JPH0238368A - Production of sintered material of aluminum nitride - Google Patents
Production of sintered material of aluminum nitrideInfo
- Publication number
- JPH0238368A JPH0238368A JP63186816A JP18681688A JPH0238368A JP H0238368 A JPH0238368 A JP H0238368A JP 63186816 A JP63186816 A JP 63186816A JP 18681688 A JP18681688 A JP 18681688A JP H0238368 A JPH0238368 A JP H0238368A
- Authority
- JP
- Japan
- Prior art keywords
- earth element
- compound
- rare earth
- alkaline earth
- aluminum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000000463 material Substances 0.000 title abstract description 5
- 239000000654 additive Substances 0.000 claims abstract description 27
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 26
- 238000005245 sintering Methods 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims abstract description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 abstract description 23
- 230000000996 additive effect Effects 0.000 abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 15
- 239000001301 oxygen Substances 0.000 abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 abstract description 15
- 239000002245 particle Substances 0.000 abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 5
- 150000001768 cations Chemical class 0.000 abstract description 2
- 229910000765 intermetallic Inorganic materials 0.000 abstract 1
- 150000002910 rare earth metals Chemical class 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 150000003623 transition metal compounds Chemical class 0.000 description 7
- -1 aluminum compound Chemical class 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000280 densification Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 229920005822 acrylic binder Polymers 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 150000002222 fluorine compounds Chemical class 0.000 description 3
- 150000001247 metal acetylides Chemical class 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 238000001272 pressureless sintering Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910021610 Silver(III) fluoride Inorganic materials 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000013001 point bending Methods 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 241000218220 Ulmaceae Species 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 235000019646 color tone Nutrition 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 238000005259 measurement Methods 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
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Ceramic Products (AREA)
Abstract
Description
【発明の詳細な説明】
［発明の目的コ
（産業上の利用分野）
本発明は、窒化アルミニウム焼結体の製造方法に関する
。DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention (Industrial Application Field) The present invention relates to a method for producing an aluminum nitride sintered body.
（従来の技術）
窒化アルミニウム（ｌ Ｎ）は常温から高温まで高強度
性を保持し、かつ溶融金属に濡れず、更に電気絶縁性が
高く、高熱伝導性である等、多くの優れた特性を有する
ことから新素材として注目されている。特に、近年、Ａ
４７Ｎ焼結体の半導体基板への応用研究が盛んに行われ
、量産可能なＡｆｉＮ焼結体の熱伝導率は数年前までは
４０〜６０Ｗ／ｍ−にであったものが、特殊な焼結方法
の採用により〜２００Ｗ／ｍ−ｋまで改良されるに到っ
ている。(Prior technology) Aluminum nitride (lN) maintains high strength from room temperature to high temperature, does not get wet with molten metal, and has many excellent properties such as high electrical insulation and high thermal conductivity. It is attracting attention as a new material because of its properties. In particular, in recent years, A
Research into the application of 47N sintered bodies to semiconductor substrates has been actively conducted, and until a few years ago, the thermal conductivity of AfiN sintered bodies that could be mass-produced was 40 to 60 W/m. By adopting this method, the power consumption has been improved to ~200 W/m-k.
このようなＡｊ７Ｎ焼結体の高熱伝導率化は、高純度Ａ
ΩＮ原料、特に酸素含有量の少ないＡΩＮ粉末の量産が
可能になったことが第１の要因である。酸素含有量の少
ないＡ１１Ｎ粉末を主成分とし、焼結助剤の最適化によ
り高熱伝導性のＡΩＮ焼結体が得られるようになったが
、一方、酸素含有量が少なくなるに伴って焼結性が低下
する傾向があり、緻密な焼結体を得るためには従来に比
べてより高温、長時間での焼結が必要となってきた。即
ち、酸素含有量の多いＡＩＮ粉末を原料して得られた焼
結体は熱伝導率が低いものの、焼結性に優れ、緻密化が
可能となる。The high thermal conductivity of such Aj7N sintered body is achieved by high purity A
The first factor is that it has become possible to mass produce ΩN raw materials, especially AΩN powder with low oxygen content. The main component is A11N powder with low oxygen content, and by optimizing the sintering aid, it has become possible to obtain AΩN sintered bodies with high thermal conductivity.However, as the oxygen content decreases, sintering There is a tendency for the properties to decrease, and in order to obtain a dense sintered body, it has become necessary to sinter at a higher temperature and for a longer time than in the past. That is, although a sintered body obtained using AIN powder with a high oxygen content as a raw material has a low thermal conductivity, it has excellent sinterability and can be densified.
半導体装基板への応、用を考える時、現在広く使用され
ているアルミナ基板との代替が考えられるが、上述した
状況では徹底的な低コスト化が必要であり、焼結温度の
上昇、長時間化は製造コストの増加となり、好ましくな
いものである。When considering its application to semiconductor substrates, it is possible to consider replacing it with alumina substrates, which are currently widely used. Extending the time increases manufacturing costs, which is undesirable.
ところで、Ａ、ＩＩＩＮ焼結体をホットプレス以外の方
法で得ようとする場合、焼結体の緻密化及びＡｇＮ原料
粉末の不純物酸素のＡΩＮ粒内への固溶を防止するため
には、従来より焼結助剤として希土類元素酸化物、アル
カリ土類元素酸化物等を添加することが行われている（
特開昭６０−１２７２６７号、特開昭６１−１００７１
号、特開昭６０−７１５７５号等）。By the way, when attempting to obtain an A,IIIN sintered body by a method other than hot pressing, conventional methods are required to prevent densification of the sintered body and solid solution of the impurity oxygen of the AgN raw powder into the AΩN grains. Rare earth element oxides, alkaline earth element oxides, etc. are being added as sintering aids (
JP-A-60-127267, JP-A-61-10071
No., JP-A-60-71575, etc.).
これらの焼結助剤はＡｇＮ原料粉末の不純物酸素と反応
し、液相を生成して焼結体の緻密化を達成すると共に、
この不純物酸素を粒界相として固定（酸素トラップ）し
、高熱伝導率化を達成すると考えられている。These sintering aids react with the impurity oxygen in the AgN raw material powder to generate a liquid phase and achieve densification of the sintered body.
It is believed that high thermal conductivity is achieved by fixing this impurity oxygen as a grain boundary phase (oxygen trap).
このように焼結助剤をＡΩＮ粉末原料に添加することに
より確かにＡＩＮ焼結体の緻密化、高熱伝導率化を達成
することが可能となるが、上記焼結助剤ではいずれも１
７００〜１９００℃の高温で、長時間の焼結が必要であ
るため、Ａ、１７Ｎ焼結体の低コストの障害となってい
た。By adding a sintering aid to the AΩN powder raw material in this way, it is certainly possible to achieve densification and high thermal conductivity of the AIN sintered body, but the above sintering aid does not
Since sintering is required at a high temperature of 700 to 1900° C. for a long time, it has been an obstacle to the low cost of A, 17N sintered bodies.
（発明が解決しようとする課題）
本発明は、上記従来の課題を解決するためになされたも
ので、高熱伝導性を損うことなく焼結温度の低下、焼結
時間の短縮化を達成したＡＪＮ焼結体の製造方法を提供
しようとするものである。(Problems to be Solved by the Invention) The present invention has been made to solve the above-mentioned conventional problems, and has achieved lowering of sintering temperature and shortening of sintering time without impairing high thermal conductivity. The present invention aims to provide a method for manufacturing an AJN sintered body.
［発明の構成］
（課題を解決するための手段）
本発明は、窒化アルミニウムを主成分とし、これに（Ａ
）フッ化アルミニウムと、（Ｂ）アルカリ土類元素化合
物、希土類元素化合物、アルカリ土類元素希土類元素化
合物、アルカリ土類元素アルミニウム化合物、希土類元
素アルミニウム化合物及びアルカリ土類元素希土類元素
アルミニウム化合物から選ばれる少なくとも１種とを必
須成分とする添加物を陽イオン種の元素換算でｏ、１〜
２０重量％加えて焼結することを特徴とする窒化アルミ
ニウム焼結体の製造方法である。[Structure of the invention] (Means for solving the problem) The present invention has aluminum nitride as a main component, and (A
) aluminum fluoride; and (B) selected from alkaline earth element compounds, rare earth element compounds, alkaline earth element rare earth element compounds, alkaline earth element aluminum compounds, rare earth element aluminum compounds, and alkaline earth element rare earth element aluminum compounds. Additives containing at least one kind as an essential component are o, 1 to
This is a method for producing an aluminum nitride sintered body, characterized in that 20% by weight of the aluminum nitride sintered body is added and sintered.
上記ＡｇＮとしては、酸素が０．１〜３重量％含み、遠
心沈降法による平均粒径が０．１〜２．５μｍのものを
用いることが望ましい。It is desirable to use AgN that contains 0.1 to 3% by weight of oxygen and has an average particle size of 0.1 to 2.5 μm as determined by centrifugal sedimentation.
上記添加物としては、次のような形態のものを挙げるこ
とができる。Examples of the above-mentioned additives include the following types.
■、上記（Ａ）成分及び（Ｂ）成分のみからなる添加物
。(2) An additive consisting only of the above components (A) and (B).
■、上記（Ａ）成分、（Ｂ）成分及び遷移金属化合物か
らなる添加物。(2) An additive comprising the above-mentioned component (A), component (B), and a transition metal compound.
■、上記（Ａ）成分、（Ｂ）成分及びアルミニウム酸化
物からなる添加物。(2) An additive consisting of component (A), component (B), and aluminum oxide.
■、上記（Ａ）成分、（Ｂ）成分、遷移金属化合物及び
アルミニウム酸化物からなる添加物。(2) An additive consisting of the above component (A), component (B), a transition metal compound, and an aluminum oxide.
上記（Ｂ）成分中のアルカリ土類元素化合物としては、
例えばＭｇ、Ｃａ、５ｒＳＢａの酸化物、フッ化物、窒
化物又は炭化物を挙げることができ、特にＣａ５Ｓｒの
化合物が好ましい。As the alkaline earth element compound in the above component (B),
For example, oxides, fluorides, nitrides, or carbides of Mg, Ca, and 5rSBa can be used, and compounds of Ca5Sr are particularly preferred.
上記（Ｂ）成分中の希土類元素化合物としては、例えば
Ｓａｓ ＹＳＬａｓ Ｃｅ、３０１％ Ｅｕ５ＴＩｌ１
％Ｔｂｓ Ｄｙ５Ｎｄｓ Ｇｄ、Ｐｒ５ＨｏＳＥｒｓＹ
ｂの酸化物、フッ化物、窒化物又は炭化物を挙げること
ができ、特にＹ ＳＬ ａ ＳＣｅの化合物が好ましい
。Examples of the rare earth element compound in the component (B) include Sas YSLas Ce, 301% Eu5TIl1
%Tbs Dy5Nds Gd, Pr5HoSErsY
Examples include oxides, fluorides, nitrides, and carbides of b, and compounds of Y SL a SCe are particularly preferred.
上記（Ｂ）成分中のアルカリ土類元素希土類元素化合物
としては、例えばアルカリ土類元素をＲ１希土類元素を
Ｌｎとした時、ＲＬ ｎ Ｏ％Ｒ−Ｌｎ−ＦＳＲ−Ｌ
ｎ−Ｃ，Ｒ−Ｌｎ −Ｎで表わされる化合物を挙げるこ
とができ、特にＲＬｎ ４０７ 、ＲＬｎ ２０４ 、
ＲＬｎ ４ Ｆ＋４が望ましい。As the alkaline earth element rare earth element compound in the above component (B), for example, when the alkaline earth element is R1 and the rare earth element is Ln, RL n O% R-Ln-FSR-L
Examples include compounds represented by n-C, R-Ln-N, particularly RLn 407 , RLn 204 ,
RLn 4 F+4 is desirable.
上記（Ｂ）成分中のアルカリ土類元素アルミニウム化合
物としては、例えばアルカリ土類元素をＲとした時、Ｒ
２ＡＸ）２０５ ＲＡΩ２０．１、Ｒ１□ＡＲ＋４０
３ｉ、Ｒ３ＡΩ２０６で表わされる酸化物等を挙げるこ
とができる。As the alkaline earth element aluminum compound in the above component (B), for example, when the alkaline earth element is R, R
2AX) 205 RAΩ20.1, R1□AR+40
Examples include oxides represented by 3i, R3AΩ206, and the like.
上記（Ｂ）成分中の希土類元素アルミニウム化合物とし
ては、例えば希土類元素をＬｎとした時、Ｌｎ ３Ａ、
Ｑ ５０．。、ＬｎＡΩ０３、Ｌｎ４ＡΩ２０９で表わ
される酸化物等を挙げることができる。As the rare earth element aluminum compound in the component (B), for example, when the rare earth element is Ln, Ln 3A,
Q50. . , LnAΩ03, and Ln4AΩ209.
上記（Ｂ）成分中のアルカリ土類元素希土類元素アルミ
ニウム化合物としては、アルカリ土類元素をＲ１希土類
元素をＬｎとした時、Ｒ−Ｌｎ−Ａｇ−０系の複合酸化
物で表わされるものであり、特にＲＬｎ ＡＮ ０４
、ＲＬｎ Ａ、Ｑ ３０７が望ましい。The alkaline earth element rare earth element aluminum compound in the above component (B) is represented by a composite oxide of the R-Ln-Ag-0 system, where the alkaline earth element is R1 and the rare earth element is Ln. , especially RLn AN 04
, RLn A, Q 307 is desirable.
上記添加物中に含まれる遷移金属化合物としては、例え
ばＴＩ Ｚｒ、ＨｒＳＮｉＳＣｒＳＭｔ＋。Examples of the transition metal compound contained in the additive include TI Zr and HrSNiSCrSMt+.
Ｆｅ、Ｃｏ５Ｖの酸化物、フッ化物、窒化物又は炭化物
を挙げることができ、特にＴｉ 、Ｚｒ 。Mention may be made of oxides, fluorides, nitrides or carbides of Fe, Co5V, in particular Ti, Zr.
Ｈｒの化合物が好ましい。Compounds of Hr are preferred.
上記添加物中に含まれるアルミニウム酸化物としては、
例えばα−Ａ、ｌ） ２０３ 、γ−ＡＮ２０３を挙げ
ることができる。The aluminum oxide contained in the above additives is:
Examples include α-A, l) 203 and γ-AN203.
上記添加物のＡｇＮ粉末に対する量は、陽イオン換算で
０．１〜２０重量％、より好ましくは０．２〜１５重量
％の範囲することが望ましい。この理由は、添加物の量
を０．１重量％未満にすると焼結体の特性改善の効果が
充分ではなく、一方その量が２０重量％をを越えると熱
伝導率、高温強度等の特性劣化が無視できなくなる恐れ
があるからである。また、添加物中のフッ化アルミニウ
ムの量は０．０５〜５重量％とするこが望ましく、０．
０５重量％未満にすると特性改善効果を充分に達成し難
く、かといって５重量％を越えると焼結体中に気泡が残
留する場合があり、緻密な焼結体が得難くなるからであ
る。更に、添加物中に遷移金属化合物及びアルミニウム
酸化物を含ませる場合、各成分は夫々０．０１〜３重量
％添加することが望ましい。この理由は、遷移金属化合
物の添加量を０．０１重量％未満にすると焼結体の高強
度化や着色化を充分に達成できず、かといって３重量％
を越えると焼結体の熱伝導率を低下させる恐れがあるか
らである。アルミニウム酸化物の添加量を０．０１重量
％未満にすると該酸化物の添加効果である焼結性の向上
化を充分に達成できず、かといって３重量％を越えると
焼結体の熱伝導率を低下させる恐れがあるからである。The amount of the above-mentioned additive relative to the AgN powder is desirably in the range of 0.1 to 20% by weight, more preferably 0.2 to 15% by weight in terms of cations. The reason for this is that when the amount of additives is less than 0.1% by weight, the effect of improving the properties of the sintered body is not sufficient, whereas when the amount exceeds 20% by weight, the properties such as thermal conductivity and high temperature strength are This is because the deterioration may become impossible to ignore. Further, the amount of aluminum fluoride in the additive is preferably 0.05 to 5% by weight, and 0.05 to 5% by weight.
If it is less than 0.05% by weight, it will be difficult to achieve a sufficient property improvement effect, but if it exceeds 5% by weight, air bubbles may remain in the sintered body, making it difficult to obtain a dense sintered body. . Furthermore, when a transition metal compound and an aluminum oxide are included in the additives, it is desirable to add each component in an amount of 0.01 to 3% by weight. The reason for this is that if the amount of the transition metal compound added is less than 0.01% by weight, it is not possible to sufficiently increase the strength and coloration of the sintered body;
This is because if it exceeds this, the thermal conductivity of the sintered body may be reduced. If the amount of aluminum oxide added is less than 0.01% by weight, it will not be possible to sufficiently improve the sinterability, which is the effect of adding the oxide, but if it exceeds 3% by weight, the heat of the sintered body will increase. This is because there is a possibility that the conductivity will be lowered.
上記各添加物は、遠心沈降法による平均粒径が０．３〜
２．０μｍの粉末又は液相としてＡ、ＱＮ原料粉末に加
えることが望ましい。液相として加える例としては、陽
イオン種元素の硝酸塩をアルコールに溶解してＡ、ＱＮ
原料粉末に加える方法、又は同陽イオン種元素のアルコ
キシドをＡＩＮ原ｆ４ 粉末に加えた後、加水分解させ
る方法等を採用し得る。Each of the above additives has an average particle size of 0.3 to 0.3 by centrifugal sedimentation.
It is desirable to add it to the A, QN raw material powder as a 2.0 μm powder or liquid phase. An example of adding it as a liquid phase is to dissolve nitrate of a cationic species element in alcohol and add A, QN.
A method of adding it to the raw material powder, or a method of adding an alkoxide of the same cationic element to the raw AIN f4 powder and then hydrolyzing it can be adopted.
次に、本発明の製造方法をより具体的に説明する。Next, the manufacturing method of the present invention will be explained in more detail.
ます、ＡｐＮ粉末に添加物を加え、ボールミル等を用い
て粉砕、混合して原料を調製する。但し、常圧焼結の場
合は前記ボールミル等で粉砕、混合したものに更にバイ
ンダを加え、混練、造粒を行なって原料を調製する。つ
づいて、バインダを含む原料を金型、静水圧又はシート
成形等の手段により成形した後、成形体をＮ２ガス気流
中にて加熱してバインダを除去する。次いで、成形体を
黒鉛、窒化硼素又は窒化アルミニウムからなる容器にセ
ットし、Ｎ２ガス雰囲気中にて１４００〜１８５０℃で
常圧焼結を行なう。一方、ホットプレス焼結の場合は前
記ボールミルで粉砕、混合して調製した原料を１４００
〜１８００℃の温度でホットプレスを行なつＯ
（作用）
本発明によれば、窒化アルミニウムを主成分とし、これ
に（Ａ）フッ化アルミニウムと、（Ｂ）アルカリ土類元
素化合物、希土類元素化合物、アルカリ土類元素希土類
元素化合物、アルカリ土類元素アルミニウム化合物、希
土類元素アルミニウム化合物及びアルカリ土類元素希土
類元素アルミニウム化合物から選ばれる少なくとも１種
とを必須成分とする添加物を陽イオン種の元素換算で０
．１〜２０重量％加えて焼結することによって、低い焼
結温度、短時間で緻密かつ高熱伝導率のＡｇＮ焼結体を
製造できる。こうした作用については、明らかではない
が、次のようなメカニズムによるものと推定される。First, additives are added to ApN powder, and a raw material is prepared by grinding and mixing using a ball mill or the like. However, in the case of pressureless sintering, a binder is further added to the pulverized and mixed material using the ball mill, kneading, and granulation to prepare the raw material. Subsequently, after molding the raw material containing the binder using a mold, hydrostatic pressure, sheet molding, or other means, the molded body is heated in a N2 gas stream to remove the binder. Next, the molded body is set in a container made of graphite, boron nitride, or aluminum nitride, and pressureless sintering is performed at 1400 to 1850° C. in an N2 gas atmosphere. On the other hand, in the case of hot press sintering, the raw materials prepared by crushing and mixing in the ball mill are
Hot pressing is carried out at a temperature of ~1800° C. (Operation) According to the present invention, aluminum nitride is the main component, and (A) aluminum fluoride and (B) an alkaline earth element compound and a rare earth element compound are added to the aluminum nitride as a main component. , an alkaline earth element rare earth element compound, an alkaline earth element aluminum compound, a rare earth element aluminum compound, and an alkaline earth element rare earth element aluminum compound. 0 at
．． By adding 1 to 20% by weight and sintering, a dense AgN sintered body with high thermal conductivity can be produced at a low sintering temperature and in a short time. Although this effect is not clear, it is presumed that it is due to the following mechanism.
即ち、添加物の主要成分であるフッ化アルミニラム（Ａ
Ｎ Ｆ３ ）による反応促進効果が挙げられる。ＡｇＦ
３は、通常の雰囲気下では融点を持たず、加熱すれば分
解しないで昇華する。そして、蒸気圧は１３００℃付近
で１気圧に達する。ＡｇＮ原料粉末の焼結に際しては、
ＡｇＮ原料粉末中に不可避的に混入する不純物酸素と添
加物との反応により液相を生成し、液相焼結により緻密
化が進行するものと考えられる。Ａ、９Ｆ３は、この反
応をより低温、短時間で進行させる効果があるものと考
えられる。例えば、添加物としてＹ２Ｏ３をＡΩＮ原料
に加えた系を考えると、焼結後の粒界付近にはＹ−Ａｇ
−０系の複合酸化物が生成しており、これらの生成物が
焼結温度で液相となる。That is, aluminum fluoride (A
One example is the reaction promoting effect of N F3 ). AgF
No. 3 has no melting point in a normal atmosphere, and sublimates without decomposing when heated. The vapor pressure reaches 1 atm near 1300°C. When sintering AgN raw material powder,
It is thought that a liquid phase is generated by the reaction between impurity oxygen, which is inevitably mixed in the AgN raw material powder, and the additive, and densification progresses by liquid phase sintering. A, 9F3 is considered to have the effect of allowing this reaction to proceed at a lower temperature and in a shorter time. For example, considering a system in which Y2O3 is added as an additive to the AΩN raw material, Y-Ag exists near the grain boundaries after sintering.
A -0-based composite oxide is produced, and these products become a liquid phase at the sintering temperature.
この場合、生成相がＹ３ＡΩ５０１□とするとその液相
温度は１７６０℃と考えられており、緻密なＡｇＮ焼結
体を得るためにはこれ以上の温度（約１８００℃）で焼
結する必要がある。これは、−見Ｙ２Ｏ３とＡｇ２Ｏ３
の二成分系の反応と類似しており、事実、酸素を含むＡ
ｇＮ原料粉末を非酸化性雰囲気で加熱しても１３００℃
付近からαＡＤ２０３の生成が確認される。In this case, if the generated phase is Y3AΩ501□, its liquidus temperature is thought to be 1760°C, and in order to obtain a dense AgN sintered body, it is necessary to sinter at a temperature higher than this (approximately 1800°C). . This is −Y2O3 and Ag2O3
is similar to the binary system reaction of A
gN raw material powder heated to 1300℃ in a non-oxidizing atmosphere
Generation of αAD203 is confirmed from nearby.
本発明者らは、Ｙ２Ｏ３とＡＩ）２０３粉末を３Ｙ２０
３５ＡΩ２０３又は２Ｙ２０３Ａ！１２０３などの定地
組成となるように混合し、空気中で１５００℃まで加熱
すると、定地組成物の他に未反応のＹ２Ｏ３とＡｇ２Ｏ
３が多く存在するが、ＡｇＦ３を微量（例えば０．５重
量％程度）加えると、同一条件下で全て定地組成物に変
換されており、未反応物は残っていないことを確認した
。The present inventors used Y2O3 and AI)203 powder as 3Y20
35AΩ203 or 2Y203A! 1203, etc., and heated to 1500°C in air, unreacted Y2O3 and Ag2O are added in addition to the fixed composition.
Although a large amount of AgF3 was present, it was confirmed that when a small amount (for example, about 0.5% by weight) of AgF3 was added, it was all converted into a solid composition under the same conditions, and that no unreacted substances remained.
また、添加物のもう一つの（Ｂ）成分であるアルカリ土
類元素化合物、希土類元素化合物等は従来の技術で説明
したように焼結性を向上してＡｇＮ焼結体の緻密化及び
高熱伝導率化に寄与するものである。In addition, the other (B) component of the additive, such as an alkaline earth element compound or a rare earth element compound, improves sinterability as explained in the conventional technology, resulting in densification of the AgN sintered body and high thermal conductivity. This contributes to increasing efficiency.
更に、前述した遷移金属化合物を含む■、■の添加物を
使用することによってＡＩＩＮ焼結体の高強度化及び着
色化を達成できる。即ち、遷移金属化合物を含む系の添
加物はＡΩＮ原料の焼結及び粒成長を阻害することなく
焼結体内に均一に分布し、ピンニング効果による焼結体
の強度増加を達成できる。しかも、焼結体を着色し、ま
た他の成分との組合わせにより各種の色調が得られ、焼
結体の色むらを隠蔽して美観を高め、更に半導体メモリ
の放熱基板として用いた場合に該メモリの誤動作の原因
となる光を遮蔽することができる。また、前述したアル
ミニウム酸化物を含ム■、■の添加物を使用することに
よって、ＡｇＮ焼結体の焼結性の改善化を達成できる。Further, by using the additives (1) and (4) containing the transition metal compound described above, it is possible to increase the strength and color of the AIIN sintered body. That is, the additive containing the transition metal compound is uniformly distributed within the sintered body without inhibiting the sintering and grain growth of the AΩN raw material, and the strength of the sintered body can be increased by the pinning effect. Moreover, various color tones can be obtained by coloring the sintered body or by combining it with other components, concealing color irregularities in the sintered body and enhancing its aesthetic appearance, and furthermore, when used as a heat dissipation substrate for semiconductor memory. Light that causes malfunction of the memory can be blocked. Furthermore, by using the additives (1) and (3) containing aluminum oxide, the sinterability of the AgN sintered body can be improved.
とりわけ、不純物酸素量が少なく、かっ粒径の大きいＡ
、１ｌｌＮ粉末の焼結や成形後の脱バインダが不十分で
残留炭素量の多い成形体の焼結性を効果的に改善できる
。In particular, A with a small amount of impurity oxygen and a large grain size
, 111N powder and in which binder removal after sintering or molding is insufficient and the sinterability of a molded body with a large amount of residual carbon can be effectively improved.
（発明の実施例） 以下、本発明の実施例を詳細に説明する。(Example of the invention) Examples of the present invention will be described in detail below.
実施例１
まず、不純物酸素を０．７重量％含有し、平均粒径が１
，２μｍのＡｊ；ＩＮ粉末に添加物として平均粒径１．
０μｍのＹ２Ｏ３３重量％（Ｙ換算、 ２．３６重量％
）及び平均粒径１．３μｍのＡｆｉ Ｆ２Ｏ，３重量％
（ｌ換算、 ０．０９４重量％）を加え、ボールミルを
用いて解砕、混合して原料を調製した。つづいて、この
原料にアクリル系バインダを７重量％添加して造粒した
後、５００ Ｋｇ／ ｃｉの圧力でプレス成形して５０
ｎ Ｘ ５０ＣｍＸ ８ ｃｒｔｔの寸法の圧粉体とし
た。Example 1 First, a sample containing 0.7% by weight of impurity oxygen and an average particle size of 1
, 2 μm Aj; average particle size 1.0 μm as an additive to IN powder.
0 μm Y2O3 3% by weight (Y conversion, 2.36% by weight
) and 3% by weight of Afi F2O with an average particle size of 1.3 μm.
(0.094% by weight in terms of l) was added, crushed and mixed using a ball mill to prepare a raw material. Next, 7% by weight of an acrylic binder was added to this raw material and granulated, followed by press molding at a pressure of 500 kg/ci to give 50 kg/cm.
The compact was made into a compact with dimensions of n x 50 cm x 8 crtt.
ひきつづき、この圧粉体を窒素ガス雰囲気で７００℃ま
で加熱してアクリル系バインダを除去した。Subsequently, this green compact was heated to 700° C. in a nitrogen gas atmosphere to remove the acrylic binder.
次いで、この圧粉体をカーボン製容器中にセットし、窒
素ガス雰囲気下にて１７００℃で３０分間常圧焼結して
ＡｇＮ焼結体を製造した。Next, this green compact was set in a carbon container and sintered under normal pressure at 1700° C. for 30 minutes in a nitrogen gas atmosphere to produce an AgN sintered body.
実施例２〜１１、比較例１〜３
原料として後掲する第１表に示すＡＪ７Ｎ粉末、添加物
である混合粉末からなるものを用いた以外、実施例１と
同様な方法により１３種のＡｇＮ焼結体を製造した。但
し、ＣａＯはＣａＣＯ３を重量換算して添加し、平均粒
径はｎ−ブタノールを分散媒とした時の遠心沈降径を示
す。Examples 2 to 11, Comparative Examples 1 to 3 Thirteen types of AgN were produced in the same manner as in Example 1, except that AJ7N powder shown in Table 1 listed below and a mixed powder as an additive were used as raw materials. A sintered body was manufactured. However, CaO is added in terms of CaCO3 by weight, and the average particle size indicates the centrifugal sedimentation diameter when n-butanol is used as a dispersion medium.
しかして、本実施例１〜１１及び比較例１〜３で得られ
た各Ａ［Ｎ焼結体の密度を測定した。また、各ＡｇＮ焼
結体を研削して直径１０Ｍ１厚さ２．５ｍｍの円板を作
製し、これらを試験片としてレーザフラッシュ法によっ
て熱伝導率を、４Ｐｊ定した。なお、測定に際しての温
度は２１℃±２℃とした。これらの結果を後掲する第１
表に示す。Thus, the density of each A[N sintered body obtained in Examples 1 to 11 and Comparative Examples 1 to 3 was measured. Further, each AgN sintered body was ground to produce a disk with a diameter of 10M and a thickness of 2.5 mm, and these were used as test pieces to determine the thermal conductivity of 4Pj by a laser flash method. Note that the temperature during the measurement was 21°C±2°C. These results are listed below in Part 1.
Shown in the table.
後掲する第１表から明らかなように本実施例１〜１１の
ＡｇＮ焼結体は、比較例１〜３のＡｊ７Ｎ焼結体に比べ
て緻密性及び熱伝導率のいずれの特性についても優れて
いることがわかる。As is clear from Table 1 below, the AgN sintered bodies of Examples 1 to 11 are superior to the Aj7N sintered bodies of Comparative Examples 1 to 3 in terms of both compactness and thermal conductivity. It can be seen that
実施例１２
まず、不純物酸素を０．９重】％含有し、平均粒径が１
．５μｍのＡΩＮ粉末に添加物として平均粒径０．８μ
ｍのＣａ ＣＯ３をＣａＯ換算で１．０重量％（Ｃａ換
算、 ０．７１４重量％）及び平均粒径１．３μｍのＡ
ｇＦ３０．５重量％（ｉ換算、 ０．１６１重量％）を
加え、ボールミルを用いて解砕、混合して原料を調製し
た。つづいて、この原料にアクリル系バインダを７重量
％添加して造粒した後、５００に’ｊ／ｃｄの圧力でプ
レス成形して３０ｃｍＸ ３０ｃｍ Ｘｇ ｃｍの寸法
の圧粉体とした。ひきつづき、圧粉体を窒素ガス雰囲気
で７００℃まで加熱してアクリル系バインダを除去した
。次いで、この圧粉体をカーボン製容器中にセットし、
窒素ガス雰囲気下にて１６００℃で夫々１０分間、３０
分間、６０分間、１．８０分間、３００分間及び７２０
分間常圧焼結して６種のＡｇＮ焼結体を製造した。Example 12 First, a sample containing impurity oxygen of 0.9% by weight and an average particle size of 1
．． Additive to 5μm AΩN powder with average particle size of 0.8μ
1.0% by weight of Ca CO3 in terms of CaO (0.714% by weight in terms of Ca) and A with an average particle size of 1.3 μm.
A raw material was prepared by adding 30.5% by weight of gF (0.161% by weight in i terms), crushing and mixing using a ball mill. Subsequently, 7% by weight of an acrylic binder was added to this raw material and granulated, followed by press molding at a pressure of 500 cm/cd to obtain a green compact with dimensions of 30 cm x 30 cm x g cm. Subsequently, the compact was heated to 700° C. in a nitrogen gas atmosphere to remove the acrylic binder. Next, this green compact is set in a carbon container,
30 minutes each at 1600℃ under nitrogen gas atmosphere.
minutes, 60 minutes, 1.80 minutes, 300 minutes and 720 minutes
Six types of AgN sintered bodies were manufactured by atmospheric pressure sintering for a minute.
比較例４
まず、不純物酸素を０．９重量％含有し、平均粒径が１
．５μｍのＡΩＮ粉末に添加物として平均粒径０．８μ
ｍのＣａＣＯ３をＣａＯ換算で１．０重量％を加え、ボ
ールミルを用いて解砕、混合して原料を調製した。つづ
いて、この原料を用いて実施例１２と同様な方法により
常圧焼結して６種のＡＪ７Ｎ焼結体を製造した。Comparative Example 4 First, a sample containing 0.9% by weight of impurity oxygen and an average particle size of 1
．． Additive to 5μm AΩN powder with average particle size of 0.8μ
A raw material was prepared by adding 1.0% by weight of CaCO3 (calculated as CaO) and crushing and mixing using a ball mill. Subsequently, six types of AJ7N sintered bodies were manufactured by pressureless sintering using this raw material in the same manner as in Example 12.
しかして、本実施例１２及び比較例４で得られた各Ａｇ
Ｎ焼結体について密度及び室温での熱伝導率を測定した
。これらの結果を後掲する第２表に示す。Therefore, each Ag obtained in Example 12 and Comparative Example 4
The density and thermal conductivity at room temperature of the N sintered body were measured. These results are shown in Table 2 below.
後掲する第２表から明らかなように本実施例１２では６
０分間という短時間の焼結においても高密度で高熱伝導
率のＡ４７Ｎ焼結体を得ることができることがわかる。As is clear from Table 2 below, in Example 12, 6
It can be seen that an A47N sintered body with high density and high thermal conductivity can be obtained even during sintering for a short time of 0 minutes.
実施例１３〜２１、比較例５．６
原料として後掲する第３表に示すＡＩＮ粉末、添加物で
ある混合粉末からなるものを用い、これらを同第３表に
示す条件で焼結した以外、実施例１と同様な方法により
１１種のＡｇＮ焼結体を製造した。但し、ＣａＯはＣａ
ＣＯ３を重量換算して添加し、平均粒径はｎ−ブタノ
ールを分散媒とした時の遠心沈降径を示す。Examples 13 to 21, Comparative Example 5.6 Other than using the AIN powder shown in Table 3 listed below as the raw material and the mixed powder as an additive, and sintering these under the conditions shown in Table 3. Eleven types of AgN sintered bodies were manufactured by the same method as in Example 1. However, CaO is Ca
CO3 was added in terms of weight, and the average particle diameter indicates the centrifugal sedimentation diameter when n-butanol was used as a dispersion medium.
しかして、本実施例１３〜２１及び比較例５．６のＡ、
ＱＮ焼結体について実施例１と同様に方法により密度及
び室温での熱伝導率を測定した。また、各ＡｇＮ焼結体
を研削して幅４ ｍｍ、厚さ３Ｍ、長さ４０Ｍの６棒を
夫々Ｇ本作製し、これらを抗折強度測定用試験片として
、支点間圧ｉ！＋ｆ２０ Ｅｌｍ ｓクロスヘツド速度
０．５ ｍｙ／ ｍｉｎの条件で３点曲げ強度を測定し
た。更に、各Ａ４７Ｎ焼結体の色を観察した。Therefore, A of Examples 13 to 21 and Comparative Example 5.6,
The density and thermal conductivity at room temperature of the QN sintered body were measured in the same manner as in Example 1. In addition, each AgN sintered body was ground to produce 6 rods each with a width of 4 mm, a thickness of 3M, and a length of 40M, and these were used as specimens for measuring bending strength, and the inter-fulcrum pressure i! The three-point bending strength was measured under the conditions of +f20 Elms and a crosshead speed of 0.5 my/min. Furthermore, the color of each A47N sintered body was observed.
これらの結果を後掲する第３表に併記した。These results are also listed in Table 3 below.
後掲する第３表から明らかなように、本実施例１３〜２
１のＡｇＮ焼結体は比較例５．６の焼結体に比べて密度
、熱伝導率及び３点曲げ強度のいずれも優れていること
かわかる。As is clear from Table 3 below, Examples 13 to 2
It can be seen that the AgN sintered body of No. 1 is superior to the sintered body of Comparative Example 5.6 in terms of density, thermal conductivity, and three-point bending strength.
［発明の効果コ
以上詳述した如く、本発明によれば高熱伝導性を損うこ
となく、焼結温度の低下、焼結時間の短縮化を達成でき
、ひいては緻密かつ高熱伝導率を有する回路基板等に好
適なＡ、ＱＮ焼結体を高歩留りでかつ低コストで製造し
得る方法を提供できる。[Effects of the Invention] As described in detail above, according to the present invention, it is possible to lower the sintering temperature and shorten the sintering time without impairing high thermal conductivity, and as a result, it is possible to achieve a circuit that is dense and has high thermal conductivity. It is possible to provide a method for manufacturing A, QN sintered bodies suitable for substrates and the like with high yield and at low cost.
Claims (1)
ルカリ土類元素希土類元素化合物、アルカリ土類元素ア
ルミニウム酸化物、希土類元素アルミニウム酸化物及び
アルカリ土類元素希土類元素アルミニウム化合物から選
ばれる少なくとも１種と を必須成分とする添加物を陽イオン種の元素換算で０．
１〜２０重量％加えて焼結することを特徴とする窒化ア
ルミニウム焼結体の製造方法。[Scope of Claims] Aluminum nitride is the main component, and (A) aluminum fluoride, (B) alkaline earth element compound, rare earth element compound, alkaline earth element rare earth element compound, alkaline earth element aluminum oxide. Additives containing at least one selected from the group consisting of rare earth element aluminum oxides, rare earth element aluminum oxides, and alkaline earth element rare earth element aluminum compounds are 0.0.
A method for producing an aluminum nitride sintered body, which comprises adding 1 to 20% by weight and sintering it.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63186816A JP2735227B2 (en) | 1988-07-28 | 1988-07-28 | Manufacturing method of aluminum nitride sintered body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63186816A JP2735227B2 (en) | 1988-07-28 | 1988-07-28 | Manufacturing method of aluminum nitride sintered body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0238368A true JPH0238368A (en) | 1990-02-07 |
| JP2735227B2 JP2735227B2 (en) | 1998-04-02 |
Family
ID=16195098
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63186816A Expired - Fee Related JP2735227B2 (en) | 1988-07-28 | 1988-07-28 | Manufacturing method of aluminum nitride sintered body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2735227B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6953761B2 (en) | 2002-12-27 | 2005-10-11 | Hitachi, Ltd. | Aluminum nitride sintered body and substrate for electronic devices |
| CN113200747A (en) * | 2021-05-12 | 2021-08-03 | 深圳市丁鼎陶瓷科技有限公司 | Low-temperature sintered aluminum nitride ceramic material, aluminum nitride casting slurry and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63195175A (en) * | 1987-02-09 | 1988-08-12 | 川崎製鉄株式会社 | Composition for sintering aluminum nitride |
-
1988
- 1988-07-28 JP JP63186816A patent/JP2735227B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63195175A (en) * | 1987-02-09 | 1988-08-12 | 川崎製鉄株式会社 | Composition for sintering aluminum nitride |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6953761B2 (en) | 2002-12-27 | 2005-10-11 | Hitachi, Ltd. | Aluminum nitride sintered body and substrate for electronic devices |
| CN113200747A (en) * | 2021-05-12 | 2021-08-03 | 深圳市丁鼎陶瓷科技有限公司 | Low-temperature sintered aluminum nitride ceramic material, aluminum nitride casting slurry and application |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2735227B2 (en) | 1998-04-02 |
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