WO2015060245A1 - Pâte d'argent et dispositif à semi-conducteur utilisant cette dernière et procédé de production pour pâte d'argent - Google Patents

Pâte d'argent et dispositif à semi-conducteur utilisant cette dernière et procédé de production pour pâte d'argent Download PDF

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Publication number
WO2015060245A1
WO2015060245A1 PCT/JP2014/077830 JP2014077830W WO2015060245A1 WO 2015060245 A1 WO2015060245 A1 WO 2015060245A1 JP 2014077830 W JP2014077830 W JP 2014077830W WO 2015060245 A1 WO2015060245 A1 WO 2015060245A1
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Prior art keywords
silver
silver particles
silver paste
paste
protective agent
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PCT/JP2014/077830
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English (en)
Japanese (ja)
Inventor
石川 大
松本 博
名取 美智子
偉夫 中子
田中 俊明
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日立化成株式会社
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Publication of WO2015060245A1 publication Critical patent/WO2015060245A1/fr

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20Conductive material dispersed in non-conductive organic material
    • H01B1/22Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05Metallic powder characterised by the size or surface area of the particles
    • B22F1/054Nanosized particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05Metallic powder characterised by the size or surface area of the particles
    • B22F1/054Nanosized particles
    • B22F1/056Submicron particles having a size above 100 nm up to 300 nm
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102Metallic powder coated with organic material
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    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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    • H01L24/00Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/27Manufacturing methods
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    • H01L24/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
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    • H01L24/31Structure, shape, material or disposition of the layer connectors after the connecting process
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    • H01L2224/28Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001Core members of the layer connector
    • H01L2224/29099Material
    • H01L2224/29198Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
    • H01L2224/29298Fillers
    • H01L2224/29299Base material
    • H01L2224/293Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/29338Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/29339Silver [Ag] as principal constituent
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    • H01L2224/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321Disposition
    • H01L2224/32151Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32245Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
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    • H01L2224/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42Wire connectors; Manufacturing methods related thereto
    • H01L2224/47Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805Shape
    • H01L2224/4809Loop shape
    • H01L2224/48091Arched
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
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    • H01L2224/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42Wire connectors; Manufacturing methods related thereto
    • H01L2224/47Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481Disposition
    • H01L2224/48151Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48247Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
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    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732Location after the connecting process
    • H01L2224/73251Location after the connecting process on different surfaces
    • H01L2224/73265Layer and wire connectors
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    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/838Bonding techniques
    • H01L2224/8384Sintering
    • HELECTRICITY
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    • H01L24/00Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/42Wire connectors; Manufacturing methods related thereto
    • H01L24/47Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L24/48Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
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    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/73Means for bonding being of different types provided for in two or more of groups H01L24/10, H01L24/18, H01L24/26, H01L24/34, H01L24/42, H01L24/50, H01L24/63, H01L24/71
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    • H01L2924/0001Technical content checked by a classifier
    • H01L2924/00014Technical content checked by a classifier the subject-matter covered by the group, the symbol of which is combined with the symbol of this group, being disclosed without further technical details
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    • H01L2924/00Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10Details of semiconductor or other solid state devices to be connected
    • H01L2924/11Device type
    • H01L2924/12Passive devices, e.g. 2 terminal devices
    • H01L2924/1204Optical Diode
    • H01L2924/12041LED
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    • H01ELECTRIC ELEMENTS
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    • H01L2924/15Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/151Die mounting substrate
    • H01L2924/156Material
    • H01L2924/157Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2924/15738Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950 C and less than 1550 C
    • H01L2924/15747Copper [Cu] as principal constituent
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    • H01L2924/15Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181Encapsulation

Definitions

  • the semiconductor element is die-bonded and bonded by heat curing to obtain a semiconductor device.
  • a method is mentioned.
  • the characteristics required for the silver paste are broadly classified into the contents relating to the construction method at the time of bonding and the contents relating to the physical properties of the silver sintered body after bonding.
  • the silver particles having a particle diameter of 1 ⁇ m to 20 ⁇ m are desirably plate-like silver particles or a mixture of plate-like silver particles and spherical silver particles.
  • the present invention is also a method for producing a silver paste, wherein a silver paste is obtained by mixing silver particles and a solvent, wherein the silver particles have a particle diameter of 1 ⁇ m to 20 ⁇ m and a boiling point under atmospheric pressure.
  • a method for producing a silver paste using silver particles coated with a protective agent having a temperature of less than 130 ° C. and having a particle diameter of 1 nm to 300 nm.
  • 4 is a TG-DTA measurement result of the silver nanoparticles of Comparative Example 1.
  • 4 is a SEM photograph of a connection cross section of a semiconductor member of Comparative Example 1.
  • 4 is a SEM photograph of a connection cross section of a semiconductor member of Comparative Example 2.
  • 10 is a SEM photograph of a connection cross section of a semiconductor member of Comparative Example 3.
  • the silver paste according to this embodiment is a silver paste containing silver particles and a solvent, and the silver particles are silver particles having a particle diameter of 1 ⁇ m to 20 ⁇ m, and a protective material having a boiling point of less than 130 ° C. under atmospheric pressure. And silver particles having a particle diameter of 1 nm to 300 nm coated with an agent.
  • the silver particles used in the present embodiment are particles coated with silver particles having a particle diameter of 1 ⁇ m to 20 ⁇ m (hereinafter “silver microparticles”) and a protective agent having a boiling point of less than 130 ° C. under atmospheric pressure. Silver particles having a diameter of 1 nm to 300 nm (hereinafter “silver nanoparticles”).
  • the shape of the silver microparticle and the silver nanoparticle is not particularly limited, and a shape that increases the filling property when the silver microparticle and the silver nanoparticle are mixed may be used as appropriate.
  • plate-like silver particles, spherical silver particles, a mixture thereof, and the like can be used as appropriate.
  • a silver microparticle and a silver nanoparticle both a single crystal and a polycrystal can be used.
  • the desorption temperature of the protective agent for silver microparticles and silver nanoparticles is preferably 300 ° C. or lower, and 250 ° C. The following is more desirable.
  • the protective agent for silver nanoparticles is an organic compound having a boiling point of less than 130 ° C., desirably an organic compound having a boiling point of 120 ° C. or less, more desirably an organic compound having a boiling point of 110 ° C. or less.
  • the lower limit of the boiling point of the protective agent is not particularly limited, but is, for example, 70 ° C. or higher.
  • the boiling point in this specification means the boiling point under atmospheric pressure (1013 hPa).
  • the mass ratio can be obtained from the mass change before and after the measurement by heating the silver nanoparticles or silver microparticles to a temperature at which the desorption of the protective agent is sufficiently performed.
  • Example 1 silver nanoparticles coated with N, N-dimethylethylenediamine (Tokyo Chemical Industry Co., Ltd., boiling point 107 ° C.) as a protective agent, and silver microparticles (AgC239 (AgC239) coated with dodecanoic acid as a protective agent Fukuda Metal Foil Co., Ltd.)) is used in combination.
  • TG-DTA measurement results of silver nanoparticles and silver microparticles are shown in FIGS. 1 and 2, respectively.
  • FIG. 1 shows that N, N-dimethylethylenediamine on the surface of the silver nanoparticles is desorbed at about 225.degree.
  • FIG. 2 shows that dodecanoic acid on the surface of the silver microparticles is desorbed at about 250 ° C.
  • FIG. 3 shows the results of TG-DTA measurement of a silver paste prepared by mixing these silver particles.
  • the temperature at which the desorption of the organic substance from the silver paste is completed is about 250 ° C., and the weight loss is about 9.5% by weight.
  • the desorption temperature of the organic substance in TG-DTA measurement is 250 ° C., but if it is heated to some degree even at about 200 ° C., the same weight loss (9.5% by weight) as when heated at 250 ° C. is obtained.
  • the silver paste of Example 1 can be sintered at about 200 ° C. with the organic matter completely removed. Also, since the difference in desorption temperature between the protective agent for silver nanoparticles and the protective agent for silver microparticles is as small as 25 ° C., the silver nanoparticles and the silver microparticles can be sintered almost simultaneously, and a dense silver sintered body Can be formed. As a result, the characteristics (die shear strength, volume resistivity and thermal conductivity) of the silver sintered body are also good.
  • the solvent in this embodiment is not particularly limited as long as it is liquid at normal temperature (20 ° C.), and a known solvent can be used.
  • Solvents can be selected from alcohols, aldehydes, carboxylic acids, ethers, esters, amines, monosaccharides, polysaccharides, linear hydrocarbons, fatty acids, aromatics, etc. It is also possible to use a combination of a plurality of the above solvents.
  • the boiling point of the solvent is not particularly limited, but is preferably 100 ° C to 350 ° C, more preferably 130 ° C to 300 ° C, and further preferably 150 ° C to 250 ° C.
  • the boiling point of the solvent is 100 ° C. or higher, it is possible to prevent the solvent from volatilizing at room temperature when the silver paste is used, and as a result, it is possible to ensure the viscosity stability, applicability, and the like of the silver paste.
  • the boiling point of the solvent is 350 ° C. or less, it is possible to suppress the solvent from being evaporated in the silver sintered body at a temperature at which the semiconductor element is connected to the support member. The characteristics can be kept better.
  • silver nanoparticles, silver microparticles, and a solvent are collectively or divided into a stirrer, a separator, What is necessary is just to combine dispersion
  • the method for heating and sintering the silver paste a known method can be used. In addition to external heating by a heater, an ultraviolet lamp, laser, microwave, or the like can be suitably used.
  • the heating temperature of the silver paste is preferably equal to or higher than the temperature at which the protective agent, solvent and additive are desorbed from the system. Specifically, the range of the heating temperature is desirably 150 ° C. or more and 300 ° C. or less, and more desirably 150 ° C. or more and 250 ° C. or less.
  • a general semiconductor member is connected by setting the heating temperature to 300 ° C. or lower, damage to the member can be avoided, and by setting the heating temperature to 150 ° C. or higher, Desorption is likely to occur.
  • the process for heating the silver paste can be appropriately determined.
  • sintering is performed at a temperature exceeding the boiling point of the solvent, pre-heating at a temperature lower than the boiling point of the solvent, and after performing the sintering after volatilizing the solvent to some extent, a denser silver sintered body Easy to get.
  • the rate of temperature increase when heating the silver paste is not particularly limited when sintering is performed below the boiling point of the solvent. In the case of sintering at a temperature exceeding the boiling point of the solvent, it is desirable to set the heating rate to 1 ° C./second or less, or to perform a preheating step.
  • AgC239 (Fukuda Metal Foil Co., Ltd.) was used as the silver microparticles.
  • the treatment for coating AgC239 with dodecanoic acid as a protective agent was performed as follows. That is, first, 100 g of AgC239, 10 g of dodecanoic acid (Wako Pure Chemical Industries, Ltd., boiling point 299 ° C.) and 500 mL of 1-propanol (Wako Pure Chemical Industries, Ltd., boiling point 97 ° C.) were added to the eggplant flask. did. The reaction solution was reacted by heating at 60 ° C. for 3 hours while stirring at about 200 rpm with a magnetic stirrer.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Conductive Materials (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Die Bonding (AREA)

Abstract

La présente invention porte sur une pâte d'argent qui est une pâte d'argent qui contient des particules d'argent et un solvant. Les particules d'argent contiennent des particules d'argent ayant un diamètre de particule de 1-20 μm et des particules d'argent ayant un diamètre de particule de 1-300 nm et qui sont recouvertes d'un agent protecteur qui a un point d'ébullition inférieur à 130 °C sous pression atmosphérique.
PCT/JP2014/077830 2013-10-22 2014-10-20 Pâte d'argent et dispositif à semi-conducteur utilisant cette dernière et procédé de production pour pâte d'argent WO2015060245A1 (fr)

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JP2013-219283 2013-10-22
JP2013219283A JP6303392B2 (ja) 2013-10-22 2013-10-22 銀ペースト及びそれを用いた半導体装置、並びに銀ペーストの製造方法

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018055848A1 (fr) * 2016-09-21 2018-03-29 矢崎総業株式会社 Pâte électriquement conductrice et tableau de connexions l'utilisant
CN110213883A (zh) * 2019-06-28 2019-09-06 智玻蓝新科技(武汉)有限公司 一种玻璃基电路板导电线路制备工艺
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