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WO2023128687A1 - Composition d'alliage de nickel pour couche de liaison au cuivre pour substrat de nitrure lié au cuivre - Google Patents

Composition d'alliage de nickel pour couche de liaison au cuivre pour substrat de nitrure lié au cuivre Download PDF

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Publication number
WO2023128687A1
WO2023128687A1 PCT/KR2022/021694 KR2022021694W WO2023128687A1 WO 2023128687 A1 WO2023128687 A1 WO 2023128687A1 KR 2022021694 W KR2022021694 W KR 2022021694W WO 2023128687 A1 WO2023128687 A1 WO 2023128687A1
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WIPO (PCT)
Prior art keywords
copper
layer
nitride substrate
substrate
bonded
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2022/021694
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English (en)
Korean (ko)
Inventor
배진원
김건호
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Cuprum Materials Corp
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Cuprum Materials Corp
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Filing date
Publication date
Priority claimed from KR1020220189272A external-priority patent/KR102606192B1/ko
Application filed by Cuprum Materials Corp filed Critical Cuprum Materials Corp
Priority to CN202280086499.5A priority Critical patent/CN118574800A/zh
Publication of WO2023128687A1 publication Critical patent/WO2023128687A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
    • C04B37/02—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/88—Metals

Definitions

  • the present application relates to a nitride substrate such as AlN, Si 3 N 4 to which a copper layer is bonded, and more particularly, to a composition of a copper bonding layer formed to increase bonding strength and thermoelectric properties between a nitride substrate and a copper layer, and a laminated substrate , It relates to a manufacturing method of the substrate.
  • Circuit substrates used in power modules, etc. are made of alumina, zirconium toughened alumina, silicon nitride (Si 3 N 4 ), and aluminum nitride (AlN) for reasons such as thermal conductivity, cost, and safety. Ceramic substrates such as these are mainly used. These ceramic substrates are used as circuit boards by bonding metal circuit boards or heat sinks such as copper or aluminum. These are used as substrates for mounting electronic components with high heat dissipation due to their excellent insulating properties and heat dissipation properties with respect to resin substrates or metal substrates using a resin layer as an insulating material.
  • a ceramic circuit board in which a metal circuit board is bonded to the surface of a ceramic substrate with an active metal solder material and a semiconductor element is mounted at a predetermined position on the metal circuit board is used.
  • a ceramic substrate of an aluminum nitride sintered body or a silicon nitride sintered body having high thermal conductivity has been used in response to an increase in the amount of heat generated from the semiconductor device due to high integration, high frequency, and high output of the semiconductor device.
  • the aluminum nitride substrate has high thermal conductivity but low mechanical strength or toughness, it has a disadvantage in that cracks are easily generated when cracks occur due to tightening in an assembly process or when a thermal cycle is added.
  • power modules applied under severe load and thermal conditions such as automobiles, electric railways, machine tools, and robots, these disadvantages become remarkable.
  • silicon nitride substrates have lower thermal conductivity than AlN but have high durability, so high durability is required for electric vehicles and the like, and are suitable as ceramic circuit boards for mounting electronic components with high heat dissipation.
  • a ceramic circuit board using such a nitride ceramic substrate is produced by an active metal bonding (AMB) method.
  • AMB active metal bonding
  • Such an active metal method is a method of bonding a metal plate on a ceramic substrate through a solder material layer containing an active metal such as a group 4A element or a group 5A element.
  • a silver-copper-titanium solder material is applied to the silicon nitride substrate
  • the main surface is screen-printed, a metal circuit board and a metal heat sink are placed on the printed surface, and the ceramic substrate and the metal plate are bonded by heat treatment at an appropriate temperature.
  • a surface conductor layer In order to use the sintered nitride ceramics as a substrate for semiconductors, a surface conductor layer must be formed and wired.
  • Methods for forming this surface conductor layer include an active metal method in which a copper plate or the like is integrally joined as a conductor layer using an active metal to a sintered substrate, or a conductor on a ceramic substrate using a printing paste containing copper and glass frit.
  • There is a paste sintering method in which a pattern is formed and fired at a high temperature to form a substrate and a conductor layer.
  • the paste sintering method in which metal powder particles are fired at high temperatures, is being studied in order to expand its use, but it has disadvantages in bonding strength and electrical resistance (conductivity) and needs improvement.
  • a plate or paste with an AgCuTiSn composition was used with a thickness of 10um as AMB (active metal bonding).
  • AMB active metal bonding
  • Ag-containing The material cost of the AMB plate is high, and the process cost is cheap in the case of AMB paste, but the organic solvent evaporates at a high temperature and voids between the copper and the active layer frequently occur, which reduces durability and yield.
  • titanium used among active metals forms TiO2, which is titanium oxide, in AlN, which is effective for interfacial bonding, but it is difficult to form TiO 2 in Si 3 N 4 and has a disadvantage in that bonding properties are poor.
  • the diffusion bonding method which primarily forms IMC (intermetallic compound) at the interface between copper and ceramic substrate at high temperature and performs a heat treatment process, has excellent interfacial bonding properties.
  • IMC intermetallic compound
  • diffusion bonding is possible for a copper-bonded AlN substrate bonded by CuO generated at the Cu/AlN interface, but in the case of a Si 3 N 4 substrate in which CuO is not formed, it is difficult to manufacture a copper-bonded ceramic substrate having excellent bonding strength.
  • the inventors of the present invention formed a thin sputter layer with improved bonding strength and thermoelectric properties at the interface so that bonding strength between the Si 3 N 4 substrate and the copper layer on the substrate is improved, thereby forming a copper-bonded silicon nitride substrate having excellent thermal durability.
  • a nickel alloy composition for a copper bonding layer for a Si 3 N 4 substrate, a laminated substrate, and a method for manufacturing the substrate were developed.
  • Patent Document 0001 Korea Patent Registration No. 10-2339805
  • a composition of a copper bonding layer formed to increase the bonding strength and thermoelectric properties between the nitride substrate and the copper layer, a laminated substrate, and the substrate It is an object to provide a manufacturing method of.
  • a first aspect of the present application provides a copper bonding layer nickel alloy composition for a copper bonding nitride substrate.
  • a second aspect of the present application provides a method for manufacturing a copper bonded nitride substrate.
  • a third aspect of the present application provides a copper bonded nitride laminated board.
  • a copper bonding nitride substrate having improved bonding strength may be manufactured by forming an alloy metal layer between the nitride and the copper layer.
  • FIG. 1 is a diagram showing the structure of a test specimen of the present invention.
  • FIG. 2 is a flowchart illustrating a heat dissipation substrate manufacturing process applied to a power semiconductor and a driving semiconductor for a vehicle.
  • FIG. 3 is a diagram showing a high-temperature and low-temperature rising rate and temperature holding time for a thermal shock test prior to evaluating the bondability of a copper-bonded ceramic substrate manufactured according to the present invention.
  • FIG. 4 is a view showing photographs of a copper-bonded silicon nitride substrate on which micropatterns are formed using the nickel-chrome bonding layer of the present application before and after a thermal shock test.
  • FIG. 5 is a view showing photographs of test samples of cylinder and square pillar patterns manufactured by the manufacturing method of the present invention for interfacial bonding force test of copper bonded nitride substrates.
  • FIG. 6 is a view showing the results of confirming the bonding force with the Si 3 N 4 substrate, the thermal conductivity, and the etching characteristics in the copper etchant according to the composition of the NiCr binary copper underlayer (copper bonding layer).
  • FIG. 7 is a view showing the result of confirming the bonding force for each condition of FIG. 6 using a die shear device.
  • FIG. 8 is a diagram showing the results of measuring the thermal conductivity of each sample to determine the thermal conductivity of copper formed on a ceramic substrate.
  • the term “combination(s) of these” included in the expression of the Markush form means a mixture or combination of one or more selected from the group consisting of the components described in the expression of the Markush form, It means including one or more selected from the group consisting of the above components.
  • a first aspect of the present application provides a copper underlayer nickel alloy composition for a copper junction nitride substrate.
  • the copper underlayer nickel alloy composition for a copper-bonded nitride substrate of the present application may form a thin film deposited by sputtering capable of improving bonding strength and thermoelectric characteristics at an interface.
  • copper junction layer used throughout the present specification is a thin film deposited by a sputtering method, and refers to a film (copper lower film) positioned below the copper layer in the laminated substrate structure of the present application.
  • Nickel alloy which is the copper bonding layer, may be raised by various methods such as electrolysis, electroless plating, chemical vapor deposition, and evaporation in addition to sputtering.
  • sputtering used throughout the present specification means that particles with high energy collide with the surface of a target material (metal) to transfer energy to target atoms on the surface, and the target atoms are emitted. tell how to deposit
  • the sputtering (sputtering) deposited thin film (copper bonding layer) of the present application can be improved bonding strength between the upper copper and the lower substrate by containing Ni as a main component and a small amount of Cr.
  • the composition of the Ni-Cr alloy may be 95 wt % to 70 wt % of Ni and 5 wt % to 30 wt % of Cr.
  • the bonding strength is increased by 300% or more compared to when pure copper is used alone.
  • CuO 0.3 ⁇ m crystal sizes
  • CuO 0.3 ⁇ m crystal sizes
  • a second aspect of the present application provides a method for manufacturing a copper bonded nitride substrate. Content overlapping with the first aspect is also applied to the manufacturing method of the second aspect.
  • the present application includes forming a curve on the surface of a nitride substrate; Depositing a copper bonding layer (Tie-coat layer) on the nitride substrate by a sputtering method; depositing copper (Cu) on the copper junction layer to form a copper seed layer; forming a patterned mask on the copper seed layer; Performing electrolytic plating using a high speed copper plating bath; and removing a tie-coat layer and a copper seed layer through an etching process (see FIG. 2 ).
  • the nitride substrate may include AlN or Si 3 N 4 but is not limited thereto.
  • the contact area between the substrate and the adhesive layer increases, thereby improving the adhesion of the substrate.
  • the depositing of the copper bonding layer may be performed using the composition of the first aspect, but is not limited thereto.
  • the depositing of the copper junction layer may be depositing a copper junction layer to a thickness of 1 nm to 60 nm, preferably 5 nm to 50 nm.
  • the step of forming the copper seed layer may be depositing a copper seed layer thickness of 200 nm to 600 nm, preferably 300 nm to 500 nm.
  • a third aspect of the present application provides a copper bonded nitride laminated board. Contents overlapping with those of the first and second sides are also applied to the substrate of the third side.
  • the laminated substrate of the present application is a nitride substrate; a copper bonding layer laminated on a nitride substrate by a sputtering method using the composition of the first side; and a copper layer formed on the copper bonding layer, but is not limited thereto.
  • the nitride substrate may include AlN or Si 3 N 4 but is not limited thereto.
  • Example 3 showed a higher bonding strength than Example 2. That is, as the content of chromium in the nickel-chromium alloy increased, the bonding strength was improved. On the other hand, when the chromium content was excessively high, such as 40 wt%, as in Comparative Example 2, the bonding strength was rather deteriorated. , it was found that the thermal stress due to the difference in the thermal expansion coefficient of copper was generated at the interface and the bonding strength at the interface was deteriorated. As in Comparative Example 3, when only copper was loaded without an interlayer bonding material, the interfacial bonding force was measured to be very weak compared to the sample with a nickel-chromium alloy bonding material. When the number of thermal shocks increased more than 50 times, some test patterns were lost.
  • thermal conductivity of copper formed on a ceramic substrate was measured at 25 °C and 180 °C using Laser Flash Apparatus equipment from NETZCH.
  • the thermal conductivity tended to decrease when the chromium content increased.
  • the value was 130 W/m.k or less at room temperature.
  • etching property is one of the important process factors in a copper etchant.
  • an etching test was performed on the Si 3 N 4 substrate/copper bonding layer/copper specimen using a ferric chloride (FeCl 3 ) etchant. The etching test was performed by depositing about 10 to 50 nm of copper bonding composition on a ceramic substrate through a sputtering process, forming a 1000 nm copper layer thereon, forming a pattern, and then using a spray etching method.
  • Thermal conductivity was marked as O when it was 130 W/m*K or more at room temperature (acceptable), and X when it was less than 130 W/m*K (unsuitable).
  • etching property (etching rate) was 20 A/sec or more, it was marked as O (suitable), and when it was less than 20 A/sec, it was marked as X (unsuitable).
  • NiCr when Ni exceeds 95 wt % in the composition of the Ni-Cr alloy (Cr is less than 5 wt %), bonding strength and thermal conductivity are significantly reduced, while Ni is less than 70 wt % (Cr is less than 5 wt %). When it exceeds 30 wt %), it was confirmed that bonding strength, thermal conductivity, and etching properties are all deteriorated (see FIG. 6).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un substrat de nitrure tel que l'AlN et le Si3N4 auquel est liée une couche de cuivre et, plus spécifiquement, une composition pour une couche de liaison au cuivre, un substrat stratifié et un procédé de fabrication du substrat, la composition améliorant la résistance de liaison et les propriétés thermoélectriques entre le substrat de nitrure et la couche de cuivre. En utilisant la composition d'alliage de nickel pour une couche de liaison au cuivre pour un substrat de nitrure lié au cuivre selon la présente invention, un substrat de nitrure lié au cuivre ayant une force de liaison améliorée peut être fabriqué par formation d'une couche métallique d'alliage entre un nitrure et une couche de cuivre.
PCT/KR2022/021694 2021-12-30 2022-12-30 Composition d'alliage de nickel pour couche de liaison au cuivre pour substrat de nitrure lié au cuivre Ceased WO2023128687A1 (fr)

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Application Number Priority Date Filing Date Title
CN202280086499.5A CN118574800A (zh) 2021-12-30 2022-12-30 铜接合氮化物基板用铜接合层镍合金组合物

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KR20210192899 2021-12-30
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KR10-2022-0189272 2022-12-29
KR1020220189272A KR102606192B1 (ko) 2021-12-30 2022-12-29 구리 접합 질화물 기판용 구리 접합층 니켈 합금 조성물

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100891346B1 (ko) * 2007-06-19 2009-04-01 주식회사 나디스 프로브 카드 및 그 제조방법
KR20090113995A (ko) * 2008-04-29 2009-11-03 주식회사 피앤아이 금속 촉매층 및 금속 시드층을 포함하는 전해도금용 기판,및 이를 이용한 인쇄회로기판의 제조 방법
KR101199816B1 (ko) * 2007-12-27 2012-11-12 제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤 2 층 동장 적층판의 제조 방법 및 2 층 동장 적층판
KR20130078280A (ko) * 2011-12-30 2013-07-10 삼성전자주식회사 질화물계 반도체 소자 및 그 제조 방법
KR20170133996A (ko) * 2016-05-27 2017-12-06 엘지이노텍 주식회사 인쇄회로기판 및 이의 제조 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100891346B1 (ko) * 2007-06-19 2009-04-01 주식회사 나디스 프로브 카드 및 그 제조방법
KR101199816B1 (ko) * 2007-12-27 2012-11-12 제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤 2 층 동장 적층판의 제조 방법 및 2 층 동장 적층판
KR20090113995A (ko) * 2008-04-29 2009-11-03 주식회사 피앤아이 금속 촉매층 및 금속 시드층을 포함하는 전해도금용 기판,및 이를 이용한 인쇄회로기판의 제조 방법
KR20130078280A (ko) * 2011-12-30 2013-07-10 삼성전자주식회사 질화물계 반도체 소자 및 그 제조 방법
KR20170133996A (ko) * 2016-05-27 2017-12-06 엘지이노텍 주식회사 인쇄회로기판 및 이의 제조 방법

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PETEVES, S.D.: "Joining Nitride Ceramics", CERAMICS INTERNATIONAL, ELSEVIER, AMSTERDAM., NL, vol. 22, no. 6, 1 January 1996 (1996-01-01), NL , pages 527 - 533, XP004040629, ISSN: 0272-8842, DOI: 10.1016/0272-8842(95)00134-4 *

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