JPH07106885B2 - Method for producing crystalline silicon nitride powder - Google Patents
Method for producing crystalline silicon nitride powderInfo
- Publication number
- JPH07106885B2 JPH07106885B2 JP1149562A JP14956289A JPH07106885B2 JP H07106885 B2 JPH07106885 B2 JP H07106885B2 JP 1149562 A JP1149562 A JP 1149562A JP 14956289 A JP14956289 A JP 14956289A JP H07106885 B2 JPH07106885 B2 JP H07106885B2
- Authority
- JP
- Japan
- Prior art keywords
- silicon nitride
- nitride powder
- nitrogen
- plasma
- crystalline silicon
- 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.)
- Expired - Fee Related
Links
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、高温構造用材料として有用な窒化ケイ素質焼
結体の製造用原料として好適な結晶質窒化ケイ素粉末の
製造に関する。TECHNICAL FIELD The present invention relates to the production of crystalline silicon nitride powder suitable as a raw material for producing a silicon nitride sintered body useful as a high-temperature structural material.
（従来技術及びその問題点） 非晶質窒化ケイ素粉末及び／又は含窒素シラン化合物を
不活性ガス雰囲気下又は還元性ガス雰囲気下に焼成し
て、結晶質窒化ケイ素粉末を製造する方法は、すでに知
られている。ところで、この方法では、焼成時に針状又
は柱状結晶が多数生成するために、得られる結晶質窒化
ケイ素粉末は、充填密度が小さく、これを焼結用原料と
して用いた場合には、嵩密度の低い成形体しか得られな
いという欠点がある。(Prior Art and Its Problems) A method for producing a crystalline silicon nitride powder by firing an amorphous silicon nitride powder and / or a nitrogen-containing silane compound in an inert gas atmosphere or a reducing gas atmosphere has already been disclosed. Are known. By the way, in this method, since a large number of needle-like or columnar crystals are generated during firing, the crystalline silicon nitride powder obtained has a low packing density, and when this is used as a sintering raw material, it has a bulk density of It has the drawback that only low compacts can be obtained.
そこで、微細な粒状粒子からなる結晶質窒化ケイ素粉末
を製造する方法として、特開昭59−21506号公報には、
焼成前に非晶質窒化ケイ素粉末及び／又は含窒素シラン
化合物を摩砕し、かつ昇温過程において、被焼成物を12
50〜1430℃の範囲の温度に１時間以上保持する方法が提
案されている。Therefore, as a method of producing a crystalline silicon nitride powder consisting of fine granular particles, JP-A-59-21506,
Before firing, the amorphous silicon nitride powder and / or the nitrogen-containing silane compound is ground, and during firing,
A method of holding at a temperature in the range of 50 to 1430 ° C for 1 hour or more has been proposed.
この方法によれば、微細な粒状粒子からなる結晶質窒化
ケイ素粉末を製造することができるが、摩砕条件の制御
が難しく、また昇温スケジュールが複雑で焼成に長時間
を要するため、生産性が低いという問題があった。According to this method, it is possible to produce a crystalline silicon nitride powder consisting of fine granular particles, but it is difficult to control the grinding conditions, and the heating schedule is complicated and it takes a long time for firing, so productivity is improved. There was a problem of low.
（発明の目的） 本発明の目的は、前記問題点を解決し、粒子形状及びサ
イズの一定した高品質の結晶質窒化ケイ素粉末を低コス
トで生産できる新規な製法を提供するものである。(Object of the Invention) An object of the present invention is to solve the above problems and to provide a new production method capable of producing a high-quality crystalline silicon nitride powder having a uniform particle shape and size at a low cost.
（問題点を解決するための手段） 本発明は、非晶質窒化ケイ素粉末及び／又は含窒素シラ
ン化合物を不活性ガス雰囲気下又は還元性ガス雰囲気下
に焼成して、結晶質窒化ケイ素粉末を製造するに際し、
焼成前に非晶質窒化ケイ素粉末及び／又は含窒素シラン
化合物の粒子表面に、プラズマ窒化法により、厚みが１
〜50Åの窒化反応層を形成させることを特徴とする結晶
質窒化ケイ素粉末の製法に関するものである。(Means for Solving Problems) The present invention provides a crystalline silicon nitride powder by firing an amorphous silicon nitride powder and / or a nitrogen-containing silane compound in an inert gas atmosphere or a reducing gas atmosphere. When manufacturing,
Before the firing, the amorphous silicon nitride powder and / or the nitrogen-containing silane compound particles have a thickness of 1 on the surface thereof by the plasma nitriding method.
The present invention relates to a method for producing a crystalline silicon nitride powder, which is characterized by forming a nitriding reaction layer of up to 50Å.
本発明における含窒素シラン化合物としては、シリコン
ジイミド、シリコンテトラアミド、シリコンニトロゲン
イミド、シリコンクロルイミド等が用いられる。これら
は、公知方法、例えば、四塩化ケイ素、四臭化ケイ素、
四沃化ケイ素等のハロゲン化ケイ素とアンモニアとを気
相で反応させる方法、液状の前記ハロゲン化ケイ素と液
体アンモニアとを反応させる方法などによって製造され
る。As the nitrogen-containing silane compound in the present invention, silicon diimide, silicon tetraamide, silicon nitrogen imide, silicon chlorimide and the like are used. These are known methods, for example, silicon tetrachloride, silicon tetrabromide,
It is produced by a method of reacting a silicon halide such as silicon tetraiodide with ammonia in a gas phase, a method of reacting the liquid silicon halide with liquid ammonia, and the like.
また、非晶質窒化ケイ素粉末は、公知方法、例えば、前
記含窒素シラン化合物を窒素又はアンモニアガス雰囲気
下に600〜1200℃の範囲の温度で加熱分解する方法、四
塩化ケイ素、四臭化ケイ素、四沃化ケイ素等のハロゲン
化ケイ素とアンモニアとを高温で反応させる方法などに
よって製造されたものが用いられる。非晶質窒化ケイ素
粉末及び含窒素シラン化合物の平均粒子径は、通常、0.
005〜0.05μｍである。Further, the amorphous silicon nitride powder is a known method, for example, a method of thermally decomposing the nitrogen-containing silane compound at a temperature in the range of 600 to 1200 ° C. under a nitrogen or ammonia gas atmosphere, silicon tetrachloride, silicon tetrabromide. Those produced by a method of reacting silicon halide such as silicon tetraiodide with ammonia at a high temperature are used. The average particle size of the amorphous silicon nitride powder and the nitrogen-containing silane compound is usually 0.
005 to 0.05 μm.
本発明においては、焼成前に非晶質窒化ケイ素粉末及び
／又は含窒素シラン化合物をプラズマ窒化法により表面
処理する。In the present invention, the amorphous silicon nitride powder and / or the nitrogen-containing silane compound is surface-treated by a plasma nitriding method before firing.
プラズマとは、正、負の荷電粒子が共存する電気的に中
性な導電性ガス集団のことであり、これには、電子、イ
オン、原子が熱的に平衡状態にある熱プラズマと、電子
温度のみ数万℃に上がり、イオンや原子は常温付近とい
う、熱的非平衡状態にある低温プラズマがあるが、本発
明においてはいずれも用いられる。Plasma is a group of electrically neutral electrically conductive gases in which positive and negative charged particles coexist. These include thermal plasma in which electrons, ions, and atoms are in thermal equilibrium, and electron There is a low temperature plasma in a thermal non-equilibrium state in which only the temperature rises to tens of thousands of degrees Celsius, and ions and atoms are near room temperature, but any of them is used in the present invention.
プラズマ発生方法としては、電流アークプラズマ、高周
波誘電プラズア及びこれらを組み合わせたハイブリッド
プラズマ、ECRマグネトロン放電、イオンプレーティン
グなどの種々のプラズマ発生方法が用いられる。As a plasma generating method, various plasma generating methods such as current arc plasma, high frequency dielectric plasma and hybrid plasma combining these, ECR magnetron discharge, and ion plating are used.
プラスマ窒化法における反応性ガスとしては、窒素又は
アンモニア、ヒドラジン等の窒素含有化合物ガスが用い
られる。この方法によれば、非晶質窒化ケイ素及び／又
は含窒素シラン化合物の粒子表面に不可避的に存在する
酸化物が酸化原子を引き抜かれて窒化される。As the reactive gas in the plasma nitriding method, nitrogen or a nitrogen-containing compound gas such as ammonia or hydrazine is used. According to this method, the oxides inevitably present on the surface of the particles of the amorphous silicon nitride and / or the nitrogen-containing silane compound are nitrided by extracting the oxide atoms.
プラズマ処理条件は、プラズマ発生装置、反応性ガスの
種類、非晶質窒化ケイ素粉末及び／又は含窒素シラン化
合物の処理量によって種々異なり、一律に規定すること
はできないが、窒化反応層の厚みが１〜50Åとなるよう
な条件を選べば十分である。The plasma treatment conditions vary depending on the plasma generator, the type of reactive gas, the treatment amount of the amorphous silicon nitride powder and / or the nitrogen-containing silane compound, and cannot be uniformly defined. It is sufficient to select the conditions that will be 1 to 50Å.
非晶質窒化ケイ素粉末及び／又は含窒素シラン化合物を
プラズマ処理することによって、粒子表面が著しく活性
化され、焼成時の窒化ケイ素の結晶化速度が高められ、
かつ微粒の粒状粒子が効率良く得られる。この理由は未
だ明らかではないが、プラズマ処理により、粒子表面の
欠陥が増加すると共に、表面原子の電子状態が変化する
ためと考えられる。By plasma-treating the amorphous silicon nitride powder and / or the nitrogen-containing silane compound, the particle surface is significantly activated, and the crystallization rate of silicon nitride during firing is increased,
Moreover, fine granular particles can be efficiently obtained. The reason for this is not clear yet, but it is considered that the number of defects on the particle surface is increased and the electronic state of the surface atoms is changed by the plasma treatment.
本発明においては、プラズマ処理された非晶質窒化ケイ
素粉末及び／又は含窒素シラン化合物を不活性ガス雰囲
気下又は還元性ガス雰囲気下に焼成する。In the present invention, the plasma-treated amorphous silicon nitride powder and / or the nitrogen-containing silane compound is fired in an inert gas atmosphere or a reducing gas atmosphere.
不活性ガスとしては、窒素、アルゴン、ヘリウム等が挙
げられる。また、還元性ガスとしては、水素、アンモニ
ア、一酸化炭素等が挙げられる。Examples of the inert gas include nitrogen, argon and helium. Further, examples of the reducing gas include hydrogen, ammonia, carbon monoxide and the like.
焼成温度は1350〜1700℃の範囲が好ましい。焼成温度が
1350℃より低いと、窒化ケイ素の結晶化が十分に進行し
ない。また、焼成温度が1700℃を越えると、生成した窒
化ケイ素粉末の分解が始まるので好ましくない。また、
急激な昇温は、粒子形状を均一にする上で好ましくな
く、1150〜1350℃の範囲を１時間以上かけてゆっくり昇
温することが望ましい。The firing temperature is preferably in the range of 1350 to 1700 ° C. Firing temperature
If it is lower than 1350 ° C, crystallization of silicon nitride does not proceed sufficiently. Further, if the firing temperature exceeds 1700 ° C., the generated silicon nitride powder begins to decompose, which is not preferable. Also,
A rapid temperature rise is not preferable in order to make the particle shape uniform, and it is desirable to raise the temperature slowly in the range of 1150 to 1350 ° C. over 1 hour or more.
（実施例） 以下に実施例及び比較例を示し、本発明をさらに具体的
に説明する。実施例及び比較例において、結晶質窒化ケ
イ素粉末の結晶化度は、窯業協会誌93巻p394〜397（198
5）に記載の加水分解試験により、α型結晶含有率は、
セラミック・ブラティン56巻p777〜780（1977）に記載
のＸ線回折法に従って算出し、比表面積は窒素ガス吸着
法によるBET法で測定した。(Example) Hereinafter, the present invention will be described more specifically by showing Examples and Comparative Examples. In Examples and Comparative Examples, the crystallinity of the crystalline silicon nitride powder was determined by the Japan Society of Ceramics, Vol. 93, p394-397 (198).
According to the hydrolysis test described in 5), the α-type crystal content rate was
The value was calculated according to the X-ray diffraction method described in Ceramic Bulletin, Vol. 56, p777-780 (1977), and the specific surface area was measured by the BET method based on the nitrogen gas adsorption method.
実施例１ シリコンジイミドを1000℃で加水分解して得られた比表
面積390m2/gの非晶質窒化ケイ素粉末50gを、容量結合方
式の円筒型プラズマ装置内の容器に充填し、容器を回転
させて粉末を流動化させた。次いでベルジャー内を0.05
Torr以下に真空脱気後、窒素ガスを導入し、系内の圧力
を1.0Torrに保った。周波数13.56MHzの高周波発振機よ
り、出力100Wの高周波を放電コイルに印加し、窒素プラ
ズマを発生させて、20分間プラズマ処理を行った。Example 1 50 g of amorphous silicon nitride powder having a specific surface area of 390 m 2 / g obtained by hydrolyzing silicon diimide at 1000 ° C. was filled in a container in a cylindrical plasma device of a capacitive coupling system, and the container was rotated. To fluidize the powder. Then in the bell jar 0.05
After vacuum degassing to below Torr, nitrogen gas was introduced to maintain the internal pressure of the system at 1.0 Torr. A high frequency power of 100 W was applied to the discharge coil from a high frequency oscillator with a frequency of 13.56 MHz to generate nitrogen plasma and plasma treatment was performed for 20 minutes.
処理後の粉末を黒鉛質るつぼに充填し、窒素雰囲気下に
昇温して1500゜で１時間保持した。The treated powder was filled in a graphite crucible, heated in a nitrogen atmosphere and kept at 1500 ° for 1 hour.
得られた窒化ケイ素粉末の特性を第１表に示す。The characteristics of the obtained silicon nitride powder are shown in Table 1.
実施例２〜３ プラズマ処理を第１表に示す条件で行ったほかは、実施
例１と同様にして、窒化ケイ素粉末を製造した。Examples 2 to 3 Silicon nitride powder was produced in the same manner as in Example 1 except that the plasma treatment was performed under the conditions shown in Table 1.
得られた窒化ケイ素粉末の特性を第１表に示す。The characteristics of the obtained silicon nitride powder are shown in Table 1.
実施例４ シリコンジイミドを700℃で加熱分解して得られた比表
面積480m2/gの非晶質窒化ケイ素と未分解の含窒素シラ
ン化合物との混合粉末50gを、マイクロ波プラズマ装置
内の容器に充填し、粉末を流動化させた。ベルジャー内
を２×10-5Torr以下の高真空に排気後、窒素ガスを導入
し、系内の圧力を0.01Torrに保った。次いで、マグネト
ロンで発生させた2.45GHzのマイクロ波（出力180W）を
導波管を通して放電室に導入し、窒素プラズマを発生さ
せて、15分間プラズマ処理を行った。Example 4 50 g of a mixed powder of amorphous silicon nitride having a specific surface area of 480 m 2 / g obtained by heating and decomposing silicon diimide at 700 ° C. and an undecomposed nitrogen-containing silane compound was placed in a container in a microwave plasma apparatus. And the powder was fluidized. The inside of the bell jar was evacuated to a high vacuum of 2 × 10 −5 Torr or less, and then nitrogen gas was introduced to keep the pressure in the system at 0.01 Torr. Then, a 2.45 GHz microwave (output 180 W) generated by a magnetron was introduced into the discharge chamber through the waveguide, nitrogen plasma was generated, and plasma treatment was performed for 15 minutes.
処理後の粉末を黒鉛質るつぼに充填し、窒素雰囲気下に
昇温して1550℃で30分間保持した。The treated powder was filled in a graphite crucible, heated in a nitrogen atmosphere and kept at 1550 ° C. for 30 minutes.
得られた窒化ケイ素粉末の特性を第１表に示す。The characteristics of the obtained silicon nitride powder are shown in Table 1.
実施例５ プラズマ処理を第１表に示す条件で行ったほかは、実施
例４と同様にして、窒化ケイ素粉末を製造した。Example 5 A silicon nitride powder was produced in the same manner as in Example 4 except that the plasma treatment was performed under the conditions shown in Table 1.
得られた窒化ケイ素粉末の特性を第１表に示す。The characteristics of the obtained silicon nitride powder are shown in Table 1.
比較例１〜２ プラズマ処理を行わなかったほかは、実施例１及び実施
例４と同様にして、窒化ケイ素粉末を製造した。Comparative Examples 1-2 A silicon nitride powder was produced in the same manner as in Example 1 and Example 4, except that plasma treatment was not performed.
得られた窒化ケイ素粉末の特性を第１表に示す。The characteristics of the obtained silicon nitride powder are shown in Table 1.
（発明の効果） 本発明によれば、等軸的な粒状粒子からなり、タップ密
度が大きく、充填性の良好な結晶質窒化ケイ素粉末を生
産性良く製造することができ、コストダウンが可能とな
る。(Effect of the Invention) According to the present invention, a crystalline silicon nitride powder composed of equiaxed granular particles, having a high tap density and good filling properties can be produced with high productivity, and cost reduction is possible. Become.
Claims (1)
ラン化合物を不活性ガス雰囲気下又は還元性ガス雰囲気
下に焼成して、結晶質窒化ケイ素粉末を製造するに際
し、焼成前に非晶質窒化ケイ素粉末及び／又は含窒素シ
ラン化合物の粒子表面に、プラズマ窒化法により、厚み
が１〜50Åの窒化反応層を形成させることを特徴とする
結晶質窒化ケイ素粉末の製法。1. An amorphous silicon nitride powder and / or a nitrogen-containing silane compound is fired in an inert gas atmosphere or a reducing gas atmosphere to produce a crystalline silicon nitride powder, which is amorphous before firing. A method for producing a crystalline silicon nitride powder, characterized in that a nitriding reaction layer having a thickness of 1 to 50Å is formed on the surface of particles of a porous silicon nitride powder and / or a nitrogen-containing silane compound by a plasma nitriding method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1149562A JPH07106885B2 (en) | 1989-06-14 | 1989-06-14 | Method for producing crystalline silicon nitride powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1149562A JPH07106885B2 (en) | 1989-06-14 | 1989-06-14 | Method for producing crystalline silicon nitride powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0316903A JPH0316903A (en) | 1991-01-24 |
| JPH07106885B2 true JPH07106885B2 (en) | 1995-11-15 |
Family
ID=15477891
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1149562A Expired - Fee Related JPH07106885B2 (en) | 1989-06-14 | 1989-06-14 | Method for producing crystalline silicon nitride powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07106885B2 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3016807A1 (en) * | 1980-05-02 | 1981-11-05 | Licentia Patent-Verwaltungs-Gmbh, 6000 Frankfurt | METHOD FOR PRODUCING SILICON |
| JPS57166373A (en) * | 1981-04-02 | 1982-10-13 | Sumitomo Electric Industries | Manufacture of non-oxide ceramics |
-
1989
- 1989-06-14 JP JP1149562A patent/JPH07106885B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0316903A (en) | 1991-01-24 |
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