JP6621353B2 - Heat resistant ceramic circuit board - Google Patents
Heat resistant ceramic circuit board Download PDFInfo
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- JP6621353B2 JP6621353B2 JP2016061903A JP2016061903A JP6621353B2 JP 6621353 B2 JP6621353 B2 JP 6621353B2 JP 2016061903 A JP2016061903 A JP 2016061903A JP 2016061903 A JP2016061903 A JP 2016061903A JP 6621353 B2 JP6621353 B2 JP 6621353B2
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- ceramic circuit
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- 239000000919 ceramic Substances 0.000 title claims description 37
- 229910052802 copper Inorganic materials 0.000 claims description 44
- 239000010949 copper Substances 0.000 claims description 44
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 42
- 239000000758 substrate Substances 0.000 claims description 23
- 239000013078 crystal Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 238000005219 brazing Methods 0.000 description 9
- 238000005530 etching Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 230000003746 surface roughness Effects 0.000 description 7
- 230000017525 heat dissipation Effects 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000005304 joining Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- -1 Ammonium halide Chemical class 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001887 electron backscatter diffraction Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
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- Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
Description
本発明は、耐熱性に優れるセラミックス回路基板に関する。 The present invention relates to a ceramic circuit board having excellent heat resistance.
パワーモジュール等に利用される回路用基板として、熱伝導率やコスト、安全性等の点から、アルミナ、窒化ケイ素、窒化アルミニウム等のセラミックス基板が利用されている。これらのセラミックス基板は、両主面にＣｕやＡｌ等の金属回路や放熱板を接合しセラミックス回路基板として用いられる。 As circuit boards used for power modules and the like, ceramic substrates such as alumina, silicon nitride, and aluminum nitride are used from the viewpoint of thermal conductivity, cost, safety, and the like. These ceramic substrates are used as a ceramic circuit substrate by bonding a metal circuit such as Cu or Al or a heat sink to both main surfaces.
近年、省エネルギー化への需要の高まりやエレクトロニクス技術の発展に伴い、パワーモジュールの小型化、高出力化が求められており、従来のＳｉ半導体に変わる材料としてＳｉＣ半導体の開発が進められている。 In recent years, with the increasing demand for energy saving and the development of electronics technology, there has been a demand for miniaturization and high output of power modules, and development of SiC semiconductors as materials replacing conventional Si semiconductors has been promoted.
ＳｉＣ半導体を搭載したパワーモジュールでは、Ｓｉデバイスより高温での動作が可能であり、モジュールを構成する材料には−４０℃〜２５０℃での耐熱サイクル性を要求される。 Power modules equipped with SiC semiconductors can operate at higher temperatures than Si devices, and the materials constituting the modules are required to have heat cycle resistance at -40 ° C to 250 ° C.
−４０℃〜２５０℃の熱サイクルにおいて、セラミックス基板と銅板の熱膨張差に起因する応力歪みが粒界に蓄積し、銅板表面では粒界ずれが発生するため熱サイクルの経過に伴い表面粗さが増加する。 In a thermal cycle of -40 ° C to 250 ° C, stress strain due to the thermal expansion difference between the ceramic substrate and the copper plate accumulates at the grain boundary, and the grain boundary shift occurs on the copper plate surface, so that the surface roughness increases with the progress of the thermal cycle. Will increase.
セラミックス回路基板の銅板の表面粗さが増加すると、ＳｉＣを接合するための半田との接合性が低下し、モジュールが正常に動作しなくなることが懸念されている。 When the surface roughness of the copper plate of the ceramic circuit board is increased, there is a concern that the bondability with the solder for bonding SiC is lowered and the module does not operate normally.
この課題に対し、銅板の厚みを薄くすることで熱サイクルの経過に伴う表面粗さの増加率を抑制することが可能であるが、長期の熱サイクルにおいて表面粗さは増加するため十分に解決されたとは言えない。 To reduce this problem, it is possible to suppress the rate of increase in surface roughness over the course of the thermal cycle by reducing the thickness of the copper plate, but this is a sufficient solution because the surface roughness increases in the long-term thermal cycle. It cannot be said that it was done.
本発明の目的は、上記課題に鑑み、−４０℃〜２５０℃の長期熱サイクルにおいても銅板表面の平滑性に優れたセラミックス回路基板を提供することである。 In view of the above problems, an object of the present invention is to provide a ceramic circuit board excellent in smoothness of a copper plate surface even in a long-term thermal cycle of −40 ° C. to 250 ° C.
セラミックス基板の両面に銅板を接合してなるセラミックス回路基板において、特定の銅板を選択することにより、セラミックス基板と銅板を接合した後の銅の結晶配向率を８０％以上であることを特徴とするセラミックス回路基板である。 In a ceramic circuit board formed by bonding copper plates to both surfaces of a ceramic substrate, the specific crystal orientation of the copper after bonding the ceramic substrate and the copper plate is 80% or more by selecting a specific copper plate. It is a ceramic circuit board.
本発明によれば、長期的な−４０℃〜２５０℃の熱サイクルにおいても、銅板表面の平滑性に優れたセラミックス回路基板が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the ceramic circuit board excellent in the smoothness of the copper plate surface is provided also in a long-term thermal cycle of -40 degreeC-250 degreeC.
本発明に係るセラミックス回路基板の製造方法は特に限定されるものではなく、例えば次の方法で作製することができる。 The method for producing a ceramic circuit board according to the present invention is not particularly limited, and for example, it can be produced by the following method.
セラミックス回路基板を構成する各セラミックス基板の厚さは特に限定されないが、０．２ｍｍ〜１．０ｍｍのものを用いるのが一般的である。 The thickness of each ceramic substrate constituting the ceramic circuit board is not particularly limited, but generally 0.2 mm to 1.0 mm is used.
セラミックス基板の材質は、熱伝導性及び熱サイクルに対する信頼性から、窒化アルミニウム又は窒化ケイ素の焼結体であることが好ましい。 The material of the ceramic substrate is preferably a sintered body of aluminum nitride or silicon nitride from the viewpoint of thermal conductivity and reliability against thermal cycling.
金属板には、圧延後の平均粒子サイズ１５μｍ以下であり、結晶配向率が５０％以上の銅板を用いるのが好ましい。銅板の厚みは、放熱性の観点から０．３ｍｍ〜１．０ｍｍのものを用いるのが好ましい。 As the metal plate, it is preferable to use a copper plate having an average particle size after rolling of 15 μm or less and a crystal orientation ratio of 50% or more. The thickness of the copper plate is preferably 0.3 mm to 1.0 mm from the viewpoint of heat dissipation.
セラミックス基板に回路パターン及び放熱面を形成させるには、セラミックス基板と金属板とを接合した後にエッチングする方法、金属板から打ち抜かれた回路及び放熱面のパターンをセラミックス基板に接合する方法等によって行うことができる。 In order to form the circuit pattern and the heat dissipation surface on the ceramic substrate, the etching is performed after bonding the ceramic substrate and the metal plate, the circuit punched from the metal plate and the pattern of the heat dissipation surface are bonded to the ceramic substrate, and the like. be able to.
セラミックス基板と金属板の接合には、接合材を用いない溶湯法、活性金属ろう付け法などのいずれも採用することができるが、生産性が良く、しかも比較的低温で接合ができる活性金属ろう付け法が好ましい。Ａｇ、Ｃｕ、Ａｌ、Ｔｉ、Ｍｇなどの金属合金がろう材として好適である。ろう材はペースト又は箔として用いられる。ろう材はセラミックス基板、または、金属板のどちらに塗布、或いは配置してもよく、箔を用いる場合は予め金属板と箔をクラッド化しておくこともできる。ろう材ペーストの塗布方法は特に限定されないが、例えばスクリーン印刷法、ロールコーター法等を採用することができる。ろう材ペーストの塗布されたセラミックス基板に金属板を配置し、真空中で熱処理することで接合できる。 For joining the ceramic substrate and the metal plate, either a molten metal method that does not use a bonding material or an active metal brazing method can be employed, but an active metal brazing that has good productivity and can be bonded at a relatively low temperature. The attaching method is preferred. Metal alloys such as Ag, Cu, Al, Ti, and Mg are suitable as the brazing material. The brazing material is used as a paste or foil. The brazing material may be applied or disposed on either a ceramic substrate or a metal plate. When a foil is used, the metal plate and the foil can be clad in advance. The method for applying the brazing paste is not particularly limited, and for example, a screen printing method, a roll coater method, or the like can be employed. It can be joined by placing a metal plate on a ceramic substrate coated with a brazing material paste and heat-treating it in a vacuum.
接合体から回路パターン及び放熱面を形成するには、接合体の最上層及び最下層の金属板にエッチングレジストを塗布しエッチングする。エッチングレジストとしては、一般に使用されている紫外線硬化型や熱硬化型のものが挙げられる。また、エッチング液としては、金属板の材質が銅であるときには、塩化第２鉄溶液、塩化第２銅液、硫酸、過酸化水素水等の溶液が使用できる。エッチングによって不要な金属部分を除去したセラミックス回路基板には、塗布したろう材やその合金層・窒化物層等が残っており、ハロゲン化アンモニウム水溶液、硫酸、硝酸等の無機酸、過酸化水素水を含む溶液を用いて除去するのが一般的である。その後に、全てのエッチングレジストをアルカリ溶液によって除去する。必要に応じニッケル等のめっき処理を施すことも可能である。 In order to form a circuit pattern and a heat dissipation surface from the joined body, an etching resist is applied to the uppermost and lowermost metal plates of the joined body and etched. Examples of the etching resist include commonly used ultraviolet curable types and thermosetting types. As the etching solution, when the material of the metal plate is copper, a solution such as a ferric chloride solution, a cupric chloride solution, sulfuric acid, or hydrogen peroxide solution can be used. The ceramic circuit board from which unnecessary metal parts have been removed by etching has the applied brazing material and its alloy layer / nitride layer, etc. remaining. Ammonium halide aqueous solution, inorganic acid such as sulfuric acid and nitric acid, hydrogen peroxide solution Generally, it is removed using a solution containing. Thereafter, all the etching resist is removed with an alkaline solution. It is also possible to carry out a plating treatment of nickel or the like as necessary.
［実施例１］
両面に銀、銅、チタンを含む活性金属ろう材を塗布した厚さ０．３２ｍｍの窒化ケイ素基板と、厚さ０．３０ｍｍの銅板を両面に配置し、８４０℃で１時間加熱して接合した。両面の銅板にエッチングレジストを印刷してから、塩化銅水溶液、次いで過酸化水素と酸性フッ化アンモニウムの混合液を用いてエッチングを行い、回路パターンと放熱面を形成した。次いで、エッチングレジストをアルカリ剥離液で剥離し、銅板表面にはＮｉＰメッキおよびＡｕメッキ処理を施すことでセラミックス回路基板を得た。得られたセラミックス回路基板はエスペック社製ＴＳＥ−１１−Ａ−Ｓ装置を用いて、２５０℃気槽での保持時間１８分、−４０℃気槽での保持時間１８分を１回とする熱サイクル試験を１０００回繰り返し実施した。
[Example 1]
A 0.32 mm thick silicon nitride substrate coated with an active metal brazing material containing silver, copper, and titanium on both sides and a 0.30 mm thick copper plate were placed on both sides and joined by heating at 840 ° C. for 1 hour. . After printing an etching resist on the copper plates on both sides, etching was performed using an aqueous copper chloride solution and then a mixed solution of hydrogen peroxide and ammonium acid fluoride to form a circuit pattern and a heat dissipation surface. Next, the etching resist was stripped with an alkaline stripping solution, and the surface of the copper plate was subjected to NiP plating and Au plating to obtain a ceramic circuit board. The obtained ceramic circuit board was heated using a TSE-11-A-S apparatus manufactured by Espec Corp. with a holding time of 18 minutes in a 250 ° C. air tank and a holding time of 18 minutes in a −40 ° C. air tank. The cycle test was repeated 1000 times.
＜使用材料＞
窒化ケイ素基板：デンカ社製。寸法２８×２４ｍｍ。
銅板１：株式会社ＳＨカッパープロダクツ製無酸素銅ＯＦＣ−ＨＣ材
銅板２：ＡＵＲＵＢＩＳ社製ＤＣｕＢ１／ＰＮＡ４０１材
銅板３：三菱伸銅株式会社製無酸素銅ＯＦＣ材
<Materials used>
Silicon nitride substrate: manufactured by Denka Corporation. Dimensions 28x24mm.
Copper plate 1: Oxygen-free copper OFC-HC material manufactured by SH Copper Products Co., Ltd. Copper plate 2: DCUB1 / PNA401 material manufactured by AURUBIS Copper plate 3: Oxygen-free copper OFC material manufactured by Mitsubishi Shindoh Co., Ltd.
＜評価方法＞
銅の結晶配向率：セラミックス基板と銅板を接合した後に任意の位置でセラミックス回路基板の銅板部分の断面を作製し、８００×３００μｍの視野にて加速電圧１５ｋＶの条件で電子線後方散乱分析（日立ハイテク社製ＳＵ６６００形電界放出形走査顕微鏡、ＴＳＬ社製ＥＢＳＤ）を行い、視野内の銅板部分にて結晶方位マップを作成した後、銅の結晶方位を（００１）面、（１１１面）、（１０１）面に３値化し、各方位の面積比から最も高い値を示した面の割合を結晶配向率として評価した。
銅平均粒子径：セラミックス基板と銅板を接合した後の断面ＳＥＭ画像８００×３００μｍ視野（日立ハイテク社製ＳＵ６６００形電界放出形走査顕微鏡）から、銅の粒子サイズのヒストグラムを５μｍ幅で作成し、ヒストグラムの累積５０％の値を銅平均粒子径として評価した。
表面粗さ（Ｒａ）：２５０℃での保持時間１８分、−４０℃での保持時間１８分の条件にて熱サイクル試験を１０００回実施した後の銅板メッキ後のメッキ表面粗さＲａを接触式の表面粗さ計（ミツトヨ社製２０１Ｐ）を用いて評価した。
<Evaluation method>
Copper crystal orientation ratio: After bonding the ceramic substrate and the copper plate, a cross section of the copper plate portion of the ceramic circuit substrate is prepared at an arbitrary position, and an electron beam backscattering analysis is performed under the condition of an acceleration voltage of 15 kV in a field of 800 × 300 μm (Hitachi) After performing a high-tech SU6600 field emission scanning microscope, TSL EBSD) and creating a crystal orientation map at the copper plate portion in the field of view, the copper crystal orientation was set to (001) plane, (111 plane), ( The ratio of the surface which was trinarized to 101) plane and showed the highest value from the area ratio of each orientation was evaluated as the crystal orientation ratio.
Copper average particle diameter: A cross-sectional SEM image after bonding a ceramic substrate and a copper plate 800 × 300 μm field of view (SU6600 field emission scanning microscope manufactured by Hitachi High-Tech Co., Ltd.), a histogram of copper particle size is created with a width of 5 μm. The value of the cumulative 50% was evaluated as the copper average particle size.
Surface roughness (Ra): Contact with the plating surface roughness Ra after copper plate plating after 1000 heat cycle tests under the conditions of holding time at 250 ° C. for 18 minutes and holding time at −40 ° C. for 18 minutes. Evaluation was performed using a surface roughness meter of the formula (201P manufactured by Mitutoyo Corporation).
実施例２〜３、比較例１〜２
銅板および接合温度を表１に示す条件でセラミックス基板と銅板の接合を行うことにより、結晶配向率と平均粒子径の異なるセラミックス回路基板を作製した。
Examples 2-3 and Comparative Examples 1-2
Ceramic circuit boards having different crystal orientation ratios and different average particle diameters were produced by joining the ceramic board and the copper board under the conditions shown in Table 1 for the copper plate and the joining temperature.
表１よりセラミックス基板と銅板を接合した後の銅板断面において結晶の配向率が８０％以上である際に、熱サイクル１０００回後においても表面平滑性に優れたセラミックス回路基板が得られた。また、結晶の配向率の向上により熱サイクル後のＲａが低下し、結晶配向率９５％、銅平均粒子径９０μｍにて最も改善効果が高かった。
From Table 1, when the orientation ratio of the crystal was 80% or more in the cross section of the copper plate after joining the ceramic substrate and the copper plate, a ceramic circuit substrate excellent in surface smoothness was obtained even after 1000 thermal cycles. Moreover, Ra after the heat cycle decreased due to the improvement of the crystal orientation ratio, and the improvement effect was the highest when the crystal orientation ratio was 95% and the copper average particle diameter was 90 μm.
Claims (2)
The ceramic circuit board according to claim 1, wherein the copper average particle diameter after bonding is 100 µm or less and the crystal orientation is 95% or more.
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| JP2016061903A JP6621353B2 (en) | 2016-03-25 | 2016-03-25 | Heat resistant ceramic circuit board |
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| US20110290380A1 (en) * | 2008-11-12 | 2011-12-01 | Toyo Kohan Co., Ltd. | Method for manufacturing metal laminated substrate for semiconductor element formation and metal laminated substrate for semiconductor element formation |
| JP5463280B2 (en) * | 2010-12-28 | 2014-04-09 | 株式会社日立製作所 | Circuit board for semiconductor module |
| JP2011124585A (en) * | 2011-01-07 | 2011-06-23 | Hitachi Metals Ltd | Ceramic wiring board and manufacturing method and semiconductor module of the same |
| JP6517069B2 (en) * | 2014-06-30 | 2019-05-22 | パナソニック株式会社 | Non-aqueous electrolyte secondary battery |
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