WO2020196640A1 - Composition de pâte électriquement conductrice et cellule solaire en silicium cristallin - Google Patents

Composition de pâte électriquement conductrice et cellule solaire en silicium cristallin Download PDF

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Publication number
WO2020196640A1
WO2020196640A1 PCT/JP2020/013378 JP2020013378W WO2020196640A1 WO 2020196640 A1 WO2020196640 A1 WO 2020196640A1 JP 2020013378 W JP2020013378 W JP 2020013378W WO 2020196640 A1 WO2020196640 A1 WO 2020196640A1
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WIPO (PCT)
Prior art keywords
paste composition
conductive paste
copper
mass
silver powder
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PCT/JP2020/013378
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English (en)
Japanese (ja)
Inventor
正博 中原
マルワン ダムリン
一雄 荒川
石川　和憲
Original Assignee
東洋アルミニウム株式会社
横浜ゴム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by 東洋アルミニウム株式会社, 横浜ゴム株式会社 filed Critical 東洋アルミニウム株式会社
Priority to CN202080023253.4A priority Critical patent/CN113646903A/zh
Publication of WO2020196640A1 publication Critical patent/WO2020196640A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • 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

Definitions

  • the present invention relates to a conductive paste composition for forming electrodes of a crystalline silicon solar cell and a crystalline silicon solar cell obtained by using the conductive paste composition.
  • electrodes are generally formed on the surface of a silicon substrate using a conductive paste composition for forming electrodes for electrical connection with the outside. is there.
  • the conductive paste composition is printed on the surface of the silicon substrate by screen printing or the like, and then fired in the atmosphere at about 800 ° C. to form the electrodes. Then, when electrically connecting the electrode and the outside, it is common to join the electrode and the interconnector material by soldering.
  • Patent Document 1 relates to a method for manufacturing a film thickness electrode of a solar cell, and claims 1 include a conductive powder, a glass frit, an organic polymer of 3.5 to 12.5% by weight (wt%), and a solvent. It is disclosed that a conductive paste containing the above, wherein wt% is based on the total weight of the conductive powder, the glass frit and the organic polymer. Also claimed in claim 2 are 19-68 wt% conductive powder, 0.1-8 wt% glass frit, 2-10 wt% organic polymer and 28-72 wt% based on the total weight of the conductive paste. A conductive paste containing a solvent is disclosed.
  • the conductive paste described in Patent Document 1 has a large volume ratio of the organic polymer (binder) to the silver powder and a large heat shrinkage in the debinder process when the silver is lowered, so that after soldering. There is a problem that the adhesion strength of the solder is insufficient.
  • the present invention has been completed in view of the above problems of the prior art, and even when the content of silver powder in the conductive paste is 60% by mass or less (low silver), after electrode formation It is an object of the present invention to provide a conductive paste composition capable of obtaining excellent adhesion strength in soldering, and a crystalline silicon solar cell using the same.
  • the present inventors have set the volume ratio of the organic polymer (binder) to the silver powder in a specific range, which contains silver powder, glass powder and organic vehicle.
  • the conductive paste composition excellent adhesion strength can be obtained in soldering after electrode formation even when the content of silver powder in the conductive paste is 60% by mass or less (low silver). It was found that this was possible, and the present invention was completed.
  • the present invention relates to the following conductive paste composition and a crystalline silicon solar cell using the same.
  • a conductive paste composition containing silver powder, glass powder and an organic vehicle.
  • the organic vehicle contains an organic polymer and a solvent, and the volume ratio of the organic polymer to the silver powder is 0.25 or more and 0.40 or less.
  • a conductive paste composition characterized in that. 2.
  • the copper compounds include copper (II) acetylacetonate, copper (II) neodecanoate, copper (I) oxide, copper (II) oxide, bis (8-quinolinolato) copper (II), and bis (triphenylphosphine) copper.
  • the conductive paste composition according to Item 2 above which is at least one selected from the group consisting of tetrahydrobolate and copper (II) trifluoromethanesulfonate. 4.
  • Item 2 or 3 wherein the copper compound is contained in an amount of 0.1 part by mass or more and 1.0 part by mass or less in terms of copper with respect to 100 parts by mass of the silver powder. 5.
  • the conductive paste composition of the present invention even when the content of silver powder in the conductive paste composition is 60% by mass or less (low silver), an electrode is formed on the surface of the silicon substrate by using this. After that, it has excellent adhesion strength after soldering in the electrical connection between the electrode and the outside. Therefore, for example, when the electrode and the interconnector material are soldered, excellent adhesion strength can be ensured.
  • the conductive paste composition of the present invention contains silver powder, glass powder and an organic vehicle.
  • the organic vehicle contains an organic polymer and a solvent, and the volume ratio of the organic polymer to the silver powder is 0.25 or more and 0.40 or less. It is characterized by that.
  • the conductive paste composition of the present invention having the above characteristics, even when the content of silver powder in the conductive paste composition is 60% by mass or less (low silver), the surface of the silicon substrate is used. After forming the electrode, it has excellent adhesion strength after soldering in the electrical connection between the electrode and the outside. Therefore, for example, when the electrode and the interconnector material are soldered, excellent adhesion strength can be ensured.
  • the conductive paste composition of the present invention uses silver powder as the conductive powder. That is, the electrode formed by using the conductive paste composition of the present invention is a so-called silver electrode.
  • the shape of the silver powder is not particularly limited, and examples thereof include spherical and flake (scale) shapes. Among these, the spherical shape is preferable from the viewpoint that the effect of the present invention can be easily obtained and the strength of the obtained electrode is advantageous.
  • the spherical shape means the shape of a particle having a major axis / minor axis ratio of 2 or less.
  • the flake shape means a shape in which the ratio of the major axis / the minor axis exceeds 2.
  • the major axis and minor axis of the silver powder can be determined based on an image obtained from a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the "major axis” refers to the longest distance of the line segments passing through the substantially center of gravity of the silver powder in the particle image obtained by SEM.
  • the “minor diameter” refers to the shortest distance of the line segments passing through the substantially center of gravity of the silver powder in the particle image obtained by SEM.
  • 100 silver powders are arbitrarily selected in the above image, the major axis of the 100 silver powders is measured, and the average value calculated from the major axis of the 100 silver powders is the average of the major axis of the silver powder. (Average value). The same applies to the average minor axis of silver powder.
  • the average particle size (D50) of the silver powder is not limited, but is preferably 2.0 ⁇ m or less from the viewpoint that the effect of the present invention can be easily obtained and the strength of the obtained electrode is advantageous. It is more preferably 1.0 ⁇ m or less.
  • silver powder having an average particle diameter (D50) of several tens of nm (for example, 10 to 90 nm) called nanosilver can be used.
  • the shape of the nanosilver is not particularly limited, and examples thereof include spherical ones. Therefore, the average particle size (D50) of the silver powder is preferably set in the range of several tens of nm to 2.0 ⁇ m or less.
  • the average particle size (D50) of the silver powder is determined by measuring the particle size distribution on a volume basis using a laser diffraction type particle size distribution measuring device.
  • a laser diffraction type particle size distribution measuring device for example, micro Examples thereof include a laser diffraction / scattering type particle size distribution measuring device “Microtrac MT3000II series” manufactured by Truck Bell.
  • the major axis (width) of the flake-shaped silver powder is preferably 2.0 ⁇ m or less on average, preferably 1.0 ⁇ m or less, from the viewpoint that the effects of the present invention can be easily obtained and the strength of the obtained electrode is advantageous. Is more preferable.
  • the minor axis (thickness) of the flake-shaped silver powder is preferably less than 1.0 ⁇ m on average from the viewpoint that the effects of the present invention can be easily obtained and the strength of the obtained electrode is advantageous. It is more preferably 1 ⁇ m or less.
  • the flake-shaped silver powder for example, silver having a minor axis (thickness) average (average value) of several tens of nm (for example, 10 to 90 nm) and a major axis (width) average of 0.3 to 6 ⁇ m. Powders are preferred.
  • Examples of commercially available flaky silver powder include trade name N300, which is commercially available from Toxen Industries, Ltd.
  • the content of the silver powder in the conductive paste composition of the present invention is not limited, but due to the recent demand for lower silver content, adhesion after soldering even when the content of the silver powder is set to 60% by mass or less. The effect of being excellent in strength can be ensured. From the viewpoint of efficiently obtaining the effects of the present invention, the content of the silver powder in the conductive paste composition is more preferably 49% by mass or less, and the lower limit of the content of the silver powder is about 40% by mass.
  • Glass powder The glass powder is said to have an action of assisting the reaction between the conductive material (silver powder in the present invention) and silicon, and the sintering of the conductive material itself.
  • the glass powder is not particularly limited, and can be, for example, a known glass component contained in the paste composition used for forming the electrode layer of the solar cell.
  • Specific examples of the glass powder include a group consisting of lead (Pb), bismuth (Bi), vanadium (V), boron (B), silicon (Si), tin (Sn), phosphorus (P) and zinc (Zn). At least one selected from.
  • lead-containing glass powder or lead-free glass powder such as bismuth-based, vanadium-based, tin-phosphorus-based, zinc borosilicate-based, and alkaline borosilicate-based can be used.
  • the glass powder is B 2 O 3 , Bi 2 O 3 , ZnO, SiO 2 , Al 2 O 3 , BaO, PbO, CaO, SrO, V 2 O 5 , Sb 2 O 3 , WO 3 , P 2 It can contain at least one component selected from the group consisting of O 5 and Te O 2 .
  • ZnO and / or PbO is preferable, and PbO is more preferable, from the viewpoint that the effects of the present invention can be easily obtained and easily obtained.
  • the glass powder contains ZnO and / or PbO, it is preferable to further contain B 2 O 3 and / or SiO 2, and when the glass powder contains PbO, it is preferable to further contain SiO 2. ..
  • the softening point of the glass powder can be, for example, 750 ° C. or lower.
  • the average particle size of the particles contained in the glass powder can be, for example, 1 to 3 ⁇ m.
  • the content of the glass powder in the conductive paste composition of the present invention is not limited, but is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass. In this case, the adhesion between the silicon substrate and the passivation film (and / or the antireflection film) is good, and the electrical resistance is unlikely to increase. Further, the content of the glass powder is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5.0% by mass with respect to 100 parts by mass of the silver powder.
  • Organic vehicle contains an organic polymer (binder) and a solvent, and can further contain various additives as needed.
  • solvents can be used, and specific examples thereof include diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, and dipropylene glycol monomethyl ether.
  • the amount of the solvent used can be appropriately set within the range of the standard amount used in the field in consideration of the coatability of the conductive paste composition and the like.
  • antioxidants for example, antioxidants, corrosion inhibitors, antifoaming agents, thickeners, tack fires, coupling agents, antistatic agents, polymerization inhibitors, thixotropy agents, anti-sediment agents and the like are used. be able to.
  • polyethylene glycol ester compound polyethylene glycol ether compound, polyoxyethylene sorbitan ester compound, sorbitan alkyl ester compound, aliphatic polyvalent carboxylic acid compound, phosphoric acid ester compound, amidoamine salt of polyester acid, polyethylene oxide.
  • System compounds, fatty acid amide wax and the like can be used.
  • organic polymers such as ethyl cellulose, cellulose ester, nitrocellulose, polyvinyl butyral, phenol resin, melamine resin, urea resin, xylene resin, alkyd resin, and unsaturated polyester resin.
  • the content of the organic polymer contained in the organic vehicle may be such that the volume ratio of the organic polymer to the silver powder (that is, the organic polymer / silver powder) is 0.25 or more and 0.40 or less.
  • the volume ratio is more preferably 0.30 or more and 0.40 or less.
  • the conductive paste composition of the present invention preferably contains a copper compound, if necessary, in addition to the silver powder, the glass powder and the organic vehicle.
  • the surface of the silicon substrate is used through a passivation film (and / or an antireflection film) using a conductive paste composition.
  • the glass powder reacts with the copper compound before acting on the passivation film (and / or the antireflection film) during firing, and the glass powder forms the passivation film (and / or the antireflection film).
  • the copper compound is not limited as long as it can obtain the above action, but for example, copper (II) acetylacetonate, copper (II) neodecanoate, copper (I) oxide, copper (II) oxide, bis (8).
  • -At least one selected from the group consisting of quinolinolato) copper (II), bis (triphenylphosphine) copper tetrahydroborate and copper (II) trifluoromethanesulfonate can be preferably used.
  • at least one of copper (I) oxide, copper (II) oxide, copper (II) acetylacetonate and the like is preferable from the viewpoint of dispersibility of the copper compound in the conductive paste.
  • the content of the copper compound is preferably 0.1 part by mass or more and 1.0 part by mass or less with respect to 100 parts by mass of the silver powder.
  • the conductive paste composition of the present invention is useful as a conductive paste composition for forming electrodes of crystalline silicon solar cells. That is, in the conductive paste composition of the present invention, for example, after optionally laminating the passivation film 2 (and / or the antireflection film 2) on the silicon substrate 1 (silicon semiconductor substrate 1) as illustrated in FIG.
  • the electrode 4 can be formed by printing the conductive paste composition 3 of the present invention on an electrode shape by a method such as screen printing and then firing in the air at about 800 ° C.
  • the present invention also includes the invention of a crystalline silicon solar cell including an electrode formed by using the conductive paste composition of the present invention.
  • the test body for evaluation was manufactured as follows.
  • a silicon substrate made of p-type single crystal silicon shown in FIG. 1 (A) was prepared (substrate: 6 inches, thickness 160 ⁇ m, resistivity 2 ⁇ ⁇ cm).
  • the antireflection film 2 containing silicon nitride as a main component was formed by the plasma CVD method.
  • the conductive paste composition 3 was printed on the surface of the silicon substrate 1 via the antireflection film 2 using a screen printing machine to have a printing width of 1.5 mm. I printed it so that it would be.
  • the deployability of the conductive paste composition on the screen plate was evaluated by observing the appearance.
  • ⁇ that is less likely to be blurred and spreads evenly Those with faintness ⁇ I evaluated it.
  • a copper ribbon (width 1.0 mm) for interconnect is soldered on the electrode 4 to which flux is applied in advance at a temperature of 270 ° C. for 3 seconds. To prepare a test sample.
  • the tensile strength is greater than 2.0 N / mm, it can be said that the tensile strength is sufficiently good to withstand actual use.
  • Example 2 The same procedure as in Example 1 was carried out except that an organic vehicle in which 3.8 parts by mass of ethyl cellulose (specific gravity 1.12) was dissolved in 95.2 parts by mass of tarpineol was used.
  • Example 3 The same procedure as in Example 1 was carried out except that an organic vehicle in which 3.2 parts by mass of ethyl cellulose (specific gravity 1.12) was dissolved in 95.8 parts by mass of tarpineol was used.
  • Example 4 The same procedure as in Example 1 was carried out except that an organic vehicle in which 2.7 parts by mass of ethyl cellulose (specific gravity 1.12) was dissolved in 96.3 parts by mass of tarpineol was used.
  • Example 5 The same procedure as in Example 1 was carried out except that an organic vehicle in which 4.0 parts by mass of polyvinyl butyral (specific gravity 1.10) was dissolved in 95.0 parts by mass of tarpineol was used.
  • Example 6 Example 1 and Example 1 except that an organic vehicle in which 3.8 parts by mass of ethyl cellulose (specific gravity 1.12) was dissolved in 94.7 parts by mass of tarpineol was used and 0.5 parts by mass of copper (II) oxide was added as a copper compound. The same was true.
  • Comparative Example 1 The same procedure as in Example 1 was carried out except that an organic vehicle in which 2.5 parts by mass of ethyl cellulose (specific gravity 1.12) was dissolved in 96.5 parts by mass of tarpineol was used.
  • Comparative Example 2 The same procedure as in Example 1 was carried out except that an organic vehicle in which 4.5 parts by mass of ethyl cellulose (specific gravity 1.12) was dissolved in 94.5 parts by mass of tarpineol was used.
  • Comparative Example 3 The same procedure as in Example 1 was carried out except that an organic vehicle in which 5.0 parts by mass of polyvinyl butyral (specific gravity 1.10) was dissolved in 94.0 parts by mass of tarpineol was used.
  • Table 1 below shows the conditions and test results of each example and comparative example.

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  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
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Abstract

La présente invention concerne : une composition de pâte électriquement conductrice avec laquelle il est possible d'obtenir une excellente force d'adhérence pendant le brasage après la formation d'électrode, même lorsque la quantité d'énergie d'argent contenue dans une pâte électriquement conductrice est d'au maximum 60 % en masse (faible argent) ; et une cellule solaire en silicium cristallin dans laquelle la composition de pâte électriquement conductrice est utilisée.　La présente invention concerne, en particulier, une composition de pâte électriquement conductrice contenant de la poudre d'argent, de la poudre de verre et un véhicule organique, la composition de pâte électriquement conductrice étant caractérisée en ce que le véhicule organique contient un polymère organique et un solvant, et le rapport volumique du polymère organique par rapport à la poudre d'argent est de 0,25 à 0,40 inclus.
PCT/JP2020/013378 2019-03-27 2020-03-25 Composition de pâte électriquement conductrice et cellule solaire en silicium cristallin WO2020196640A1 (fr)

Priority Applications (1)

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CN202080023253.4A CN113646903A (zh) 2019-03-27 2020-03-25 导电性膏组合物及使用了该导电性膏组合物的晶体硅太阳能电池单元

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JP2019061640A JP7433776B2 (ja) 2019-03-27 2019-03-27 導電性ペースト組成物及びそれを用いた結晶系シリコン太陽電池セル
JP2019-061640 2019-03-27

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001015782A (ja) * 1999-06-29 2001-01-19 Kyocera Corp 太陽電池素子およびその製造方法
WO2008078374A1 (fr) * 2006-12-25 2008-07-03 Namics Corporation Pâte conductrice pour cellule solaire

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101736773B1 (ko) * 2016-04-06 2017-05-29 대주전자재료 주식회사 태양전지용 후면전극 페이스트 조성물

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001015782A (ja) * 1999-06-29 2001-01-19 Kyocera Corp 太陽電池素子およびその製造方法
WO2008078374A1 (fr) * 2006-12-25 2008-07-03 Namics Corporation Pâte conductrice pour cellule solaire

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CN113646903A (zh) 2021-11-12
JP7433776B2 (ja) 2024-02-20
JP2020161411A (ja) 2020-10-01

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