JP2008063187A - Silicon nitride sintered compact, ceramic substrate for heat dissipation and insulation, circuit board for heat dissipation and insulation and module for heat dissipation and insulation - Google Patents

Silicon nitride sintered compact, ceramic substrate for heat dissipation and insulation, circuit board for heat dissipation and insulation and module for heat dissipation and insulation Download PDF

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JP2008063187A
JP2008063187A JP2006242809A JP2006242809A JP2008063187A JP 2008063187 A JP2008063187 A JP 2008063187A JP 2006242809 A JP2006242809 A JP 2006242809A JP 2006242809 A JP2006242809 A JP 2006242809A JP 2008063187 A JP2008063187 A JP 2008063187A
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silicon nitride
nitride sintered
sintered body
insulation
heat dissipation
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Sadahiro Yamamoto
禎広 山元
Yasushi Hara
康 原
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Niterra Co Ltd
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NGK Spark Plug Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means 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
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    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
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    • H01L2924/19107—Disposition of discrete passive components off-chip wires

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silicon nitride sintered compact which has high sinterability, high compactness and high thermal conductivity without adjusting the firing environment, and a ceramic substrate for heat dissipation and insulation, a ceramic circuit board for heat dissipation and insulation and a module for heat dissipation and insulation which are obtained using the silicon nitride sintered compact and have high heat dissipation properties. <P>SOLUTION: The silicon nitride sintered compact contains Si<SB>3</SB>N<SB>4</SB>at 85-90 mol%, a light rare-earth element at 1-5 mol% in terms of an oxide, a heavy rare-earth element and/or Y at 1-5 mol% in terms of an oxide and Sr at 3-13 mol% in terms of an oxide, provided that its peak intensity ratio S1/S2 is <0.1 when the peak intensity of silicon at a frequency of 521±2 cm<SP>-1</SP>in Raman spectroscopic analysis is defined as S1 and the peak intensity of silicon nitride near a frequency of 206±2 cm<SP>-1</SP>is defined as S2. The ceramic substrate for heat dissipation and insulation, the ceramic circuit board for heat dissipation and insulation and the module for heat dissipation and insulation using the silicon nitride sintered compact are also provided. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

この発明は、窒化珪素焼結体、放熱絶縁用セラミックス基板、放熱絶縁用回路基板、及び放熱絶縁用モジュールに関し、更に詳しくは、焼成雰囲気調整を行う必要もなく高い焼結性を有して製造されることのできる、高い緻密性及び大きな熱伝導性を有する窒化珪素焼結体、並びにそのような窒化珪素焼結体を用いることにより放熱性の大きな放熱絶縁用セラミックス基板、放熱絶縁用回路基板及び放熱絶縁用モジュールに関する。   The present invention relates to a silicon nitride sintered body, a ceramic substrate for heat radiation insulation, a circuit board for heat radiation insulation, and a module for heat radiation insulation, and more specifically, manufactured with high sinterability without the need for adjusting the firing atmosphere. Silicon nitride sintered body having high density and large thermal conductivity, and ceramic substrate for heat dissipation insulation, circuit substrate for heat dissipation insulation by using such silicon nitride sintered body And a module for heat insulation.

一般的に、窒化珪素材料は難焼結性であるが、ＩＵＰＡＣ１９９０年勧告による周期律表における第３族元素酸化物を焼結助剤として添加することにより低温焼成が可能になった。また、窒化珪素材料に、さらにアルカリ土類元素、ＳｉＯ２、Ａｌ２Ｏ３、及びその他の金属酸化物を焼結助剤として配合することにより良好な焼結性が得られる。したがって、従来の多くの窒化珪素焼結体はこれらの助剤を含有することを基本としている。 In general, silicon nitride materials are difficult to sinter, but by adding a Group 3 element oxide in the periodic table according to the IUPAC 1990 recommendation as a sintering aid, low temperature firing has become possible. In addition, good sinterability can be obtained by further adding alkaline earth elements, SiO 2 , Al 2 O 3 , and other metal oxides as sintering aids to the silicon nitride material. Therefore, many conventional silicon nitride sintered bodies are based on containing these auxiliaries.

一方、窒化珪素の緻密化には、焼結助剤の他に様々な焼成条件が影響を及ぼすことはよく知られている。焼成体の揮発量に影響を与える焼成雰囲気は、窒化珪素の緻密化に影響を与える条件の１つである。   On the other hand, it is well known that various sintering conditions influence the densification of silicon nitride in addition to the sintering aid. The firing atmosphere that affects the volatilization amount of the fired body is one of the conditions that affects the densification of silicon nitride.

窒化珪素材料は焼成の過程で、焼成雰囲気の影響により、窒化珪素又は焼結助剤等の揮発を伴うことがある。前記揮発が生じると、その揮発量によっては焼結初期の段階でポーラスな揮発層が形成され、収縮が阻害されて緻密な窒化珪素焼結体が形成されないことがある。特に１０気圧以下といった低圧の窒素雰囲気下における焼成では、ホットプレス及びＨＩＰ等に比較して、揮発による緻密化阻害はより顕著になる。   The silicon nitride material may be accompanied by volatilization of silicon nitride or a sintering aid due to the influence of the firing atmosphere during the firing process. When the volatilization occurs, depending on the volatilization amount, a porous volatile layer may be formed at the initial stage of sintering, and the shrinkage may be inhibited, so that a dense silicon nitride sintered body may not be formed. In particular, in firing in a low-pressure nitrogen atmosphere of 10 atm or less, densification inhibition due to volatilization becomes more prominent than hot pressing, HIP, or the like.

一方、高熱伝導性を有する窒化珪素焼結体を得るには、熱伝導率を向上させる為にフォノン伝達を阻害する粒界層の生成量をできる限り低減させる必要がある。ところが粒界相の生成量を低減させても、僅かの揮発が焼結性を著しく低下させている。   On the other hand, in order to obtain a silicon nitride sintered body having high thermal conductivity, it is necessary to reduce as much as possible the amount of grain boundary layers that inhibit phonon transmission in order to improve thermal conductivity. However, even if the amount of grain boundary phase produced is reduced, slight volatilization significantly reduces the sinterability.

この揮発による焼結性低下を防ぐ為に、揮発量を制御する方法として、被焼成材料と同様の組成よりなる窒化珪素製焼成容器内にて被焼成材料を焼成する方法、及びＢＮ等と被焼成材料と同様のＳｉ３Ｎ４又は助剤とを加えて成る焼成雰囲気用の詰粉に被焼成材料を埋没させて焼成を行う方法等が一般的に採用されている。これらの他にも、詰粉と同様の効果を持つ雰囲気調整方法として、被焼成体表面に詰粉と同様な成分を含むコーティング材を塗布する方法もある。 In order to prevent this deterioration of sinterability due to volatilization, as a method of controlling the volatilization amount, a method of firing a material to be fired in a silicon nitride firing container having the same composition as the material to be fired, A method is generally employed in which a material to be fired is buried in a filling powder for a firing atmosphere formed by adding Si 3 N 4 or an auxiliary agent similar to the fired material, and the like. In addition to these, there is also a method of applying a coating material containing components similar to the filling powder on the surface of the object to be fired as an atmosphere adjustment method having the same effect as the filling powder.

しかしながら、前記窒化珪素製焼成容器は、焼成を繰り返すことにより前記窒化珪素製焼成容器からそれを形成する成分が揮発するなどによる劣化で、焼成雰囲気制御機能が低下する。したがって、前記窒化珪素製焼成容器の使用では焼成雰囲気を常に一定にすることが困難な上に、前記窒化珪素製焼成容器自体が高価であり、しかも耐久性が低いので、高熱伝導性を有する窒化珪素焼結体の製造コストが著しく増大していた。   However, the firing condition control function of the silicon nitride firing container is deteriorated due to deterioration due to volatilization of components forming the silicon nitride firing container due to repeated firing. Therefore, it is difficult to always make the firing atmosphere constant by using the silicon nitride firing container, and the silicon nitride firing container itself is expensive and has low durability, so that it has high thermal conductivity. The manufacturing cost of the silicon sintered body has been remarkably increased.

焼成雰囲気用の詰粉を使用することによる焼成雰囲気制御においても、焼成毎に詰粉の詰め替えが必要であり、製造コストもかかる上に、被焼成物の形状の自由度が制限されてしまう。コーティング材を塗布することによる雰囲気調整にしても、同様に製造コストが増加する。   Even in the firing atmosphere control by using the filling powder for the firing atmosphere, it is necessary to refill the filling powder every time firing is performed, and the manufacturing cost is increased, and the degree of freedom of the shape of the object to be fired is limited. Even if the atmosphere is adjusted by applying the coating material, the manufacturing cost is similarly increased.

一方、本願発明者らは、特許文献１により「熱伝導性及び機械的強度に優れ、且つ低コストの窒化珪素焼結体及びそれを用いてなる回路基板」を提案している。特許文献１に記載の窒化ケイ素焼結体は、「Ｍｇ及びＳｒの少なくとも一方を酸化物換算で合計０．１〜１０質量％、Ａｌ、Ｃａ及びＦｅのうちの少なくとも１種を酸化物換算で合計０．０５〜１質量％、並びに希土類元素のうちの少なくとも１種を酸化物換算で合計３〜１０質量％含有し、且つラマン分光分析における波数５２１ｃｍ−１付近の珪素のピーク強度をＳ１、２０６ｃｍ−１付近の窒化珪素のピーク強度をＳ２とした場合に、Ｓ１／Ｓ２で表されるピーク強度比が０．１以上であることを特徴とする窒化珪素焼結体」（特許文献１の請求項１参照）であり、この窒化珪素焼結体は「上記希土類元素として、軽希土類元素のうちの少なくとも１種を酸化物換算で合計１質量％以上、並びに重希土類元素及びＹから選ばれる少なくとも１種を酸化物換算で合計１質量％以上含有する」（特許文献１の請求項２参照）。 On the other hand, the inventors of the present application have proposed “a silicon nitride sintered body excellent in thermal conductivity and mechanical strength and low cost and a circuit board using the same” according to Patent Document 1. The silicon nitride sintered body described in Patent Document 1 is “at least one of Mg and Sr in terms of oxide in total of 0.1 to 10% by mass, and at least one of Al, Ca and Fe in terms of oxide. 0.05 to 1% by mass in total, and at least one kind of rare earth elements in total in the range of 3 to 10% by mass in terms of oxide, and the peak intensity of silicon in the vicinity of wave number 521 cm −1 in Raman spectroscopic analysis is S1, A silicon nitride sintered body characterized in that the peak intensity ratio represented by S1 / S2 is 0.1 or more when the peak intensity of silicon nitride in the vicinity of 206 cm −1 is S2 ”(Patent Document 1) The silicon nitride sintered body is “selected as the rare earth element from at least one light rare earth element in total of 1% by mass or more in terms of oxide, heavy rare earth element and Y”. Small Both one containing a total of 1 mass% or more in terms of oxide "(see claim 2 of Patent Document 1).

特開２００３−９５７４７号公報JP 2003-95747 A

特許文献１に記載された窒化珪素焼結体は、「特定の成分を特定量含有させることにより、低コストで、且つ熱伝導性及び機械的強度に優れた性質を有する焼結体とすることができる」との優れた技術的効果を奏するのであるが、本願発明者らは、同様に優れた技術的効果を奏するさらなる窒化珪素焼結体の開発に努力を重ねた。   The silicon nitride sintered body described in Patent Document 1 is “to make a sintered body having properties excellent in thermal conductivity and mechanical strength at low cost by containing a specific amount of a specific component. The present inventors have made efforts to develop a further silicon nitride sintered body having the same excellent technical effect.

この発明はこの問題を解決するためになされた。この発明は、窒化珪素製焼成容器の使用、又は焼成雰囲気用の詰粉の使用等の、特別な焼成雰囲気調整を行うことなく高い焼結性を維持し、内部から焼き肌面まで緻密に形成された窒化珪素焼結体を提供することを課題とする。また、この発明は、放熱性に優れた放熱絶縁用セラミックス基板、放熱絶縁用回路基板及び放熱絶縁用モジュールを提供することを、課題とする。   The present invention has been made to solve this problem. This invention maintains high sinterability without special firing atmosphere adjustment, such as the use of a silicon nitride firing container or a filling powder for a firing atmosphere, and it is densely formed from the inside to the grilled skin surface. It is an object of the present invention to provide a silicon nitride sintered body. Moreover, this invention makes it a subject to provide the ceramic substrate for heat radiation insulation excellent in heat dissipation, the circuit board for heat radiation insulation, and the module for heat radiation insulation.

前記課題を解決する手段として、
請求項１は、
Ｓi３Ｎ４と、ＩＵＰＡＣ１９９０年勧告による周期律表におけるランタノイドのうちＬａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、及びＳｍより成る群から選択される少なくとも１種の軽希土類元素と、ＩＵＰＡＣ１９９０年勧告による周期律表におけるランタノイドのうちＥｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、及びＬｕより成る群から選択される少なくとも１種の重希土類元素及び／又はＹと、Ｓrとを含有する窒化珪素焼結体であって、
Ｓi３Ｎ４と、前記軽希土類元素の酸化物と、前記重希土類元素及び／又はＹの酸化物と、Ｓｒの酸化物との合計が１００モル％となるように、Ｓi３Ｎ４の含有割合が８５〜９０モル％の範囲内にあり、前記軽希土類元素の含有割合が酸化物換算で１〜５モル％の範囲内にあり、前記重希土類元素及び／又はＹの含有割合が酸化物換算で１〜５モル％の範囲内にあり、Ｓrの含有割合が酸化物換算で３〜１３モル％の範囲内にあり、
ラマン分光分析における波数５２１±２ｃｍ−１の珪素ピーク強度をＳ１、２０６±２ｃｍ−１の窒化珪素のピーク強度をＳ２とした場合に、Ｓ１／Ｓ２で表されるピーク強度比が０．１未満であることを特徴とする窒化珪素焼結体であり、
請求項２は、
Ａｌを酸化物換算で、Ｓi３Ｎ４と、前記軽希土類元素の酸化物と、前記重希土類元素及び／又はＹの酸化物と、Ｓｒの酸化物との合計を１００モル％とするときに、０．４モル％以下の含有割合で含有して成る前記請求項１に記載の窒化珪素焼結体であり、
請求項３は、
前記軽希土類が、Ｌａ、Ｃｅ、Ｐｒ及びＮｄから選ばれる少なくとも１種である請求項１又は２に記載の窒化珪素焼結体であり、
請求項４は、
前記重希土類元素が、Ｈｏ、Ｅｒ、Ｙｂ及びＤｙから選ばれる１種である請求項１〜３のいずれか一項に記載の窒化珪素であり、
請求項５は、
前記請求項１〜４のいずれかに記載の窒化珪素焼結体を用いた放熱絶縁用セラミックス基板であり、
請求項６は、
前記請求項１〜４のいずれかに記載の窒化珪素焼結体を用いた放熱絶縁用セラミックス回路基板であり、
請求項７は、
前記請求項１〜４のいずれかに記載の窒化珪素焼結体を用いた放熱絶縁用モジュールである。 As means for solving the above problems,
Claim 1
Si 3 N 4 and at least one light rare earth element selected from the group consisting of La, Ce, Pr, Nd, Pm, and Sm among the lanthanoids in the periodic table according to the IUPAC 1990 recommendation, and the cycle according to the IUPAC 1990 recommendation Nitrid containing at least one heavy rare earth element and / or Y selected from the group consisting of Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu among the lanthanoids in the table and Sr A silicon sintered body,
The content of Si 3 N 4 so that the total of Si 3 N 4 , the light rare earth element oxide, the heavy rare earth element and / or Y oxide, and the Sr oxide is 100 mol%. The ratio is in the range of 85 to 90 mol%, the light rare earth element content is in the range of 1 to 5 mol% in terms of oxide, and the heavy rare earth element and / or Y content is oxide. In the range of 1 to 5 mol% in terms of conversion, the content ratio of Sr is in the range of 3 to 13 mol% in terms of oxide,
The peak intensity ratio represented by S1 / S2 is less than 0.1 when the silicon peak intensity at wave number 521 ± 2 cm −1 in Raman spectroscopic analysis is S1, and the peak intensity of silicon nitride at 206 ± 2 cm −1 is S2. It is a silicon nitride sintered body characterized by being,
Claim 2
When the total of Si 3 N 4 , the light rare earth element oxide, the heavy rare earth element and / or Y oxide, and the Sr oxide is 100 mol% in terms of oxide of Al The silicon nitride sintered body according to claim 1, wherein the silicon nitride sintered body is contained at a content ratio of 0.4 mol% or less,
Claim 3
The silicon nitride sintered body according to claim 1 or 2, wherein the light rare earth is at least one selected from La, Ce, Pr, and Nd.
Claim 4
The silicon heavy nitride according to any one of claims 1 to 3, wherein the heavy rare earth element is one selected from Ho, Er, Yb, and Dy.
Claim 5
It is a ceramic substrate for heat dissipation insulation using the silicon nitride sintered body according to any one of claims 1 to 4.
Claim 6
A ceramic circuit board for heat dissipation insulation using the silicon nitride sintered body according to any one of claims 1 to 4,
Claim 7
It is a module for thermal insulation which used the silicon nitride sintered compact in any one of the said Claims 1-4.

この発明によると、焼成雰囲気を調整することなく、換言すると、焼成雰囲気の変化に拘わらずに内部から焼き肌表面まで緻密に焼成されて成り、しかも機械的強度が大きくて熱伝導率の大きな窒化珪素焼結体が提供される。この発明によるとこのように優れた特性を有する窒化珪素焼結体を用いることにより放熱性及び絶縁性の良好な放熱絶縁用セラミックス基板、放熱絶縁用回路基板、及び放熱絶縁用モジュールを提供することができる。   According to the present invention, without adjusting the firing atmosphere, in other words, it is densely fired from the inside to the surface of the burned skin regardless of the change in the firing atmosphere, and also has high mechanical strength and high thermal conductivity. A silicon sintered body is provided. According to the present invention, by using a silicon nitride sintered body having such excellent characteristics, a heat dissipation insulating ceramic substrate, a heat dissipation insulating circuit board, and a heat dissipation insulating module are provided. Can do.

この発明に係る窒化珪素焼結体は、Ｓi３Ｎ４と、ＩＵＰＡＣ１９９０年勧告による周期律表におけるランタノイドのうちＬａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、及びＳｍより成る群から選択される少なくとも１種の軽希土類元素と、ＩＵＰＡＣ１９９０年勧告による周期律表におけるランタノイドのうちＥｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、及びＬｕより成る群から選択される少なくとも１種の重希土類元素及び／又はＹと、Ｓrとを含有する。この窒化珪素焼結体は、Ｓi３Ｎ４（以下において、「窒化珪素」と称することがある。）を、前記窒化珪素、前記軽希土類元素の酸化物、前記重希土類元素及び／又はＹの酸化物及びＳｒの酸化物の合計が１００モル％となるように８５〜９０モル％の範囲内で、好ましくは８６〜８９モル％の範囲内で含有する。この窒化珪素の含有割合が９０モル％を超えると、焼結性が低下し、また８５モル％未満であると窒化珪素自体が有する優れた機械的性質及び耐熱性等が十分ではなくなり、熱伝導性の低下した窒化珪素焼結体が得られてしまう。窒化珪素自体については特に制限がなく、α型窒化珪素及びβ型窒化珪素のいずれも使用することができる。この窒化珪素の好適な平均粒径は０．５〜１．６μｍである。平均粒径が前記０．５μｍよりも小さいと成形性を損なうと言った問題点を生じることがある。また、この窒化珪素がα型窒化珪素及びβ型窒化珪素の混合物であるときはそのα型窒化珪素の割合すなわちα率は７０〜１００％であるのが好ましい。α率が７０％未満であると焼結体の粗大粒子減少による靭性低下などの機械的特性低下と言った不都合を生じることがある。また窒化珪素に含まれる不純物としての酸素含有量は、通常、０．８〜２質量％である。前記酸素含有量が少ないと焼結性低下、多いと耐熱性低下や熱伝導率低下といった不都合を生じることがある。 The silicon nitride sintered body according to the present invention is Si 3 N 4 and at least one selected from the group consisting of La, Ce, Pr, Nd, Pm, and Sm among lanthanoids in the periodic table according to the IUPAC 1990 recommendation. And at least one heavy rare earth element selected from the group consisting of Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu among the lanthanides in the periodic table according to the IUPAC 1990 recommendation, and / Or Y and Sr are contained. This silicon nitride sintered body is composed of Si 3 N 4 (hereinafter sometimes referred to as “silicon nitride”), silicon nitride, light rare earth element oxide, heavy rare earth element and / or Y It is contained in the range of 85 to 90 mol%, preferably in the range of 86 to 89 mol%, so that the total of the oxide and the oxide of Sr is 100 mol%. If the silicon nitride content exceeds 90 mol%, the sinterability decreases, and if it is less than 85 mol%, the excellent mechanical properties, heat resistance, etc. of silicon nitride itself are not sufficient, and heat conduction Thus, a silicon nitride sintered body with reduced properties is obtained. Silicon nitride itself is not particularly limited, and both α-type silicon nitride and β-type silicon nitride can be used. A suitable average particle diameter of this silicon nitride is 0.5 to 1.6 μm. If the average particle size is smaller than 0.5 μm, there may be a problem that moldability is impaired. When the silicon nitride is a mixture of α-type silicon nitride and β-type silicon nitride, the proportion of α-type silicon nitride, that is, the α rate is preferably 70 to 100%. If the α ratio is less than 70%, there may be inconveniences such as mechanical property deterioration such as toughness reduction due to the reduction of coarse particles in the sintered body. Moreover, the oxygen content as an impurity contained in silicon nitride is 0.8-2 mass% normally. If the oxygen content is small, there may be a problem that the sinterability decreases, and if it is large, the heat resistance and thermal conductivity decrease.

この発明に係る窒化珪素焼結体は、前記窒化珪素と前記軽希土類元素の酸化物と前記重希土類元素及び／又はＹの酸化物及びＳｒの酸化物との合計が１００モル％になるように軽希土類元素を酸化物換算で１〜５モル％、好ましくは１〜４モル％の範囲内で含有する。前記軽希土類元素としては、ＩＵＰＡＣ１９９０年勧告による周期律表におけるランタノイドのうちＬａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、及びＥｕを挙げることができる。これらの中でもＬａ、Ｃｅ、Ｐｒ、及びＮｄが好ましい。これらの軽希土類に属する少なくとも一種の元素が窒化珪素焼結体中に酸化物換算の前記割合で配合されていると、焼成雰囲気の調整をすることなく緻密な焼結体に形成することができるとともに熱伝導率の大きな窒化珪素焼結体が実現される。軽希土類元素として特にＬａ、Ｃｅ、Ｐｒ、及びＮｄが含まれているとこれらはイオン半径が大きいので、焼結後の窒化珪素の粒子がこれら軽希土類元素のイオン半径に影響を受けて、焼成雰囲気の調整をすることなく緻密な窒化珪素焼結体が形成される。ともあれ、軽希土類元素が１モル％未満の割合で窒化珪素焼結体中に含まれていると、焼結性の低下した窒化珪素焼結体となり、また５モル％を越える割合で窒化珪素焼結体中に含まれていると、熱伝導性の低下した窒化珪素焼結体が得られてしまい、この発明の目的が達成されない。   In the silicon nitride sintered body according to the present invention, the total of the silicon nitride, the light rare earth element oxide, the heavy rare earth element and / or the Y oxide and the Sr oxide is 100 mol%. A light rare earth element is contained in the range of 1 to 5 mol%, preferably 1 to 4 mol% in terms of oxide. Examples of the light rare earth element include La, Ce, Pr, Nd, Pm, Sm, and Eu among lanthanoids in the periodic table according to the IUPAC 1990 recommendation. Among these, La, Ce, Pr, and Nd are preferable. When at least one element belonging to these light rare earths is blended in the silicon nitride sintered body at the above-mentioned ratio in terms of oxide, it can be formed into a dense sintered body without adjusting the firing atmosphere. At the same time, a silicon nitride sintered body having a high thermal conductivity is realized. When light rare earth elements include La, Ce, Pr, and Nd in particular, they have a large ionic radius, so that the sintered silicon nitride particles are affected by the ionic radius of these light rare earth elements and fired. A dense silicon nitride sintered body is formed without adjusting the atmosphere. Anyway, if the light rare earth element is contained in the silicon nitride sintered body in a proportion of less than 1 mol%, the silicon nitride sintered body has a reduced sinterability, and the silicon nitride sintered body in a proportion exceeding 5 mol%. If it is contained in the sintered body, a silicon nitride sintered body with reduced thermal conductivity is obtained, and the object of the present invention is not achieved.

この発明に係る窒化珪素焼結体は、前記窒化珪素と前記軽希土類元素の酸化物と前記重希土類元素及び／又はＹの酸化物とＳｒの酸化物との合計が１００モル％になるように、前記重希土類元素及びＹから選ばれる少なくとも１種の元素を酸化物換算で１〜５モル％、好ましくは１〜４モル％含有する。前記重希土類元素及び／又はＹの窒化珪素焼結体中の含有量が前記範囲の下限値未満であると、焼結性の低下した窒化珪素焼結体となり、前記重希土類元素及び／又はＹの窒化珪素焼結体中の含有量が前記上限値を超えると、焼結中に揮発成分の揮発量が増加して焼結性が低下した窒化珪素焼結体となる。ここで、前記重希土類元素としては、ＩＵＰＡＣ１９９０年勧告による周期律表におけるランタノイドのうちＥｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、及びＬｕを挙げることができ、これらのうち特にＨｏ、Ｅｒ、Ｙｂ及びＤｙよりなる群から選択される少なくとも一種が好ましい。   In the silicon nitride sintered body according to the present invention, the total of the silicon nitride, the light rare earth element oxide, the heavy rare earth element and / or the Y oxide and the Sr oxide is 100 mol%. In addition, at least one element selected from the heavy rare earth elements and Y is contained in an amount of 1 to 5 mol%, preferably 1 to 4 mol% in terms of oxide. When the content of the heavy rare earth element and / or Y in the silicon nitride sintered body is less than the lower limit of the above range, a silicon nitride sintered body with reduced sinterability is obtained, and the heavy rare earth element and / or Y When the content in the silicon nitride sintered body exceeds the upper limit, the volatile component is increased in volatilization during the sintering, resulting in a silicon nitride sintered body having reduced sinterability. Here, examples of the heavy rare earth element include Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu among lanthanoids in the periodic table according to the IUPAC 1990 recommendation. , Er, Yb and Dy are preferred.

この発明に係る窒化珪素焼結体は、前記窒化珪素と前記軽希土類元素の酸化物と前記重希土類元素及び／又はＹの酸化物とＳｒの酸化物との合計が１００モル％になるように、Ｓｒを酸化物換算で３〜１３モル％、好ましくは３〜８モル％の割合で含有する。Ｓｒの含有量が前記範囲の下限値を下回ると焼結性の低下した窒化珪素焼結体となり、また、Ｓｒの含有量が前記範囲の上限値を上回ると熱伝導性の低下した窒化珪素焼結体となってしまう、いずれもこの発明の目的を達成することができない。   In the silicon nitride sintered body according to the present invention, the total of the silicon nitride, the light rare earth element oxide, the heavy rare earth element and / or the Y oxide and the Sr oxide is 100 mol%. , Sr is contained in an amount of 3 to 13 mol%, preferably 3 to 8 mol% in terms of oxide. When the Sr content is below the lower limit of the above range, a silicon nitride sintered body with reduced sinterability is obtained, and when the Sr content exceeds the upper limit of the above range, the silicon nitride sintered product with reduced thermal conductivity is obtained. In any case, the object of the present invention cannot be achieved.

この発明に係る更に好適な窒化珪素焼結体は、前記窒化珪素と前記軽希土類元素の酸化物と前記重希土類元素及び／又はＹの酸化物とＳｒの酸化物との合計が１００モル％になるように、窒化珪素を８６〜８９モル％の範囲内で、前記軽希土類の元素を酸化物換算で１〜４モル％の範囲内で、前記重希土類元素及び／又はＹを酸化物換算で１〜４モル％の範囲内で、Ｓｒを酸化物換算で３〜８モル％の範囲内で、含有する。このような含有割合で前記特定の成分を含有する窒化珪素焼結体は、焼結性及び熱伝導率のバランスがより優れている。   In a further preferred silicon nitride sintered body according to the present invention, the sum of the silicon nitride, the light rare earth element oxide, the heavy rare earth element and / or the Y oxide and the Sr oxide is 100 mol%. Thus, silicon nitride is in the range of 86 to 89 mol%, the light rare earth element is in the range of 1 to 4 mol% in terms of oxide, and the heavy rare earth element and / or Y is in terms of oxide. Sr is contained within a range of 3 to 8 mol% in terms of oxide within a range of 1 to 4 mol%. The silicon nitride sintered body containing the specific component in such a content ratio has a better balance between sinterability and thermal conductivity.

また、この窒化珪素焼結体はＡｌを含有するのが好ましい。窒化珪素焼結体に含まれるＡｌの含有割合は、前記窒化珪素、前記軽希土類元素の酸化物、前記重希土類元素及び／又はＹの酸化物及びＳｒの酸化物の合計１００モル％に対して、０．４モル％以下である。窒化珪素焼結体中に含まれるＡｌの含有量が０．４モル％を超えると、窒化珪素粒子へのＡｌ固溶により、焼結体の熱伝導率が低下することがある。   The silicon nitride sintered body preferably contains Al. The content ratio of Al contained in the silicon nitride sintered body is 100 mol% in total of the silicon nitride, the light rare earth element oxide, the heavy rare earth element and / or the oxide of Y and the oxide of Sr. 0.4 mol% or less. When the content of Al contained in the silicon nitride sintered body exceeds 0.4 mol%, the thermal conductivity of the sintered body may be lowered due to Al solid solution in the silicon nitride particles.

この発明に係る窒化珪素焼結体は、ラマン分光分析における波数５２１±２ｃｍ−１の珪素ピーク強度をＳ１、２０６±２ｃｍ−１の窒化珪素のピーク強度をＳ２とした場合に、Ｓ１／Ｓ２で表されるピーク強度比が０．１未満であることが一つの特徴である。前記ピーク強度比が０．１以上であると、窒化珪素焼結体の耐電圧が低下することがある。珪素は比較的ラマン活性が強いので、ラマン分光分析では、例えばＸ線回折法では検出できない微量な珪素を検出することが可能である。なお、珪素のピークの波数を５２１±２ｃｍ−１、及び窒化珪素のピークの波数を２０６±２ｃｍ−１としたのは、各々の波数において、通常、±２ｃｍ−１以内のピークのズレがあるからである。 The silicon nitride sintered body according to the present invention has S1 / S2 when the silicon peak intensity of wave number 521 ± 2 cm −1 in Raman spectroscopic analysis is S1, and the peak intensity of silicon nitride of 206 ± 2 cm −1 is S2. One characteristic is that the expressed peak intensity ratio is less than 0.1. When the peak intensity ratio is 0.1 or more, the withstand voltage of the silicon nitride sintered body may decrease. Since silicon has a relatively strong Raman activity, it is possible to detect a small amount of silicon that cannot be detected by, for example, the X-ray diffraction method in the Raman spectroscopic analysis. The reason why the peak wave number of silicon is 521 ± 2 cm −1 and the peak wave number of silicon nitride is 206 ± 2 cm −1 is that there is usually a deviation of the peak within ± 2 cm −1 in each wave number. Because.

この発明に係る窒化珪素焼結体は、粒界がガラス相であることが好ましい。粒界が結晶化すると粒界と窒化珪素粒子との結合力が大きくなったり、粒界ガラス量が減少したりして、クラックが粒界を通り難くなってクラックディフラクション効果が低下して、靭性が低下することがある。粒界がガラス相であれば、このような原因で靭性が低下することはない。Ｘ線回折により粒界結晶相が検出されなければ、粒界はガラス相であると判断できる。   In the silicon nitride sintered body according to the present invention, the grain boundary is preferably a glass phase. When the grain boundary is crystallized, the bonding force between the grain boundary and the silicon nitride particle is increased, the amount of the grain boundary glass is reduced, cracks are difficult to pass through the grain boundary, and the crack diffusion effect is reduced, Toughness may decrease. If the grain boundary is a glass phase, the toughness is not lowered due to such a cause. If a grain boundary crystal phase is not detected by X-ray diffraction, it can be determined that the grain boundary is a glass phase.

この発明に係る窒化珪素焼結体は、その室温での強度が少なくとも５００ＭＰａであり、好ましくは６００〜１５００ＭＰａであり、特に好ましくは７００〜１５００ＭＰａであり、その靭性が５〜８ＭＰａｍ０．５であり、好ましくは５．５〜８．０ＭＰａｍ０．５であり、その熱伝導率が５０〜１５０Ｗ／ｍＫであり、好ましくは６０〜１５０Ｗ／ｍＫであり、特に好ましくは７０〜１５０Ｗ／ｍＫであるのが望ましい。なお、これらの上限値を越えるとこの発明の目的を達成することができないというわけではないが、一般的な上限値としての目安を示すに過ぎない。 The silicon nitride sintered body according to the present invention has a strength at room temperature of at least 500 MPa, preferably 600 to 1500 MPa, particularly preferably 700 to 1500 MPa, and a toughness of 5 to 8 MPam 0.5 . , Preferably 5.5 to 8.0 MPam 0.5 , and its thermal conductivity is 50 to 150 W / mK, preferably 60 to 150 W / mK, particularly preferably 70 to 150 W / mK. Is desirable. It should be noted that exceeding these upper limits does not mean that the object of the present invention cannot be achieved, but merely shows a guideline as a general upper limit.

この室温での強度は、三点曲げ強度測定法（ＪＩＳ Ｒ１６０１）により測定される。靭性は破壊靭性とも称され、ＩＦ法（ＪＩＳ Ｒ１６０７）により測定される。また、熱伝導率はＪＩＳ Ｒ１６１１ に規定される測定法により測定される。   The strength at room temperature is measured by a three-point bending strength measurement method (JIS R1601). Toughness is also called fracture toughness and is measured by IF method (JIS R1607). The thermal conductivity is measured by a measuring method specified in JIS R1611.

この窒化珪素焼結体の前記強度が前記５００ＭＰａ以上であるとともに靭性が５ＭＰａ０．５以上であると、回路基板の耐熱サイクル性が良好であり、この窒化珪素焼結体を利用して放熱絶縁用セラミックス基板を好適に製造することができる。この窒化珪素焼結体の熱伝導率が５０Ｗ／ｍＫ未満であると、このような熱伝導率を有する窒化珪素焼結体はアルミナ（一般的に４０Ｗ／ｍＫ以下）よりも優れた放熱性を実現することができないことがある。 When the strength of the silicon nitride sintered body is 500 MPa or more and the toughness is 5 MPa 0.5 or more, the heat cycle performance of the circuit board is good. The ceramic substrate for use can be suitably manufactured. When the silicon nitride sintered body has a thermal conductivity of less than 50 W / mK, the silicon nitride sintered body having such a thermal conductivity has a heat dissipation property superior to that of alumina (generally 40 W / mK or less). Sometimes it cannot be realized.

この発明に係る窒化珪素焼結体は次のようにして製造することができる。   The silicon nitride sintered body according to the present invention can be manufactured as follows.

この発明に係る窒化珪素焼結体の原料として、Ｓi３Ｎ４と、軽希土類元素の化合物と、重希土類元素及びＹよりなる群から選択される少なくとも一種の元素の化合物と、更にストロンチウム化合物とを、前記した含有量範囲から選択された割合で含有する粉末混合物を、先ず調製する。粉末混合物の調製にあたり、提供される原料の形態に応じて粉砕混合処理をする。この粉砕混合処理に使用される粉砕混合処理装置として、振動ミル、回転ミル、又はアトライターミル等が挙げられる。この粉砕混合処理は、水、又は有機溶媒例えばアルコール等を使用する湿式法、又は乾燥法で行われることができる。粉砕時間は、粉砕方式及び処理量等により異なり、粉砕後に得られる粉末の平均粒径が好ましくは０．５〜１μｍになるように、適宜に調整するのがよい。湿式粉砕法により粉砕する時には、粉砕混合して得られた粉末を乾燥し、造粒する。得られた粒子を、通常の乾式プレス成形法、押出し成形法、スリップキャスト成形法、ドクターブレード成形法及び静水圧プレス法のいずれか又はこれらの組み合わせにより、所定の形状の成形体に成形する。この成形体が焼成される。焼成は、成形体を、通常、０．１〜１ＭＰａのＮ２圧力のもとで１８５０〜２０００℃に３〜１２時間加熱することにより、行われる。また、この発明においては、焼成に際して、成形体の焼成雰囲気を調整する必要がない。従来におけるように窒化珪素を主成分とする被焼成物を詰粉内に埋めて焼成するといった焼成操作をすることなく、この発明に係る窒化珪素焼結体を得ることができることは、この発明の特筆するべき有利な効果である。 As raw materials for the silicon nitride sintered body according to the present invention, Si 3 N 4 , a compound of a light rare earth element, a compound of at least one element selected from the group consisting of heavy rare earth elements and Y, and a strontium compound, Is first prepared at a ratio selected from the above-described content range. In preparation of the powder mixture, pulverization and mixing are performed according to the form of the raw material provided. Examples of the pulverizing and mixing apparatus used for the pulverizing and mixing process include a vibration mill, a rotary mill, and an attritor mill. This pulverization and mixing treatment can be performed by water, a wet method using an organic solvent such as alcohol, or a drying method. The pulverization time varies depending on the pulverization method, the amount of treatment, and the like, and is appropriately adjusted so that the average particle size of the powder obtained after pulverization is preferably 0.5 to 1 μm. When pulverizing by the wet pulverization method, the powder obtained by pulverization and mixing is dried and granulated. The obtained particles are formed into a molded body having a predetermined shape by any one of a normal dry press molding method, an extrusion molding method, a slip cast molding method, a doctor blade molding method and an isostatic pressing method, or a combination thereof. This molded body is fired. Firing is usually performed by heating the compact to 1850-2000 ° C. for 3-12 hours under a N 2 pressure of 0.1-1 MPa. In the present invention, it is not necessary to adjust the firing atmosphere of the molded body during firing. The silicon nitride sintered body according to the present invention can be obtained without performing a firing operation such as burying a fired material mainly composed of silicon nitride in a filling powder as in the prior art. This is an advantageous effect to be noted.

この発明に係る窒化珪素焼結体は、それ自体が優れた緻密性、大きな強度及び大きな熱伝導性を有するので、例えば半導体用絶縁基板等の半導体装置用及びＯＡ機器等の各種部品に好適に採用されることができる。特に、この発明に係る窒化珪素焼結体のうち、室温強度が５００ＭＰａ以上である共に靭性が５ＭＰａｍ０．５以上であり、熱伝導率が５０Ｗ／ｍＫ以上である窒化珪素焼結体は、その優れた熱伝導率の故に、例えば放熱絶縁用セラミック基板、放熱絶縁用セラミックス回路基板及び放熱絶縁用モジュールに好適に採用されることができる。 Since the silicon nitride sintered body according to the present invention itself has excellent denseness, large strength, and large thermal conductivity, it is suitable for various parts such as semiconductor devices such as an insulating substrate for semiconductors and OA equipment. Can be adopted. In particular, among the silicon nitride sintered bodies according to the present invention, a silicon nitride sintered body having a room temperature strength of 500 MPa or more and a toughness of 5 MPam 0.5 or more and a thermal conductivity of 50 W / mK or more is Because of its excellent thermal conductivity, it can be suitably used for, for example, a ceramic substrate for heat radiation insulation, a ceramic circuit board for heat radiation insulation, and a module for heat radiation insulation.

この発明に係る放熱絶縁用セラミック基板はさらに放熱絶縁用セラミックス回路基板に利用可能である。この発明に係る放熱絶縁用セラミックス回路基板として、前記窒化珪素焼結体で形成された基板（以下において窒化珪素焼結体基板と称することがある。）と電気的回路（以下において単に回路と称することがある。）とを有する限り様々の放熱絶縁用セラミックス回路基板を挙げることができる。放熱絶縁用セラミックス回路基板として、例えば、図１に示されるように、この発明に係る窒化珪素焼結体からなる放熱絶縁用セラミック基板１の一方の面に回路金属２を、また他方の面に導電性物質たとえば金属、導電性ペースト等で形成された回路３を形成してなる放熱絶縁用セラミックス回路基板４を挙げることができる。   The ceramic substrate for heat radiation insulation according to the present invention can be further used as a ceramic circuit substrate for heat radiation insulation. As the ceramic circuit substrate for heat radiation insulation according to the present invention, a substrate formed of the silicon nitride sintered body (hereinafter sometimes referred to as a silicon nitride sintered substrate) and an electric circuit (hereinafter simply referred to as a circuit). And various ceramic circuit boards for heat insulation. As shown in FIG. 1, for example, as shown in FIG. 1, a circuit metal 2 is disposed on one surface of a ceramic substrate 1 for heat radiation insulation, and the other surface is disposed on the other surface. A ceramic circuit board 4 for heat radiation insulation formed by forming a circuit 3 made of a conductive material such as metal or conductive paste can be given.

また、図示はしないが、放熱絶縁用セラミックス回路基板として、窒化珪素焼結体からなる２枚の基板で銅放熱板を挟持し、更に一方の窒化珪素焼結体からなる基板の銅放熱板とは反対側の表面に導電層からなる回路を形成してなる放熱絶縁用セラミックス回路基板、及び
窒化珪素焼結体基板の表面に、銅箔及びアルミ箔等の金属箔又は金属の微粉末を使った導電ペースト材で電気回路を形成してなる放熱絶縁用セラミックス回路基板等を挙げることができる。 Although not shown, as a ceramic circuit board for heat radiation insulation, a copper heat sink is sandwiched between two substrates made of a silicon nitride sintered body, and the copper heat sink of the substrate made of one silicon nitride sintered body Use a metal foil such as copper foil and aluminum foil or fine metal powder on the surface of the ceramic circuit board for heat dissipation insulation formed by forming a circuit composed of a conductive layer on the opposite surface, and the silicon nitride sintered body substrate Examples thereof include a ceramic circuit board for heat insulation and formed by forming an electric circuit with a conductive paste material.

さらにまた、放熱回路用基板として、例えば、窒化珪素焼結体基板の一方の表面に、発熱性部品を搭載可能に形成された回路の配線パターンを有する樹脂系耐熱配線板を貼着して成る放熱絶縁用セラミックス回路基板、及び窒化珪素焼結体基板の一方の表面に絶縁層を形成し、その絶縁層の前記窒化珪素焼結体基板に向う表面とは反対側の表面に、導電物質例えば銀ペースト又は金属箔等で回路を形成してなる放熱絶縁用セラミックス回路基板等を挙げることができる。   Furthermore, as the heat dissipation circuit substrate, for example, a resin heat resistant wiring board having a circuit wiring pattern formed so as to be capable of mounting a heat-generating component is attached to one surface of a silicon nitride sintered substrate. An insulating layer is formed on one surface of the ceramic circuit board for heat dissipation insulation and the silicon nitride sintered body substrate, and a conductive material such as a surface of the insulating layer opposite to the surface facing the silicon nitride sintered body substrate is provided. Examples thereof include a ceramic circuit board for heat insulation and formed by forming a circuit with silver paste or metal foil.

この発明に係る放熱絶縁用セラミック基板は、例えば、ハイブリッド自動車、電気自動車、燃料電池自動車等に搭載されるインバータユニット用パワーモジュールに使用される回路基板に好適に使用されることができる。   The ceramic substrate for heat radiation insulation according to the present invention can be suitably used for a circuit board used for a power module for an inverter unit mounted on, for example, a hybrid vehicle, an electric vehicle, a fuel cell vehicle and the like.

この発明に係る窒化珪素焼結体を利用してこの発明に係る放熱絶縁用モジュールが形成される。   The module for heat radiation insulation according to the present invention is formed using the silicon nitride sintered body according to the present invention.

図２に示されるように、この発明に係る放熱絶縁用モジュールの一例としての放熱絶縁用モジュール５は、モジュールケース６と、そのモジュールケース６の底面に嵌着された、この発明の一例である放熱用セラミック基板である窒化珪素焼結体基板１を搭載した放熱板７と、その放熱板７の上面に搭載された放熱用セラミック基板１と、その基板１の上面に形成された半導体チップ９及び回路１０と、モジュールケースの回路設置部８の上面に形成された回路１１と、前記半導体チップ９と回路１０とを電気的に結合するワイヤボンディング１２及び前記回路１０と回路１１とを電気的に結合するワイヤボンディング１２と、これらをモールドする樹脂封止部材１３とを有して形成される。   As shown in FIG. 2, a heat dissipation / insulation module 5 as an example of a heat dissipation / insulation module according to the present invention is an example of the present invention fitted to a module case 6 and the bottom surface of the module case 6. A heat radiating plate 7 on which a silicon nitride sintered substrate 1 that is a heat radiating ceramic substrate is mounted, a heat radiating ceramic substrate 1 mounted on the upper surface of the heat radiating plate 7, and a semiconductor chip 9 formed on the upper surface of the substrate 1. And the circuit 10, the circuit 11 formed on the upper surface of the circuit installation portion 8 of the module case, the wire bonding 12 that electrically couples the semiconductor chip 9 and the circuit 10, and the circuit 10 and the circuit 11 are electrically connected. The wire bonding 12 is bonded to the resin, and the resin sealing member 13 for molding them is formed.

また、図示はしないが、この発明に係る放熱絶縁用モジュールとして、例えば、銅板又は銅合金板の表面に、アルミニウム板、窒化珪素基板及びパワーデバイスをこの順に積層してなるパワーモジュール、２枚の窒化珪素基板で銅放熱板を挟持し、更に一方の窒化珪素基板の銅放熱板とは反対側の表面に導電層からなる回路を形成し、更に前記回路にパワーデバイスを搭載してなるパワーモジュール、及び、Ｐ型半導体とＮ型半導体とを交互に配列すると共にこれらＰ型半導体とＮ型半導体とを電気的に直列に接続することにより直列接続体を形成し、この直列接続体を２枚の窒化珪素基板で挟んでなる、ペルチエ素子でもあるサーモモジュール等を挙げることができる。   Although not shown in the drawings, as the heat radiation insulating module according to the present invention, for example, a power module in which an aluminum plate, a silicon nitride substrate and a power device are laminated in this order on the surface of a copper plate or a copper alloy plate, A power module in which a copper heat sink is sandwiched between silicon nitride substrates, a circuit made of a conductive layer is formed on the surface of one silicon nitride substrate opposite to the copper heat sink, and a power device is mounted on the circuit. In addition, the P-type semiconductor and the N-type semiconductor are alternately arranged and the P-type semiconductor and the N-type semiconductor are electrically connected in series to form a series connection body. Two series connection bodies are formed. And a thermo module which is also a Peltier element sandwiched between two silicon nitride substrates.

（実施例１〜６及び比較例１〜１２）
表１に示される配合割合の、平均粒径が０．５μｍである窒化珪素原料粉末と、表１及び表２に示される配合割合の、表１及び表２に示される元素の酸化物とを配合し、得られる配合物をエタノール中にて粉砕混合した。次いで、エタノールを除去して乾燥することにより調合粉末を得、この調合粉末をプレス成形して直径２０ｍｍ及び厚さ１０ｍｍの成形体に成形した。この成形体をさらに２トンの圧力でＣＩＰ処理をして加圧成形体を得た。この加圧成形体を炭化珪素で形成された焼成容器に収容し、１９００℃で４時間焼成を行った。この焼成処理に際し、炭化珪素製焼成容器自体に焼成雰囲気処理をせず、また、焼成雰囲気として詰粉を使用せず、要するに焼成雰囲気調整を全く行わなかった。 (Examples 1-6 and Comparative Examples 1-12)
A silicon nitride raw material powder having an average particle size of 0.5 μm with a blending ratio shown in Table 1 and an oxide of an element shown in Table 1 and Table 2 with a blending ratio shown in Tables 1 and 2 The resulting blend was pulverized and mixed in ethanol. Subsequently, ethanol was removed and dried to obtain a blended powder. The blended powder was press-molded to form a molded body having a diameter of 20 mm and a thickness of 10 mm. This molded body was further subjected to CIP treatment at a pressure of 2 tons to obtain a pressure molded body. This press-molded body was accommodated in a firing container formed of silicon carbide and fired at 1900 ° C. for 4 hours. During this firing treatment, the firing atmosphere treatment was not performed on the silicon carbide firing container itself, and no filling powder was used as the firing atmosphere. In short, the firing atmosphere was not adjusted at all.

焼成後に得られた窒化珪素焼結体は、アルキメデス法によりその密度が測定された。理論密度との相関からこれらの窒化珪素焼結体の緻密度が評価された。   The density of the silicon nitride sintered body obtained after firing was measured by the Archimedes method. The density of these silicon nitride sintered bodies was evaluated from the correlation with the theoretical density.

また、これらの窒化珪素焼結体の熱伝導率は、これらの窒化珪素焼結体を直径１０ｍｍ及び厚さ２ｍｍのテストピースに加工し、このテストピースにつきレーザーフラッシュ法により、測定された。   Moreover, the thermal conductivity of these silicon nitride sintered bodies was measured by laser flashing the test pieces after processing these silicon nitride sintered bodies into test pieces having a diameter of 10 mm and a thickness of 2 mm.

これらの窒化珪素焼結体の強度及び靭性が強度はＪＩＳ Ｒ１６０１、靭性はＪＩＳ Ｒ１６０７に準拠して測定された。   The strength and toughness of these silicon nitride sintered bodies were measured according to JIS R1601 and toughness according to JIS R1607.

これらの窒化珪素焼結体の耐電圧は以下のようにして測定された。   The withstand voltage of these silicon nitride sintered bodies was measured as follows.

前記窒化珪素焼結体を０．３ｍｍに研磨加工した後、ＪＩＳ Ｃ２１１０「固体電気絶縁材料の絶縁耐力の試験方法」に基づく常態油中耐電圧測定を行うことにより求めた。ここで、絶縁破壊電圧測定の際に使用した電極形状を図３に示す。図３において、２１で示すのは上部電極であり、２２で示すのは試料である窒化珪素焼結体であり、２３で示すのは下部電極である。尚、ＪＩＳ規格での試料厚さは２ｍｍあるいは３ｍｍであるが、半導体用絶縁基板への適用においては、実際の基板厚さが約０．３ｍｍで使用されることが多いために、本試験での試料厚さは０．３ｍｍとした。   After the silicon nitride sintered body was polished to 0.3 mm, it was obtained by performing withstand voltage measurement in normal oil based on JIS C2110 “Test Method for Dielectric Strength of Solid Electrical Insulating Material”. Here, the electrode shape used in the measurement of the dielectric breakdown voltage is shown in FIG. In FIG. 3, reference numeral 21 denotes an upper electrode, reference numeral 22 denotes a silicon nitride sintered body as a sample, and reference numeral 23 denotes a lower electrode. Note that the sample thickness in the JIS standard is 2 mm or 3 mm, but in application to an insulating substrate for semiconductors, the actual substrate thickness is often used at about 0.3 mm. The sample thickness was 0.3 mm.

前記窒化珪素焼結体のラマンピーク強度比（Ｓ１／Ｓ２）は以下のようにして測定された。   The Raman peak intensity ratio (S1 / S2) of the silicon nitride sintered body was measured as follows.

下記の測定条件によるラマン分光分析における波数５２１±２ｃｍ−１の珪素のピーク強度（Ｓ１）及び２０６±２ｃｍ−１の窒化珪素のピーク強度（Ｓ２）によりピーク強度比（Ｓ１／Ｓ２）を求めた。 Peak intensity ratio (S1 / S2) was determined by the peak intensity of silicon nitride wave number 521 silicon peak intensity at ± 2cm -1 (S1) and 206 ± 2 cm -1 in the Raman spectroscopic analysis (S2) by the following measuring conditions .

測定条件：ラマン分光分析装置は、フランスＩＳＡ社製「Ｌａｂｒａｍ Ａｒレーザー（波長５１４．５ｍｍ）」を用いた。レーザー出力は２０ｍＷ、レーザービームのスポット径は約１０μｍ、レーザービームの試料に対する積算照射時間は約１０秒、及び散乱光はＣＣＤセンサーにより検出した。   Measurement conditions: The Raman spectroscopic analyzer used was a “Labram Ar laser (wavelength 514.5 mm)” manufactured by France ISA. The laser output was 20 mW, the laser beam spot diameter was about 10 μm, the integrated irradiation time of the laser beam sample was about 10 seconds, and the scattered light was detected by a CCD sensor.

これらの測定結果を表１に示した。   These measurement results are shown in Table 1.

Figure 2008063187
Figure 2008063187

Figure 2008063187
Figure 2008063187

結晶相は希土類のシリコンオキシナイトライド（RESiO2N）が主であった。 The crystal phase was mainly rare earth silicon oxynitride (RESiO 2 N).

図１はこの発明の放熱絶縁用回路基板の一例を示す断面説明図である。FIG. 1 is a cross-sectional explanatory view showing an example of a circuit board for heat radiation insulation of the present invention. 図２はこの発明の放熱絶縁用モジュールの一例を示す断面説明図である。FIG. 2 is an explanatory cross-sectional view showing an example of a module for heat radiation insulation of the present invention. 図３は絶縁破壊電圧測定の際に使用した電極形状を示す模式図である。FIG. 3 is a schematic diagram showing the electrode shape used in measuring the dielectric breakdown voltage.

符号の説明Explanation of symbols

１ 放熱用セラミック基板
２ 回路金属
３ 回路金属
４ 放熱絶縁用回路基板
５ 放熱絶縁用モジュール
６ モジュールケース
７ 放熱板
８ モジュールケースの回路設置部
９ 半導体チップ
１０ 回路
１１ 回路
１２ ワイヤボンディング
１３ 樹脂封止部材
２１ 上部電極
２２ 試料
２３ 下部電極 DESCRIPTION OF SYMBOLS 1 Ceramic substrate for heat radiation 2 Circuit metal 3 Circuit metal 4 Circuit board for heat radiation insulation 5 Module for heat radiation insulation 6 Module case 7 Heat sink 8 Circuit installation part 9 of a module case Semiconductor chip 10 Circuit 11 Circuit 12 Wire bonding 13 Resin sealing member 21 Upper electrode 22 Sample 23 Lower electrode

Claims (7)

Ｓi３Ｎ４と、ＩＵＰＡＣ１９９０年勧告による周期律表におけるランタノイドのうちＬａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、及びＳｍより成る群から選択される少なくとも１種の軽希土類元素と、ＩＵＰＡＣ１９９０年勧告による周期律表におけるランタノイドのうちＥｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、及びＬｕより成る群から選択される少なくとも１種の重希土類元素及び／又はＹと、Ｓrとを含有する窒化珪素焼結体であって、
Ｓi３Ｎ４と、前記軽希土類元素の酸化物と、前記重希土類元素及び／又はＹの酸化物と、Ｓｒの酸化物との合計が１００モル％となるように、Ｓi３Ｎ４の含有割合が８５〜９０モル％の範囲内にあり、前記軽希土類元素の含有割合が酸化物換算で１〜５モル％の範囲内にあり、前記重希土類元素及び／又はＹの含有割合が酸化物換算で１〜５モル％の範囲内にあり、Ｓrの含有割合が酸化物換算で３〜１３モル％の範囲内にあり、
ラマン分光分析における波数５２１±２ｃｍ−１の珪素ピーク強度をＳ１、２０６±２ｃｍ−１の窒化珪素のピーク強度をＳ２とした場合に、Ｓ１／Ｓ２で表されるピーク強度比が０．１未満であることを特徴とする窒化珪素焼結体。 Si 3 N 4 and at least one light rare earth element selected from the group consisting of La, Ce, Pr, Nd, Pm, and Sm among the lanthanoids in the periodic table according to the IUPAC 1990 recommendation, and the cycle according to the IUPAC 1990 recommendation Nitrid containing at least one heavy rare earth element and / or Y selected from the group consisting of Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu among the lanthanoids in the table and Sr A silicon sintered body,
The content of Si 3 N 4 so that the total of Si 3 N 4 , the light rare earth element oxide, the heavy rare earth element and / or Y oxide, and the Sr oxide is 100 mol%. The ratio is in the range of 85 to 90 mol%, the light rare earth element content is in the range of 1 to 5 mol% in terms of oxide, and the heavy rare earth element and / or Y content is oxide. In the range of 1 to 5 mol% in terms of conversion, the content ratio of Sr is in the range of 3 to 13 mol% in terms of oxide,
The peak intensity ratio represented by S1 / S2 is less than 0.1 when the silicon peak intensity at wave number 521 ± 2 cm −1 in Raman spectroscopic analysis is S1, and the peak intensity of silicon nitride at 206 ± 2 cm −1 is S2. A silicon nitride sintered body characterized by being: Ａｌを酸化物換算で、Ｓi３Ｎ４と、前記軽希土類元素の酸化物と、前記重希土類元素及び／又はＹの酸化物と、Ｓｒの酸化物との合計を１００モル％とするときに、０．４モル％以下の含有割合で含有して成る前記請求項１に記載の窒化珪素焼結体。 When the total of Si 3 N 4 , the light rare earth element oxide, the heavy rare earth element and / or Y oxide, and the Sr oxide is 100 mol% in terms of oxide of Al The silicon nitride sintered body according to claim 1, wherein the silicon nitride sintered body is contained at a content ratio of 0.4 mol% or less. 前記軽希土類が、Ｌａ、Ｃｅ、Ｐｒ及びＮｄから選ばれる少なくとも１種である請求項１又は２に記載の窒化珪素焼結体。   The silicon nitride sintered body according to claim 1 or 2, wherein the light rare earth is at least one selected from La, Ce, Pr, and Nd. 前記重希土類元素が、Ｈｏ、Ｅｒ、Ｙｂ及びＤｙから選ばれる１種である請求項１〜３のいずれか一項に記載の窒化珪素焼結体。   The silicon nitride sintered body according to any one of claims 1 to 3, wherein the heavy rare earth element is one selected from Ho, Er, Yb, and Dy. 前記請求項１〜４のいずれかに記載の窒化珪素焼結体を用いた放熱絶縁用セラミックス基板。   A ceramic substrate for heat dissipation insulation using the silicon nitride sintered body according to any one of claims 1 to 4. 前記請求項１〜４のいずれかに記載の窒化珪素焼結体を用いた放熱絶縁用セラミックス回路基板。   A ceramic circuit board for heat dissipation insulation using the silicon nitride sintered body according to any one of claims 1 to 4. 前記請求項１〜４のいずれかに記載の窒化珪素焼結体を用いた放熱絶縁用モジュール。   A module for heat dissipation insulation using the silicon nitride sintered body according to any one of claims 1 to 4.
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