JP2002274964A - Method of manufacturing joined body - Google Patents
Method of manufacturing joined bodyInfo
- Publication number
- JP2002274964A JP2002274964A JP2001069822A JP2001069822A JP2002274964A JP 2002274964 A JP2002274964 A JP 2002274964A JP 2001069822 A JP2001069822 A JP 2001069822A JP 2001069822 A JP2001069822 A JP 2001069822A JP 2002274964 A JP2002274964 A JP 2002274964A
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- Prior art keywords
- copper
- ceramic body
- copper plate
- bonding
- temperature
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、パワーモジュール
に使用される回路基板の製造に好適なセラミック体と銅
板との接合体の製造方法に関する。The present invention relates to a method for manufacturing a joined body of a ceramic body and a copper plate suitable for manufacturing a circuit board used for a power module.
【０００２】[0002]
【従来の技術】近年、ロボット・モーター等の産業機器
の高性能化にともない、大電力・高効率インバーター等
大電力モジュールの変遷が進み、半導体素子から発生す
る熱も増加の一途をたどっている。この熱を効率よく放
散させるため、大電力モジュール基板では、良好な熱伝
導を有する窒化アルミニウム又は窒化珪素を主体とする
セラミック体（以下、「窒化アルミニウム等基板」とい
う。」）とその表裏両面に銅板を接合し、エッチングに
よって一方の面に銅回路、他方の面に放熱銅板を形成さ
せた後、そのままあるいはメッキ等の処理を施して回路
基板となし、その銅回路部分に半導体素子を実装すると
ともに、反対面をベース銅板と半田付けしてからヒート
シンクに取り付けて使用されている。2. Description of the Related Art In recent years, high-performance modules such as high-power and high-efficiency inverters have been transitioning with the advancement of industrial equipment such as robots and motors, and the heat generated from semiconductor elements has been increasing steadily. . In order to efficiently dissipate this heat, in a high power module substrate, a ceramic body mainly composed of aluminum nitride or silicon nitride having good thermal conductivity (hereinafter, referred to as “aluminum nitride substrate”) and its front and back surfaces are used. After joining a copper plate and forming a copper circuit on one side and a heat-dissipating copper plate on the other side by etching, it is processed as it is or by plating, etc. to form a circuit board, and a semiconductor element is mounted on the copper circuit portion At the same time, the opposite surface is soldered to a base copper plate and then attached to a heat sink.
【０００３】[0003]
【発明が解決しようとする課題】当該分野における今日
の課題は、これまでと同等又はそれ以上の高信頼性回路
基板を低コストで製造することである。The present problem in the art is to produce, at low cost, a reliable circuit board that is as good or better than before.
【０００４】本発明の目的は、上記課題を解決すること
であり、高信頼性回路基板を低コストで製造することで
ある。本発明の目的は、回路基板の製造工程において最
も設備等のコストがかかる接合工程の改善、特に上記接
合体の製造を活性金属ろう付け法を用いる高真空雰囲気
下の熱処理から活性金属ろ付け法による窒素雰囲気下の
焼成に変更し、諸条件を適正化することによって達成さ
せることができる。An object of the present invention is to solve the above-mentioned problems, and to manufacture a highly reliable circuit board at low cost. SUMMARY OF THE INVENTION An object of the present invention is to improve the joining process which requires the most equipment and the like in the circuit board manufacturing process. Can be achieved by changing to baking in a nitrogen atmosphere by the above method and optimizing various conditions.
【０００５】[0005]
【課題を解決するための手段】すなわち、本発明は、窒
化アルミニウム又は窒化珪素を主体とするセラミック体
と銅板とを、銀４０〜６４％、銅１２〜２８％、錫１２
〜２２％、ジルコニウム８〜１６％（金属成分の合計が
１００％）を含むろう材を介して積層し、それを１．０
ＭＰａ以上の圧力で加圧しつつ、酸素濃度１〜１００ｐ
ｐｍの窒素雰囲気中、温度７５０〜８５０℃で０．５〜
２時間保持した後、冷却する方法であって、しかも７５
０℃までの昇温速度と７５０℃からの降温速度をいずれ
も３００℃／時以上とすることを特徴とする接合体の製
造方法である。That is, according to the present invention, a ceramic body mainly composed of aluminum nitride or silicon nitride and a copper plate are made of 40 to 64% of silver, 12 to 28% of copper, and 12 to 28% of tin.
-22% and zirconium 8-16% (total of metal components is 100%) through a brazing filler metal,
Oxygen concentration of 1-100p
pm in a nitrogen atmosphere at a temperature of 750 to 850 ° C.
After holding for 2 hours, it is a method of cooling
A method for manufacturing a joined body, wherein a rate of temperature rise to 0 ° C. and a rate of temperature decrease from 750 ° C. are both 300 ° C./hour or more.
【０００６】[0006]
【発明の実施の形態】以下、更に詳しく本発明を説明す
ると、本発明の特徴は、ろう材の金属成分割合、加圧接
合、接合雰囲気及び接合時間の各条件を適正化したこと
にある。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. The feature of the present invention is that the conditions of the metal component ratio of the brazing material, pressure bonding, bonding atmosphere and bonding time are optimized.
【０００７】本発明で用いられるろう材において、金属
成分の合計中、銀が４０％未満となると、銅と錫の金属
間化合物の生成量が増大して接合層が脆弱なものとな
り、機械的強度の信頼性が大きく低下する。また、６４
％を超えると、ろう材の銅板に対する濡れ性が低下し、
接合層中にボイドが形成されて接合強度が低下する。In the brazing filler metal used in the present invention, if silver is less than 40% of the total metal components, the amount of intermetallic compound of copper and tin increases and the bonding layer becomes brittle, and the Strength reliability is greatly reduced. Also, 64
%, The wettability of the brazing material to the copper plate decreases,
Voids are formed in the bonding layer to lower the bonding strength.
【０００８】銅が１２％未満ではろう材の融点が著しく
上がり、ろう材の濡れ性が悪くなる。２８％を超える
と、銅と錫の金属間化合物の生成量が増大して接合層が
脆弱なものとなり、機械的強度の信頼性が大きく低下す
る。[0008] When the content of copper is less than 12%, the melting point of the brazing material is significantly increased, and the wettability of the brazing material is deteriorated. If it exceeds 28%, the amount of the intermetallic compound of copper and tin increases, the bonding layer becomes brittle, and the reliability of mechanical strength is greatly reduced.
【０００９】錫が１２％未満であると、ろう材が酸化さ
れやすくなり、ろう材の融点が上昇し、接合温度を高め
なければならぬとともに、接合層にボイドが形成されて
接合強度が大きく低下する。また、２２％を超えると、
銅と錫の金属間化合物の生成量が増大して接合層が脆弱
なものとなり、機械的強度の信頼性が大きく低下する。If the tin content is less than 12%, the brazing filler metal is easily oxidized, the melting point of the brazing filler metal rises, the joining temperature must be raised, and voids are formed in the joining layer to increase the joining strength. descend. Also, if it exceeds 22%,
The production amount of the intermetallic compound of copper and tin increases, the bonding layer becomes brittle, and the reliability of mechanical strength is greatly reduced.
【００１０】活性金属としては、ジルコニウムを選択す
る。ジルコニウムが８％未満では、セラミック体と接合
層との接合強度が弱く、また１６％を超えると、接合層
が脆弱なものとなり、機械的強度の信頼性が低下する。As the active metal, zirconium is selected. If the zirconium content is less than 8%, the bonding strength between the ceramic body and the bonding layer is weak, and if it exceeds 16%, the bonding layer becomes brittle and the reliability of the mechanical strength decreases.
【００１１】本発明において、ジルコニウム成分はセラ
ミック体に拡散し、錫成分は銀成分と銅成分の銅板に対
する濡れ性を改善する結果、高真空下の焼成でなくても
酸素の極微量を含む窒素雰囲気下の焼成によって、セラ
ミック体と銅板とが強固に接合する。In the present invention, the zirconium component diffuses into the ceramic body, and the tin component improves the wettability of the silver component and the copper component on the copper plate. By firing in an atmosphere, the ceramic body and the copper plate are firmly joined.
【００１２】ろう材の金属成分は、それら単体又は合金
の箔や粉末をそのまま用いることができるが、好ましく
はペーストを調合し、それをセラミック体と銅板との間
に介在させて熱処理することである。ペースト調合の一
例を示せば、金属成分１００部あたり、ポリイソブチル
メタアクリレート（ＰＩＢＭＡ）等の媒体４〜１０部で
ある。ペーストの塗布量は、乾燥基準で９〜１０ｍｇ／
ｍ2 とすることが好ましい。ペーストはセラミック体及
び／又は銅板に塗布される。As the metal component of the brazing material, a foil or powder of such a simple substance or an alloy can be used as it is. Preferably, a paste is prepared, and the mixture is heat-treated by being interposed between a ceramic body and a copper plate. is there. An example of the paste formulation is 4 to 10 parts of a medium such as polyisobutyl methacrylate (PIBMA) per 100 parts of the metal component. The application amount of the paste is 9 to 10 mg / dry basis.
m 2 is preferable. The paste is applied to a ceramic body and / or a copper plate.
【００１３】ろう材を挟んだセラミック体と銅板の積層
体は、圧力１．０ＭＰａ以上で加圧しつつ焼成される。
１．０ＭＰａ未満であると、ろう材が雰囲気に曝される
隙間が大きくなるため、接合が不十分となる。加圧力の
上限には限定はないが、２ＭＰａ程度で十分である。The laminate of the ceramic body and the copper plate sandwiching the brazing material is fired while applying a pressure of 1.0 MPa or more.
If it is less than 1.0 MPa, the gap where the brazing material is exposed to the atmosphere becomes large, so that the bonding becomes insufficient. The upper limit of the pressing force is not limited, but about 2 MPa is sufficient.
【００１４】積層体の接合雰囲気は、酸素濃度１〜１０
０ｐｐｍの窒素雰囲気である。酸素濃度が１００ｐｐｍ
を超えると、ろう材が酸化され、接合が不十分となる。
また、酸素濃度１ｐｐｍ未満では、ろう材の濡れ性が極
端に良くなり、温度制御が困難となるため好ましくな
い。また、装置が大がかりなものとなるので製品コスト
が十分に下がらない。The bonding atmosphere of the laminated body has an oxygen concentration of 1 to 10
It is a nitrogen atmosphere of 0 ppm. Oxygen concentration is 100ppm
Exceeding the limit will result in oxidation of the brazing material and insufficient bonding.
On the other hand, when the oxygen concentration is less than 1 ppm, the wettability of the brazing material is extremely improved, and the temperature control becomes difficult. In addition, the cost of the product is not sufficiently reduced because the device becomes large-scale.
【００１５】接合は、温度７５０〜８５０℃で０．５〜
２時間保持して行われる。７５０℃未満では接合が十分
でなく、また８５０℃を超えると、銀や錫の銅板への拡
散が過度となり、接合層が脆弱なものとなる。この温度
範囲における保持時間が０．５時間よりも短いと接合が
不十分となり、また２時間よりも長くなると、同様に銀
や錫の銅板への拡散が過度となり、接合層が脆弱なもの
となる。The bonding is performed at a temperature of 750-850 ° C. for 0.5-
Hold for 2 hours. If the temperature is lower than 750 ° C., the bonding is not sufficient, and if the temperature exceeds 850 ° C., the diffusion of silver or tin into the copper plate becomes excessive, and the bonding layer becomes brittle. If the holding time in this temperature range is shorter than 0.5 hour, the bonding becomes insufficient, and if it is longer than 2 hours, the diffusion of silver or tin into the copper plate becomes excessive, and the bonding layer becomes fragile. Become.
【００１６】本発明においては、昇温開始から７５０℃
までの昇温速度と、７５０℃から室温等の取り出し温度
までの冷却速度も重要であり、いずれも３００℃／時間
以上とする。昇温速度が３００℃／時間未満の速度であ
ると、ろう材が酸化されてしまい、接合が不十分とな
る。冷却速度が３００℃／時間未満であると、特に６０
０℃以上の温度範囲ではろう材層中のＡｇやＳｎ等の成
分が銅板側へ拡散し、回路基板の信頼性が低下する。ま
た、６００℃よりも低温域において冷却速度が遅いこと
は生産性の向上につながらない。In the present invention, 750.degree.
The rate of temperature rise up to 750 ° C. and the rate of cooling from 750 ° C. to a take-out temperature such as room temperature are also important. If the rate of temperature rise is less than 300 ° C./hour, the brazing material will be oxidized and bonding will be insufficient. If the cooling rate is less than 300 ° C./hour,
In a temperature range of 0 ° C. or more, components such as Ag and Sn in the brazing material layer diffuse to the copper plate side, and the reliability of the circuit board is reduced. In addition, a slow cooling rate in a lower temperature range than 600 ° C. does not lead to an improvement in productivity.
【００１７】本発明で用いられるセラミック体は、窒化
アルミニウム又は窒化珪素を主体とするものである。窒
化アルミニウムを主体とするものとしては、強度と熱伝
導率純度が４００ＭＰａ以上、１５０Ｗ／ｍＫ以上、９
３％以上であることが好ましく、また窒化珪素を主体と
するものとしては強度と熱伝導率純度が６００ＭＰａ以
上、５０Ｗ／ｍＫ以上、９３％以上であることが好まし
い。これらのセラミック体には、市販品があるのでそれ
を用いることができる。The ceramic body used in the present invention is mainly composed of aluminum nitride or silicon nitride. As a material mainly composed of aluminum nitride, strength and thermal conductivity purity are 400 MPa or more, 150 W / mK or more, 9
It is preferably at least 3%, and for those mainly composed of silicon nitride, the strength and the thermal conductivity purity are preferably at least 600 MPa, at least 50 W / mK, and at least 93%. These ceramic bodies are commercially available and can be used.
【００１８】本発明で用いられる銅板は、無酸素銅板、
特に酸素量が５０ｐｐｍ以下、特に３０ｐｐｍ以下の無
酸素銅板であることが好ましい。The copper plate used in the present invention is an oxygen-free copper plate,
It is particularly preferable that the oxygen-free copper plate has an oxygen content of 50 ppm or less, particularly 30 ppm or less.
【００１９】本発明によって製造される接合体は、接合
層の厚みが８〜１３μｍであることが好ましい。接合層
の厚み８μｍ未満であると接合が不十分となり、また１
３μｍを超えると、銅と錫の金属間化合物の生成量が増
大し、接合層が脆弱なものとなる。接合層の厚みは、ろ
う材厚みによって容易に調節することができる。The joined body produced by the present invention preferably has a joining layer having a thickness of 8 to 13 μm. If the thickness of the bonding layer is less than 8 μm, the bonding becomes insufficient and
If it exceeds 3 μm, the amount of intermetallic compound of copper and tin increases, and the bonding layer becomes brittle. The thickness of the joining layer can be easily adjusted by the thickness of the brazing material.
【００２０】[0020]
【実施例】以下、本発明を実施例、比較例をあげて具体
的に説明する。なお、本明細書に記載の「％」、「部」
はいずれも質量基準である。EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples. In addition, "%", "part" described in this specification
Are based on mass.
【００２１】実施例１〜７ 比較例１〜１５ 銀粉末（１．１μｍ、９９．３％）、銅粉末（１４．１
μｍ、９９．８％）、錫粉末（５．０μｍ、９９．９
％）、ジルコニウム粉末（５．５μｍ、９９．９％）を
表１の割合で配合し、ポリイソブチルメタアクリレート
のテルピネオール溶液を加えて混練し、金属成分７１．
４％を含むろう材ペーストを調製した。Examples 1 to 7 Comparative Examples 1 to 15 Silver powder (1.1 μm, 99.3%), copper powder (14.1)
μm, 99.8%), tin powder (5.0 μm, 99.9)
%) And zirconium powder (5.5 μm, 99.9%) were blended at the ratio shown in Table 1, and a terpineol solution of polyisobutyl methacrylate was added and kneaded to obtain a metal component.
A brazing filler metal paste containing 4% was prepared.
【００２２】このろう材ペーストを窒化アルミニウム基
板（サイズ：６０ｍｍ×３６ｍｍ×０．６５ｍｍ 曲げ
強さ：５００ＭＰａ 熱伝導率：１５５Ｗ／ｍＫ、純度
９５％以上）又は窒化珪素基板（サイズ：５７ｍｍ×３
４ｍｍ×０．６５ｍｍ 曲げ強さ：７００ＭＰａ 熱伝
導率：７０Ｗ／ｍＫ、純度９２％以上）の両面にロール
コーターによって全面に塗布した。その際の塗布量は乾
燥基準で９ｍｇ／ｃｍ 2 である。This brazing material paste is made of aluminum nitride based
Board (size: 60mm × 36mm × 0.65mm bending)
Strength: 500MPa Thermal conductivity: 155W / mK, purity
95% or more) or silicon nitride substrate (size: 57 mm x 3)
4mm × 0.65mm Flexural strength: 700MPa Heat transfer
Conductivity: 70W / mK, purity 92% or more)
The entire surface was coated with a coater. The amount of coating at that time is dry
9mg / cm on a dry basis TwoIt is.
【００２３】つぎに、セラミック体の銅回路形成面に５
６ｍｍ×３２ｍｍ×０．３ｍｍの無酸素銅板（酸素量：
１０ｐｐｍ）を、また放熱銅板形成面に５６ｍｍ×３２
ｍｍ×０．１５ｍｍの無酸素銅板（酸素量：１０ｐｐ
ｍ）を接触配置してから、表１に示す接合条件で接合し
た。そして、銅回路形成面には所定形状の回路パターン
を、放熱銅板形成面に放熱板パターンを形成させるよう
に、レジストインクをスクリーン印刷してから銅板と接
合層のエッチングを行い、無電解Ｎｉ−Ｐメッキ（厚み
３μｍ）を行って回路基板を作製した。Next, 5
6 mm x 32 mm x 0.3 mm oxygen-free copper plate (oxygen content:
10 ppm) and 56 mm × 32
mm x 0.15mm oxygen-free copper plate (oxygen amount: 10pp
m) was placed in contact and then joined under the joining conditions shown in Table 1. Then, a resist ink is screen-printed so as to form a circuit pattern of a predetermined shape on the copper circuit forming surface and a heat radiating plate pattern on the heat radiating copper plate forming surface, and then the copper plate and the bonding layer are etched to form an electroless Ni- A circuit board was manufactured by performing P plating (thickness: 3 μm).
【００２４】回路基板の接合層の厚み、ピール強度及び
接合特性を以下に従って測定し、表１に示した。The thickness, peel strength and bonding characteristics of the bonding layer of the circuit board were measured according to the following, and are shown in Table 1.
【００２５】（１）接合層の厚み：回路基板の断面を研
磨後、ＥＰＭＡ装置（日本電子社製「ＪＸＡ８６０
０」）にて測定した。 （２）ピール強度：シンポ工業社製プッシュプルゲージ
「ＤＦＧ−２０ＴＲ」を用いて測定した。 （３）接合特性（ボイド率）：接合層中のボイド（円相
当直径が１．０ｍｍ以上の未接合部分）の面積を超音波
探傷装置（本多電子社製「ＨＡ−７０１」）を用いて測
定し、セラミック体と銅板の接合面積に対する比率を算
出した。(1) Thickness of bonding layer: After polishing the cross section of the circuit board, an EPMA apparatus (“JXA860” manufactured by JEOL Ltd.)
0 "). (2) Peel strength: measured using a push-pull gauge “DFG-20TR” manufactured by Shinpo Kogyo KK (3) Bonding characteristics (void ratio): Using an ultrasonic flaw detector (“HA-701” manufactured by Honda Electronics Co., Ltd.) for the area of voids (unbonded portions having a circle equivalent diameter of 1.0 mm or more) in the bonding layer. The ratio of the ceramic body and the copper plate to the joint area was calculated.
【００２６】[0026]
【表１】 [Table 1]
【００２７】[0027]
【発明の効果】本発明によれば、窒化アルミニウム又は
窒化珪素を主体とするセラミック体と銅板との接合を、
窒素雰囲気下の焼成によって、高真空焼成に匹敵する接
合強度を実現できるので、安価な回路基板の提供が可能
となる。According to the present invention, the joining of a ceramic body mainly composed of aluminum nitride or silicon nitride and a copper plate is performed.
By firing in a nitrogen atmosphere, bonding strength equivalent to high vacuum firing can be realized, so that an inexpensive circuit board can be provided.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） // Ｂ２３Ｋ 35/30 ３１０ Ｂ２３Ｋ 35/30 ３１０Ｂ Ｈ０５Ｋ 3/38 Ｈ０５Ｋ 3/38 Ｅ Ｂ２３Ｋ 101:42 Ｂ２３Ｋ 101:42 103:12 103:12 Ｆターム(参考） 4G026 BA16 BA17 BB22 BF16 BG02 BG27 BH07 5E343 AA24 BB24 BB55 BB67 DD43 DD76 EE22 ER13 ER37 ER39 GG02 GG20 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) // B23K 35/30 310 B23K 35/30 310B H05K 3/38 H05K 3/38 E B23K 101: 42 B23K 101 : 42 103: 12 103: 12 F term (reference) 4G026 BA16 BA17 BB22 BF16 BG02 BG27 BH07 5E343 AA24 BB24 BB55 BB67 DD43 DD76 EE22 ER13 ER37 ER39 GG02 GG20
Claims (1)
するセラミック体と銅板とを、銀４０〜６４％、銅１２
〜２８％、錫１２〜２２％、ジルコニウム８〜１６％
（金属成分の合計が１００％）を含むろう材を介して積
層し、それを１．０ＭＰａ以上の圧力で加圧しつつ、酸
素濃度１〜１００ｐｐｍの窒素雰囲気中、温度７５０〜
８５０℃で０．５〜２時間保持した後、冷却する方法で
あって、しかも７５０℃までの昇温速度と７５０℃から
の降温速度をいずれも３００℃／時以上とすることを特
徴とする接合体の製造方法。1. A ceramic body mainly composed of aluminum nitride or silicon nitride and a copper plate are made of 40 to 64% of silver and 12% of copper.
~ 28%, tin 12 ~ 22%, zirconium 8 ~ 16%
(A total of 100% of metal components) are laminated via a brazing material, which is pressed at a pressure of 1.0 MPa or more in a nitrogen atmosphere having an oxygen concentration of 1 to 100 ppm and a temperature of 750 to 750.
A method of cooling after holding at 850 ° C. for 0.5 to 2 hours, and wherein the rate of temperature rise to 750 ° C. and the rate of temperature decrease from 750 ° C. are both 300 ° C./hour or more. Manufacturing method of joined body.
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| JP2001069822A JP4674983B2 (en) | 2001-03-13 | 2001-03-13 | Manufacturing method of joined body |
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|---|---|---|---|
| JP2001069822A JP4674983B2 (en) | 2001-03-13 | 2001-03-13 | Manufacturing method of joined body |
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| Publication Number | Publication Date |
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| JP2002274964A true JP2002274964A (en) | 2002-09-25 |
| JP4674983B2 JP4674983B2 (en) | 2011-04-20 |
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ID=18927797
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| Application Number | Title | Priority Date | Filing Date |
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| JP2001069822A Expired - Lifetime JP4674983B2 (en) | 2001-03-13 | 2001-03-13 | Manufacturing method of joined body |
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| JP (1) | JP4674983B2 (en) |
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| JP2005322451A (en) * | 2004-05-06 | 2005-11-17 | Ngk Spark Plug Co Ltd | Ceramic assembly and solid electrolyte form fuel cell using it |
| JP2011037259A (en) * | 2009-08-18 | 2011-02-24 | Shenzhen Futaihong Precision Industrial Co Ltd | Gold inlaying method and housing of electronic device inlaid with gold decoration material by the same method |
| JP2013237100A (en) * | 2012-02-29 | 2013-11-28 | Hitachi Metals Ltd | Method for producing ceramic circuit board, and ceramic circuit board |
| JP2015180600A (en) * | 2012-02-01 | 2015-10-15 | 三菱マテリアル株式会社 | Power module substrate, power module substrate with heat sink, power module, method for manufacturing power module substrate, and paste for bonding copper member |
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| JPH04305073A (en) * | 1991-03-29 | 1992-10-28 | Tanaka Kikinzoku Kogyo Kk | Ceramic bonding brazer |
| JP2001048670A (en) * | 1991-11-29 | 2001-02-20 | Toshiba Corp | Ceramics-metal joined body |
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| JP2005322451A (en) * | 2004-05-06 | 2005-11-17 | Ngk Spark Plug Co Ltd | Ceramic assembly and solid electrolyte form fuel cell using it |
| JP2011037259A (en) * | 2009-08-18 | 2011-02-24 | Shenzhen Futaihong Precision Industrial Co Ltd | Gold inlaying method and housing of electronic device inlaid with gold decoration material by the same method |
| US10375825B2 (en) | 2012-02-01 | 2019-08-06 | Mitsubishi Materials Corporation | Power module substrate, power module substrate with heat sink, power module, method of manufacturing power module substrate, and copper member-bonding paste |
| JP2015180600A (en) * | 2012-02-01 | 2015-10-15 | 三菱マテリアル株式会社 | Power module substrate, power module substrate with heat sink, power module, method for manufacturing power module substrate, and paste for bonding copper member |
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| JP2013237100A (en) * | 2012-02-29 | 2013-11-28 | Hitachi Metals Ltd | Method for producing ceramic circuit board, and ceramic circuit board |
| JP2022003010A (en) * | 2016-07-28 | 2022-01-11 | 株式会社東芝 | Method for producing junction and method for producing circuit board |
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| US11452204B2 (en) | 2017-04-25 | 2022-09-20 | Denka Company Limited | Ceramic circuit board, method for manufacturing ceramic circuit board, and module using ceramic circuit board |
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| WO2022244769A1 (en) * | 2021-05-19 | 2022-11-24 | 株式会社 東芝 | Bonded object production method and production method for ceramic circuit substrate using same |
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