JP2000272968A - Silicon nitride sintered body and method for producing the same - Google Patents
Silicon nitride sintered body and method for producing the sameInfo
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- JP2000272968A JP2000272968A JP11083552A JP8355299A JP2000272968A JP 2000272968 A JP2000272968 A JP 2000272968A JP 11083552 A JP11083552 A JP 11083552A JP 8355299 A JP8355299 A JP 8355299A JP 2000272968 A JP2000272968 A JP 2000272968A
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- sintered body
- silicon nitride
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- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 54
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 13
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 13
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 13
- 238000013001 point bending Methods 0.000 claims abstract description 7
- 238000005245 sintering Methods 0.000 claims description 57
- 239000000843 powder Substances 0.000 claims description 39
- 239000012298 atmosphere Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 16
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 16
- 230000001590 oxidative effect Effects 0.000 claims description 16
- 239000011863 silicon-based powder Substances 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011812 mixed powder Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 150000004767 nitrides Chemical class 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 11
- 230000004580 weight loss Effects 0.000 description 11
- 238000009826 distribution Methods 0.000 description 9
- 238000005121 nitriding Methods 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 150000003949 imides Chemical class 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000013585 weight reducing agent Substances 0.000 description 3
- PCTMTFRHKVHKIS-BMFZQQSSSA-N (1s,3r,4e,6e,8e,10e,12e,14e,16e,18s,19r,20r,21s,25r,27r,30r,31r,33s,35r,37s,38r)-3-[(2r,3s,4s,5s,6r)-4-amino-3,5-dihydroxy-6-methyloxan-2-yl]oxy-19,25,27,30,31,33,35,37-octahydroxy-18,20,21-trimethyl-23-oxo-22,39-dioxabicyclo[33.3.1]nonatriaconta-4,6,8,10 Chemical compound C1C=C2C[C@@H](OS(O)(=O)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2.O[C@H]1[C@@H](N)[C@H](O)[C@@H](C)O[C@H]1O[C@H]1/C=C/C=C/C=C/C=C/C=C/C=C/C=C/[C@H](C)[C@@H](O)[C@@H](C)[C@H](C)OC(=O)C[C@H](O)C[C@H](O)CC[C@@H](O)[C@H](O)C[C@H](O)C[C@](O)(C[C@H](O)[C@H]2C(O)=O)O[C@H]2C1 PCTMTFRHKVHKIS-BMFZQQSSSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- 238000007088 Archimedes method Methods 0.000 description 1
- 206010053567 Coagulopathies Diseases 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000035602 clotting Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 239000002470 thermal conductor Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Ceramic Products (AREA)
Abstract
(57)【要約】
【課題】 電子部品材料等として好適な高熱伝導性の窒
化ケイ素焼結体、及びその生産性に優れた製造方法を提
供する。
【解決手段】 窒化ケイ素以外の第一成分として希土類
元素の少なくとも１種、第二成分としてアルカリ土類元
素、Ｌｉ、Ｓｒの少なくとも１種を含み、酸化物に換算
したモル比率で第一成分が０.９５〜７.７モル％及び第
二成分が０.４９〜４.７モル％であって、第一成分の濃
度は中心部イより表面部ロが相対的に高く、第二成分の
濃度は表面部ロより中心部イが相対的に高い。特に開気
孔率が５％以下で且つ熱伝導率が１００Ｗ／ｍ・Ｋ以上
であり、４点曲げ強度が７００ＭＰａ以上の焼結体が得
られる。
PROBLEM TO BE SOLVED: To provide a highly thermally conductive silicon nitride sintered body suitable as an electronic component material and the like, and a production method excellent in productivity thereof. SOLUTION: The first component other than silicon nitride contains at least one rare earth element as a first component, and at least one alkaline earth element, Li, and Sr as a second component, and the first component has a molar ratio converted to oxide. 0.95 to 7.7 mol% and the second component is 0.49 to 4.7 mol%, and the concentration of the first component is relatively higher at the surface than at the center a and the concentration of the second component is higher. The concentration is relatively higher at the central part than at the surface part. In particular, a sintered body having an open porosity of 5% or less, a thermal conductivity of 100 W / m · K or more, and a four-point bending strength of 700 MPa or more is obtained.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、例えば半導体基
板、プリント配線基板等の電気絶縁材料や、高熱伝導性
の機械部品材料として適しており、特に１００Ｗ／ｍ・
Ｋ以上の高い熱伝導性を有する窒化ケイ素焼結体、及び
その製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is suitable as an electrical insulating material for a semiconductor substrate, a printed wiring board, or the like, or a high thermal conductive mechanical component material.
The present invention relates to a silicon nitride sintered body having high thermal conductivity of K or more, and a method for producing the same.
【０００２】[0002]
【従来の技術】窒化ケイ素（Ｓｉ3Ｎ4）セラミックス
は、高い機械的特性と耐熱衝撃性を有することから、従
来より構造用部品であるエンジン部品及びガスタービン
用部品等としての利用が試みられている。しかし、窒化
アルミニウム（ＡｌＮ）や炭化ケイ素（ＳｉＣ）のよう
なセラミックスと比較して、機械的特性には優れている
ものの熱伝導率が低いため、例えば半導体用部品のよう
な特に放熱性を要求される分野への利用が進まないとい
う問題があった。2. Description of the Related Art Silicon nitride (Si 3 N 4 ) ceramics have high mechanical properties and thermal shock resistance, and have been conventionally used as structural parts such as engine parts and gas turbine parts. ing. However, as compared with ceramics such as aluminum nitride (AlN) and silicon carbide (SiC), they have excellent mechanical properties but low thermal conductivity. There is a problem that the use in the field to be performed does not progress.
【０００３】近年、このような問題を解決するために、
高熱伝導性を持つ窒化ケイ素セラミックスが開発されつ
つある。例えば、特許第２７７４７６１号公報には、希
土類酸化物を２〜７.５重量％、Ｔｉ、Ｚｒ、Ｈｆ、
Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗの化合物の少なくとも
１種を０.２〜３.０重量％、及びＬｉ、Ｎａ、Ｋ、Ｆ
ｅ、Ｃａ、Ｍｇ、Ｓｒ、Ｂａ、Ｍｎ、Ｂの化合物の少な
くとも１種を０.３重量％以下含有する高熱伝導性の窒
化ケイ素焼結体が開示されている。In recent years, in order to solve such a problem,
Silicon nitride ceramics having high thermal conductivity are being developed. For example, Japanese Patent No. 2774761 discloses that a rare earth oxide contains 2 to 7.5% by weight of Ti, Zr, Hf,
V, Nb, Ta, Cr, Mo, W, at least one compound of 0.2 to 3.0% by weight, and Li, Na, K, F
A highly thermally conductive silicon nitride sintered body containing at least 0.3% by weight of at least one of compounds of e, Ca, Mg, Sr, Ba, Mn, and B is disclosed.
【０００４】[0004]
【発明が解決しようとする課題】上記の特許第２７７４
７６１号公報に記載された窒化ケイ素焼結体は、熱伝導
率が高いといっても８５Ｗ／ｍ・Ｋ程度に過ぎず、１０
０Ｗ／ｍ・Ｋを越えることは殆どない。このため、現状
の窒化アルミニウムや炭化ケイ素のような高熱伝導セラ
ミックスの代替品として使用するためには、更に熱伝導
率を高める必要があった。The above-mentioned patent No. 2774
The silicon nitride sintered body described in Japanese Patent No. 761 has a high thermal conductivity of only about 85 W / m · K,
It hardly exceeds 0 W / m · K. For this reason, in order to use it as a substitute for the current high thermal conductive ceramics such as aluminum nitride and silicon carbide, it was necessary to further increase the thermal conductivity.
【０００５】このように窒化ケイ素焼結体の熱伝導率が
低い原因として考えられる要因は、窒化ケイ素の焼結に
焼結助剤が不可欠であり、この焼結助剤からなる粒界相
の熱伝導率が低いことによる。従って、熱伝導率向上の
ための一手段として、焼結助剤の添加量を減らし、焼結
体中の粒界相を減少させる方法が考えられる。[0005] As a factor considered as a cause of the low thermal conductivity of the silicon nitride sintered body, a sintering aid is indispensable for sintering of silicon nitride, and a grain boundary phase composed of the sintering aid is formed. Due to low thermal conductivity. Therefore, as one means for improving the thermal conductivity, a method of reducing the addition amount of the sintering aid and reducing the grain boundary phase in the sintered body can be considered.
【０００６】しかし、一般に窒化ケイ素の焼結では、焼
結助剤を少なくすると焼結性が低下することが知られて
おり、その場合には２０００℃以上の高い温度で焼結す
るなど、焼結性を促進させる特別な方法が必要となる。
このため、生産性が低下したり、通常の常圧焼結では焼
結体の開気孔率が５％以上に増加して、半導体用等の電
子部品材料として適さなくなるなどの問題があった。However, in sintering silicon nitride, it is generally known that the sinterability decreases when the amount of the sintering aid is reduced. In this case, sintering is performed at a high temperature of 2000 ° C. or more. A special method is needed to promote clotting.
For this reason, there have been problems such as a decrease in productivity and an increase in the open porosity of the sintered body to 5% or more in ordinary normal pressure sintering, which makes the sintered body unsuitable as an electronic component material for semiconductors and the like.
【０００７】本発明は、かかる従来の事情に鑑み、電子
部品材料等として好適な高熱伝導性の窒化ケイ素焼結
体、及びその生産性に優れた製造方法を提供することを
目的としている。The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a silicon nitride sintered body having high thermal conductivity suitable as an electronic component material and the like, and a manufacturing method excellent in productivity thereof.
【０００８】[0008]
【課題を解決するための手段】上記目的を達成するた
め、本発明が提供する窒化ケイ素焼結体は、窒化ケイ素
を主成分とし、それ以外の第一成分として希土類元素の
少なくとも１種、及び第二成分としてアルカリ土類元素
及びＬｉ、Ｓｒからなる群から選ばれた少なくとも１種
を含み、前記第一成分の酸化物に換算したモル比率が
０.９５〜７.７モル％、前記第二成分の酸化物に換算し
たモル比率が０.４９〜４.７モル％であって、第一成分
の濃度は中心部より表面部が相対的に高く、且つ第二成
分の濃度は表面部より中心部が相対的に高いことを特徴
とする。In order to achieve the above object, a silicon nitride sintered body provided by the present invention comprises silicon nitride as a main component, and at least one rare earth element as a first component other than the above. The second component contains at least one element selected from the group consisting of alkaline earth elements, Li, and Sr, and has a molar ratio of 0.95 to 7.7 mol% in terms of the oxide of the first component. The molar ratio in terms of the two-component oxide is 0.49 to 4.7 mol%, the concentration of the first component is relatively higher at the surface than at the center, and the concentration of the second component is higher than the surface. It is characterized in that the central part is relatively high.
【０００９】上記の窒化ケイ素焼結体は、開気孔率が５
％以下であって且つ熱伝導率が１００Ｗ／ｍ・Ｋ以上で
あることを特徴とする。また、ＪＩＳ Ｒ１６０１に準
拠した４点曲げ強度が、７００ＭＰａ以上である。The above silicon nitride sintered body has an open porosity of 5
% Or less and a thermal conductivity of 100 W / m · K or more. Further, the four-point bending strength according to JIS R1601 is 700 MPa or more.
【００１０】また、本発明の窒化ケイ素焼結体の製造方
法の一つは、窒化ケイ素粉末に、第一成分として希土類
元素の少なくとも１種の化合物粉末を酸化物に換算した
モル比率で０.９８〜７.７モル％、及び第二成分として
アルカリ土類元素及びＬｉ、Ｓｒからなる群から選ばれ
た少なくとも１種の化合物粉末を酸化物に換算したモル
比率で０.５０〜６.４モル％となるように混合し、その
混合粉末の成形体を窒素含有非酸化性雰囲気中にて１８
００〜２１００℃の温度範囲で焼結して、２〜２０重量
％の範囲で重量減少させると共に、第一成分の酸化物に
換算したモル比率を０.９５〜７.７モル％、及び第二成
分の酸化物に換算したモル比率を０.４９〜４.７モル％
とすることを特徴とする。Further, one of the methods for producing a silicon nitride sintered body of the present invention is a method in which at least one compound powder of a rare earth element as a first component is added to silicon nitride powder in a molar ratio of 0.1 as an oxide. 98 to 7.7 mol%, and at least one compound powder selected from the group consisting of alkaline earth elements, Li, and Sr as the second component in a molar ratio of 0.50 to 6.4 in terms of oxide. Mol%, and the compact of the mixed powder is mixed in a nitrogen-containing non-oxidizing atmosphere at 18%.
Sintering in the temperature range of 00 to 2100 ° C. to reduce the weight in the range of 2 to 20% by weight, and the molar ratio converted to the oxide of the first component is 0.95 to 7.7% by mole; The molar ratio converted to the two-component oxide is 0.49 to 4.7 mol%
It is characterized by the following.
【００１１】本発明の窒化ケイ素焼結体の他の製造方法
は、ケイ素粉末又はケイ素粉末と窒化ケイ素粉末に、第
一成分として希土類元素の化合物の少なくとも１種の化
合物粉末を酸化物に換算したモル比率がケイ素を窒化ケ
イ素に換算したとき０.９８〜７.７モル％、及び第二成
分としてアルカリ土類元素及びＬｉ、Ｓｒからなる群か
ら選ばれた少なくとも１種の化合物粉末を酸化物に換算
したモル比率がケイ素を窒化ケイ素に換算したとき０.
５０〜６.４モル％となるように混合し、その混合粉末
の形成体を窒素含有非酸化性雰囲気中にて１２００〜１
４００℃の温度範囲で窒化し、得られた窒化体を窒素含
有非酸化性雰囲気中にて１８００〜２１００℃の温度範
囲で焼結して、２〜２０重量％の範囲で重量減少させる
と共に、第一成分の酸化物に換算したモル比率を０.９
５〜７.７モル％、及び第二成分の酸化物に換算したモ
ル比率を０.４９〜４.７モル％とすることを特徴とす
る。According to another method for producing a silicon nitride sintered body of the present invention, at least one compound powder of a compound of a rare earth element as a first component is converted into an oxide in a silicon powder or a silicon powder and a silicon nitride powder. A molar ratio of 0.98 to 7.7 mol% when silicon is converted to silicon nitride, and at least one compound powder selected from the group consisting of an alkaline earth element, Li, and Sr as a second component; When converted to silicon nitride, the molar ratio is calculated as 0.1.
50 to 6.4 mol%, and the formed product of the mixed powder is mixed in a nitrogen-containing non-oxidizing atmosphere at 1200 to 1 mol%.
Nitriding in a temperature range of 400 ° C., and sintering the obtained nitride in a nitrogen-containing non-oxidizing atmosphere at a temperature range of 1800 to 2100 ° C. to reduce weight in a range of 2 to 20% by weight; The molar ratio converted to the oxide of the first component is 0.9.
It is characterized in that the molar ratio in terms of 5 to 7.7 mol% and the oxide of the second component is 0.49 to 4.7 mol%.
【００１２】[0012]
【発明の実施の形態】本発明の窒化ケイ素焼結体は、窒
化ケイ素の外に、焼結助剤に由来する成分として、希土
類元素の少なくとも１種からなる第一成分と、アルカリ
土類元素及びＬｉ、Ｓｒからなる群から選ばれた少なく
とも１種の第二成分とを含んでいる。第一成分として好
ましい希土類元素は、例えばＹ、Ｙｂ、Ｓｍ、Ｎｄ、Ｅ
ｒ等が挙げられる。尚、このような希土類元素からなる
第一成分を用いることによって、焼結後の色ムラの低減
を図ることもできる。また、第二成分としては、Ｍｇ、
Ｃａ、Ｂａ等のアルカル土類元素と、Ｌｉ及びＳｒがあ
る。これら第二成分の添加により、低温で緻密化を促進
させることができ、焼結性が向上するほか、焼結体の高
熱伝導化を図ることができる。BEST MODE FOR CARRYING OUT THE INVENTION The silicon nitride sintered body of the present invention comprises, in addition to silicon nitride, a first component comprising at least one rare earth element as a component derived from a sintering aid, and an alkaline earth element. And at least one second component selected from the group consisting of Li and Sr. Rare earth elements preferable as the first component include, for example, Y, Yb, Sm, Nd, E
r and the like. The use of the first component made of such a rare earth element can reduce color unevenness after sintering. Further, as the second component, Mg,
There are alkaline earth elements such as Ca and Ba, and Li and Sr. By the addition of these second components, densification can be promoted at a low temperature, sinterability is improved, and high thermal conductivity of the sintered body can be achieved.
【００１３】窒化ケイ素焼結体中の第一成分及び第二成
分の含有量は、それぞれ酸化物に換算したモル比率で、
第一成分が０.９５〜７.７モル％、及び第二成分が０.
４９〜４.７モル％である。これをＳｉ3Ｎ4−第一成分
−第二成分の３元組成図で表わすと、図１のＡＢＣＤで
囲まれた斜線の範囲となる。上記第一成分の含有量が
０.９５モル％未満の場合、焼結に必要な助剤成分が少
なくなるため密度が上がらず、結果的に得られる焼結体
の熱伝導率が低下する。また、第一成分の含有量が７.
７モル％を越える場合、粒界相が増加するため、同じく
焼結体の熱伝導率が低下する。一方、上記第二成分の含
有量が０.４９モル％未満では、緻密化が困難になるほ
か、焼結中にポアーや色ムラが発生し、品質歩留が低下
する。特に電子部品等の用途に必要な開気孔率は５％以
下であり、この開気孔率を越えることが多くなる。逆に
第二成分の含有量が４.７モル％を越えると、粒界相の
量が多くなるため、焼結体の熱伝導特性が低下する。The contents of the first component and the second component in the silicon nitride sintered body are each represented by a molar ratio in terms of oxide,
The first component is 0.95 to 7.7 mol%, and the second component is 0.9%.
49-4.7 mol%. When this is represented by a ternary composition diagram of Si 3 N 4 -first component-second component, it is a hatched area surrounded by ABCD in FIG. When the content of the first component is less than 0.95 mol%, the auxiliary component necessary for sintering is reduced, so that the density does not increase, and the thermal conductivity of the resulting sintered body decreases. The content of the first component is 7.
If it exceeds 7 mol%, the grain boundary phase increases, and the thermal conductivity of the sintered body similarly decreases. On the other hand, if the content of the second component is less than 0.49 mol%, it becomes difficult to obtain a fine structure, and pores and color unevenness occur during sintering, thereby lowering the quality yield. In particular, the open porosity required for applications such as electronic components is 5% or less, and often exceeds this open porosity. Conversely, if the content of the second component exceeds 4.7 mol%, the amount of the grain boundary phase increases, and the thermal conductivity of the sintered body deteriorates.
【００１４】また、本発明の窒化ケイ素焼結体において
は、上記第一成分の濃度は中心部よりも表面部が相対的
に高く、第二成分の濃度は逆に表面部より中心部が相対
的に高くなっている。このような濃度分布を焼結初期で
形成することによって、焼結中期以降の表面からの助剤
成分、特に第二成分の過度な蒸発が抑えられる。また同
時に、適度な量の助剤成分が焼結体の粒界相に残るた
め、焼結性を損なうことなく、高い熱伝導率で且つ高強
度の焼結体を得ることができる。In the silicon nitride sintered body of the present invention, the concentration of the first component is relatively higher at the surface than at the center, and the concentration of the second component is relatively higher at the center than at the surface. It is high. By forming such a concentration distribution in the early stage of sintering, excessive evaporation of the auxiliary component, particularly the second component, from the surface after the middle stage of sintering can be suppressed. At the same time, since an appropriate amount of the auxiliary component remains in the grain boundary phase of the sintered body, a sintered body having high thermal conductivity and high strength can be obtained without impairing sinterability.
【００１５】本発明において中心部及び表面部は以下の
ように定義する。焼結後の未加工の焼結体を三次元的に
見たときの中心をθとし、この中心θを含む焼結体の任
意の表面上の任意の点Ｐと中心θとを結んだ直線の延長
線上にある焼結体の別の表面上の点をＱとする。この線
分ＰＱの長さをｄとし、これを１０等分したとき、中心
θから０.１ｄの距離範囲内の領域を中心部とし、中心
θから０.３ｄ〜０.４ｄの距離範囲内の領域を表面部と
する。例えば、直方体形状の焼結体の場合、焼結体の中
心θを含む断面を示す図３の（ａ）のように、線分ＰＱ
を描くことができ、この線分ＰＱを面内の縦横方向に１
０等分して分割線を引くと、斜線を施したイの領域が中
心部であり、逆方向の斜線を施したロの領域が表面部と
なる。また、例えば図３の（ｂ）に示すように円形の断
面では、その中心θを通る径方向に線分ＰＱを引くこと
ができ、この線分ＰＱを１０等分して同心円状の分割線
を描くことができる。この場合、中心部は斜線を施した
イの領域であり、表面部は逆方向の斜線を施したロの領
域である。尚、未加工表面から０.１ｄ未満の最表面領
域を除くのは、この領域では第一成分及び第二成分共に
濃度が薄く、その相対的な評価を行うのが困難なためで
ある。また、通常の焼結体厚みｄは０.５〜７ｍｍ程度
である。In the present invention, the central part and the surface part are defined as follows. The center when the unprocessed sintered body after sintering is three-dimensionally viewed as θ, and a straight line connecting an arbitrary point P on the arbitrary surface of the sintered body including the center θ and the center θ. A point on another surface of the sintered body that is on an extension of the above is referred to as Q. When the length of this line segment PQ is d, and this is divided into ten equal parts, the area within a distance range of 0.1 d from the center θ is defined as the center, and the area within a range of 0.3 d to 0.4 d from the center θ. Region is defined as a surface portion. For example, in the case of a rectangular parallelepiped sintered body, as shown in FIG. 3A showing a cross section including the center θ of the sintered body, a line segment PQ
Can be drawn, and this line segment PQ is
When the dividing line is drawn by dividing the line into 0 equal parts, the area indicated by the hatched area A is the center and the area indicated by the hatched area in the opposite direction is the surface. Further, for example, in a circular cross section as shown in FIG. 3B, a line segment PQ can be drawn in a radial direction passing through the center θ, and the line segment PQ is divided into ten equal parts to form a concentric dividing line. Can be drawn. In this case, the central portion is a region indicated by an oblique line A, and the surface portion is a region indicated by a reverse oblique line B. The reason why the outermost surface region less than 0.1d is excluded from the unprocessed surface is that the concentration of both the first component and the second component is low in this region, and it is difficult to make a relative evaluation. Further, the normal sintered body thickness d is about 0.5 to 7 mm.
【００１６】以上に説明した特徴を備える本発明の窒化
ケイ素焼結体は、従来に比べて開気孔率が比較的大きい
にも拘らず、高い熱伝導率を有し、更には高い機械的強
度を備えるという特徴を有している。具体的には、開気
孔率が５％以下であって且つ熱伝導率が１００Ｗ／ｍ・
Ｋ以上である窒化ケイ素焼結体が得られ、ＪＩＳ Ｒ１
６０１に準拠した４点曲げ強度を７００ＭＰａ以上とす
ることができる。The silicon nitride sintered body of the present invention having the features described above has a high thermal conductivity and a high mechanical strength despite its relatively large open porosity as compared with the prior art. It has the feature of having. Specifically, the open porosity is 5% or less and the thermal conductivity is 100 W / m ·
A silicon nitride sintered body having a K of not less than K is obtained, and JIS R1
The four-point bending strength according to 601 can be 700 MPa or more.
【００１７】次に、本発明の窒化ケイ素焼結体の製造方
法について説明する。まず、第１の方法は窒化ケイ素粉
末を主原料とするものであり、この窒化ケイ素粉末に、
焼結助剤の第一成分として希土類元素の少なくとも１種
の化合物粉末を、酸化物に換算したモル比率で０.９８
〜７.７モル％、及び第二成分としてアルカリ土類元素
及びＬｉ、Ｓｒからなる群から選ばれた少なくとも１種
の化合物粉末を、酸化物に換算したモル比率で０.５０
〜６.４モル％となるように混合する。この添加割合を
Ｓｉ3Ｎ4−第一成分−第二成分の３元組成図で表わす
と、図２のａｂｃｄで囲まれた斜線の範囲となる。Next, a method for producing the silicon nitride sintered body of the present invention will be described. First, the first method uses silicon nitride powder as a main raw material.
As a first component of the sintering aid, at least one compound powder of a rare earth element is added in a molar ratio of 0.98 in terms of oxide.
7.7 mol%, and at least one compound powder selected from the group consisting of alkaline earth elements, Li, and Sr as the second component in a molar ratio of 0.50 in terms of oxide.
Mix so as to be ~ 6.4 mol%. When this addition ratio is represented by a ternary composition diagram of Si 3 N 4 -first component-second component, it is a range indicated by oblique lines surrounded by abcd in FIG.
【００１８】上記の混合粉末を所定の形状に成形し、得
られた成形体を窒素含有非酸化性雰囲気中において焼結
し、窒化ケイ素焼結体とする。この焼結の際に、焼結温
度、昇温速度、焼結時間等の条件を適宜選択して最適化
することにより、焼結助剤成分を主体に蒸発させて２〜
２０重量％の範囲で重量減少させると共に、焼結体中の
焼結助剤成分である第一成分及び第二成分の含有量を前
記した図１のＡＢＣＤで囲まれた斜線の範囲内に制御す
る。即ち、酸化物に換算したモル比率で、第一成分が
０.９５〜７.７モル％、及び第二成分が０.４９〜４.７
モル％となるように制御する。The above mixed powder is formed into a predetermined shape, and the obtained formed body is sintered in a nitrogen-containing non-oxidizing atmosphere to obtain a silicon nitride sintered body. During the sintering, the conditions such as the sintering temperature, the heating rate, and the sintering time are appropriately selected and optimized so that the sintering aid component is mainly evaporated and the
The weight is reduced within the range of 20% by weight, and the contents of the first and second components, which are sintering aid components, in the sintered body are controlled within the hatched area surrounded by ABCD in FIG. 1 described above. I do. That is, the first component has a molar ratio of 0.95 to 7.7 mol% and the second component has a molar ratio of 0.49 to 4.7 in terms of the oxide.
It controls so that it may become mol%.
【００１９】上記焼結は窒素含有非酸化性雰囲気中にて
１８００〜２１００℃の範囲の温度で行う。焼結温度が
１８００℃未満では、焼結体の重量減少が少なく、前記
のような高熱伝導体としての最適な構造を取ることがで
きない。また、焼結温度が２１００℃を越えると、重量
減少が大きくなり過ぎるため、焼結体中にポアーが発生
し、開気孔率が増大して電子部品材料として適さない。
好ましい焼結温度範囲は１８００〜２０５０℃であり、
このように比較的低い温度で焼結が可能であるため生産
性にも優れている。尚、窒素含有非酸化性雰囲気として
は、窒素ガス、窒素を含む不活性ガス等である。The above sintering is performed at a temperature in the range of 1800 to 2100 ° C. in a nitrogen-containing non-oxidizing atmosphere. When the sintering temperature is lower than 1800 ° C., the weight loss of the sintered body is small, and the above-mentioned optimum structure as a high thermal conductor cannot be obtained. On the other hand, if the sintering temperature exceeds 2100 ° C., the weight loss becomes too large, so that pores are generated in the sintered body and the open porosity increases, which is not suitable as a material for electronic parts.
A preferred sintering temperature range is 1800 to 2050 ° C,
Since sintering can be performed at a relatively low temperature, productivity is excellent. The nitrogen-containing non-oxidizing atmosphere includes a nitrogen gas and an inert gas containing nitrogen.
【００２０】焼結前後の重量減少は、前記第一及び第二
成分からなる粒界相成分又は一部の窒化ケイ素成分が蒸
発・昇華することによって生じると考えられ、特に第二
成分が低温で液相成分を発生させ、蒸発・昇華を促進す
る役割を果していると考えられる。この重量減少を２〜
２０重量％の範囲に調整することによって、得られる窒
化ケイ素焼結体中の焼結助剤成分の濃度分布を、上記し
たように第一成分の濃度は中心部よりも表面部を相対的
に高くし、且つ第二成分の濃度は逆に表面部より中心部
を相対的に高くすることが可能となる。It is considered that the weight loss before and after sintering is caused by the evaporation and sublimation of the grain boundary phase component composed of the first and second components or a part of the silicon nitride component. It is considered that it plays a role of generating a liquid phase component and promoting evaporation and sublimation. This weight loss
By adjusting the concentration in the range of 20% by weight, the concentration distribution of the sintering aid component in the obtained silicon nitride sintered body is adjusted so that the concentration of the first component is relatively higher at the surface than at the center as described above. On the contrary, the concentration of the second component can be made relatively higher in the central portion than in the surface portion.
【００２１】この焼結体全体の重量減少が２％未満で
は、粒界相成分が多く残り、熱伝導率が低下する。重量
減少が２０％を越えると、焼結体の開気孔率が大きくな
ると共に、熱伝導率が低下したり、色ムラが発生したり
するため、電子部品材料として適さなくなる。ここで、
重量減少とは、１００×（成形体重量−焼結体重量）／
成形体重量（％）で定義される。尚、上記の成形体と
は、脱バインダー工程を経た後の試料である。If the weight loss of the entire sintered body is less than 2%, a large amount of the grain boundary phase component remains, and the thermal conductivity decreases. If the weight loss exceeds 20%, the open porosity of the sintered body increases, the thermal conductivity decreases, and color unevenness occurs, which makes the sintered body unsuitable as an electronic component material. here,
Weight reduction is 100 × (molded product weight−sintered product weight) /
It is defined by the weight (%) of the molded body. In addition, the said molded object is a sample after having passed through the binder removal process.
【００２２】上記第１の製造方法において、主原料の窒
化ケイ素粉末としては、酸素を含有しているイミド分解
粉、直接窒化粉のいずれも使用することができる。ま
た、最終的な形態として窒化ケイ素を形成すればよいこ
とから、Ｓｉ粉末を主原料に用いる窒化焼結によること
も可能である。尚、焼結助剤又は主原料中の酸素量のレ
ベルを適宜変えることにより、焼結性等をコントロール
することができる。In the first production method, as the silicon nitride powder as the main raw material, any of imide decomposition powder containing oxygen and direct nitride powder can be used. In addition, since silicon nitride may be formed as a final form, nitriding sintering using Si powder as a main material is also possible. The sintering property and the like can be controlled by appropriately changing the level of the oxygen amount in the sintering aid or the main raw material.
【００２３】即ち、主原料にケイ素粉末を用いる方法が
本発明の第２の製造方法であり、ケイ素粉末のみか又は
ケイ素粉末と窒化ケイ素粉末とを主原料とする。この主
原料に、第一成分の希土類元素の化合物粉末と、第二成
分のアルカリ土類元素、Ｌｉ又はＳｒの化合物粉末と
を、上記第１の製造方法と同じモル比率で、即ち図２の
ａｂｃｄで囲まれた斜線の範囲内となるように混合す
る。ただし、この第２の方法の場合の第一及び第二成分
のモル比率は、ケイ素を窒化ケイ素に換算した主原料を
基準にして、第１の方法と同じく第一成分を０.９８〜
７.７モル％及び第二成分を０.５０〜６.４モル％とす
る。That is, the method of using silicon powder as the main raw material is the second production method of the present invention, and uses only silicon powder or silicon powder and silicon nitride powder as main raw materials. To this main raw material, a compound powder of a rare earth element as a first component and a compound powder of an alkaline earth element, Li or Sr as a second component were mixed in the same molar ratio as in the first production method, that is, in FIG. Mixing is performed so as to be within the range of oblique lines surrounded by abcd. However, the molar ratio of the first and second components in the case of the second method is 0.98 to 0.98 in the same manner as in the first method, based on the main raw material obtained by converting silicon to silicon nitride.
7.7 mol% and the second component are 0.50 to 6.4 mol%.
【００２４】上記混合粉末の成形体は、まず窒素含有非
酸化性雰囲気中において１２００〜１４００℃の温度範
囲で焼成して窒化する。次に、得られた窒化体を窒素含
有非酸化性雰囲気中において１８００〜２１００℃の温
度範囲で焼結し、窒化ケイ素焼結体を得る。この焼結の
際に、焼結温度、昇温速度、焼結時間等の条件を適宜選
択して最適化することによって、２〜２０重量％の範囲
で重量減少させると共に、図１のＡＢＣＤで示す斜線の
範囲内に、即ち酸化物に換算したモル比率で、第一成分
が０.９５〜７.７モル％及び第二成分が０.４９〜４.７
モル％となるように制御する。The compact of the mixed powder is fired and nitrided in a nitrogen-containing non-oxidizing atmosphere at a temperature of 1200 to 1400 ° C. Next, the obtained nitride is sintered in a nitrogen-containing non-oxidizing atmosphere in a temperature range of 1800 to 2100 ° C. to obtain a silicon nitride sintered body. At the time of this sintering, the weight is reduced in the range of 2 to 20% by weight by appropriately selecting and optimizing conditions such as a sintering temperature, a heating rate, and a sintering time. The first component is 0.95 to 7.7 mol% and the second component is 0.49 to 4.7 within the range of the hatched lines shown, that is, in a molar ratio converted to oxide.
It controls so that it may become mol%.
【００２５】窒化時の温度が１２００℃未満では窒化が
不十分であり、逆に１４００℃を越えるとＳｉの融点に
達し、Ｓｉの窒化反応の前にＳｉの溶出反応が生じるた
め、得られる焼結体中に未窒化のＳｉが残留し、このＳ
ｉが熱伝導率や強度の低下の原因となるので好ましくな
い。また、焼結温度を１８００〜２１００℃とする理由
は、前記第１の方法の場合と同じである。尚、窒素含有
非酸化性雰囲気も前記と同様である。If the temperature at the time of nitriding is lower than 1200 ° C., the nitriding is insufficient. On the contrary, if it exceeds 1400 ° C., the melting point of Si is reached, and the elution reaction of Si occurs before the nitriding reaction of Si. Unnitrided Si remains in the compact, and this S
i is not preferable because it causes a decrease in thermal conductivity and strength. The reason for setting the sintering temperature to 1800 to 2100 ° C. is the same as in the case of the first method. The nitrogen-containing non-oxidizing atmosphere is the same as described above.
【００２６】上記した本発明の各製造方法により得られ
る窒化ケイ素焼結体は、前記したように、特に開気孔が
５％以下の材料において、熱伝導率１００Ｗ／ｍ・Ｋ以
上のものが得られる。また、通常ＪＩＳ Ｒ１６０１に
準拠した４点曲げ強度が７００ＭＰａ以上となり、従来
から電子部品基板として使用されていた窒化アルミニウ
ムと比較して高い破壊強度を得ることが可能である。As described above, the silicon nitride sintered body obtained by each of the production methods of the present invention has a thermal conductivity of 100 W / m · K or more, particularly in a material having an open pore of 5% or less. Can be Further, the four-point bending strength based on the normal JIS R1601 is 700 MPa or more, and it is possible to obtain a higher breaking strength than aluminum nitride which has been conventionally used as an electronic component substrate.
【００２７】[0027]
【実施例】実施例１ イミド分解粉により作製されたα型Ｓｉ3Ｎ4粉末（酸素
量１.０重量％、平均粒径１.０μｍ）を原料とし、下記
表１に示す配合割合で焼結助剤粉末を添加した後、エタ
ノール中で分散させた。その後乾燥させ、金型プレスで
直径２０ｍｍ×４ｍｍのペレット状の成形体を作製し
た。次に、この成形体を窒素含有非酸化性雰囲気中に
て、１９００℃で５時間焼成して焼結体を得た。尚、焼
結助剤粉末として、第一成分はＹ2Ｏ3、及び第二成分は
ＭｇＯを用いた。 Example 1 α-type Si 3 N 4 powder (oxygen content: 1.0% by weight, average particle size: 1.0 μm) produced from imide decomposition powder was used as a raw material and calcined at the compounding ratio shown in Table 1 below. After the binder powder was added, it was dispersed in ethanol. Thereafter, it was dried and a pellet-shaped molded body having a diameter of 20 mm x 4 mm was produced by a mold press. Next, this molded body was fired at 1900 ° C. for 5 hours in a nitrogen-containing non-oxidizing atmosphere to obtain a sintered body. As the sintering aid powder, the first component was Y 2 O 3 and the second component was MgO.
【００２８】[0028]
【表１】焼結助剤配合割合(モル％) 試料 第一成分(Y2O3) 第二成分(MgO) 1＊ 0.9 3.0 2 1.0 3.0 3 3.0 3.0 4 6.0 3.0 5 7.5 3.0 6＊ 8.0 3.0 7＊ 3.0 0.4 8 3.0 0.6 9 3.0 5.0 10 3.0 6.0 11＊ 3.0 7.0 （注）表中の＊を付した試料は比較例である。[Table 1] Sintering aid compounding ratio (mol%) Sample first component (Y 2 O 3 ) Second component (MgO) 1 * 0.9 3.0 2 1.0 3.0 3 3.0 3.0 4 6.0 3.0 5 7.5 3.0 6 * 8.0 3.0 7 * 3.0 0.4 8 3.0 0.6 9 3.0 5.0 10 3.0 6.0 11 * 3.0 7.0 Note: Samples marked with * in the table are comparative examples.
【００２９】得られた各Ｓｉ3Ｎ4焼結体について、焼結
前の成形体と焼結体の各重量を測定して重量減少を求め
ると共に、化学分析により焼結体全体の上記各助剤成分
の平均的な含有量（酸化物に換算したモル％）を求め
た。また、アルキメデス法による開気孔率、レーザーフ
ラッシュ法による室温での熱伝導率、及びＪＩＳ Ｒ１
６０に準拠する４点曲げ強度をそれぞれ測定した。尚、
焼結体の開気孔率の算定は、１００×（飽水重量−乾燥
重量）／（飽水重量−水中重量）の計算によって行っ
た。飽水重量とは焼結体を水中に吊るして水を含浸させ
た際の飽和含水状態での重量であり、乾燥重量はこれを
乾燥して一定重量となったときの水を含まない状態での
重量である。これらの結果を下記表２に示した。With respect to each of the obtained Si 3 N 4 sintered bodies, the weight of each of the molded body and the sintered body before sintering was measured to determine the weight reduction, and the above-mentioned auxiliary of the whole sintered body was determined by chemical analysis. The average content of the agent components (mol% in terms of oxide) was determined. The open porosity according to the Archimedes method, the thermal conductivity at room temperature according to the laser flash method, and JIS R1
The four-point bending strength according to No. 60 was measured. still,
The open porosity of the sintered body was calculated by calculating 100 × (saturated weight−dry weight) / (saturated weight−water weight). The saturated weight is the weight in a saturated water-containing state when the sintered body is suspended in water and impregnated with water, and the dry weight is a state in which water is not contained when this is dried to a constant weight. Is the weight. The results are shown in Table 2 below.
【００３０】更に、上記各助剤成分の焼結体中における
濃度分布を調査するために、焼結体を所定の位置で切断
後、その断面を研削及び研磨し、１０００倍の視野に拡
大してＥＰＭＡ元素定量分析により元素濃度を測定し
た。その際、測定箇所である焼結体の中心部が図３に示
すイの部分となり、表面部が図３のロの部分のうち中心
部イの軸方向上下に位置する部分となるように、それぞ
れ焼結体を切断して測定試料片を作成した。各試料の中
心部と表面部の各２カ所について第一成分と第二成分の
金属元素の検出強度をカウントし、カウント量を算術平
均してそれぞれの箇所の成分濃度とし、これを用いて中
心部と表面部のモル比を算定した。その結果、全ての試
料において、第一成分は中心部よりも表面部が高濃度で
あり、第二成分は表面部よりも中心部が高濃度になって
いた。Further, in order to investigate the concentration distribution of each auxiliary component in the sintered body, the sintered body was cut at a predetermined position, and the cross section was ground and polished to enlarge the field of view to 1000 times. The element concentration was measured by EPMA elemental quantitative analysis. At this time, the central portion of the sintered body, which is the measurement point, is a portion shown in FIG. 3 and the surface portion is a portion of the portion shown in FIG. Each of the sintered bodies was cut to prepare a measurement sample piece. The detection intensities of the metal elements of the first component and the second component were counted at each of the two portions of the central portion and the surface portion of each sample, and the count amounts were arithmetically averaged to obtain the component concentration at each portion. The molar ratio between the part and the surface part was calculated. As a result, in all samples, the first component had a higher concentration at the surface than at the center, and the second component had a higher concentration at the center than the surface.
【００３１】[0031]
【表２】 重量減少 助剤成分量(モル％) 開気孔率 熱伝導率 曲げ強度試料 (％) 第一成分 第二成分 (％) (W／mK) (MPa) 1＊ 1.5 0.8 1.5 5.5 82 650 2 3.0 0.95 1.7 2.0 103 720 3 4.5 2.3 1.9 3.5 106 900 4 5.0 4.9 1.8 0.8 115 920 5 8.0 7.1 1.9 0.9 111 750 6＊ 9.0 7.8 1.9 1.5 85 620 7＊ 3.0 2.6 0.1 11.0 75 400 8 3.8 2.5 0.5 4.9 102 720 9 5.5 2.2 3.0 3.2 105 720 10 7.0 2.0 3.2 3.2 101 710 11＊ 9.0 1.8 3.8 3.3 70 600 （注）表中の＊を付した試料は比較例である。[Table 2] Amount of the weight-reducing auxiliary component (mol%) Open porosity Thermal conductivity Flexural strength sample (%) First component Second component (%) (W / mK) (MPa) 1 * 1.5 0.8 1.5 5.5 82 650 2 3.0 0.95 1.7 2.0 103 720 3 4.5 2.3 1.9 3.5 106 900 4 5.0 4.9 1.8 0.8 115 920 5 8.0 7.1 1.9 0.9 111 750 6 * 9.0 7.8 1.9 1.5 85 620 7 * 3.0 2.6 0.1 11.0 75 400 8 3.8 2.5 0.5 4.9 102 720 9 5.5 2.2 3.0 3.2 105 720 10 7.0 2.0 3.2 3.2 101 710 11 * 9.0 1.8 3.8 3.3 70 600 Note: Samples marked with * in the table are comparative examples.
【００３２】上記表２に示す結果から、重量減少が２〜
２０重量％の範囲内にあり、第一成分が０.９５〜７.７
モル％及び第二成分が０.４９〜４.７モル％の範囲で含
まれているとき、第一成分は中心部よりも表面部が高濃
度で且つ第二成分は表面部よりも中心部が高濃度になっ
ていて、熱伝導率及び曲げ強度とも高い窒化ケイ素焼結
体が得られることが分かる。From the results shown in Table 2 above, the weight loss was 2 to
20% by weight, and the first component is 0.95 to 7.7.
When the mol% and the second component are contained in the range of 0.49 to 4.7 mol%, the first component has a higher concentration at the surface than at the center and the second component has a higher concentration at the center than the surface. It can be seen that a silicon nitride sintered body having a high concentration and a high thermal conductivity and high bending strength can be obtained.
【００３３】実施例２ 上記実施例１と同じＳｉ3Ｎ4粉末を使用し、下記表３に
示す各焼結助剤粉末を酸化物換算モル比率において第一
成分が６モル％、同じく第二成分が３モル％、残部の９
１モル％がＳｉ3Ｎ4となるように添加し、エタノール中
で分散させた。その後、実施例１と同様にペレット状の
成形体を作製した後、窒素含有非酸化性雰囲気中にて１
８００℃、５時間の条件で焼結させた。[0033]Example 2 The same Si as in the first embodiment.ThreeNFourUsing powder, see Table 3 below
The sintering aid powders shown are
6 mol% of the component, 3 mol% of the second component, and 9
1 mol% is SiThreeNFourAnd add it in ethanol
And dispersed. After that, pellet-like as in Example 1
After forming the molded body, the molded body is placed in a nitrogen-containing non-oxidizing atmosphere for 1 hour.
Sintering was performed at 800 ° C. for 5 hours.
【００３４】[0034]
【表３】使用焼結助剤の種類 試料 第一成分 第二成分 12 Ｙ2Ｏ3 ＭｇＯ 13 Ｙ2Ｏ3 ＣａＣＯ3 14 Ｙ2Ｏ3 ＢａＯ 15 Ｙ2Ｏ3 ＳｒＯ 16 Ｙ2Ｏ3 ＬｉＯ 17 Ｓｍ2Ｏ3 ＭｇＯ 18 Ｅｒ2Ｏ3 ＭｇＯ 19 Ｄｙ2Ｏ3 ＭｇＯ 20 Ｈｏ2Ｏ3 ＭｇＯ 21 Ｔｍ2Ｏ3 ＭｇＯ 22 Ｌｕ2Ｏ3 ＭｇＯ[Table 3] Types of sintering aids used Sample first component Second component 12 Y 2 O 3 MgO 13 Y 2 O 3 CaCO 3 14 Y 2 O 3 BaO 15 Y 2 O 3 SrO 16 Y 2 O 3 LiO 17 Sm 2 O 3 MgO 18 Er 2 O 3 MgO 19 Dy 2 O 3 MgO 20 Ho 2 O 3 MgO 21 Tm 2 O 3 MgO 22 Lu 2 O 3 MgO
【００３５】得られた各Ｓｉ3Ｎ4焼結体について、上記
実施例１と同様にして、焼結前後での重量減少、助剤成
分の平均的な含有量（酸化物に換算したモル％）、開気
孔率、熱伝導率（室温）、及びＪＩＳ Ｒ１６０に準拠
する４点曲げ強度をそれぞれ測定し、その結果を下記表
４に示した。また、実施例１と同様にして、各焼結体中
の中心部と表面部における助剤成分の濃度分布を求めた
ところ、いずれの試料においても、第一成分は中心部よ
りも表面部が高濃度であり、第二成分は表面部よりも中
心部が高濃度であった。For each of the obtained Si 3 N 4 sintered bodies, the weight loss before and after sintering and the average content of the auxiliary component (mol% in terms of oxide) were measured in the same manner as in Example 1 above. ), Open porosity, thermal conductivity (room temperature), and four-point bending strength according to JIS R160 were measured, and the results are shown in Table 4 below. In addition, when the concentration distribution of the auxiliary component in the central part and the surface part in each sintered body was determined in the same manner as in Example 1, the surface area of the first component was greater than that of the central part in any of the samples. The concentration of the second component was higher in the central part than in the surface part.
【００３６】この結果から、実施例１とは別の焼結助剤
であっても、第一成分が希土類元素の少なくとも１種、
及び第二成分がアルカリ土類元素、Ｌｉ、Ｓｒの少なく
とも１種であれば、高い曲げ強度で且つ高い熱伝導率を
示すＳｉ3Ｎ4焼結体が得られることが分かる。尚、試料
１９〜２２については、焼結体に若干の色ムラの発生が
認められた。From this result, even if the sintering aid is different from that of Example 1, the first component is at least one rare earth element,
It can be seen that when the second component is at least one of alkaline earth elements, Li and Sr, a Si 3 N 4 sintered body having high bending strength and high thermal conductivity can be obtained. In samples 19 to 22, slight color unevenness was observed in the sintered body.
【００３７】[0037]
【表４】 重量減少 助剤成分量(モル％) 開気孔率 熱伝導率 曲げ強度試料 (％) 第一成分 第二成分 (％) (W／mK) (MPa) 12 5.0 4.8 1.9 2.0 112 950 13 3.0 5.2 1.5 1.5 105 880 14 4.0 5.5 1.8 3.0 102 820 15 6.0 4.5 1.7 2.8 106 750 16 5.3 4.7 1.6 2.5 104 780 17 6.0 4.8 1.9 2.1 139 900 18 5.5 4.6 1.8 2.5 130 920 19 6.5 4.5 1.8 2.3 110 980 20 5.8 4.6 1.7 1.5 102 1000 21 5.5 4.7 1.8 2.1 105 970 22 5.2 4.8 1.8 1.8 105 1050[Table 4] Amount (mol%) of open weight porosity Thermal conductivity Flexural strength sample (%) First component Second component (%) (W / mK) (MPa) 12 5.0 4.8 1.9 2.0 112 950 13 3.0 5.2 1.5 1.5 105 880 14 4.0 5.5 1.8 3.0 102 820 15 6.0 4.5 1.7 2.8 106 750 16 5.3 4.7 1.6 2.5 104 780 17 6.0 4.8 1.9 2.1 139 900 18 5.5 4.6 1.8 2.5 130 920 19 6.5 4.5 1.8 2.3 110 980 20 5.8 4.6 1.7 1.5 102 1000 21 5.5 4.7 1.8 2.1 105 970 22 5.2 4.8 1.8 1.8 105 1050
【００３８】実施例３前記実施例１の試料４と同様に
し、ただし下記表５に示すように焼結温度のみを変えて
焼結を行った。得られた各Ｓｉ3Ｎ4焼結体について、実
施例１と同様に各評価を実施して、その結果を表５に併
せて示した。尚、比較例の試料２３と２８の焼結体には
色ムラが発生していた。 Example 3 Sintering was carried out in the same manner as in Sample 4 of Example 1 except that only the sintering temperature was changed as shown in Table 5 below. Each of the obtained Si 3 N 4 sintered bodies was evaluated in the same manner as in Example 1, and the results are shown in Table 5. In addition, color unevenness occurred in the sintered bodies of Samples 23 and 28 of the comparative example.
【００３９】また、実施例１と同様にして、各焼結体中
の中心部と表面部における助剤成分の濃度分布を求めた
ところ、本発明の試料２４〜２７では、第一成分は中心
部よりも表面部が高濃度であり、第二成分は表面部より
も中心部が高濃度であった。しかし、比較例の試料２３
では、第一成分は中心部と表面部でほぼ同一濃度であ
り、第二成分は表面部よりも中心部が高濃度であった。
また、比較例の試料２８では、第一成分は中心部より表
面部が高濃度であったが、第二成分については全体の含
有量が極めて少ないため測定が不可能であった。Further, the concentration distribution of the auxiliary component in the central part and the surface part in each sintered body was determined in the same manner as in Example 1. In Samples 24 to 27 of the present invention, the first component was the central component. The surface part had a higher concentration than the part, and the second component had a higher concentration in the center part than the surface part. However, the comparative sample 23
In Example 1, the first component had substantially the same concentration at the center and the surface, and the second component had a higher concentration at the center than at the surface.
In the sample 28 of the comparative example, the surface concentration of the first component was higher than that of the central portion, but the measurement of the second component was impossible because the total content was extremely small.
【００４０】[0040]
【表５】 焼結温度 重量減少 助剤成分量(モル％) 開気孔率 熱伝導率 曲げ強度試料 (℃) (％) 第一成分 第二成分 (％) (W／mK) (MPa) 23＊ 1750 1.8 5.8 2.5 7.0 70 500 24 1800 4.2 5.5 1.9 0.3 104 1050 25 1900 5.0 4.9 1.8 0.8 115 920 26 2050 10.0 4.5 1.5 1.0 130 920 27 2100 14.0 4.7 1.2 2.2 140 820 28＊ 2200 25.0 4.8 0.1 7.1 102 650 （注）表中の＊を付した試料は比較例である。[Table 5] Sintering temperature Weight reduction aid component amount (mol%) Open porosity Thermal conductivity Flexural strength sample (° C) (%) First component Second component (%) (W / mK) (MPa) 23 * 1750 1.8 5.8 2.5 7.0 70 500 24 1800 4.2 5.5 1.9 0.3 104 1050 25 1900 5.0 4.9 1.8 0.8 115 920 26 2050 10.0 4.5 1.5 1.0 130 920 27 2100 14.0 4.7 1.2 2.2 140 820 28 * 2200 25.0 4.8 0.1 7.1 102 650 ( Note) Samples marked with * in the table are comparative examples.
【００４１】この結果から分かるように、焼結温度が１
８００℃未満では、重量減少が２重量％未満になるた
め、表面部と中心部の第一成分及び第二成分の濃度分布
が均等になりやすく、その結果焼結体が緻密化せず、開
気孔率が５％を越えるうえ、曲げ強度も熱伝導率も低下
している。また、焼結温度が２１００℃を越えると、重
量減少が２０重量％を越えるため、特に第二成分が表面
部で測定できないほど著しく減少し、開気孔率も大幅に
増加し、熱伝導率及び曲げ強度も低下することが分か
る。As can be seen from the results, the sintering temperature was 1
If the temperature is lower than 800 ° C., the weight loss is less than 2% by weight, so that the concentration distribution of the first component and the second component in the surface portion and the central portion tends to be uniform, and as a result, the sintered body is not densified. The porosity exceeds 5%, and the bending strength and the thermal conductivity are reduced. Further, when the sintering temperature exceeds 2100 ° C., the weight loss exceeds 20% by weight. In particular, the second component is remarkably reduced so that it cannot be measured on the surface portion, the open porosity greatly increases, and the thermal conductivity and It can be seen that the bending strength also decreases.
【００４２】実施例４ 直接窒化によるＳｉ3Ｎ4粉末（酸素量１.２重量％、平
均粒径１.２μｍ、α率９１％）か、又はＳｉ粉末（酸
素量０.９重量％、平均粒径０.９μｍ）を主原料とし、
これらの主原料粉末に焼結助剤として前記実施例１と同
じＹ2Ｏ3粉末とＭｇＯ粉末をそれぞれ前記表１の試料４
と同一のモル比率で添加した。混合粉末をエタノール中
で５時間混合し、乾燥させた後、実施例１と同様にペレ
ット状の成形体を作製した。 Example 4 Si 3 N 4 powder by direct nitriding (oxygen content: 1.2% by weight, average particle size: 1.2 μm, α ratio: 91%) or Si powder (oxygen content: 0.9% by weight, average (Particle size 0.9 μm) as the main raw material,
The same Y 2 O 3 powder and MgO powder as in Example 1 were used as sintering aids for these main raw material powders, respectively, as Sample 4 in Table 1 above.
Was added in the same molar ratio as. The mixed powder was mixed in ethanol for 5 hours and dried, and then a pellet-shaped molded body was produced in the same manner as in Example 1.
【００４３】得られた成形体については、Ｓｉ3Ｎ4粉末
を主原料とする試料２９では、そのまま窒素含有非酸化
性雰囲気中にて１８００℃で５時間焼結した。また、Ｓ
ｉ粉末を主原料とする試料３０の場合は、窒素含有非酸
化性雰囲気中にて１２００℃〜１４００℃の条件で窒化
反応を行った後、上記と同様に窒素含有非酸化性雰囲気
中にて１８００℃で５時間焼結した。The obtained molded body was sintered as it was at 1800 ° C. for 5 hours in a nitrogen-containing non-oxidizing atmosphere for sample 29 using Si 3 N 4 powder as a main raw material. Also, S
In the case of the sample 30 using i powder as a main raw material, after performing a nitriding reaction under the condition of 1200 ° C. to 1400 ° C. in a nitrogen-containing non-oxidizing atmosphere, in the same manner as described above, It was sintered at 1800 ° C. for 5 hours.
【００４４】得られた各Ｓｉ3Ｎ4焼結体について、実施
例１と同様に各評価を実施して、その結果を下記表６に
示した。尚、参考例として、前記実施例１と同じイミド
分解によるＳｉ3Ｎ4粉末を用いた以外は、上記と同様に
して得た試料３１の焼結体についても同様の評価を行
い、その結果を表６に併せて示した。また、実施例１と
同様にして、各焼結体中の中心部と表面部における助剤
成分の分布を求めたところ、いずれの試料においても、
第一成分は中心部よりも表面部が高濃度であり、第二成
分は表面部よりも中心部が高濃度であった。Each of the obtained Si 3 N 4 sintered bodies was evaluated in the same manner as in Example 1, and the results are shown in Table 6 below. As a reference example, the same evaluation was performed on the sintered body of the sample 31 obtained in the same manner as above, except that the same imide decomposition Si 3 N 4 powder as in Example 1 was used. The results are shown in Table 6. In addition, in the same manner as in Example 1, the distribution of the auxiliary component at the center and the surface in each sintered body was determined.
The first component had a higher concentration at the surface than at the center, and the second component had a higher concentration at the center than the surface.
【００４５】[0045]
【表６】 重量減少 助剤成分量(モル%) 開気孔率 熱伝導率 曲げ強度試料 主原料粉末 (％) 第一成分 第二成分 (％) (W／mK) (MPa) 29 直接窒化Si3N4 5.5 4.9 1.8 0.5 105 1000 30 Si粉末 4.5 5.0 1.7 0.2 125 1040 31 イミト゛分解Si3N4 5.0 4.9 1.8 0.8 115 1050[Table 6] Amount of the weight-reducing auxiliary component (mol%) Open porosity Thermal conductivity Flexural strength Sample main raw material powder (%) First component Second component (%) (W / mK) (MPa) 29 Direct nitrided Si 3 N 4 5.5 4.9 1.8 0.5 105 1000 30 Si powder 4.5 5.0 1.7 0.2 125 1040 31 Imitated Si 3 N 4 5.0 4.9 1.8 0.8 115 1050
【００４６】直接窒化によるＳｉ3Ｎ4粉末も、イミド分
解によるＳｉ3Ｎ4粉末と同様に使用でき、同様に優れた
特性の焼結体が得られた。また、Ｓｉ粉末のみを主原料
として窒化焼結により得られた焼結体は、イミド分解に
よるＳｉ3Ｎ4粉末とほぼ同様な特性を示すことが認めら
れた。The Si 3 N 4 powder obtained by direct nitriding can be used in the same manner as the Si 3 N 4 powder obtained by decomposition of imide, and a sintered body having similarly excellent characteristics was obtained. In addition, it was confirmed that the sintered body obtained by nitriding sintering using only Si powder as a main raw material exhibited almost the same characteristics as Si 3 N 4 powder by imide decomposition.
【００４７】[0047]
【発明の効果】本発明によれば、特定の焼結助剤成分を
使用し、その成分の焼結体における含有量や濃度分布及
び焼結による重量減少を制御することによって、熱伝導
率の高い窒化ケイ素焼結体を得ることができる。特に、
焼結温度を比較的低くでき、開気孔率が電子部品材料等
として好適な範囲内で従来よりも大きめであって、しか
も熱伝導率及び強度に優れた窒化ケイ素焼結体を提供す
ることができる。According to the present invention, by using a specific sintering aid component and controlling the content and concentration distribution of the component in the sintered body and the weight loss due to sintering, the thermal conductivity is reduced. A high silicon nitride sintered body can be obtained. In particular,
It is possible to provide a silicon nitride sintered body that can have a relatively low sintering temperature, has a larger open porosity than a conventional one within a range suitable for an electronic component material or the like, and has excellent thermal conductivity and strength. it can.
【図１】本発明の窒化ケイ素焼結体中に含まれる第一成
分と第二成分のモル比率を示す３元組成図である。FIG. 1 is a ternary composition diagram showing a molar ratio between a first component and a second component contained in a silicon nitride sintered body of the present invention.
【図２】本発明の窒化ケイ素焼結体の製造方法において
窒化ケイ素粉末に添加する第一成分と第二成分のモル比
率を示す３元組成図である。FIG. 2 is a ternary composition diagram showing a molar ratio of a first component and a second component added to a silicon nitride powder in the method for producing a silicon nitride sintered body of the present invention.
【図３】本発明の窒化ケイ素焼結体の第一成分と第二成
分の濃度分布を測定する際の中心部と表面部を説明する
ための焼結体の断面図であり、（ａ）は直方体の断面の
場合、（ｂ）は円形の断面の場合を示す。FIG. 3 is a cross-sectional view of the sintered body for explaining the central portion and the surface portion when measuring the concentration distribution of the first component and the second component of the silicon nitride sintered body of the present invention, and FIG. Indicates a case of a rectangular parallelepiped cross section, and (b) indicates a case of a circular cross section.
イ 中心部 ロ 表面部 B Center B Surface
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4G001 BA01 BA05 BA06 BA08 BA09 BA32 BA62 BA81 BB01 BB05 BB06 BB07 BB08 BB09 BB32 BC12 BC13 BC46 BC48 BC52 BC54 BC57 BD03 BD14 BD23 BE15 BE33 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4G001 BA01 BA05 BA06 BA08 BA09 BA32 BA62 BA81 BB01 BB05 BB06 BB07 BB08 BB09 BB32 BC12 BC13 BC46 BC48 BC52 BC54 BC57 BD03 BD14 BD23 BE15 BE33
Claims (5)
一成分として希土類元素の少なくとも１種、及び第二成
分としてアルカリ土類元素及びＬｉ、Ｓｒからなる群か
ら選ばれた少なくとも１種を含み、前記第一成分の酸化
物に換算したモル比率が０.９５〜７.７モル％、前記第
二成分の酸化物に換算したモル比率が０.４９〜４.７モ
ル％であって、第一成分の濃度は中心部より表面部が相
対的に高く、且つ第二成分の濃度は表面部より中心部が
相対的に高いことを特徴とする窒化ケイ素焼結体。Claims 1. A silicon nitride as a main component, at least one rare earth element as a first component, and at least one selected from the group consisting of an alkaline earth element, Li, and Sr as a second component. A molar ratio calculated as the oxide of the first component is 0.95 to 7.7 mol%, and a molar ratio calculated as the oxide of the second component is 0.49 to 4.7 mol%. A silicon nitride sintered body, wherein the concentration of the first component is relatively higher at the surface than at the center, and the concentration of the second component is relatively higher at the center than at the surface.
が１００Ｗ／ｍ・Ｋ以上であることを特徴とする、請求
項１に記載の窒化ケイ素焼結体。2. The silicon nitride sintered body according to claim 1, wherein the open porosity is 5% or less and the thermal conductivity is 100 W / m · K or more.
強度が７００ＭＰａ以上であることを特徴とする、請求
項１又は２に記載の窒化ケイ素焼結体。3. The silicon nitride sintered body according to claim 1, wherein the four-point bending strength according to JIS R1601 is 700 MPa or more.
類元素の少なくとも１種の化合物粉末を酸化物に換算し
たモル比率で０.９８〜７.７モル％、及び第二成分とし
てアルカリ土類元素及びＬｉ、Ｓｒからなる群から選ば
れた少なくとも１種の化合物粉末を酸化物に換算したモ
ル比率で０.５０〜６.４モル％となるように混合し、 その混合粉末の成形体を窒素含有非酸化性雰囲気中にて
１８００〜２１００℃の温度範囲で焼結して、２〜２０
重量％の範囲で重量減少させると共に、第一成分の酸化
物に換算したモル比率を０.９５〜７.７モル％、及び第
二成分の酸化物に換算したモル比率を０.４９〜４.７モ
ル％とすることを特徴とする窒化ケイ素焼結体の製造方
法。4. A silicon nitride powder in which at least one compound powder of a rare earth element as a first component is 0.98 to 7.7 mol% in terms of a molar ratio in terms of oxide, and an alkaline earth as a second component. At least one compound powder selected from the group consisting of element, Li, and Sr is mixed so as to have a molar ratio of 0.50 to 6.4 mol% in terms of oxide, and a compact of the mixed powder is formed. Sintering in a nitrogen-containing non-oxidizing atmosphere at a temperature of 1800 to 2100 ° C.
In addition to reducing the weight within the range of weight%, the molar ratio converted to the oxide of the first component is 0.95 to 7.7 mol%, and the molar ratio converted to the oxide of the second component is 0.49 to 4 A method for producing a silicon nitride sintered body, the content being 0.7 mol%.
粉末に、第一成分として希土類元素の化合物の少なくと
も１種の化合物粉末を酸化物に換算したモル比率がケイ
素を窒化ケイ素に換算したとき０.９８〜７.７モル％、
及び第二成分としてアルカリ土類元素及びＬｉ、Ｓｒか
らなる群から選ばれた少なくとも１種の化合物粉末を酸
化物に換算したモル比率がケイ素を窒化ケイ素に換算し
たとき０.５０〜６.４モル％となるように混合し、 その混合粉末の形成体を窒素含有非酸化性雰囲気中にて
１２００〜１４００℃の温度範囲で窒化し、 得られた窒化体を窒素含有非酸化性雰囲気中にて１８０
０〜２１００℃の温度範囲で焼結して、２〜２０重量％
の範囲で重量減少させると共に、第一成分の酸化物に換
算したモル比率を０.９５〜７.７モル％、及び第二成分
の酸化物に換算したモル比率を０.４９〜４.７モル％と
することを特徴とする窒化ケイ素焼結体の製造方法。5. A silicon powder or a mixture of silicon powder and silicon nitride powder, in which at least one compound powder of a compound of a rare earth element as a first component is converted to an oxide in a molar ratio of 0. 98-7.7 mol%,
And at least one compound powder selected from the group consisting of alkaline earth elements, Li, and Sr as the second component is converted into an oxide in a molar ratio of 0.50 to 6.4 when silicon is converted into silicon nitride. Mol%, and the formed body of the mixed powder is nitrided in a nitrogen-containing non-oxidizing atmosphere in a temperature range of 1200 to 1400 ° C., and the obtained nitride is placed in a nitrogen-containing non-oxidizing atmosphere. 180
Sintering in the temperature range of 0-2100 ° C, 2-20% by weight
And the molar ratio converted to the oxide of the first component is 0.95 to 7.7 mol%, and the molar ratio converted to the oxide of the second component is 0.49 to 4.7. A method for producing a silicon nitride sintered body, characterized in that the content is mol%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11083552A JP2000272968A (en) | 1999-03-26 | 1999-03-26 | Silicon nitride sintered body and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11083552A JP2000272968A (en) | 1999-03-26 | 1999-03-26 | Silicon nitride sintered body and method for producing the same |
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| Publication Number | Publication Date |
|---|---|
| JP2000272968A true JP2000272968A (en) | 2000-10-03 |
Family
ID=13805683
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11083552A Pending JP2000272968A (en) | 1999-03-26 | 1999-03-26 | Silicon nitride sintered body and method for producing the same |
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| Country | Link |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000344577A (en) * | 1999-06-07 | 2000-12-12 | Hitachi Metals Ltd | Production of highly heat-conductive silicon nitride sintered compact and the sintered compact |
| JP2001010864A (en) * | 1999-06-23 | 2001-01-16 | Hitachi Metals Ltd | Highly heat conductive silicon nitride-based sintered compact |
| JP2001335368A (en) * | 2000-05-25 | 2001-12-04 | Hitachi Metals Ltd | Highly heat conductive silicon nitride sinterd compact |
| JP2002356376A (en) * | 2001-05-31 | 2002-12-13 | Kyocera Corp | Wiring board and method of manufacturing the same |
| JP2007197226A (en) * | 2006-01-24 | 2007-08-09 | National Institute Of Advanced Industrial & Technology | High thermal conductivity silicon nitride ceramics with high reliability and manufacturing method thereof |
| JP2009029665A (en) * | 2007-07-27 | 2009-02-12 | Kyocera Corp | Circuit board and manufacturing method thereof |
| WO2009119421A1 (en) * | 2008-03-28 | 2009-10-01 | 独立行政法人海洋研究開発機構 | Pressure container, and buoyant body and exploring device which are provided with the same |
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1999
- 1999-03-26 JP JP11083552A patent/JP2000272968A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000344577A (en) * | 1999-06-07 | 2000-12-12 | Hitachi Metals Ltd | Production of highly heat-conductive silicon nitride sintered compact and the sintered compact |
| JP2001010864A (en) * | 1999-06-23 | 2001-01-16 | Hitachi Metals Ltd | Highly heat conductive silicon nitride-based sintered compact |
| JP2001335368A (en) * | 2000-05-25 | 2001-12-04 | Hitachi Metals Ltd | Highly heat conductive silicon nitride sinterd compact |
| JP2002356376A (en) * | 2001-05-31 | 2002-12-13 | Kyocera Corp | Wiring board and method of manufacturing the same |
| JP2007197226A (en) * | 2006-01-24 | 2007-08-09 | National Institute Of Advanced Industrial & Technology | High thermal conductivity silicon nitride ceramics with high reliability and manufacturing method thereof |
| JP2009029665A (en) * | 2007-07-27 | 2009-02-12 | Kyocera Corp | Circuit board and manufacturing method thereof |
| WO2009119421A1 (en) * | 2008-03-28 | 2009-10-01 | 独立行政法人海洋研究開発機構 | Pressure container, and buoyant body and exploring device which are provided with the same |
| JP5059938B2 (en) * | 2008-03-28 | 2012-10-31 | 独立行政法人海洋研究開発機構 | Pressure vessel, buoyant body and exploration device provided with the same |
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