KR20240036849A - Electrode material for semiconductor magnetic composition - Google Patents
Electrode material for semiconductor magnetic composition Download PDFInfo
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- KR20240036849A KR20240036849A KR1020220115387A KR20220115387A KR20240036849A KR 20240036849 A KR20240036849 A KR 20240036849A KR 1020220115387 A KR1020220115387 A KR 1020220115387A KR 20220115387 A KR20220115387 A KR 20220115387A KR 20240036849 A KR20240036849 A KR 20240036849A
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- electrode
- mass
- powder
- electrode material
- glass frit
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- 239000007772 electrode material Substances 0.000 title claims abstract description 30
- 239000000203 mixture Substances 0.000 title claims description 17
- 239000004065 semiconductor Substances 0.000 title claims description 7
- 239000000843 powder Substances 0.000 claims abstract description 36
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000011521 glass Substances 0.000 claims abstract description 34
- 238000009792 diffusion process Methods 0.000 claims abstract description 22
- 239000011701 zinc Substances 0.000 claims abstract description 21
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 20
- 238000005476 soldering Methods 0.000 claims abstract description 14
- 229910052709 silver Inorganic materials 0.000 claims abstract description 12
- 239000004332 silver Substances 0.000 claims abstract description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 26
- 239000000919 ceramic Substances 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 229910052810 boron oxide Inorganic materials 0.000 claims description 7
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 27
- 239000002184 metal Substances 0.000 abstract description 27
- 239000002003 electrode paste Substances 0.000 abstract description 15
- 238000010438 heat treatment Methods 0.000 abstract description 12
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002075 main ingredient Substances 0.000 abstract description 3
- 238000011160 research Methods 0.000 abstract 4
- 238000011161 development Methods 0.000 abstract 2
- 238000012827 research and development Methods 0.000 abstract 2
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- 238000000034 method Methods 0.000 description 17
- 239000002245 particle Substances 0.000 description 17
- 230000007423 decrease Effects 0.000 description 12
- 238000002844 melting Methods 0.000 description 12
- 230000008018 melting Effects 0.000 description 12
- 238000010304 firing Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002270 dispersing agent Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 229910002113 barium titanate Inorganic materials 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 239000002952 polymeric resin Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229920003002 synthetic resin Polymers 0.000 description 6
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- 239000004094 surface-active agent Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
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- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
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- 239000003960 organic solvent Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 description 1
- WMDZKDKPYCNCDZ-UHFFFAOYSA-N 2-(2-butoxypropoxy)propan-1-ol Chemical compound CCCCOC(C)COC(C)CO WMDZKDKPYCNCDZ-UHFFFAOYSA-N 0.000 description 1
- GZMAAYIALGURDQ-UHFFFAOYSA-N 2-(2-hexoxyethoxy)ethanol Chemical compound CCCCCCOCCOCCO GZMAAYIALGURDQ-UHFFFAOYSA-N 0.000 description 1
- XYVAYAJYLWYJJN-UHFFFAOYSA-N 2-(2-propoxypropoxy)propan-1-ol Chemical compound CCCOC(C)COC(C)CO XYVAYAJYLWYJJN-UHFFFAOYSA-N 0.000 description 1
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 description 1
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 1
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 description 1
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical group COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 1
- UPGSWASWQBLSKZ-UHFFFAOYSA-N 2-hexoxyethanol Chemical compound CCCCCCOCCO UPGSWASWQBLSKZ-UHFFFAOYSA-N 0.000 description 1
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910003322 NiCu Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/02—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
- H01C7/022—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient mainly consisting of non-metallic substances
- H01C7/023—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient mainly consisting of non-metallic substances containing oxides or oxidic compounds, e.g. ferrites
- H01C7/025—Perovskites, e.g. titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
- C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
- C04B35/4682—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates based on BaTiO3 perovskite phase
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Manufacturing & Machinery (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Thermistors And Varistors (AREA)
Abstract
BaTiO3형 페롭스카이트 구조 PTC 소자용 전극 재료로서 Silver, Zinc, Glass Frit을 주성분으로 하고 Diffusion 특성 제어를 위해 첨가되는 Metal 분말, 그리고 Lead Wire와 Soldering 특성을 개선하기 위한 Sn 분말을 포함하는 전극 페이스트로서 면저항 및 계면저항이 적고 균일한 전극 재료.
이 발명을 지원한 국가연구개발사업
과제고유번호
S2894373
부처명
중소벤처기업부
연구관리전문기관
중소기업기술정보진흥원
연구사업명
지역특화산업육성+(R&D)
연구과제명
전기자동차 실내 난방에 사용되는 PTC Thermistor용 전극 Paste 개발
기여율
1/1
주관기관
씨피에스(주)
연구기간
2020. 05. 01 ∼ 2022. 03. 31As an electrode material for BaTiO3-type perovskite structure PTC devices, it is an electrode paste containing silver, zinc, and glass frit as main ingredients, metal powder added to control diffusion characteristics, and Sn powder to improve lead wire and soldering characteristics. An electrode material with low sheet and interface resistance and uniformity.
National research and development project that supported this invention
Assignment identification number S2894373
Ministry of SMEs and Startups
Small and Medium Business Technology Information Promotion Agency, a research management agency
Research Project Name Regional Specialized Industry Development + (R&D)
Research project name: Development of electrode paste for PTC thermistor used for indoor heating of electric vehicles
Contribution rate 1/1
Host organization CPS Co., Ltd.
Research period 2020. 05. 01 ∼ 2022. 03. 31
Description
본 발명은 반도체 자기 조성물에 전극을 형성한 세라믹 면상발열 소자용 전극 재료에 관한 것이다.The present invention relates to an electrode material for a ceramic planar heating element in which electrodes are formed on a semiconductor ceramic composition.
PTC(Positive Temperature Coefficient : 정온도계수) 서미스터란 온도가 상승함에 따라 저항이 증가하는 특성을 갖는 소자로 BaTiO3 Perovskite 구조를 갖는 세라믹 소자를 주로 사용하고 있다. BaTiO3 는 일반적으로 120전후에서 큐리점이 형성되나 Pb, Sr, Bi 등의 원소를 첨가함으로서 큐리온도를 낮추거나 높일 수 있는 것으로 알려져 있다. PTC 서미스터는 낮은 온도에서는 비교적 작은 저항치를 갖지만 어떤 온도에 도달하면, 이 온도부터 급격히 저항이 증가하게 되며, 그 증가폭도 대단히 커지게 되는데, 이는 결정입계에 형성된 저항(쇼트키 장벽에 의한 저항)이 증가하기 때문에 일어나는 것으로 알려져 있다.A PTC (Positive Temperature Coefficient) thermistor is a device whose resistance increases as the temperature increases, and a ceramic device with a BaTiO3 Perovskite structure is mainly used. The Curie point of BaTiO3 is generally formed around 120, but it is known that the Curie temperature can be lowered or increased by adding elements such as Pb, Sr, and Bi. PTC thermistors have a relatively small resistance at low temperatures, but when a certain temperature is reached, the resistance increases rapidly from this temperature, and the extent of the increase becomes very large. This is due to the resistance formed at the grain boundaries (resistance due to the Schottky barrier). It is known to occur because of an increase.
이러한 PTC 서미스터는 온도의 변화에 민감하게 저항이 증가하는 소자라는점에서 온도센서, 온도로 전류를 제한하는 소자, 스스로가 저항체이므로, 과다한 전류가 흐르면 발열하여 저항이 급증하게 되고 이로인해 전류를 억제하는 과전류보호용 소자로 사용되어져 왔으나 최근들어 과열보호용 소자, 그리고 전기자동차 실내 난방을 위한 히터용으로 사용되어지고 있다. This PTC thermistor is a temperature sensor in that it is a device whose resistance increases sensitively to changes in temperature, and is a device that limits current by temperature. Since it is itself a resistor, when excessive current flows, it generates heat and resistance increases rapidly, which suppresses the current. It has been used as an overcurrent protection device, but recently, it has been used as an overheat protection device and as a heater for indoor heating of electric vehicles.
특히 히터용 PTC서미스터의 경우 전압인가 시 별도의 센서 및 온도컨트롤 회로 없이 일정온도로 발열하는 정온발열 특성을 이용하여 안정성, 신뢰성이 요구되는 자동차, 이미용기구 등 히터부품으로 확대 적용되고 있다.In particular, in the case of PTC thermistors for heaters, they are being widely applied to heater parts such as automobiles and hairdressing equipment that require stability and reliability by using the constant temperature heating characteristic of generating heat at a constant temperature without a separate sensor or temperature control circuit when voltage is applied.
BaTiO3 세라믹 PTC소자는 소자 자체만으로는 PTC 특성을 발휘할 수 없어 소자 양면에 전극을 형성하게 되는데, 기존 상용 BaTiO3 세라믹 PTC소자에 전극을 형성하기 위하여 일반적으로 세라믹 소자와 금속전극간의 저항 접촉을 위하여 Ohmic Contact용 Ag-Zn Paste를 이용하여 전극을 형성한 후 임피던스를 낮추고, 접촉저항을 낮추며 전자부품으로 사용될 경우 PCB기판과 연결을 위한 LEAD Wire와 Soldering을 위하여 Cover용 Ag 전극을 형성하는 2단계 전극 형성공정을 진행하고 있다. The BaTiO3 ceramic PTC device cannot exhibit PTC characteristics by itself, so electrodes are formed on both sides of the device. In order to form electrodes in existing commercial BaTiO3 ceramic PTC devices, Ohmic Contact is generally used for resistance contact between the ceramic device and the metal electrode. After forming the electrode using Ag-Zn Paste, a two-step electrode formation process is performed to lower the impedance and contact resistance, and when used as an electronic component, to form a LEAD wire for connection to the PCB board and an Ag electrode for the cover for soldering. It's in progress.
PTC소자의 양면에 Ohmic Contact용 전극을 형성하기 위하여 일반적으로 증착, 도금, 인쇄를 통해 전극을 형성하는 방법을 사용하고 있다.To form electrodes for Ohmic contact on both sides of a PTC device, methods of forming electrodes through deposition, plating, and printing are generally used.
특허문헌 1에는 PTC 소자에 전극을 형성하는 방법으로 스퍼터링, 증착, 전해 석출, 화학석출 등의 방법으로 제작함을 명시하고 있다.Patent Document 1 specifies that electrodes in PTC devices are formed using sputtering, vapor deposition, electrolytic precipitation, and chemical precipitation.
특허문헌 2에는 BaTiO3계 조성물을 주성분으로 하여 Ba의 일부가 알칼리 금속, Bi, 및 희토류로 치환되고, Ba와 Ti의 몰비가 0.990에서 0.999 사이인것을 특징으로 하는 PTC소자 조성물이 기재되어 있다, 이에 전극 처리로, 도금, 스퍼터링, 전극 베이킹 등에 의해 외부전극을 형성하고, 이에의해 PTC 써미스터가 얻어짐을 기재하고 있다. 구체적인 실시예로 건식 도금을 실시하며 NiCr/NiCu/Ag의 3중 구조의 외부전극을 형성하고 있다.Patent Document 2 describes a PTC device composition that contains a BaTiO 3 -based composition as the main component, wherein part of Ba is replaced with an alkali metal, Bi, and rare earth, and the molar ratio of Ba and Ti is between 0.990 and 0.999. Accordingly, it is described that external electrodes are formed through electrode processing, such as plating, sputtering, and electrode baking, and thereby a PTC thermistor is obtained. In a specific example, dry plating is performed to form an external electrode with a triple structure of NiCr/NiCu/Ag.
일반적으로 전극 형성 방법은 도금법, 스퍼터링, 증착 등의 방법들이 많이 사용되나 이러한 방법들은 PTC소자와 전극 사이 게면의 저항을 낮출 수 있는 장접이 있으나 고가의 장비 및 공정 관리로 인해 많은 비용이 들게 된다. In general, methods such as plating, sputtering, and deposition are widely used to form electrodes. Although these methods include joint welding that can lower the resistance of the surface between the PTC device and the electrode, they are expensive due to expensive equipment and process management.
보다 저렴한 방법으로 전극을 형성할 수 있는 방법으로 금속 분말과 각종 첨가제를 고점도의 페이스트로 제조 한후 인쇄를 통해 소자에 도포하고, 열처리를 통해 전극을 형성하는 방법이 있다. A cheaper way to form electrodes is to manufacture metal powder and various additives into a high-viscosity paste, apply it to the device through printing, and then form electrodes through heat treatment.
특허문헌 3에서는 BaTiO3 소결체를 제조하는데 있어 Ba 대신 Na 또는 K를 일부 대체하고, Ti 대신 V, Nb, Ta를 일부 대체함으로써 PTC소자의 특성을 개선하고, 이의 전극재료로 Ag-Zn 혼합 Paste를 사용함으로서 PTC 써머스터 소자를 제조하는 방법이 게시되어 있다.In Patent Document 3, in manufacturing BaTiO 3 sintered body, the characteristics of the PTC device are improved by partially replacing Ba with Na or K, and partially replacing Ti with V, Nb, and Ta, and Ag-Zn mixed paste is used as the electrode material. A method of manufacturing a PTC thermostat element using the method has been published.
특허문헌 4에서는 이를 개선하기 위하여 Aluminum 분말에 질화 붕소, 그리고 글라스 프릿으로 이루어지는 전극 페이스트가 게시되어 있다. 이렇게 제조된 전극 페이스트를 공기중에서 850∼900℃에서 소결함으로써 세라믹 기재와 오믹콘택을 갖는 전극을 형성하는 것으로 되어 있다. In order to improve this, Patent Document 4 discloses an electrode paste made of aluminum powder, boron nitride, and glass frit. The electrode paste prepared in this way is sintered in air at 850-900°C to form an electrode having ohmic contact with a ceramic substrate.
본 발명은 BaTiO3와 같은 페롭스카이트구조의 PTC소자용 전극을 형성하는데 있어 기존 Ceramic BaTiO3에 Ohmic Contact을 위한 Ag-Zn Paste 이용하여 전극을 형성하고, 이후에 Cover용 Ag Paste를 이용하여 전극을 형성하는 2단계 전극 형성공정을 1종류의 전극 Past만 사용하여 1단계 공정으로 전극을 형성할 수 있는 전극 Paste 조성을 통해 전기적 특성이 우수하고 공정 단순화를 통한 제조공정 단축을 통한 비용과 공정시간을 단축할 수 있는 전극 재료를 제공하고자 한다.In the present invention, in forming an electrode for a PTC device with a perovskite structure such as BaTiO 3 , the electrode is formed using Ag-Zn Paste for Ohmic Contact on the existing ceramic BaTiO 3 , and then the electrode is formed using Ag Paste for a cover. The two-step electrode forming process uses only one type of electrode paste to form an electrode in a one-step process. The electrode paste composition has excellent electrical properties and reduces cost and process time by shortening the manufacturing process through process simplification. The aim is to provide an electrode material that can be shortened.
본 발명은 BaTiO3계 페롭스카이트 구조를 갖는 PTC소자의 전극 재료 조성물에 있어, 금속성분을 Silver와 Zinc, 고온에서 Diffusion 특성 제어를 위한 첨가제, 그리고 글라스프릿을 주 성분으로 하고, 여기에 전기저항을 낮추고, LEAD Wire와 Soldering 특성을 개선하기 위하여 Sn 분말을 포함하고, 스크린 인쇄를 통하여 전극을 형성하기 위하여 유기용제와, 고분자 수지, 분산제 등과 금속성분을 혼합하고, 분산시켜 전극 페이스트를 제조하게 된다.The present invention relates to an electrode material composition for a PTC device having a BaTiO 3 -based perovskite structure, which mainly consists of silver and zinc as metal components, additives for controlling diffusion characteristics at high temperatures, and glass frit, which contain electrical resistance. In order to lower the LEAD wire and soldering characteristics, it contains Sn powder, and to form an electrode through screen printing, an electrode paste is produced by mixing and dispersing organic solvent, polymer resin, dispersant, etc. and metal components. .
제조된 전극 페이스트를 스크린 인쇄 후 400℃ 이상의 고온에서 열처리를 통하여 용제와 고분자수지, 분산제를 제거하여 전극을 형성 하는 조성물에 관한 것으로 PTC소자와의 접촉저항이 낮고, 전극형성 온도 범위가 넓은 전극 재료이다.It relates to a composition that forms an electrode by screen printing the manufactured electrode paste and then heat-treating it at a high temperature of 400℃ or higher to remove the solvent, polymer resin, and dispersant. It is an electrode material that has low contact resistance with the PTC element and has a wide electrode formation temperature range. am.
본 발명의 전극 페이스트는 BaTiO3계 페롭스카이트 구조인 PTC 소자에 전극을 인쇄한 후 인쇄 및 소성 후 전극두께는 5∼20㎛ 두께로 형성되 게되는데, 기존 PTC소자의 Ohmic Contact용 전극 Paste의경우 전극의 면저항이 200∼30mΩ/□범를 형성하는 반면, 본 발열을 통한 전극의 면저항은 30∼80mΩ/□범위에 형성되며, 전극 형성 후 소자저항이 2∼5,000Ω인 PTC 소자용 전극 페이스트이다.The electrode paste of the present invention prints an electrode on a PTC device with a BaTiO 3 -based perovskite structure, and after printing and firing, the electrode thickness is formed to be 5 to 20㎛. In the case of electrode paste for Ohmic Contact of existing PTC devices, While the sheet resistance of the electrode is in the range of 200~30mΩ/□, the sheet resistance of the electrode through this heat generation is formed in the range of 30~80mΩ/□, and it is an electrode paste for PTC devices with a device resistance of 2~5,000Ω after forming the electrode.
본 발명의 상기 전극재료는 Silver와 Zinc 분말을 주 원료로 하여 첨가제로 전극 소성 시 확산을 제어해 줄수 있는 첨가제, 그리고 글라스 프릿과 Lead Wire와의 Soldering 특성을 개선하기 위한 Sn 분말의 합계를 100으로 하여 Silver 분말을 40질량%이상 85질량% 이하를 포함하고, Zinc 분말은 5질량% 이상 50질량% 이하, 그리고 Diffusion 특성 제어를 위한 첨가제 0.1질량% 이상 20질량% 이하, 글라스 프릿은 0.1질량% 이상 10질량%이하, 그리고 Sn분말이 0.1질량% 이상 10질량%이하로 포함하는 것으로 할 수 있다.The electrode material of the present invention uses silver and zinc powder as main raw materials, an additive that can control diffusion during electrode firing, and Sn powder to improve soldering characteristics between glass frit and lead wire, with the total of 100. Contains not less than 40% by mass and not more than 85% by mass of silver powder, not less than 5% by mass but not more than 50% by mass of zinc powder, and not less than 0.1% by mass and not more than 20% by mass of additives for controlling diffusion characteristics, and not less than 0.1% by mass of glass frit. It may be 10 mass% or less, and may contain Sn powder in an amount of 0.1 mass% or more and 10 mass% or less.
본 발명의 전극재료는 스크린 인쇄를 통해전극을 형성하고, 이를 200℃ 내외에서 건조를 통해 용제를 제거 한 후 450℃이상의 온도에서 소성을 진행함으로써 전극이 형성된다.The electrode material of the present invention is formed by forming an electrode through screen printing, removing the solvent by drying it at around 200°C, and then firing it at a temperature of 450°C or higher.
본 발명의 상기 PTC 소자용 전극 재료는 소성공정을 통하여 계면저항이 작은 PTC 소자를 제공할 수 있고, 소성 공정 중 온도산포에 의해 처리 온도 범위가 넓어도 균일한 소자저항을 얻게되어 생산성 및 효율이 우수한 PTC소자를 제공할 수 있다.The electrode material for the PTC device of the present invention can provide a PTC device with low interfacial resistance through a sintering process, and uniform device resistance is obtained even over a wide processing temperature range due to temperature distribution during the sintering process, thereby improving productivity and efficiency. Excellent PTC devices can be provided.
도 1 : 본 발명에 의해 제조된 PTC전극이 형성된 PTC소자 단면 Image
도 2 : 본 발명에 의해 제조된 PTC 전극이 형성된 PTC소자 표면 ImageFigure 1: Cross-sectional image of a PTC device with a PTC electrode manufactured according to the present invention
Figure 2: Image of the surface of the PTC device on which the PTC electrode manufactured according to the present invention is formed
본 발명은 Silver 분말 과 Zinc 분말을 주성분으로 하고, 여기에 고온에서 Diffusion 특성제어를 위한 첨가제 요소를 구성하고, 여기에 글라스프릿과 Sn 분말을 사용함으로써 전극의 밀착력 및 소성안정성, Soldering 특성을 부여하는 것으로 인해 전극 조성물이 구성된다. The present invention uses silver powder and zinc powder as main ingredients, and adds additive elements for controlling diffusion characteristics at high temperatures, and uses glass frit and Sn powder to provide electrode adhesion, plasticity stability, and soldering properties. This constitutes an electrode composition.
본발명에 있어 Silver 분말은 평균입도 0.1㎛ 이상 5㎛ 이하의 분말을 사용하게 된다. Silver 분말의 평균입도가 0.1㎛ 이하의 입자를 사용하게 되면 높은 비표면적으로 인해 페이스트 제조 시 점도 상승을 초래하게 되고, 소성 후 내부 미세공극으로 인하여 전극의 저항이 커질 수 있다. 평균 입도가 5㎛ 이상의 Silver 분말을 사용하게 되면 전극 사이의 공극이 커져 저항이 커질 뿐만 아니라 전극 두께 상승 및 표면 불균일을 초래하게 되어 적합하지 않다. 바람직하게는 Silver 분말의 평균입도가 0.1㎛ 이상 2.0㎛ 이하가 적합하다.In the present invention, silver powder is used with an average particle size of 0.1 ㎛ or more and 5 ㎛ or less. When silver powder particles with an average particle size of 0.1㎛ or less are used, the viscosity increases during paste production due to the high specific surface area, and the resistance of the electrode may increase due to internal micropores after firing. Using silver powder with an average particle size of 5㎛ or more is not suitable as the gap between electrodes increases, which not only increases resistance, but also increases electrode thickness and causes surface unevenness. Preferably, the average particle size of silver powder is 0.1㎛ or more and 2.0㎛ or less.
본 발명에서 전극재료는 Silver 분말, Zinc 분말, Diffusion 특성 제어를 위해 사용되어지는 Metal 분말, 글라스 프릿 분말, Soldering특성개선을 위한 Zn분말 합을 100질량%로 했을때 Silver 분말의 함량이 40질량% 이상, 85질량% 이하가 바람직하다. Silver 분말이 40% 이하를 사용하게 되면 첨가되는 Zinc, Diffusion 특성 제어를 위해 사용되어지는 Metal 분말, Glass Frit 함량이 높아져 저항이 높아지게 되고, Silver 분말의 함량이 85% 이상이 되게 되면 전극의 면저항은 감소하나 본 발명의 주요 목적인 세라믹 PTC소자와 전극간의 계면저항이 상승하고, 밀착력이 떨어지게 되어 품질저하를 초래하게 된다.In the present invention, the electrode material is silver powder, zinc powder, metal powder used to control diffusion properties, glass frit powder, and Zn powder for improving soldering properties. When the sum of the powder is 100% by mass, the content of silver powder is 40% by mass. Above and 85% by mass or less is preferable. If less than 40% of silver powder is used, the added zinc, metal powder used to control diffusion properties, and glass frit content increase, resulting in higher resistance. If the content of silver powder exceeds 85%, the sheet resistance of the electrode increases. However, the interfacial resistance between the ceramic PTC device and the electrode, which is the main purpose of the present invention, increases, and the adhesion decreases, resulting in quality deterioration.
본 발명의 전극재료 조성물에 포함되는 Zinc 분말의 평균입자크기는 0.5㎛이상 12㎛ 이하가 좋다. Zinc 분말의 평균입도가 0.5㎛이하를 사용하게 되면 Nano Size 효과로 인하여 Zinc의 용융점인 419.5℃ 이하에서 용융되기 시작하여 용융된 Zinc 성분들끼리 뭉쳐져 전극 형성 후 전극의 균일성이 떨어지고, 과용융된 Zinc 성분들이 전극 표면으로 돌출되어 표면저항 상승을 초래 할 수 있다. The average particle size of the zinc powder included in the electrode material composition of the present invention is preferably 0.5 ㎛ or more and 12 ㎛ or less. If the average particle size of the zinc powder is 0.5㎛ or less, it begins to melt below 419.5℃, the melting point of zinc, due to the nano size effect, and the molten zinc components clump together, reducing the uniformity of the electrode after forming the electrode and causing overmelt. Zinc components may protrude onto the electrode surface, causing an increase in surface resistance.
일반적으로 본 발명의 전극 페이스트를 인쇄 및 소성 후 전극의 두께가 12㎛ 내외로 형성되게 되는데, Zinc 분말의 평균입도가 12㎛이상의 분말을 사용하게 되면 Zinc 입자 크기로 인하여 전극 표면이 거칠어지게 되고, Zinc 분말의 분포가 균일하지 못하여 전극 면저항 및 표면저항 산포가 커져 전극 품질저하를 초래하게 된다.Generally, after printing and firing the electrode paste of the present invention, the thickness of the electrode is formed to be around 12㎛. If zinc powder with an average particle size of 12㎛ or more is used, the electrode surface becomes rough due to the size of the zinc particles. Since the distribution of zinc powder is not uniform, the electrode sheet resistance and surface resistance distribution increase, resulting in a decrease in electrode quality.
전극 소재에 포함되는 Zinc 분말은 Silver, Znic, Diffusion 특성 제어를 위해 사용되어지는 Metal 분말, 글라스프릿함계를 100질량%로 했을때, 5질량% 이상, 65 질량% 이하가 좋다, Zinc의 함량이 5% 이하로 첨가되게 되면 소체와 원활한 Ohmic Contact이 이루어지지 않아 소자저항이 상승하여 소자의 특성 저하를 초래하게 되고, Zinc의 함량이 65% 이상 첨가되게 되면 전극의 면저항이 급격히 상승하여 소자 특성을 저해하게 된다. 더욱 바람직하게는 Zinc의 함량이 10%질량% 이상, 45 질량% 이하가 바람직 하다. Zinc powder included in the electrode material is silver, zinc, and metal powder used to control diffusion characteristics. When the glass frit content is 100% by mass, the zinc content is preferably 5% by mass or more and 65% by mass or less. If the zinc content is added at 5% or less, smooth Ohmic contact with the element is not achieved, resulting in an increase in device resistance, resulting in deterioration of the device characteristics. If the Zinc content is added at more than 65%, the sheet resistance of the electrode increases rapidly, deteriorating the device characteristics. It will be hindered. More preferably, the zinc content is 10% by mass or more and 45% by mass or less.
전극 소재에 포함되는 Diffusion 특성을 제어하기 위해 첨가되는 분말은 본발명의 주 성분인 Zinc 분말의 용융점인 419.5℃ 보다 용융온도가 높고, Silver 분말의 용융점인 960℃ 보다 용융온도가 낮은 온도범위에서 용융되는 금속 또는 금속 산화물 분말을 사용하는 것이 좋다. 이는 용융점 차이가 큰 두 Metal 재료의 중간영역에서 열처리시 용융 buffer 역할을 함으로서 전극 소성 온도 범위를 넓히게 되어 균일한 소자저항 산포가 구현 가능하여 소성 공정 마진을 넓힐 수 있어 PTC소자의 생산 안정성에 도움을 주는 역할을 한다. 본 발명에서 사용되는 Diffusion 특성을 제어하기 위해 첨가되는 Metal 또는 산화물 분말는 용융온도가 420℃이상, 950℃범위 인 Metal 또는 산화물 분말이 바람직하며, 이의 예로는 Aluminum, Magnesium 등 저융점 Metal 그리고 산화물로는 Boron Oxide 분말을 들수 있으나 이들 성분으로 한정하는것은 아니다.The powder added to control the diffusion characteristics contained in the electrode material melts in a temperature range that is higher than the melting point of 419.5°C, the melting point of Zinc powder, the main ingredient of the present invention, and lower than 960°C, the melting point of Silver powder. It is recommended to use metal or metal oxide powder. This serves as a melting buffer during heat treatment in the middle area of two metal materials with large melting point differences, widening the range of electrode firing temperature, enabling uniform device resistance distribution and widening the firing process margin, helping with the production stability of PTC devices. It plays a role in giving. The metal or oxide powder added to control the diffusion characteristics used in the present invention is preferably a metal or oxide powder with a melting temperature of 420℃ or more and 950℃, examples of which include low melting point metals such as aluminum and magnesium, and oxides. Boron oxide powder may be included, but it is not limited to these ingredients.
본 발명의 Diffusion 특성 제어를 위해 첨가되는 Metal 또는 산화물 분말은 평균입도가 0.5㎛ 이상, 10㎛이하가 바람직하다. 첨가되는 Metal 또는 산화 분말의 평균입도가 0.5㎛이하 이면, Nano Size 효과에 의해 금속 고유 용융온도 이하의 온도에서 용융되게 되어 본 발명의 첨가되는 금속의 요구 물성인 용윤온도가 420℃ 이상을 만족하기 못하게 되어 Diffusion 특성 제어가 어렵게 되고, 첨가되는 Metal 또는 산화물 분말의 평균입도가 10㎛ 이상일 경우 첨가되는 금속성분의 분포를 균일하게 하기 위하여 첨가량을 증가 시켜야만 된고, 첨가량이 많아질 경우 전극의 면저항 상승을 초래하게 되어 전극 특성 저하를 초래하게 된다. The metal or oxide powder added to control the diffusion characteristics of the present invention preferably has an average particle size of 0.5 ㎛ or more and 10 ㎛ or less. If the average particle size of the added metal or oxidized powder is 0.5㎛ or less, it melts at a temperature below the metal's inherent melting temperature due to the Nano Size effect, so that the melting temperature, which is the required physical property of the added metal of the present invention, satisfies 420°C or more. This makes it difficult to control diffusion characteristics, and if the average particle size of the added metal or oxide powder is more than 10㎛, the amount added must be increased to make the distribution of the added metal component uniform. If the amount added increases, the sheet resistance of the electrode increases. This results in a decrease in electrode characteristics.
본 발명에 있어서 Silver, Znic, Diffusion 특성을 제어하기 위해 첨가되는 Metal 또는 산화물 분말, 글라스프릿, Soldering 특성 개선을 위한 Sn 분말 합계를 100질량%로 했을때, Diffusion 특성을 제어하기 위해 첨가되는 Metal 분말은 0.2질량% 이상, 10질량% 이하를 포함하는것이 바람직하다. Diffusion 특성을 제어하기 위해 첨가되는 Metal 분말 함량이 0.2% 이하로 첨가되게 되면 양이 충분하지 않아 Diffusion 특성 제어가 되지않게 되어 고온의 전극 소성 공정에서 소자저항이 급격하게 상승하게 되어 공정마진이 적어 대량 양산공정에서 불량율이 높아 질 수 있으며, Diffusion 특성을 제어하기 위해 첨가되는 Metal 분말의 함량이 10%이상 첨가되게 되면 전극의 면저항이 상승하게 되어 PTC소자의 전기적 특성저하를 초래하게 된다.. 더욱 바람직하게는 0.5질량% 이상 8질량% 이하가 바람직하다.In the present invention, when the total of silver, zinc, metal or oxide powder added to control diffusion properties, glass frit, and Sn powder for improving soldering properties is 100% by mass, metal powder added to control diffusion properties It is preferable that it contains 0.2 mass% or more and 10 mass% or less. If the amount of metal powder added to control diffusion characteristics is added below 0.2%, the amount is not sufficient and diffusion characteristics cannot be controlled. As a result, device resistance rises rapidly during the high-temperature electrode sintering process, resulting in low process margins and large volume production. The defect rate may increase during the mass production process, and if the content of metal powder added to control diffusion characteristics exceeds 10%, the sheet resistance of the electrode increases, resulting in a decrease in the electrical characteristics of the PTC device. More desirable. More preferably, it is 0.5% by mass or more and 8% by mass or less.
본 발명에서 전극 소재에 포함되는 글라스프릿은 Bi2O3-SiO2-Al2O3-B2O3 계 또는 V2O5-SiO2-Al2O3계 글라스프릿이 바람직하며, 첨가되는 글라스프릿의 용융 전이점(Tg)이 280℃ 이상 550℃ 이하가 바람직하다. 본 발명에서 글라스프릿은 전극 재료의 주 성분인 Silver 분말, Zinc 분말과 PTC 소체인 BaTiO3 세라믹 소체사이에 접착력을 증대시켜 주는 역할을 하게 된다. 일반적으로 열팽창 계수가 다른 두개의 금속간 또는 금속과 세라믹 사이에서 열처리를 통한 용융접합에 있어서 서로다른 열 챙창 계수로 인하여 열처리 후 냉각공정에서 수축율이 달라 접합이 깨지게 된다. 글라스 프릿은 두가지 금속 또는 금속과 세라믹 사이의 접합에 있어서 저온에서 용융되는 유리성분인 글라스프릿을 첨가하여 두가지 서로다른 물질의 접합을 접착시켜주는 역할을 하게 된다. In the present invention, the glass frit included in the electrode material is preferably Bi 2 O 3 -SiO 2 -Al 2 O 3 -B 2 O 3 based or V 2 O 5 -SiO 2 -Al 2 O 3 based glass frit. The melt transition point (Tg) of the glass frit is preferably 280°C or higher and 550°C or lower. In the present invention, the glass frit serves to increase the adhesion between silver powder and zinc powder, which are the main components of the electrode material, and the BaTiO3 ceramic body, which is a PTC element. Generally, in fusion bonding between two metals with different thermal expansion coefficients or between a metal and a ceramic through heat treatment, the shrinkage rate is different during the cooling process after heat treatment due to the different thermal expansion coefficients, causing the bond to break. Glass frit plays a role in bonding two different materials by adding glass frit, a glass component that melts at low temperatures, in the bonding between two metals or metals and ceramics.
본 발명에서 첨가되는 그라스프릿은 Tg가 280℃ 이하인 글라스프릿을 사용하게 되면, PTC 소체의 최대 발열 온도가 280℃∼300℃인 소체에 적용할 경우 전극이 PTC소체의 발열에 의하여 전극이 용융되어 전극 내구성이 저하되게 되며 Tg가 550℃ 이상인 글라스프릿을 사용하게 되면 본 발명의 전극 재료의 평균 열처리 온도보다 재료의 용융온도가 높아 BaTiO3 소체와 전극재료와의 접합강도가 떨어져 내구성 저하를 초래하게 되고, 용융되지 않음 부도체 성분 첨가로 인하여 전극의 저항이 상승하게 된다.When the glass spray added in the present invention is used with a Tg of 280°C or lower, when applied to a body where the maximum heating temperature of the PTC body is 280°C to 300°C, the electrode melts due to heat generation from the PTC body. The durability of the electrode decreases, and if a glass frit with a Tg of 550°C or higher is used, the melting temperature of the material is higher than the average heat treatment temperature of the electrode material of the present invention, and the bonding strength between the BaTiO3 body and the electrode material decreases, resulting in a decrease in durability. , does not melt. The resistance of the electrode increases due to the addition of non-conducting components.
본 발명에 펌가되는 글라스프릿의 양은 0.1질량% 이상 10질량% 이하가 바람직 하다. 글라스 프릿 함량이 0.1질량% 이하가 첨가되게 되면 전극의 강도가 약해져 PTC소자로 부터 쉽게 박리되어 내 스크래치성이 약하게 되고, 글라스프릿 함량이 10% 이상이 되게 되면 도막 강도는 우수하나 전기저항이 크게 상승하여 전기적 특성 저하를 초래하게 된다.The amount of glass frit applied in the present invention is preferably 0.1% by mass or more and 10% by mass or less. If the glass frit content is 0.1% by mass or less, the strength of the electrode is weakened and it easily peels off from the PTC element, resulting in poor scratch resistance. If the glass frit content is more than 10%, the film strength is excellent, but the electrical resistance is high. As it rises, it causes a decrease in electrical characteristics.
상기 글라스 프릿은 Bi2O3-SiO2-Al2O3계 또는 V2O5-SiO2-Al2O3계에 용융온도 조절 및 특성 조절을 위하여 추가되는 구성 성분으로 SrO, AgO, CuO, V2O5, K2O, Li2O, Na2O B2O3, ZnO 등이 추가 될 수 있으며, 추가되는 성분은 이에 한정하지는 않는다. The glass frit is a component added to the Bi 2 O 3 -SiO 2 -Al 2 O 3 system or V 2 O 5 -SiO 2 -Al 2 O 3 system to control the melting temperature and properties and includes SrO, AgO, and CuO. , V 2 O 5 , K 2 O, Li 2 O, Na 2 OB 2 O 3 , ZnO, etc. may be added, but the added components are not limited thereto.
본 발명에서 Silver, Znic, Diffusion 특성을 제어하기 위해 첨가되는 Metal 또는 산화물 분말, 글라스프릿, Soldering 특성 개선을 위한 Sn 분말 합계를 100질량%로 했을때, PTC 소체와 Lead Wire와 Soldering 특성 부여를 위해서 첨가되는 Sn 분말은 0.2질량% 이상, 10질량% 이하를 포함하는것이 바람직하다. Soldering 특성을 제어하기 위해 첨가되는 Sn 분말 함량이 0.2% 이하로 첨가되게 되면 Soldering 특성이 개선되지 않고, 전극 저항만 상승시키게 되고, Soldering 특성을 제어하기 위해 첨가되는 Sn 분말의 함량이 10%이상 첨가되게 되면 전극의 면저항이 상승하게 되어 PTC소자의 전기적 특성저하를 초래하게 된다. 본발명에서 첨가되는 Sn분말은 함량은 더욱 바람직하게는 2질량% 이상 8질량% 이하가 바람직하다.In the present invention, when the total of metal or oxide powder, glass frit, and Sn powder for improving soldering properties added to control silver, zinc, and diffusion properties is set to 100% by mass, the PTC body and lead wire are used to provide soldering properties. The Sn powder to be added preferably contains 0.2% by mass or more and 10% by mass or less. If the content of Sn powder added to control soldering characteristics is added below 0.2%, soldering characteristics are not improved and only the electrode resistance increases, and if the content of Sn powder added to control soldering characteristics is added more than 10% If this happens, the sheet resistance of the electrode increases, resulting in a decrease in the electrical characteristics of the PTC device. The content of Sn powder added in the present invention is more preferably 2% by mass or more and 8% by mass or less.
페이스트 제조를 위해 사용되는 용제는 b.p 180℃ 이상, 300℃ 이하가 적당하다. 용제의 b.p가 180℃ 이하이면 스크린 인쇄도중 페이스트가 스크린 마스크에서 건조되어 마스크 막힘 현상이 발생할 수 있으며, 이로 인해 인쇄 불량을 초래할 수 있다. 용제의 b.p.가 300℃ 이상이 되게되면 스크린 인쇄 후 고온에서 건조를 해야 되는 문제가 있다. The solvent used to produce the paste is suitable at a temperature of 180℃ or higher and 300℃ or lower b.p. If the b.p. of the solvent is 180°C or lower, the paste may dry on the screen mask during screen printing, causing mask clogging, which may cause printing defects. If the b.p. of the solvent exceeds 300℃, there is a problem of having to dry at high temperature after screen printing.
상기 용제는 트리프로필렌글리콜 메틸에테르, 디프로필렌글리콜 n-프로필에테르, 디프로필렌글리콜 n-부틸에테르, 트리프로필렌글리콜 n-부틸에테르, 프로필렌글리콜 페닐에테르, 디에틸렌글리콜 에틸에테르, 디에틸렌글리콜 n-부틸에테르, 디에틸렌글리콜 헥실에테르, 에틸렌글리콜헥 실에테르, 트리에틸렌글리콜 메틸에테르, 트리에틸렌글리콜 에틸에테르, 트리에틸렌글리콜 n-부틸에테르 및 에틸렌글리콜 페닐에테르, 터피놀, Texanol로 이루어진 군에서 선택되는 1종 또는 2종 이상인 것이 바람직하다.The solvent is tripropylene glycol methyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, diethylene glycol ethyl ether, diethylene glycol n-butyl. 1 selected from the group consisting of ether, diethylene glycol hexyl ether, ethylene glycol hexyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, triethylene glycol n-butyl ether and ethylene glycol phenyl ether, terpinol, and Texanol. It is preferable that there are one species or two or more species.
비중이 다른 Silver, Zinc, Aluminum, 글라스 프릿의 원활한 분산 홉합을 위해서 분산제로 계면활성제를 사용해야만 한다. 분산제 함량은 Silver, Zinc, Diffusion 특성제어를 위한 첨가제인 Aluminum 또는 Magnesium, 글라스 프릿을 100 질량%에 대하여 0.1질량% 이상 10질량% 이하가 바람직하다. 분산제 함량이 0.1질량% 이하가 되게 되면 첨가되는 분산제의 효과 발휘가 미비하여 분산 안정성 저하를 초래하게 되고, 분산제 함량이 10질량% 이상 첨가되게 되면 응집이 발생하게 되어 분산안정성이 저하되게 된다.In order to smoothly disperse and combine silver, zinc, aluminum, and glass frit with different specific gravity, a surfactant must be used as a dispersant. The dispersant content is preferably 0.1% by mass or more and 10% by mass or less based on 100% by mass of silver, zinc, aluminum or magnesium, which are additives for controlling diffusion properties, and glass frit. If the dispersant content is less than 0.1% by mass, the effect of the added dispersant is insufficient, resulting in a decrease in dispersion stability. If the content of the dispersant is more than 10% by mass, agglomeration occurs and dispersion stability decreases.
상기 분산제로서는 계면활성제를 이용할 수 있고, 상기의 계면활성제로는, 비이온성 계면활성제, 고분자 계면활성제 및 양이온성 계면활성제로 이루어진 군에서 선택되는 1종 또는 2종 이상을 혼합하여 사용될 수 있다A surfactant can be used as the dispersant, and the surfactant may be one or a mixture of two or more selected from the group consisting of nonionic surfactants, polymeric surfactants, and cationic surfactants.
상기 계면활성제의 상품명으로 하이퍼머(hypermer) KD(Uniqema 제조), AKM 0531(일본유지㈜ 제조), KP(신에쯔가가꾸 고교㈜ 제조), 폴리플로우(POLYFLOW)(교에이샤 가가꾸㈜ 제조), 에프톱(EFTOP)(토켐 프로덕츠사 제조),아사히가드(Asahi guard), 서플론(Surflon)(이상, 아사히 글라스㈜ 제조), 솔스퍼스(SOLSPERSE)(제네까㈜제조), EFKA(EFKA 케미칼스사 제조) 및 PB 821(아지노모또㈜ 제조) BYK-9077, BYK-185, BYK-2150(BYK사) 등을 들 수 있다.The brand names of the above surfactants include hypermer KD (manufactured by Uniqema), AKM 0531 (manufactured by Nippon Oil Oil Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), and POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.) manufactured by EFTOP (manufactured by Tochem Products), Asahi guard, Surflon (manufactured by Asahi Glass Co., Ltd.), SOLSPERSE (manufactured by Zeneca Co., Ltd.), EFKA ( EFKA Chemicals Co., Ltd.) and PB 821 (Ajinomoto Co., Ltd.) BYK-9077, BYK-185, BYK-2150 (BYK Co., Ltd.).
상기 전극 재료의 페이스트화를 위해서는 고분자 수지를 사용할 수 있다. 고분자 수지로는 폴리비닐피롤리돈, 폴리비닐알코올, 폴리에틸렌글리콜, 에틸셀룰로오스, 로진, 페놀수지, 아크릴 수지 등을 들 수 있다. 고분자 수지의 함량은 유기 비히클 용액 총 중량에 대하여 1~25 중량%, 바람직하게는 5~25 중량%가 좋다. 고분자수지의 첨가량이 1 중량% 미만일 경우 페이스트의 인쇄성 및 분산 안정성이 저하되고, 25 중량%를 초과할 경우에는 페이스트가 인쇄되지 않는 문제를 초래 할 수 있다.To paste the electrode material, polymer resin can be used. Polymer resins include polyvinyl pyrrolidone, polyvinyl alcohol, polyethylene glycol, ethyl cellulose, rosin, phenol resin, and acrylic resin. The content of the polymer resin is preferably 1 to 25% by weight, preferably 5 to 25% by weight, based on the total weight of the organic vehicle solution. If the amount of polymer resin added is less than 1% by weight, the printability and dispersion stability of the paste deteriorates, and if it exceeds 25% by weight, the paste may not be printed.
23mm x 19.5mm x 2.0T 크기의 BaTiO3 페롭스카이트 구조의 PTC 소자에 상기 전극 페이스트를 스크린 프린트를 이용하여 양면을 인쇄 한 후 200℃에서 2분간 건조 한후 이를 450℃ 에서 650℃ 사이의 온도에서 소성을 진행한다. 최고온도에서의 체류시간은 1분 이상 30분 이하가 적당하다. 더욱 바람직하게는 5분이상 20분이하가 바람직하다The electrode paste was printed on both sides of a BaTiO3 perovskite structure PTC device measuring 23mm proceed. The appropriate residence time at the highest temperature is between 1 minute and 30 minutes. More preferably, it is more than 5 minutes and less than 20 minutes.
소성 후 형성된 전극 두께는 3㎛이상 20㎛ 이하가 적당하다. 전극 두께가 3㎛이하이면 전극 박리가 발생하기 쉽고, 충분한 양의 전극 재료가 도포되지 않아 전기적 특성 저하를 초래하기 쉽고, 전극 두께가 20㎛ 이상이면 전극 비용이 상승하게 되어 경제적으로 좋지 못하다. 바람직하게는 5㎛ 이상 15㎛ 이하가 적당하다. The appropriate thickness of the electrode formed after firing is 3㎛ or more and 20㎛ or less. If the electrode thickness is less than 3㎛, electrode peeling is likely to occur, and a sufficient amount of electrode material is not applied, which can easily lead to a decrease in electrical properties. If the electrode thickness is more than 20㎛, the cost of the electrode increases, which is not economically good. Preferably, 5㎛ or more and 15㎛ or less are appropriate.
제조된 전극 이형성된 PTC소자는 4-point Probe를 이용하여 면저항을 측정하고, 소자 양단에 형성되어 있는 전극을 저항 측정기를 이용하여 저항을 측정한다.The sheet resistance of the manufactured PTC device with released electrodes is measured using a 4-point probe, and the resistance of the electrodes formed on both ends of the device is measured using a resistance meter.
실시예 1Example 1
평균입경이 1.5㎛인 Silver 분말 입자 52질량부로 하여 여기에 평균입경이 5.0㎛인 Zinc 분을 20질량부, 평균입경이 4.0인 Aluminum 분말 5질량부, Tg = 302℃인 V2O5-SiO2-Al2O3계 글라스프릿 3질량부, 평균입경이 5.0㎛인 Sn 분말 5중량부를 첨가하고, 여기에 분산제와 유기바인데, 유기용제를 첨가하여 고형분 85%인 전극 페이스트를 제조하였다. 52 parts by mass of silver powder particles with an average particle diameter of 1.5㎛, 20 parts by mass of zinc powder with an average particle diameter of 5.0㎛, 5 parts by mass of aluminum powder with an average particle diameter of 4.0, and V 2 O 5 -SiO with Tg = 302℃. 3 parts by mass of 2 -Al 2 O 3 -based glass frit and 5 parts by mass of Sn powder with an average particle diameter of 5.0 ㎛ were added, and a dispersant and an organic solvent were added to prepare an electrode paste with a solid content of 85%.
제조된 페이스트를 23mm x 19.5mm x 2.0T크기의 BaTiO3조성의 PTC소체(소체저항 1,100±300Ω)의 양면에 인쇄, 건조 한 후 550℃에서 10분간 소성을 진행하여 전극이 형성된 PTC소자를 제조하였다. The prepared paste was printed on both sides of a BaTiO 3 composition PTC cell (body resistance 1,100±300Ω) measuring 23mm x 19.5mm did.
이렇게 제조된 PTC 소자의 양면에 형성된 전극의 면저항을 4-point probe로 측정하고, HIOKI 멀티미터를 이용하여 PTC소자의 저항을 측정하였다.The sheet resistance of the electrodes formed on both sides of the PTC device manufactured in this way was measured using a 4-point probe, and the resistance of the PTC device was measured using a HIOKI multimeter.
실시예 2∼5와 비교예 1∼5는 상기 실시예 1에서 Silver 분말, Zinc 분말, Aluminum 분말 및 글라스 프릿, 그리고 Sn의 함량을 변경해 가며 실시 하였다. 이에 얻어진 평가 결과를 표 1에 나타낸다.Examples 2 to 5 and Comparative Examples 1 to 5 were conducted by changing the contents of silver powder, zinc powder, aluminum powder, glass frit, and Sn in Example 1. The evaluation results obtained are shown in Table 1.
(질량%)Silver rate
(mass%)
(질량%)Zinc ratio
(mass%)
(질량%)Aluminum ratio
(mass%)
(질량%)Sn content
(mass%)
(질량%)Glasssprit ratio
(mass%)
(mΩ/□)Sheet resistance
(mΩ/□)
(N)Soldering tensile strength
(N)
(kΩ)element resistance
(kΩ)
비교예 6은 실시예 1을 기준으로 Diffusion 특성 제어를 위한 Aluminum 분말과 Boron Oxide 첨가 유무에 따른 서송 온도별 정기적 특성을 평가하였다. 이의 조성을 표 2에 나타내었고, 소성온도별 전기적 특성평가결과를 표3에 나타내었다.Comparative Example 6 evaluated the regular characteristics at each temperature according to the presence or absence of aluminum powder and boron oxide for controlling diffusion characteristics based on Example 1. Its composition is shown in Table 2, and the results of electrical property evaluation by firing temperature are shown in Table 3.
(질량 %)Silver rate
(mass %)
(질량 %)Zinc ratio
(mass %)
(성분/질량 %)Firing aid
(Component/Mass %)
(질량 %)Glass Sprit
(mass %)
(질량 %)Sn content
(mass %)
(㏀)corpuscle resistance
(㏀)
(mΩ/□)Sheet resistance
(mΩ/□)
본 발명은 전기자동차 및 난방용 난방 모듈에 사용되는 PTC소자의 전극 재료로서 전극 Paste의 공정 온도범위를 넓게 확보함으로서 제조 공정중 온조편차로 인해 발생할 수 있는 불량율을 최소화 함으로써 생산성이 향상되어 PTC소자 및 난방용 모듈의 가격 경쟁력 확보에 도움될것으로 기대된다.The present invention is an electrode material for PTC devices used in electric vehicles and heating modules. It secures a wide process temperature range for electrode paste and minimizes the defect rate that may occur due to temperature deviation during the manufacturing process, thereby improving productivity and improving PTC devices and heating modules. It is expected that this will help secure the price competitiveness of modules.
Claims (5)
상기 전극 재료는 Silver 분말과 Zinc 분말, Glass Frit을 주성분으로 하고, Diffusion 특성을 제어하기 위해 Aluminum 또는 Boron Oxide 분말, Soldering 특성을 개선하기 위한 Sn 분말을 포함하고 있는 전극 재료.
As an electrode material of a semiconductor magnetic composition with BaTiO 3 type perovskite structure
The electrode material is mainly composed of silver powder, zinc powder, and glass frit, and contains aluminum or boron oxide powder to control diffusion characteristics and Sn powder to improve soldering characteristics.
Diffusion 특성 제어를 위해 사용되어지는 Aluminum 또는 Boron Oxide 분말의 함량이 0.1중량 %이상, 10중량 %이하인 반도체 자기조성물용 전극재료
In claim 1,
Electrode material for semiconductor ceramic compositions containing more than 0.1% by weight and less than 10% by weight of aluminum or boron oxide powder used to control diffusion characteristics
글라스프릿은 Bi2O3-SiO2-Al2O3-B2O3계인 것을 특징으로 하고, 전이온도(Tg)가 300℃ 이상 550℃ 이하인 것을 특징으로 하는 반도체 자기 조성물의 전극 재료.
In claim 1,
The glass frit is an electrode material for a semiconductor ceramic composition, characterized in that it is of the Bi 2 O 3 -SiO 2 -Al 2 O 3 -B 2 O 3 system and has a transition temperature (Tg) of 300°C or more and 550°C or less.
상기 전극 재료는 Silver, Zinc, 글라스프릿 및 Aluminum또는 Boron Oxide, 그리고 Sn의 합계를 100질량%로 하여, 글라스프릿이 0.1질량% 이상 10질량% 이하인 것을 특징으로 하는 반도체 자기 조성물의 전극 재료.
In claim 1,
The electrode material is an electrode material of a semiconductor ceramic composition, characterized in that the total of silver, zinc, glass frit, aluminum or boron oxide, and Sn is 100 mass%, and the glass frit is 0.1 mass% or more and 10 mass% or less.
상기 전극 재료는 Silver, Zinc, 글라스프릿 및 Aluminum또는 Boron Oxide, 그리고 Sn의 합계를 100질량%로 하여, Sn이 2질량% 이상 10질량% 이하인 것을 특징으로 하는 반도체 자기 조성물의 전극 재료.
In claim 1,
The electrode material is an electrode material of a semiconductor ceramic composition, characterized in that the total of Silver, Zinc, glass frit, aluminum or boron oxide, and Sn is 100% by mass, and Sn is 2% by mass or more and 10% by mass or less.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03233805A (en) | 1990-02-08 | 1991-10-17 | Nichicon Corp | Electrode of electronic part |
| KR101289808B1 (en) | 2008-12-12 | 2013-07-26 | 가부시키가이샤 무라타 세이사쿠쇼 | Semiconductor ceramic and positive temperature coefficient thermistor |
| KR101644412B1 (en) | 2013-10-03 | 2016-08-01 | 티디케이가부시기가이샤 | Semiconductor ceramic composition and ptc thermistor |
| JP2022501988A (en) | 2018-09-21 | 2022-01-06 | レカテック オサケユイチア | Linear electric machine |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03233805A (en) | 1990-02-08 | 1991-10-17 | Nichicon Corp | Electrode of electronic part |
| KR101289808B1 (en) | 2008-12-12 | 2013-07-26 | 가부시키가이샤 무라타 세이사쿠쇼 | Semiconductor ceramic and positive temperature coefficient thermistor |
| KR101644412B1 (en) | 2013-10-03 | 2016-08-01 | 티디케이가부시기가이샤 | Semiconductor ceramic composition and ptc thermistor |
| JP2022501988A (en) | 2018-09-21 | 2022-01-06 | レカテック オサケユイチア | Linear electric machine |
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