JP6047276B2 - Silver powder for sintered conductive paste - Google Patents
Silver powder for sintered conductive paste Download PDFInfo
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- JP6047276B2 JP6047276B2 JP2011146386A JP2011146386A JP6047276B2 JP 6047276 B2 JP6047276 B2 JP 6047276B2 JP 2011146386 A JP2011146386 A JP 2011146386A JP 2011146386 A JP2011146386 A JP 2011146386A JP 6047276 B2 JP6047276 B2 JP 6047276B2
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- silver
- silver powder
- conductive paste
- aqueous solution
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims description 159
- 229910052709 silver Inorganic materials 0.000 claims description 77
- 239000004332 silver Substances 0.000 claims description 77
- 239000002245 particle Substances 0.000 claims description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- 229910052799 carbon Inorganic materials 0.000 claims description 32
- 239000000758 substrate Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 8
- 238000004438 BET method Methods 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 description 62
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 58
- 229910001961 silver nitrate Inorganic materials 0.000 description 29
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 15
- 108010010803 Gelatin Proteins 0.000 description 14
- 229920000159 gelatin Polymers 0.000 description 14
- 239000008273 gelatin Substances 0.000 description 14
- 235000019322 gelatine Nutrition 0.000 description 14
- 235000011852 gelatine desserts Nutrition 0.000 description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 description 13
- 239000000706 filtrate Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- 238000004220 aggregation Methods 0.000 description 10
- 230000002776 aggregation Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 8
- 238000005245 sintering Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 239000011231 conductive filler Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- -1 silver ions Chemical class 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000003130 blood coagulation factor inhibitor Substances 0.000 description 1
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 239000013522 chelant Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229960004279 formaldehyde Drugs 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229960001031 glucose Drugs 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229960004337 hydroquinone Drugs 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- YWXYYJSYQOXTPL-SLPGGIOYSA-N isosorbide mononitrate Chemical compound [O-][N+](=O)O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 YWXYYJSYQOXTPL-SLPGGIOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010956 nickel silver Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000003685 thermal hair damage Effects 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- ZFZQOKHLXAVJIF-UHFFFAOYSA-N zinc;boric acid;dihydroxy(dioxido)silane Chemical compound [Zn+2].OB(O)O.O[Si](O)([O-])[O-] ZFZQOKHLXAVJIF-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
-
- 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
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for 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
Description
本発明は、焼結型導電性ペーストに好適に用いることができる銀粉、中でも太陽電池電極用の焼結型導電性ペーストとして好適に用いることができる銀粉に関する。 The present invention relates to a silver powder that can be suitably used for a sintered conductive paste, and particularly to a silver powder that can be suitably used as a sintered conductive paste for a solar cell electrode.
導電性ペーストは、樹脂系バインダーと溶媒からなるビヒクル中に導電フィラーを分散させた流動性組成物であり、電気回路の形成や、セラミックコンデンサの外部電極の形成などに広く用いられている。
この種の導電性ペーストには、樹脂の硬化によって導電性フィラーが圧着され導通を確保する樹脂硬化型と、高温焼結によって有機成分が揮発し導電性フィラーが焼結して導通を確保する焼結型とがある。
The conductive paste is a fluid composition in which a conductive filler is dispersed in a vehicle composed of a resin binder and a solvent, and is widely used for forming an electric circuit, an external electrode of a ceramic capacitor, and the like.
This type of conductive paste includes a resin-curing type in which conductive fillers are pressure-bonded by hardening of the resin to ensure conduction, and a sintered type in which organic components are volatilized by high-temperature sintering and the conductive filler is sintered to ensure conduction. There is a type.
このうちの焼結型導電性ペーストは、一般に導電フィラー（金属粉末）とガラスフリットとを有機ビヒクル中に分散させてなるペースト状組成物であり、４００〜８００℃にて焼結することにより、有機ビヒクルが揮発し、さらに導電フィラーが焼結することによって導通を確保するものである。この際、ガラスフリットは、この導電膜を基板に接着させる作用を有し、有機ビヒクルは、金属粉末およびガラスフリットを印刷可能にするための有機液体媒体として作用する。 Of these, the sintered conductive paste is a paste-like composition in which a conductive filler (metal powder) and glass frit are generally dispersed in an organic vehicle. By sintering at 400 to 800 ° C., The organic vehicle is volatilized and the conductive filler is sintered to ensure conduction. At this time, the glass frit has a function of adhering the conductive film to the substrate, and the organic vehicle functions as an organic liquid medium for enabling printing of the metal powder and the glass frit.
このような焼結型導電性ペーストに用いる銀粉として、従来、例えば特許文献１には、銀イオンを含有する水性反応系に還元剤含有水溶液を添加して銀粒子を還元析出させることにより、５００℃における熱収縮率が５〜１５％、６００℃における熱収縮率が１０〜２０％、平均粒径Ｄ５０が５μｍ以下、タップ密度が２ｇ／ｃｍ３以上、ＢＥＴ比表面積が５ｍ２／ｇ以下の球状銀粉が開示されている。 As silver powder used for such a sintered conductive paste, for example, in Patent Document 1, for example, by adding a reducing agent-containing aqueous solution to an aqueous reaction system containing silver ions to reduce and precipitate silver particles, 500 5 to 15% at 600 ° C., 10 to 20% at 600 ° C., average particle diameter D 50 is 5 μm or less, tap density is 2 g / cm 3 or more, and BET specific surface area is 5 m 2 / g or less. A spherical silver powder is disclosed.
また、特許文献２には、４１０℃での熱収縮率が５〜１５％であり、好ましくは、さらに５００℃での熱収縮率が１０〜２０％である銀粉、具体的には平均粒径Ｄ５０が２μｍ以下である銀粉が開示されている。 Patent Document 2 discloses that silver powder having a heat shrinkage rate at 410 ° C. of 5 to 15%, more preferably 10 to 20% at 500 ° C., specifically an average particle diameter. D 50 is 2μm or less silver powder is disclosed.
導電性ペーストは、塗布する素地や用いる用途によって様々な温度で焼成されるが、焼成温度での銀の熱収縮率と素地との相性が悪いと、素地と銀膜との間に剥離が生じたり、反りや変形、クラックなどが生じたりするなどの不具合が生じることになる。 Conductive pastes are fired at various temperatures depending on the substrate to be applied and the application used. However, if the thermal contraction rate of silver at the firing temperature is not compatible with the substrate, peeling occurs between the substrate and the silver film. Or problems such as warping, deformation, or cracks.
結晶シリコン型太陽電池は、一般的にシリコン基板（ｐ型）にｎ型拡散層を形成してｐｎ接合を形成し、シリコン基板（ｐ型）の裏面側に酸化膜を介して裏面電極を積層する一方、ｎ型拡散層の受光面側（表面側）には、反射防止膜を積層すると共に、銀ペーストを印刷及び焼成して銀電極を形成する構成のものが一般的であり、シリコン基板の熱ダメージを考慮して５００℃付近で銀ペーストを焼成して電極を形成するのが一般的である。 In a crystalline silicon solar cell, an n-type diffusion layer is generally formed on a silicon substrate (p-type) to form a pn junction, and a back electrode is laminated on the back side of the silicon substrate (p-type) via an oxide film. On the other hand, an antireflection film is laminated on the light-receiving surface side (surface side) of the n-type diffusion layer, and a silver electrode is generally formed by printing and baking a silver paste. In general, an electrode is formed by baking a silver paste at around 500 ° C. in consideration of thermal damage.
このような太陽電池の電極作製に使用する導電性ペースト用銀粉としては、シリコン基板との相性を考慮すると、太陽電池作製時の焼成温度すなわち５００℃における銀粉の熱収縮率が８．７〜１３．０％であるのが好ましいことが分かってきた。
Examples of such a solar cell silver powder for a conductive paste used for electrode production, considering the compatibility with divorced substrate, the thermal shrinkage of the silver powder in the sintering temperature, ie 500 ° C. at the time of the solar cell produced 8.7～ It has been found that 13.0% is preferred.
そこで本発明は、５００℃における熱収縮率が８．７〜１３．０％となる新たな銀粉を提供せんとするものである。 Therefore, the present invention provides a new silver powder having a thermal shrinkage rate of 8.7 to 13.0% at 500 ° C.
本発明は、ＢＥＴ法により測定される比表面積から算出される粒子径（「ＢＥＴ径」と称する）が１．１０μｍ〜２．６０μｍであり、炭素含有量が０．１１〜０．２２質量％であることを特徴とする焼結型導電性ペースト用銀粉を提案するものである。 In the present invention, the particle diameter (referred to as “BET diameter”) calculated from the specific surface area measured by the BET method is 1.10 μm to 2.60 μm, and the carbon content is 0.11 to 0.22% by mass. The present invention proposes a silver powder for a sintered conductive paste characterized by the above.
ＢＥＴ径及び炭素含有量が所定の範囲である焼結型導電性ペースト用銀粉であれば、５００℃における銀粉の熱収縮率が８．７〜１３．０％となるため、太陽電池の電極を作製する場合の焼成の際、シリコン基板と銀膜との接着性を高めることができ、太陽電池の電極作製に好適に使用することができる。 If the silver powder for sintered conductive paste has a BET diameter and a carbon content within a predetermined range, the thermal shrinkage rate of the silver powder at 500 ° C. is 8.7 to 13.0%. In the case of firing, the adhesion between the silicon substrate and the silver film can be increased, and it can be suitably used for producing an electrode of a solar cell.
次に、本発明を実施するための形態例に基づいて本発明を説明するが、本発明が次に説明する実施形態に限定されるものではない。 Next, although this invention is demonstrated based on the example for implementing this invention, this invention is not limited to embodiment described next.
＜本銀粉＞
本実施形態に係る焼結型導電性ペースト用銀粉（以下、「本銀粉」と称する）は、ＢＥＴ径が１．１０μｍ〜２．６０μｍであり、炭素含有量が０．１１〜０．２２質量％であることを特徴とする銀粉である。
以下、本銀粉の特徴についてさらに説明する。
<Silver powder>
The silver powder for sintered conductive paste according to this embodiment (hereinafter referred to as “main silver powder”) has a BET diameter of 1.10 μm to 2.60 μm and a carbon content of 0.11 to 0.22 mass. % Silver powder.
Hereinafter, the characteristics of the present silver powder will be further described.
（炭素含有量）
本銀粉は、炭素含有量０．１１質量％以上０．２０質量％未満であることが重要である。
炭素含有量が０．１１質量％未満では、炭素が焼結助剤として有効に作用しなくなるため、熱収縮率に寄与しなくなる可能性がある一方、０．２０質量％を超えると、焼結が進み過ぎるだけでなく、焼結時のガス発生が多くなり、導体の膨張などを引き起こすことになるから好ましくない。
このような観点から、本銀粉の炭素含有量は０．１１質量％以上０．２０質量％未満であるのが好ましく、中でも０．１２質量％以上であるのが好ましく、中でも０．１３質量％以上であるのがより一層好ましい。
炭素含有量を調整するには、ステアリン酸ナトリウムなどのステアリン酸塩や、ゼラチンなどの凝集抑制剤の種類と量を調整する方法を挙げることができる。但し、凝集抑制剤の種類又は量を変化させると、粒子の比表面積や凝集度、反応液中の親和性などの物性も変化し、その結果、銀粉粒子に含まれる炭素量も変化するため、凝集抑制剤の添加量を増やせばそれだけ炭素含有量が増加するというものではない。
(Carbon content)
It is important that this silver powder has a carbon content of 0.11 % by mass or more and less than 0.20% by mass .
If the carbon content is less than 0.11% by mass, carbon will not effectively act as a sintering aid, and may not contribute to the thermal shrinkage. On the other hand, if the carbon content exceeds 0.20% by mass , sintering will occur. This is not preferable because not only excessively proceeds, but also gas generation during sintering increases, which causes expansion of the conductor.
From such a viewpoint, the carbon content of the silver powder is preferably 0.11 % by mass or more and less than 0.20% by mass, more preferably 0.12% by mass or more, and especially 0.13% by mass. The above is even more preferable.
In order to adjust the carbon content, a method of adjusting the type and amount of a stearate such as sodium stearate or an aggregation inhibitor such as gelatin can be mentioned. However, changing the type or amount of the aggregation inhibitor also changes the physical properties such as the specific surface area and the degree of aggregation of the particles, the affinity in the reaction solution, and as a result, the amount of carbon contained in the silver powder particles also changes. Increasing the addition amount of the aggregation inhibitor does not increase the carbon content accordingly.
なお、本発明が規定する銀粉の炭素含有量は、銀粉粒子の内部に含有されるか、或いは、粒子の表面に物理的或いは化学的に吸着されている炭素の含有量である。より具体的には、銀粉を純水で洗浄したろ液の伝導率が４０μＳ／ｃｍ以下になるまで十分に洗浄した際に残存する炭素の量である。このような洗浄によって除去される炭素は、例えば銀粉粒子を還元析出した後に有機物を後混合した場合に、銀粉粒子の表面に付着している炭素である。このような炭素は、焼結助剤として機能せず、銀粉の熱収縮率に寄与しないため、本発明が規定する銀粉の炭素含有量からは除外する必要がある。
したがって、本発明が規定する銀粉の炭素含有量は、銀粉を純水で洗浄したろ液の伝導率が４０μＳ／ｃｍ以下になるまで十分に洗浄した後に炭素測定装置で測定される炭素含有量である。
In addition, the carbon content of silver powder prescribed | regulated by this invention is content of the carbon contained in the inside of silver powder particle | grains, or being physically or chemically adsorbed on the particle | grain surface. More specifically, this is the amount of carbon remaining when the silver powder is sufficiently washed until the conductivity of the filtrate obtained by washing with pure water is 40 μS / cm or less. The carbon removed by such washing is, for example, carbon adhering to the surface of the silver powder particles when the organic substance is post-mixed after the silver powder particles are reduced and deposited. Since such carbon does not function as a sintering aid and does not contribute to the thermal shrinkage rate of silver powder, it is necessary to exclude it from the carbon content of silver powder defined by the present invention.
Therefore, the carbon content of the silver powder defined by the present invention is the carbon content measured with a carbon measuring device after thoroughly washing until the conductivity of the filtrate obtained by washing the silver powder with pure water is 40 μS / cm or less. is there.
（ＢＥＴ径）
本銀粉のＢＥＴ径、すなわち、ＢＥＴ法により測定される比表面積から算出される粒子径が１．１０μｍ〜２．６０μｍであることが重要である。ＢＥＴ径が１．１０μｍ〜２．６０μｍの範囲において、炭素含有量を上記範囲に調整することで、５００℃における銀粉の熱収縮率を８．７〜１３．０％に調整することができる。
さらに、ペーストにしたときの粘性など、ペーストのハンドリングを加味すると、本銀粉のＢＥＴ径は１．１５μｍ以上或いは２．６０μｍ以下であるのが好ましく、中でも１．３０μｍ以上或いは２．１６μｍ以下であるのがより一層好ましい。
ＢＥＴ径を調整するには、ステアリン酸ナトリウムなどのステアリン酸塩やゼラチンなどの凝集抑制剤の量を調整したり、アンモニア水の添加量を調整したりする方法を挙げることができる。
(BET diameter)
It is important that the BET diameter of the present silver powder, that is, the particle diameter calculated from the specific surface area measured by the BET method is 1.10 μm to 2.60 μm. When the BET diameter is in the range of 1.10 μm to 2.60 μm, the heat shrinkage rate of the silver powder at 500 ° C. can be adjusted to 8.7 to 13.0% by adjusting the carbon content to the above range.
Furthermore, considering the handling of the paste, such as the viscosity when it is made into a paste, the BET diameter of the present silver powder is preferably 1.15 μm or more or 2.60 μm or less, particularly 1.30 μm or more or 2.16 μm or less. Is even more preferable.
In order to adjust the BET diameter, there may be mentioned a method of adjusting the amount of an aggregation inhibitor such as stearate such as sodium stearate or gelatin, or adjusting the amount of ammonia water added.
（Ｄ５０）
本銀粉のＤ５０、すなわちレーザー回折散乱式粒度分布測定法により測定して得られる体積基準粒度分布によるＤ５０は、１．５０μｍ〜３．４０μｍであるのが好ましい。
本銀粉のＤ５０が３．４０μｍ以下であれば、ペーストを印刷する際に細線を容易に形成することが可能であり、１．５０μｍ以上であれば、高アスペクト印刷を容易に行うことが可能である。よって、かかる観点から、本銀粉のＤ５０は、特に１．５１μｍ以上、或いは３．３６μｍ以下、中でも２．００μｍ以上、或いは、３．０１μｍ以下であるのがより一層好ましい。
Ｄ５０を調整するには、ステアリン酸ナトリウムなどのステアリン酸塩やゼラチンなどの凝集抑制剤の量を調整したり、硝酸銀水溶液の濃度や液量を調整したり、還元剤溶液の濃度や液量を調整したりする方法を挙げることができる。
(D50)
The D50 of the present silver powder, that is, the D50 based on the volume-based particle size distribution obtained by measurement by the laser diffraction / scattering particle size distribution measuring method is preferably 1.50 μm to 3.40 μm.
If D50 of this silver powder is 3.40 μm or less, it is possible to easily form fine lines when printing a paste, and if it is 1.50 μm or more, high aspect printing can be easily performed. is there. Therefore, from this viewpoint, D50 of the present silver powder is particularly preferably 1.51 μm or more, or 3.36 μm or less, and more preferably 2.00 μm or more, or 3.01 μm or less.
To adjust D50, adjust the amount of aggregation inhibitor such as stearates such as sodium stearate and gelatin, adjust the concentration and amount of silver nitrate aqueous solution, and adjust the concentration and amount of reducing agent solution. The method of adjusting can be mentioned.
（粒子形状）
本銀粉は、粒子形状を特に限定するものではないが、球形状或いは略球形状であるのが好ましい。また、導電性ペースト用としては、当該球形状粒子或いは略球形状の粒子を加工してなるフレーク状粒子であるのも好ましいし、また、前記球形状或いは略球形状の粒子と該フレーク状粒子の混合品も好ましい。
(Particle shape)
Although this silver powder does not specifically limit particle shape, it is preferable that it is spherical shape or substantially spherical shape. In addition, for the conductive paste, it is also preferable to use flaky particles obtained by processing the spherical particles or substantially spherical particles, and the spherical or substantially spherical particles and the flaky particles. The mixed product is also preferable.
（比表面積）
本銀粉のＢＥＴ比表面積（ＳＳＡ）は、０．６０ｍ2／ｇ未満であるのが好ましい。
本銀粉のＢＥＴ比表面積が０．６０ｍ2／ｇ未満であれば、銀粉粒子同士の凝集が比較的弱い傾向にある。他方、ある程度の比表面積を有することで、銀粉粒子同士の接点が多くなるから、焼結後の結合を強くすることができる。よって、かかる観点から、より好ましくは０．２２ｍ２／ｇ以上或いは０．５２ｍ２／ｇ以下、その中でも特に０．２６ｍ２／ｇ以上、或いは、０．５０ｍ２／ｇ以下である。
(Specific surface area)
The silver powder preferably has a BET specific surface area (SSA) of less than 0.60 m 2 / g.
If the BET specific surface area of the present silver powder is less than 0.60 m 2 / g, the aggregation of silver powder particles tends to be relatively weak. On the other hand, having a certain specific surface area increases the number of contacts between the silver powder particles, so that the bond after sintering can be strengthened. Therefore, from this point of view, more preferably 0.22 m 2 / g or more or 0.52 m 2 / g or less, among the 0.26 m 2 / g or more, or at most 0.50 m 2 / g.
（Ｄ５０／ＢＥＴ径）
現実の銀粉の粉粒は、個々の粒子が完全に分離した、いわゆる単分散粉ではなく、複数個の粉粒が凝集した状態になっているのが通常である。粉粒の凝集状態が少なく、単分散に近いほど、Ｄ５０が小さくなり、Ｄ５０／ＢＥＴ径は１に近づいてくる。
本銀粉は、Ｄ５０／ＢＥＴ径で表される凝集度が３．００未満であれば、凝集が強くなくて均質なペーストを作製することができるため、３．００未満であるのが好ましく、中でも２．９３以下、その中でも１．５６以下であるのがさらに好ましい。
(D50 / BET diameter)
The actual silver powder is not a so-called monodispersed powder in which individual particles are completely separated, but is usually in a state where a plurality of powders are aggregated. D50 becomes smaller and the D50 / BET diameter approaches 1 as the aggregated state of the powder particles is smaller and closer to monodispersion.
If the degree of aggregation represented by D50 / BET diameter is less than 3.00, the present silver powder is preferably not less than 3.00 because the aggregation is not strong and a homogeneous paste can be produced. 2.93 or less, more preferably 1.56 or less.
（熱収縮率）
本銀粉は、前述したように、太陽電池に使用するシリコン基板との接着性、より具体的に言えば、５００℃で焼成した際に生じる銀粉の収縮によるシリコン基板の剥離などを生じない接着性の観点から、本銀粉の５００℃における熱収縮率は８．７〜１３．０％であることが重要であり、特に８．９０以上、或いは１２．４２以下、中でも特に１０．３７以上、或いは１１．９３以下であるのが好ましい。
ＢＥＴ径及び炭素含有量を所定の範囲に調整することにより、５００℃における銀粉の熱収縮率が８．７〜１３．０％とすることができる。
(Heat shrinkage)
As described above, the present silver powder has an adhesive property with a silicon substrate used in a solar cell, more specifically, an adhesive property that does not cause peeling of the silicon substrate due to shrinkage of the silver powder that occurs when fired at 500 ° C. From this point of view, it is important that the heat shrinkage rate of the present silver powder at 500 ° C. is 8.7 to 13.0%, particularly 8.90 or more, or 12.42 or less, particularly 10.37 or more, or It is preferably 11.93 or less.
By adjusting the BET diameter and the carbon content within a predetermined range, the thermal shrinkage rate of the silver powder at 500 ° C. can be set to 8.7 to 13.0%.
＜製法＞
次に、本銀粉の好ましい製造方法について説明する。
<Production method>
Next, the preferable manufacturing method of this silver powder is demonstrated.
本銀粉の製造方法の一例として、硝酸銀などの銀溶液に還元剤を加える前に、ステアリン酸ナトリウムなどのステアリン酸塩を適当な量に加えて還元する方法を挙げることができる。すなわち、還元剤を加える前に、ステアリン酸ナトリウムなどのステアリン酸塩やゼラチンなどの凝集抑制剤を加えてその量を調整することにより、銀粉のＢＥＴ径を調整することができ、しかも、ステアリン酸やゼラチンなどに起因する炭素量を調整することができる。 As an example of a method for producing the present silver powder, before adding a reducing agent to a silver solution such as silver nitrate, a method of adding a suitable amount of stearate such as sodium stearate to reduce it can be mentioned. That is, before adding the reducing agent, the BET diameter of the silver powder can be adjusted by adding a coagulation inhibitor such as stearic acid salt such as sodium stearate or gelatin and adjusting the amount thereof. It is possible to adjust the amount of carbon caused by gelatin and gelatin.
より具体的に言えば、硝酸銀などの銀水溶液に錯化剤を加えた後、還元剤を添加すると共に、ステアリン酸ナトリウムなどのステアリン酸塩や、ゼラチン水溶液などの凝集抑制剤を適当な量加えて撹拌し、次いで必要に応じて分散剤を添加して撹拌させながら反応させて銀粒子を還元析出させ、その後、ろ過、洗浄、乾燥させて本銀粉を製造することができる。 More specifically, after adding a complexing agent to an aqueous silver solution such as silver nitrate, a reducing agent is added, and an appropriate amount of a stearate such as sodium stearate or an aggregation inhibitor such as an aqueous gelatin solution is added. Then, if necessary, a dispersing agent is added and reacted while stirring to cause silver particles to be reduced and deposited, and then filtered, washed and dried to produce the present silver powder.
この際、ステアリン酸塩やゼラチン水溶液の量が少ないと、炭素含有量を所定範囲に調整することができないばかりか、ＢＥＴ径を所定の範囲に調整することができないため、ステアリン酸塩を加える量は、銀１ｍｏｌに対してステアリン酸塩を１．００×１０-3〜４．００×１０-３ｍｏｌであるのが好ましい。また、ゼラチン水溶液を加える量は、銀１ｍｏｌに対してゼラチンを０．３０ｇ〜０．５０ｇであるのが好ましい。 At this time, if the amount of stearate or gelatin aqueous solution is small, not only the carbon content cannot be adjusted to the predetermined range, but also the BET diameter cannot be adjusted to the predetermined range. Is preferably 1.00 × 10 −3 to 4.00 × 10 −3 mol of stearate per 1 mol of silver. The amount of the gelatin aqueous solution added is preferably 0.30 g to 0.50 g of gelatin with respect to 1 mol of silver.
なお、硝酸銀などの銀水溶液は、硝酸銀、銀塩錯体、及び銀中間体のいずれかを含有する水溶液、又はスラリーを使用することができる。
また、錯化剤としては、例えばアンモニア水、アンモニウム塩、キレート化合物等を挙げることができる。
還元剤としては、例えばアスコルビン酸、亜硫酸塩、アルカノールアミン、過酸化水素水、ギ酸、ギ酸アンモニウム、ギ酸ナトリウム、グリオキサール、酒石酸、次亜燐酸ナトリウム、水素化ホウ素金属塩、ジメチルアミンボラン、ヒドラジン、ヒドラジン化合物、ヒドロキノン、ピロガロール、ぶどう糖、没食子酸、ホルマリン、無水亜硫酸ナトリウム、ロンガリットなどを含む水溶液を挙げることができる。
分散剤としては、例えば脂肪酸、脂肪酸塩、界面活性剤、有機金属、キレート剤、保護コロイド等を挙げることができる。
In addition, silver solution, such as silver nitrate, can use the aqueous solution or slurry containing either silver nitrate, a silver salt complex, and a silver intermediate.
Examples of complexing agents include ammonia water, ammonium salts, chelate compounds and the like.
Examples of the reducing agent include ascorbic acid, sulfite, alkanolamine, hydrogen peroxide, formic acid, ammonium formate, sodium formate, glyoxal, tartaric acid, sodium hypophosphite, metal borohydride, dimethylamine borane, hydrazine, hydrazine. Examples thereof include an aqueous solution containing a compound, hydroquinone, pyrogallol, glucose, gallic acid, formalin, anhydrous sodium sulfite, Rongalite and the like.
Examples of the dispersant include fatty acids, fatty acid salts, surfactants, organic metals, chelating agents, protective colloids and the like.
＜用途＞
本銀粉は、導電ペースト用、特に焼結型導電性ペースト用の銀粉として好適である。
<Application>
The silver powder is suitable as a silver powder for a conductive paste, particularly for a sintered conductive paste.
焼結型導電性ペーストは、例えば有機ビヒクル中に、本銀粉をガラスフリットと共に混合することで調製することができる。
この際、ガラスフリットとしては、例えば、鉛ボロシリケートガラスや、ジンクボロシリケート等の無鉛ガラスも挙げることができる。
また、樹脂バインダーとしては、例えば任意の樹脂バインダーを使用することができる。例えばエポキシ樹脂、ポリエステル樹脂、ケイ素樹脂、ユリア樹脂、アクリル樹脂、セルロース樹脂から選ばれる１種以上を含む組成を採用するのが望ましい。
The sintered conductive paste can be prepared, for example, by mixing the present silver powder together with glass frit in an organic vehicle.
In this case, examples of the glass frit include lead-free glass such as lead borosilicate glass and zinc borosilicate.
Moreover, as a resin binder, arbitrary resin binders can be used, for example. For example, it is desirable to employ a composition containing at least one selected from an epoxy resin, a polyester resin, a silicon resin, a urea resin, an acrylic resin, and a cellulose resin.
本銀粉は、５００℃における銀粉の熱収縮率が８．７〜１３．０％であり、太陽電池におけるシリコン基板との相性が極めてよいから、本銀粉を用いた導電ペーストは、太陽電池の電極に用いるのが特に好ましい。 This silver powder has a thermal contraction rate of 8.7 to 13.0% at 500 ° C. and is extremely compatible with a silicon substrate in a solar cell. Therefore, the conductive paste using the silver powder is an electrode of a solar cell. It is particularly preferable to use it.
＜語句の説明＞
本明細書において「Ｘ〜Ｙ」（Ｘ，Ｙは任意の数字）と表現する場合、特にことわらない限り「Ｘ以上Ｙ以下」の意と共に、「好ましくはＸより大きい」或いは「好ましくはＹより小さい」の意も包含する。
また、「Ｘ以上」（Ｘは任意の数字）或いは「Ｙ以下」（Ｙは任意の数字）と表現した場合、「Ｘより大きいことが好ましい」或いは「Ｙ未満であることが好ましい」旨の意図も包含する。
<Explanation of words>
In the present specification, when expressed as “X to Y” (X and Y are arbitrary numbers), unless otherwise specified, “X is preferably greater than X” or “preferably Y”. It also includes the meaning of “smaller”.
In addition, when expressed as “X or more” (X is an arbitrary number) or “Y or less” (Y is an arbitrary number), it is “preferably greater than X” or “preferably less than Y”. Includes intentions.
以下、本発明を下記実施例及び比較例に基づいてさらに詳述する。
実施例および比較例で得られた銀粉に関して、以下に示す方法で諸特性を評価した。
Hereinafter, the present invention will be further described in detail based on the following examples and comparative examples.
With respect to the silver powder obtained in Examples and Comparative Examples, various characteristics were evaluated by the following methods.
（１）炭素含有量
伝導率４０μＳ／ｃｍ以下になるまで純水を用いて洗浄して得られた銀粉（サンプル）を、炭素測定装置（ＨＯＲＩＢＡ社製 ＥＭＩＡ「２２１Ｖ２」）で炭素含有量を測定した。
(1) Carbon content Silver content (sample) obtained by washing with pure water until the conductivity is 40 μS / cm or less is measured with a carbon measuring device (EMIA “221V2” manufactured by HORIBA). did.
（２）ＢＥＴ比表面積（ＳＳＡ）及びＢＥＴ径
ＱＵＡＮＴＡＣＨＲＯＭＥ社製のモノソーブ（商品名「ＭＳ−１８」）を用いて、ＪＩＳ Ｒ １６２６-１９９６（ファインセラミックス粉体の気体吸着ＢＥＴ 法による比表面積の測定方法）の「６．２流動法の（３．５）一点法」に準拠して、ＢＥＴ比表面積（ＳＳＡ）の測定を行った。その際、キャリアガスであるヘリウムと、吸着質ガスである窒素の混合ガスを使用した。
(2) BET specific surface area (SSA) and BET diameter JIS R 1626-1996 (Measurement of specific surface area of fine ceramic powder by gas adsorption BET method) using monosorb (trade name “MS-18”) manufactured by QUANTACHROME The BET specific surface area (SSA) was measured in accordance with “(3.5) Single point method of 6.2 flow method” of “Method”. At that time, a mixed gas of helium as a carrier gas and nitrogen as an adsorbate gas was used.
ＢＥＴ径は、上記ＢＥＴ比表面積を用いて下記式で算出した。なお、真比重は銀粉であれば１０．４９である。
ＢＥＴ径＝６÷ＢＥＴ比表面積÷真比重
The BET diameter was calculated by the following formula using the BET specific surface area. The true specific gravity is 10.49 for silver powder.
BET diameter = 6 ÷ BET specific surface area ÷ true specific gravity
（３）Ｄ５０
銀粉(サンプル)０．２ｇをＩＰＡ５０ｍＬ中に入れて超音波を照射して（３分間）分散させた後、粒度分布測定装置（日機装株式会社製「マイクロトラック（商品名）ＭＴ−３０００ＥＸII（型番）」）により、体積基準粒度分布によるＤ５０を測定した。
(3) D50
After putting 0.2 g of silver powder (sample) in 50 mL of IPA and irradiating with ultrasonic waves (for 3 minutes), the particle size distribution measuring device (“Microtrack (trade name) MT-3000EXII (model name) manufactured by Nikkiso Co., Ltd.) )) To measure D50 by volume-based particle size distribution.
（４）熱収縮率
銀粉（サンプル）０．２ｇを用い、４９３ｋｇの加重をかけてφ３．８ｍｍの円柱状に成形した。この成形体の縦方向の線収縮率（％）を、熱機械分析装置ＴＭＡ（セイコーインスツルメンツ社製「ＥＸＳＴＡＲ６０００−ＴＭＡ／ＳＳ６２００」）を用い、９８ｍＮの加重をかけながらＡｉｒ雰囲気中５℃／分の昇温速度で測定し、５００℃における熱収縮率（％）を求めた。
(4) Thermal shrinkage rate Using 0.2 g of silver powder (sample), a weight of 493 kg was applied and molded into a cylindrical shape of φ3.8 mm. Using a thermomechanical analyzer TMA (“EXSTAR6000-TMA / SS6200” manufactured by Seiko Instruments Inc.), the linear shrinkage rate (%) in the longitudinal direction of this molded body was 5 ° C./min in an Air atmosphere while applying a load of 98 mN. The heat shrinkage rate (%) at 500 ° C. was determined by measuring at a rate of temperature increase.
＜実施例１＞
銀濃度４００ｇ／Ｌの硝酸銀水溶液５０ｍＬを純水１Ｌに溶解させて硝酸銀水溶液を調製し、濃度２５質量％のアンモニア水６０ｍＬを添加して攪拌することにより、銀アンミン錯体水溶液を得た。
次いで、２０℃の銀アンミン錯体水溶液に、濃度１１．９ｇ／Ｌのヒドラジン水溶液１Ｌと、濃度２．９ｇ／Ｌのステアリン酸ナトリウム水溶液３５ｍＬ（銀１ｍｏｌに対して１．７６×１０-３ｍｏｌに相当）を混合することにより銀粒子を還元析出させた。
次いで、この銀粒子をろ過し、ろ液の伝導率が４０μＳ／ｃｍ以下となるまで水洗後、乾燥させることにより銀粉（サンプル）を得た。
<Example 1>
A silver nitrate aqueous solution was obtained by dissolving 50 mL of a silver nitrate aqueous solution having a silver concentration of 400 g / L in 1 L of pure water, adding 60 mL of ammonia water having a concentration of 25% by mass, and stirring.
Next, in a silver ammine complex aqueous solution at 20 ° C., 1 L of a hydrazine aqueous solution with a concentration of 11.9 g / L and 35 mL of a sodium stearate aqueous solution with a concentration of 2.9 g / L (1.76 × 10 −3 mol per 1 mol of silver). Silver particles were reduced and precipitated by mixing.
Then, the silver particles were filtered, washed with water until the filtrate had a conductivity of 40 μS / cm or less, and dried to obtain silver powder (sample).
＜実施例２＞
銀濃度４００ｇ／Ｌの硝酸銀水溶液５０ｍＬを純水１Ｌに溶解させて硝酸銀水溶液を調製し、濃度２５質量％のアンモニア水６０ｍＬを添加して攪拌することにより、銀アンミン錯体水溶液を得た。次いで、２０℃の銀アンミン錯体水溶液に、濃度１１．９ｇ／Ｌのヒドラジン水溶液１Ｌと、濃度２．９ｇ／Ｌのステアリン酸ナトリウム水溶液３０ｍＬ（銀１ｍｏｌに対して１．５０×１０-３ｍｏｌに相当）を混合することにより銀粒子を還元析出させた。
次いで、この銀粒子をろ過し、ろ液の伝導率が４０μＳ／ｃｍ以下となるまで水洗後、乾燥させることにより銀粉（サンプル）を得た。
<Example 2>
A silver nitrate aqueous solution was obtained by dissolving 50 mL of a silver nitrate aqueous solution having a silver concentration of 400 g / L in 1 L of pure water, adding 60 mL of ammonia water having a concentration of 25% by mass, and stirring. Next, in a silver ammine complex aqueous solution at 20 ° C., 1 L of a hydrazine aqueous solution having a concentration of 11.9 g / L and 30 mL of a sodium stearate aqueous solution having a concentration of 2.9 g / L (1.50 × 10 −3 mol with respect to 1 mol of silver) Silver particles were reduced and precipitated by mixing.
Then, the silver particles were filtered, washed with water until the filtrate had a conductivity of 40 μS / cm or less, and dried to obtain silver powder (sample).
＜実施例３＞
銀濃度４００ｇ／Ｌの硝酸銀水溶液５０ｍＬを純水１．４Ｌに溶解させて硝酸銀水溶液を調製し、濃度２５質量％のアンモニア水６０ｍＬを添加して攪拌することにより、銀アンミン錯体水溶液を得た。次いで、２０℃の銀アンミン錯体水溶液に、濃度１９．６ｇ／Ｌのヒドラジン水溶液０．６Ｌと、濃度２．９ｇ／Ｌのステアリン酸ナトリウム水溶液３０ｍＬ（銀１ｍｏｌに対して１．５０×１０-３ｍｏｌに相当）を混合することにより銀粒子を還元析出させた。
次いで、この銀粒子をろ過し、ろ液の伝導率が４０μＳ／ｃｍ以下となるまで水洗後、乾燥させることにより銀粉（サンプル）を得た。
<Example 3>
A silver nitrate aqueous solution was obtained by dissolving 50 mL of a silver nitrate aqueous solution with a silver concentration of 400 g / L in 1.4 L of pure water, adding 60 mL of ammonia water with a concentration of 25% by mass, and stirring. Next, in a silver ammine complex aqueous solution at 20 ° C., 0.6 L of a 19.6 g / L hydrazine aqueous solution and 30 mL of a 2.9 g / L sodium stearate aqueous solution (1.50 × 10 −3 per 1 mol of silver). The silver particles were reduced and precipitated by mixing (equivalent to mol).
Then, the silver particles were filtered, washed with water until the filtrate had a conductivity of 40 μS / cm or less, and dried to obtain silver powder (sample).
＜実施例４＞
銀濃度４００ｇ／Ｌの硝酸銀水溶液５０ｍＬを純水１Ｌに溶解させて硝酸銀水溶液を調製し、濃度２５質量％のアンモニア水６０ｍＬを添加して攪拌することにより、銀アンミン錯体水溶液を得た。次いで、２０℃の銀アンミン錯体水溶液に、濃度１１．９ｇ／Ｌのヒドラジン水溶液１Ｌと、濃度２．９ｇ／Ｌのステアリン酸ナトリウム水溶液４５ｍＬ（銀１ｍｏｌに対して２．３０×１０-３ｍｏｌに相当）を混合することにより銀粒子を還元析出させた。
次いで、この銀粒子をろ過し、ろ液の伝導率が４０μＳ／ｃｍ以下となるまで水洗後、乾燥させることにより銀粉（サンプル）を得た。
<Example 4>
A silver nitrate aqueous solution was obtained by dissolving 50 mL of a silver nitrate aqueous solution having a silver concentration of 400 g / L in 1 L of pure water, adding 60 mL of ammonia water having a concentration of 25% by mass, and stirring. Next, in a silver ammine complex aqueous solution at 20 ° C., 1 L of a hydrazine aqueous solution having a concentration of 11.9 g / L and 45 mL of an aqueous sodium stearate solution having a concentration of 2.9 g / L (2.30 × 10 −3 mol per 1 mol of silver) Silver particles were reduced and precipitated by mixing.
Then, the silver particles were filtered, washed with water until the filtrate had a conductivity of 40 μS / cm or less, and dried to obtain silver powder (sample).
＜実施例５＞
銀濃度４００ｇ／Ｌの硝酸銀水溶液５０ｍＬを純水１Ｌに溶解させて硝酸銀水溶液を調製し、濃度２５質量％のアンモニア水６０ｍＬを添加して攪拌することにより、銀アンミン錯体水溶液を得た。次いで、２０℃の銀アンミン錯体水溶液に、濃度１１．９ｇ／Ｌのヒドラジン水溶液１Ｌと、濃度５ｇ／Ｌのゼラチン水溶液１６ｍＬ（銀１ｍｏｌに対して０．４３ｇに相当）を混合することにより銀粒子を還元析出させた。
次いで、この銀粒子をろ過し、ろ液の伝導率が４０μＳ／ｃｍ以下となるまで水洗後、乾燥させることにより銀粉（サンプル）を得た。
<Example 5>
A silver nitrate aqueous solution was obtained by dissolving 50 mL of a silver nitrate aqueous solution having a silver concentration of 400 g / L in 1 L of pure water, adding 60 mL of ammonia water having a concentration of 25% by mass, and stirring. Next, silver particles were prepared by mixing 1 L of a 11.9 g / L hydrazine aqueous solution and 16 mL of a 5 g / L gelatin aqueous solution (corresponding to 0.43 g with respect to 1 mol of silver) into a 20 ° C. silver ammine complex aqueous solution. Was reduced and precipitated.
Then, the silver particles were filtered, washed with water until the filtrate had a conductivity of 40 μS / cm or less, and dried to obtain silver powder (sample).
＜実施例６＞
銀濃度４００ｇ／Ｌの硝酸銀水溶液５０ｍＬを純水１Ｌに溶解させて硝酸銀水溶液を調製し、濃度２５質量％のアンモニア水５０ｍＬを添加して攪拌することにより、銀アンミン錯体水溶液を得た。次いで、２０℃の銀アンミン錯体水溶液に、濃度１１．９ｇ／Ｌのヒドラジン水溶液１Ｌと、濃度５ｇ／Ｌのゼラチン水溶液１６ｍＬ（銀１ｍｏｌに対して０．４３ｇに相当）を混合することにより銀粒子を還元析出させた。
次いで、この銀粒子をろ過し、ろ液の伝導率が４０μＳ／ｃｍ以下となるまで水洗後、乾燥させることにより銀粉（サンプル）を得た。
<Example 6>
A silver nitrate aqueous solution was obtained by dissolving 50 mL of a silver nitrate aqueous solution having a silver concentration of 400 g / L in 1 L of pure water to prepare a silver nitrate aqueous solution, adding 50 mL of ammonia water having a concentration of 25% by mass and stirring. Next, silver particles were prepared by mixing 1 L of a 11.9 g / L hydrazine aqueous solution and 16 mL of a 5 g / L gelatin aqueous solution (corresponding to 0.43 g with respect to 1 mol of silver) into a 20 ° C. silver ammine complex aqueous solution. Was reduced and precipitated.
Then, the silver particles were filtered, washed with water until the filtrate had a conductivity of 40 μS / cm or less, and dried to obtain silver powder (sample).
＜比較例１＞
銀濃度４００ｇ／Ｌの硝酸銀水溶液５０ｍＬを純水１Ｌに溶解させて硝酸銀水溶液を調製し、濃度２５質量％のアンモニア水５０ｍＬを添加して攪拌することにより、銀アンミン錯体水溶液を得た。次いで、２０℃の銀アンミン錯体水溶液に、濃度１１．９ｇ／Ｌのヒドラジン水溶液１Ｌと、濃度１００ｇ／Ｌのステアリン酸ナトリウム水溶液４ｍＬ（銀１ｍｏｌに対して７．０４×１０-３ｍｏｌに相当）を混合することにより銀粒子を還元析出させた。
次いで、この銀スラリーに濃度９８質量％の硫酸２０ｍＬを添加して攪拌した。
次いで、この銀粒子をろ過し、ろ液の伝導率が４０μＳ／ｃｍ以下となるまで水洗後、乾燥させることにより銀粉（サンプル）を得た。
<Comparative Example 1>
A silver nitrate aqueous solution was obtained by dissolving 50 mL of a silver nitrate aqueous solution having a silver concentration of 400 g / L in 1 L of pure water to prepare a silver nitrate aqueous solution, adding 50 mL of ammonia water having a concentration of 25% by mass and stirring. Next, in a silver ammine complex aqueous solution at 20 ° C., 1 L of a hydrazine aqueous solution having a concentration of 11.9 g / L and 4 mL of a sodium stearate aqueous solution having a concentration of 100 g / L (corresponding to 7.04 × 10 −3 mol with respect to 1 mol of silver) The silver particles were reduced and precipitated by mixing.
Subsequently, 20 mL of sulfuric acid having a concentration of 98% by mass was added to the silver slurry and stirred.
Then, the silver particles were filtered, washed with water until the filtrate had a conductivity of 40 μS / cm or less, and dried to obtain silver powder (sample).
＜比較例２＞
銀濃度４００ｇ／Ｌの硝酸銀水溶液５０ｍＬを純水１Ｌに溶解させて硝酸銀水溶液を調製し、濃度２５質量％のアンモニア水６０ｍＬを添加して攪拌することにより、銀アンミン錯体水溶液を得た。次いで、２０℃の銀アンミン錯体水溶液に、濃度１１．９ｇ／Ｌのヒドラジン水溶液１Ｌと、濃度１００ｇ／Ｌのステアリン酸ナトリウム水溶液３ｍＬ（銀１ｍｏｌに対して５．２８×１０-３ｍｏｌに相当）を混合することにより銀粒子を還元析出させた。
次いで、この銀スラリーに濃度９８質量％の硫酸２０ｍＬを添加して攪拌した。
次いで、この銀粒子をろ過し、ろ液の伝導率が４０μＳ／ｃｍ以下となるまで水洗後、乾燥させることにより銀粉（サンプル）を得た。
<Comparative example 2>
A silver nitrate aqueous solution was obtained by dissolving 50 mL of a silver nitrate aqueous solution having a silver concentration of 400 g / L in 1 L of pure water, adding 60 mL of ammonia water having a concentration of 25% by mass, and stirring. Next, in a silver ammine complex aqueous solution at 20 ° C., 1 L of a hydrazine aqueous solution having a concentration of 11.9 g / L and 3 mL of a sodium stearate aqueous solution having a concentration of 100 g / L (corresponding to 5.28 × 10 −3 mol per 1 mol of silver) The silver particles were reduced and precipitated by mixing.
Subsequently, 20 mL of sulfuric acid having a concentration of 98% by mass was added to the silver slurry and stirred.
Then, the silver particles were filtered, washed with water until the filtrate had a conductivity of 40 μS / cm or less, and dried to obtain silver powder (sample).
＜比較例３＞
銀濃度４００ｇ／Ｌの硝酸銀水溶液５０ｍＬを純水１Ｌに溶解させて硝酸銀水溶液を調製し、濃度２５質量％のアンモニア水６０ｍＬを添加して攪拌することにより、銀アンミン錯体水溶液を得た。次いで、２０℃の銀アンミン錯体水溶液に、濃度１１．９ｇ／Ｌのヒドラジン水溶液１Ｌと、濃度３７質量％のホルマリン６ｍＬおよび、濃度５ｇ／Ｌのゼラチン水溶液１６ｍＬ（銀１ｍｏｌに対して０．４３ｇに相当）を混合することにより銀粒子を還元析出させた。
次いで、この銀粒子をろ過し、ろ液の伝導率が４０μＳ／ｃｍ以下となるまで水洗後、乾燥させることにより銀粉（サンプル）を得た。
<Comparative Example 3>
A silver nitrate aqueous solution was obtained by dissolving 50 mL of a silver nitrate aqueous solution having a silver concentration of 400 g / L in 1 L of pure water, adding 60 mL of ammonia water having a concentration of 25% by mass, and stirring. Next, in a silver ammine complex aqueous solution at 20 ° C., 1 L of a hydrazine aqueous solution having a concentration of 11.9 g / L, 6 mL of formalin having a concentration of 37% by mass, and 16 mL of a gelatin aqueous solution having a concentration of 5 g / L (0.43 g to 1 mol of silver) Silver particles were reduced and precipitated by mixing.
Then, the silver particles were filtered, washed with water until the filtrate had a conductivity of 40 μS / cm or less, and dried to obtain silver powder (sample).
＜比較例４＞
銀濃度４００ｇ／Ｌの硝酸銀水溶液７５ｍＬを純水１Ｌに溶解させて硝酸銀水溶液を調製し、濃度２５質量％のアンモニア水９０ｍＬを添加して攪拌することにより、銀アンミン錯体水溶液を得た。
次いで、２０℃の銀アンミン錯体水溶液に、濃度１１．９ｇ／Ｌのヒドラジン水溶液１Ｌと、濃度２．９ｇ／Ｌのステアリン酸ナトリウム水溶液３５ｍＬ（銀１ｍｏｌに対して１．７６×１０-３ｍｏｌに相当）を混合することにより銀粒子を還元析出させた。
次いで、この銀粒子をろ過し、ろ液の伝導率が４０μＳ／ｃｍ以下となるまで水洗後、乾燥させることにより銀粉（サンプル）を得た。
<Comparative example 4>
A silver nitrate aqueous solution was prepared by dissolving 75 mL of a silver nitrate aqueous solution having a silver concentration of 400 g / L in 1 L of pure water, adding 90 mL of ammonia water having a concentration of 25% by mass, and stirring.
Next, in a silver ammine complex aqueous solution at 20 ° C., 1 L of a hydrazine aqueous solution with a concentration of 11.9 g / L and 35 mL of a sodium stearate aqueous solution with a concentration of 2.9 g / L (1.76 × 10 −3 mol per 1 mol of silver). Silver particles were reduced and precipitated by mixing.
Then, the silver particles were filtered, washed with water until the filtrate had a conductivity of 40 μS / cm or less, and dried to obtain silver powder (sample).
＜比較例５＞
銀濃度４００ｇ／Ｌの硝酸銀水溶液５０ｍＬを純水０．８Ｌに溶解させて硝酸銀水溶液を調製し、濃度２５質量％のアンモニア水６０ｍＬを添加して攪拌することにより、銀アンミン錯体水溶液を得た。
次いで、２０℃の銀アンミン錯体水溶液に、濃度１１．９ｇ／Ｌのヒドラジン水溶液０．８Ｌと、濃度２．９ｇ／Ｌのステアリン酸ナトリウム水溶液３５ｍＬ（銀１ｍｏｌに対して１．７６×１０-３ｍｏｌに相当）を混合することにより銀粒子を還元析出させた。
次いで、この銀粒子をろ過し、ろ液の伝導率が４０μＳ／ｃｍ以下となるまで水洗後、乾燥させることにより銀粉（サンプル）を得た。
<Comparative Example 5>
A silver nitrate aqueous solution was obtained by dissolving 50 mL of a silver nitrate aqueous solution having a silver concentration of 400 g / L in 0.8 L of pure water, adding 60 mL of ammonia water having a concentration of 25% by mass and stirring.
Subsequently, 0.8 L of a hydrazine aqueous solution having a concentration of 11.9 g / L and 35 mL of a sodium stearate aqueous solution having a concentration of 2.9 g / L (1.76 × 10 −3 with respect to 1 mol of silver) were added to the 20 ° C. silver ammine complex aqueous solution. The silver particles were reduced and precipitated by mixing (equivalent to mol).
Then, the silver particles were filtered, washed with water until the filtrate had a conductivity of 40 μS / cm or less, and dried to obtain silver powder (sample).
実施例及び比較例で得た銀粉（サンプル）は、いずれも球形状であった。
実施例及びこれまで行った試験結果から、銀に対するステアリン酸塩やゼラチンの添加比率などを調整することにより、ＢＥＴ径を１．１０μｍ〜２．６０μｍとし、且つ炭素含有量を０．１１〜０．２２質量％に調整すれば、５００℃における銀粉の熱収縮率が８．７〜１３．０％とすることが分かった。
The silver powders (samples) obtained in the examples and comparative examples were all spherical.
From the examples and the results of the tests conducted so far, the BET diameter was adjusted to 1.10 μm to 2.60 μm and the carbon content was adjusted to 0.11 to 0 by adjusting the addition ratio of stearate or gelatin to silver. It was found that the heat shrinkage rate of silver powder at 500 ° C. was 8.7 to 13.0% when adjusted to 0.22 mass%.
Claims (8)
Any sintered for a solar cell electrode formed by using a silver powder according to imaging-type conductive paste of claims 1 to 6.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011146386A JP6047276B2 (en) | 2011-06-30 | 2011-06-30 | Silver powder for sintered conductive paste |
| KR1020120047319A KR102007306B1 (en) | 2011-06-30 | 2012-05-04 | Silver powder for sintered conductive paste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011146386A JP6047276B2 (en) | 2011-06-30 | 2011-06-30 | Silver powder for sintered conductive paste |
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| CN106356412A (en) * | 2015-07-17 | 2017-01-25 | 杨振民 | Crystalline silicon solar cell grid line, electrode and back surface field manufacturing process |
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| JPH0845721A (en) * | 1994-08-03 | 1996-02-16 | Sumitomo Metal Mining Co Ltd | Composition for resin bonded magnetic and manufacture of resin bonded magnet using said composition. |
| JP6184731B2 (en) * | 2013-04-25 | 2017-08-23 | Ｄｏｗａエレクトロニクス株式会社 | Silver-bismuth powder, conductive paste and conductive film |
| CN105268992B (en) * | 2015-11-20 | 2018-07-31 | 浙江海洋学院 | A kind of netted two-dimensional sheet silver powder and its liquid-phase synthesis process |
| KR101930285B1 (en) * | 2016-10-31 | 2018-12-19 | 엘에스니꼬동제련 주식회사 | Electrode Paste For Solar Cell's Electrode And Solar Cell using the same |
| KR102033542B1 (en) * | 2017-04-28 | 2019-10-17 | 대주전자재료 주식회사 | Silver particle containing inner void and method of manufacture thereof |
| TWI755565B (en) | 2017-09-29 | 2022-02-21 | 日商同和電子科技有限公司 | Silver powder and method for producing same |
| JP7090511B2 (en) | 2017-09-29 | 2022-06-24 | Ｄｏｗａエレクトロニクス株式会社 | Silver powder and its manufacturing method |
| KR102302205B1 (en) * | 2018-10-04 | 2021-09-16 | 대주전자재료 주식회사 | Silver powder manufacturing method |
| KR20200038742A (en) * | 2018-10-04 | 2020-04-14 | 대주전자재료 주식회사 | Silver powder manufacturing method |
| KR20230153015A (en) | 2022-04-28 | 2023-11-06 | 한국광기술원 | sintered adhesive composition for metal and manufacturing method thereof |
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| JP2004047856A (en) * | 2002-07-15 | 2004-02-12 | Sumitomo Metal Electronics Devices Inc | Conductive paste and printing method as well as manufacturing method of ceramic multilayer circuit board |
| JP2006002228A (en) | 2004-06-18 | 2006-01-05 | Dowa Mining Co Ltd | Spherical silver powder and its production method |
| JP2006161145A (en) * | 2004-12-10 | 2006-06-22 | Dowa Mining Co Ltd | Silver powder and method for producing the same |
| JP2007270334A (en) | 2006-03-31 | 2007-10-18 | Dowa Holdings Co Ltd | Silver powder and its manufacturing method |
| KR101280489B1 (en) * | 2007-05-09 | 2013-07-01 | 주식회사 동진쎄미켐 | A paste for producing electrode of solar cell |
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| CN106356412A (en) * | 2015-07-17 | 2017-01-25 | 杨振民 | Crystalline silicon solar cell grid line, electrode and back surface field manufacturing process |
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| Publication number | Publication date |
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| JP2013014790A (en) | 2013-01-24 |
| KR102007306B1 (en) | 2019-08-05 |
| KR20130004064A (en) | 2013-01-09 |
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