown in table 1. In table 1, "Al" indicates that the metal particles contained in the used paste composition are aluminum particles, and "Al — Si" indicates that the metal particles contained in the used paste composition are aluminum-silicon alloy particles. Further, "Al + Al — Si" means that the metal particles are mixed particles of aluminum particles and aluminum-silicon alloy particles.
In table 1, the results were obtained by mixing the following components in JIS Z8825: 2013 as a standard measurement condition, Dmin, D10, D50 and D90 were measured using a laser diffraction scattering particle size distribution measuring apparatus "Microtrac MT3000II series" manufactured by Microtrac BEL corp.
[ Table 1]
Figure BDA0001454003310000131
As shown in Table 1, when metal particles having the following particle size distribution are used, ISCAre all large, and can realize high conversion efficiency of more than 21.4 percent. The particle size distribution is that Dmin is 1.5-2.0 μm, D50 is 4.0-8.0 μm, and the value of D is more than 0.7.
When the theoretical conversion efficiency of the unit used this time is 21.5%, it can be said that the paste composition obtained in the examples exerts an excellent BSF effect. Comparative examples 4 and 5, though ISC9.83A or more, but VOCNot reaching 0.665 mV. As a result, the BSF effect is not sufficient.
Further, in comparison of the aluminum particles with the aluminum-silicon alloy particles, it was confirmed that: although not having a great influence on the conversion efficiency, the paste composition containing aluminum-silicon alloy particles suppresses the generation of voids (voids), and improves the reliability.

Claims (3)

1. A paste composition comprising at least: at least one metal particle selected from aluminum particles and aluminum-silicon alloy particles, a glass powder, and an organic vehicle,
a volume-based particle size distribution curve measured by a laser diffraction scattering method, wherein the minimum particle diameter Dmin of the metal particles is 1.5 to 2.0 [ mu ] m, the median particle diameter D50 corresponding to 50% of the points in the particle size distribution curve is 4.0 to 8.0 [ mu ] m, and the value of D represented by the following formula (1) is 0.7 or more,
D=D50/(D90-D10) (1)
in formula (1), D50 is the median particle diameter, D90 is the particle diameter corresponding to the 90% point in the particle size distribution curve, and D10 is the particle diameter corresponding to the 10% point in the particle size distribution curve.
2. The paste composition of claim 1, wherein the glass powder contains one or more elements selected from the group consisting of lead (Pb), bismuth (Bi), vanadium (V), boron (B), silicon (Si), tin (Sn), phosphorus (P), and zinc (Zn).
3. The paste composition according to claim 1 or 2, wherein the content of the glass powder is 1 part by mass or more and 8 parts by mass or less and the content of the organic vehicle is 20 parts by mass or more and 45 parts by mass or less with respect to 100 parts by mass of the metal particles.
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