JPH11116227A - Production of silicon carbide - Google Patents
Production of silicon carbideInfo
- Publication number
- JPH11116227A JPH11116227A JP9281876A JP28187697A JPH11116227A JP H11116227 A JPH11116227 A JP H11116227A JP 9281876 A JP9281876 A JP 9281876A JP 28187697 A JP28187697 A JP 28187697A JP H11116227 A JPH11116227 A JP H11116227A
- Authority
- JP
- Japan
- Prior art keywords
- silicon carbide
- sic
- grinding
- silicon
- heating
- 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.)
- Pending
Links
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 58
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 238000000227 grinding Methods 0.000 claims abstract description 45
- 238000010438 heat treatment Methods 0.000 claims abstract description 31
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000013078 crystal Substances 0.000 claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 22
- 239000010703 silicon Substances 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002002 slurry Substances 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 239000002480 mineral oil Substances 0.000 claims abstract description 13
- 235000010446 mineral oil Nutrition 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 13
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 229910021431 alpha silicon carbide Inorganic materials 0.000 abstract description 15
- 239000000203 mixture Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000010802 sludge Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000000571 coke Substances 0.000 abstract description 2
- 239000003208 petroleum Substances 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- 235000012431 wafers Nutrition 0.000 description 13
- 229910052742 iron Inorganic materials 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 239000011819 refractory material Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000006061 abrasive grain Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000002006 petroleum coke Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- -1 fatty acid ester Chemical class 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000006148 magnetic separator Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Polishing Bodies And Polishing Tools (AREA)
- Ceramic Products (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、炭化けい素研削材
とワイヤソーを用いて高純度シリコン塊からシリコンウ
エハーを切り出す際に発生する研削廃スラリーを原料と
して、研削材や耐火材用として有用な炭化けい素結晶体
を製造する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is useful as a grinding material and a refractory material, using a grinding waste slurry generated when a silicon wafer is cut from a high-purity silicon lump using a silicon carbide grinding material and a wire saw. The present invention relates to a method for producing a silicon carbide crystal.
【０００２】[0002]
【従来の技術】シリコンウエハーは、半導体デバイスや
太陽光電池等の部材として有用であり、その需要は年々
増大しつつある。かかるシリコンウエハーは、高純度シ
リコンの結晶体からダイヤモンドカッター、ワイヤソー
等を用いてウエハー状に切り出すことにより製造されて
いるが、切断機の性能等の点からワイヤソーによる切り
出しが主流になりつつある。2. Description of the Related Art Silicon wafers are useful as members for semiconductor devices and solar cells, and the demand for silicon wafers is increasing year by year. Such a silicon wafer is manufactured by cutting a crystal of high-purity silicon into a wafer using a diamond cutter, a wire saw, or the like, but cutting with a wire saw is becoming the mainstream in view of the performance of a cutting machine and the like.
【０００３】ところで、ワイヤソーによる切り出しにお
いては、切削用媒体として、通常平均粒子径１０μｍ〜
５０μｍの炭化けい素研削粒と鉱油又は水溶液とを含有
するスラリーが用いられる。このスラリーは、使用を繰
り返すことにより研削粒の摩耗、シリコン削分の増加等
により、切削能力が低下し、使用できなくなる。そして
このように使用できなくなった研削廃スラリー（研削
泥）は、現在、焼却され、産業廃棄物として処分されて
いる。[0003] By the way, in cutting with a wire saw, a medium for cutting usually has an average particle diameter of 10 µm or more.
A slurry containing 50 μm silicon carbide abrasive grains and mineral oil or an aqueous solution is used. When the slurry is repeatedly used, the cutting ability is reduced due to wear of the abrasive grains, increase in the amount of silicon shaving, and the like, and the slurry cannot be used. The grinding waste slurry (grinding mud) that can no longer be used is now incinerated and disposed of as industrial waste.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、通常の
条件で焼却された研削泥は何ら再利用できないため、経
済的にも環境的にも問題となっていた。However, since the grinding mud incinerated under normal conditions cannot be reused at all, there has been a problem both economically and environmentally.
【０００５】すなわち、ワイヤソーにてシリコンウエハ
ーを切断する際に消費される炭化けい素研削粒は８イン
チウエハーの場合ウエハー１０万枚当り１０トン程度と
されている。従って、世界全体の８インチウエハー生産
が月産４００万枚を超える時代が予見される今日、研削
泥の発生は急速に増加するものと考えられる。[0005] That is, silicon carbide grinding grains consumed when cutting a silicon wafer with a wire saw are about 10 tons per 100,000 wafers in the case of an 8-inch wafer. Therefore, it is expected that the generation of grinding mud will increase rapidly in today, when the era of worldwide 8-inch wafer production exceeding 4 million wafers is expected.
【０００６】また、炭化けい素は電熱化学により合成さ
れる電力多消費型の人造セラミックで、資源として貴重
であり、資源節約の面でも、その再利用が求められてい
る。[0006] Silicon carbide is a power-consuming artificial ceramic synthesized by electrothermal chemistry, is valuable as a resource, and is required to be reused in terms of resource saving.
【０００７】従って、本発明の目的は、上記研削泥の効
率的な再利用手段を提供することにある。Accordingly, an object of the present invention is to provide a means for efficiently reusing the above-mentioned grinding mud.
【０００８】[0008]
【課題を解決するための手段】そこで、本発明者らは、
前記課題を解決すべく種々検討した結果、研削泥に炭素
を添加して非酸化条件下で１２００℃以上の温度に加熱
すれば、当該研削泥中の金属シリコンが容易に炭化けい
素に転換でき、研削材や耐火材として利用可能な高純度
の炭化けい素結晶体が得られることを見出し、本発明を
完成するに至った。Means for Solving the Problems Accordingly, the present inventors have:
As a result of various studies to solve the above problems, if carbon is added to the grinding mud and heated to a temperature of 1200 ° C. or more under non-oxidizing conditions, metallic silicon in the grinding mud can be easily converted to silicon carbide. The present inventors have found that a high-purity silicon carbide crystal usable as an abrasive or a refractory material can be obtained, and have completed the present invention.
【０００９】すなわち、本発明は、炭化けい素研削粒を
鉱油又は水溶液とを含有する研削用スラリーを媒体とし
てワイヤソーを用いて高純度シリコン塊からウエハーを
切り出す際に発生する研削泥に、該研削泥中の金属けい
素を炭化けい素に転化するに必要な量の炭素を加え、非
酸化条件下で１２００℃以上に加熱することを特徴とす
る炭化けい素結晶体の製造法を提供するものである。That is, the present invention relates to a grinding slurry generated when a wafer is cut from a high-purity silicon lump using a wire saw with a grinding slurry containing mineral oil or an aqueous solution containing silicon carbide grinding particles. A method for producing a silicon carbide crystal characterized by adding an amount of carbon necessary for converting silicon metal in the mud to silicon carbide and heating the mixture to 1200 ° C. or more under non-oxidizing conditions. It is.
【００１０】[0010]
【発明の実施の形態】本発明製造法の原料となる研削泥
は、ワイヤソーにより高純度シリコン塊からウエハーを
切り出した際に生じる廃スラリー、すなわち、炭化けい
素研削粒と鉱油又は水溶液とを含有する研削用スラリー
を媒体としてワイヤソーを用いて高純度シリコン塊から
ウエハーを切り出す際に発生する研削廃スラリー（研削
泥）である。DETAILED DESCRIPTION OF THE INVENTION Grinding mud, which is a raw material of the production method of the present invention, contains waste slurry generated when a wafer is cut from a high-purity silicon lump by a wire saw, that is, silicon carbide grinding particles and mineral oil or an aqueous solution. This is grinding waste slurry (grinding mud) generated when a wafer is cut from a high-purity silicon lump using a wire saw with the grinding slurry as a medium.
【００１１】ここで、炭化けい素研削粒としては、特に
制限されず、例えば平均粒子径１０〜５０μｍのα型炭
化けい素（α−ＳｉＣ）である。また、鉱油としては、
特に制限されず、ナフテン系鉱物油、イソパラフィン系
鉱物油及びこれらの混合物等が挙げられる。このうち、
溶解性の点よりイソパラフィン系鉱物油が好ましい。ま
た、水溶液には、水以外にエチレングリコール、プロピ
レングリコール、水溶性増粘剤等を含んでいてもよい。Here, the ground silicon carbide grains are not particularly limited, and are, for example, α-type silicon carbide (α-SiC) having an average particle diameter of 10 to 50 μm. Also, as mineral oil,
There is no particular limitation, and examples thereof include naphthenic mineral oil, isoparaffinic mineral oil, and mixtures thereof. this house,
Isoparaffinic mineral oil is preferred from the viewpoint of solubility. In addition, the aqueous solution may contain ethylene glycol, propylene glycol, a water-soluble thickener, and the like, in addition to water.
【００１２】研削泥には、炭化けい素研削粒及び鉱油又
は水溶液以外に、金属けい素及びワイヤーから研削され
た微量の鉄分が含まれている。そして、研削泥中のこれ
らの成分の含量は、通常、炭化けい素研削粒１００重量
部に対し、金属けい素１３〜２０重量部、鉱油又は水溶
液７０〜１００重量部、及び鉄分０．６〜１．５重量部
である。The grinding mud contains, in addition to silicon carbide abrasive grains and mineral oil or an aqueous solution, silicon metal and a trace amount of iron ground from a wire. The content of these components in the grinding mud is usually 13 to 20 parts by weight of metal silicon, 70 to 100 parts by weight of mineral oil or aqueous solution, and iron to 0.6 to 100 parts by weight of silicon carbide abrasive grains. 1.5 parts by weight.
【００１３】ここで鉄分は、特に除去する必要のない場
合が多いが、研削材用炭化けい素結晶体を製造しようと
する場合は、鉄分を予め除去するのが好ましい。鉄分の
除去は、研削泥を磁選機に通すことにより行うことがで
きる。研削泥の粘稠性が高い場合には、適量の水及び界
面活性剤を加えて粘性を下げてから鉄の除去を行うのが
好ましい。Here, it is often not necessary to remove the iron component in many cases. However, it is preferable to remove the iron component in advance when manufacturing a silicon carbide crystal for an abrasive. The iron can be removed by passing the grinding mud through a magnetic separator. When the viscosity of the grinding mud is high, it is preferable to add an appropriate amount of water and a surfactant to lower the viscosity before removing iron.
【００１４】本発明においては、まず上記研削泥に該研
削泥中の金属けい素を炭化けい素に転化するのに必要な
量の炭素を添加する。ここで、炭素としては、反応性の
高いものであれば特に制限されないが、粉末状、特に粒
子径７５μｍ以下の炭素質原料、例えば石油系コークス
粉末を用いるのが好ましい。かかる炭素の添加量は、予
め研削泥中の金属けい素含量を測定して、化学量論的に
必要な量、好ましくは化学量論量と同量又は少し過剰量
である。In the present invention, first, carbon is added to the above-mentioned grinding mud in an amount necessary for converting metallic silicon in the grinding mud into silicon carbide. Here, the carbon is not particularly limited as long as it has high reactivity, but it is preferable to use a carbonaceous raw material having a particle size of 75 μm or less, for example, a petroleum-based coke powder. The amount of such carbon to be added is a stoichiometrically necessary amount, preferably the same amount as or slightly in excess of the stoichiometric amount, by previously measuring the metal silicon content in the grinding mud.
【００１５】炭素の添加後、必要に応じて攪拌して混合
するが、攪拌には通常の攪拌機を用いるのが好ましい。
また、加熱前に、鉱油、水等の液体の存在が、加熱処理
工程に支障を生じる場合には、液体をある程度分離除去
するのが好ましい。液体の分離装置としては例えば遠心
力を利用したものが適する。この際、金属けい素の微粒
子は炭化けい素に転化する有効物質であるので、液中に
漏れないように注意する。なお、これらの液体分離を行
わない場合であっても、鉱油等の加熱による気化燃焼が
安全に行われるような燃焼装置を用いればよいことはい
うまでもない。After the addition of carbon, the mixture is stirred and mixed as necessary, and it is preferable to use a usual stirrer for stirring.
If the presence of a liquid such as mineral oil or water causes a problem in the heat treatment step before heating, it is preferable to separate and remove the liquid to some extent. As a liquid separating device, for example, a device utilizing centrifugal force is suitable. At this time, since the fine particles of silicon metal are effective substances that are converted into silicon carbide, care should be taken not to leak into the liquid. Needless to say, even when these liquid separations are not performed, a combustion device that can safely perform vaporization combustion by heating mineral oil or the like may be used.
【００１６】次いで、混合物は加熱されるが、該加熱
は、被加熱物の研削泥成分が酸化しないよう、非酸化条
件下で行う必要があり、非酸化性環境を形成できる構造
の加熱炉、例えば電熱炉を用いるのが便利である。Next, the mixture is heated, and the heating must be performed under non-oxidizing conditions so that the grinding mud component of the object to be heated is not oxidized, and the heating furnace has a structure capable of forming a non-oxidizing environment. For example, it is convenient to use an electric heating furnace.
【００１７】加熱温度は１２００℃以上であれば特に制
限されないが、１４００〜２５００℃が好ましい。炭化
けい素結晶には温度に依存する不可逆的な結晶多形が存
在するが、これらの多形の生成域及び安定温度域の概要
を表１に示す。The heating temperature is not particularly limited as long as it is 1200 ° C. or higher, but is preferably 1400 to 2500 ° C. Silicon carbide crystals have irreversible crystal polymorphs depending on the temperature. Table 1 shows the outline of the formation range and stable temperature range of these polymorphs.
【００１８】[0018]
【表１】 [Table 1]
【００１９】本発明においては、炭化けい素の結晶塊は
初めから存在する研削材粒子（α−ＳｉＣ）とその周
辺、隙間等を金属けい素から転化した炭化けい素が埋め
るような形態をなす。加熱温度が２０００℃未満の場
合、転化した炭化けい素はβ−ＳｉＣからなり、結晶粒
子は細かく、一例として金属けい素の粒子サイズをさほ
ど上まわらない。一方、２０００℃以上、とりわけ２２
００℃以上で転化した炭化けい素は、α−ＳｉＣに転移
し再結晶化により結晶粒子は大きくなる。また、加熱温
度２０００℃未満で製造した炭化けい素結晶塊はα−Ｓ
ｉＣとβ−ＳｉＣの混合系となるが、β−ＳｉＣの相が
脆いので、この結晶塊をローラーミル等適当な粉砕機で
処理するとβ−ＳｉＣが優先的に微粉化され、元々存在
したα−ＳｉＣからなる研削材粒は殆ど粉砕されずに残
すことができる。従って、この粉砕物を常套手段にて分
級すれば、研削粒を回収でき、また新たなβ−ＳｉＣを
得ることができる。ここで、α−ＳｉＣは硬度が高く結
晶も大きいので、研削粒として再利用でき、一方、β−
ＳｉＣ（このβ−ＳｉＣには、α−ＳｉＣが混入してい
てもよい）は例えば耐火材用の微粉材として有用であ
る。In the present invention, the crystal mass of silicon carbide has a form in which the abrasive particles (α-SiC) existing from the beginning and the surroundings and gaps are filled with silicon carbide converted from metal silicon. . When the heating temperature is lower than 2000 ° C., the converted silicon carbide is composed of β-SiC, and the crystal grains are fine, and for example, do not significantly exceed the particle size of metal silicon. On the other hand, at least 2000 ° C, especially 22
Silicon carbide converted at 00 ° C. or higher is transformed into α-SiC, and the crystal grains are enlarged by recrystallization. The silicon carbide crystal mass produced at a heating temperature of less than 2000 ° C. is α-S
Although it becomes a mixed system of iC and β-SiC, the β-SiC phase is brittle, so if this crystal lump is treated with a suitable pulverizer such as a roller mill, β-SiC is preferentially pulverized, and the originally existing α Abrasive particles made of -SiC can be left without being pulverized. Therefore, if this pulverized material is classified by a conventional means, the abrasive grains can be collected and new β-SiC can be obtained. Here, since α-SiC has a high hardness and a large crystal, it can be reused as ground grains, while
SiC (α-SiC may be mixed with β-SiC) is useful, for example, as a fine powder for refractory materials.
【００２０】上記の如く加熱温度によってα−ＳｉＣ又
はα−ＳｉＣとβ−ＳｉＣの混合系を選択的に得ること
ができるので、その目的に応じて加熱温度を設定すれば
よい。すなわち、研削材として有用なα−ＳｉＣを得よ
うとする場合には２０００〜２５００℃に加熱すればよ
く、一方、α−ＳｉＣとβ−ＳｉＣの混合系を得ようと
する場合には１４００℃以上２０００℃未満に加熱すれ
ばよい。そして、１４００℃以上２０００℃未満に加熱
した場合には、加熱後粉砕処理し、次いで分級すること
によりα−ＳｉＣ及びβ−ＳｉＣ（このβ−ＳｉＣに
は、α−ＳｉＣが混入していてもよい）をそれぞれ得る
ことができる。As described above, α-SiC or a mixed system of α-SiC and β-SiC can be selectively obtained depending on the heating temperature. Therefore, the heating temperature may be set according to the purpose. That is, when α-SiC useful as an abrasive is to be obtained, heating to 2000 to 2500 ° C. may be performed. On the other hand, when obtaining a mixed system of α-SiC and β-SiC, 1400 ° C. What is necessary is just to heat above 2000 degreeC. When heated to 1400 ° C. or higher and lower than 2000 ° C., the powder is heated and pulverized, and then classified to obtain α-SiC and β-SiC (even if α-SiC is mixed in β-SiC). Good) can be obtained respectively.
【００２１】ここで、２０００℃以上に加熱しようとす
る場合には、加熱炉として炭化けい素製造用のアチソン
炉を用いるのが好ましい。アチソン炉では、けい砂と粉
状コークスを配合した粗原料を黒鉛質抵抗発熱体の周囲
に充填し、通電加熱することにより発熱体周辺にα−Ｓ
ｉＣの結晶を生成させることができる。本発明において
はアチソン炉の炭化けい素結晶生成域に研削泥を装入す
る方法も可能である。その際、該研削泥は、配合した粗
原料に混合し或いは混合せずに装入してもよい。この場
合は多量の粗原料が周囲に存在し、液体分を吸収するの
で研削泥の脱液体操作は必ずしも行わなくてよい。Here, when heating to 2000 ° C. or higher, it is preferable to use an Acheson furnace for producing silicon carbide as the heating furnace. In the Acheson furnace, a raw material containing silica sand and powdered coke is charged around a graphite resistance heating element, and heated by energization to form α-S around the heating element.
An iC crystal can be generated. In the present invention, a method of charging grinding mud into the silicon carbide crystal generation region of the Acheson furnace is also possible. At this time, the grinding mud may be mixed with the mixed raw material or charged without mixing. In this case, since a large amount of the raw material exists around and absorbs the liquid component, the operation of removing the liquid from the grinding mud is not necessarily performed.
【００２２】加熱時間は、目的とする反応が終了する時
期から経験的に決定することができる。The heating time can be determined empirically from the time when the desired reaction is completed.
【００２３】反応終了後、例えば２０００℃以上の加熱
を行った場合には生成した結晶はα−ＳｉＣであるので
全量研削材として利用できる。また、２０００℃未満の
加熱を行った場合には、粉砕後分級して研削材用のα−
ＳｉＣと耐火材用のβ−ＳｉＣを得ることができる。After the reaction is completed, for example, when heating is performed at 2000 ° C. or more, the generated crystal is α-SiC, so that the whole crystal can be used as an abrasive. When the heating is performed at less than 2000 ° C., the material is classified after pulverization and α-
SiC and β-SiC for refractory material can be obtained.
【００２４】[0024]
【実施例】次に実施例を挙げて本発明を詳細に説明する
が、本発明はこれら実施例に何ら限定されるものではな
い。実施例中、「部」は「重量部」を示す。Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” indicates “parts by weight”.
【００２５】実施例１ 実験に供した研削泥の組成は次のものであり、すべての
実施例に共通である。Example 1 The composition of the grinding mud subjected to the experiment is as follows, and is common to all the examples.
【００２６】[0026]
【表２】 [Table 2]
【００２７】炭素材として、固定炭素分９８％の石油コ
ークスの２００メッシュ通過粉を用いた。研削泥とコー
クス粉を所定割合に混合した後、遠心分離機にて油分を
分離し、ペースト状の沈澱（以下スラッジと称する）を
得て、このスラッジを容積５００ccの密閉型黒鉛容器に
充填した。加熱炉は１８００℃まで昇温可能なマッフル
型電炉を用いた。黒鉛容器を炉に装入した後、該容器を
粒状黒鉛で埋没させ、加熱時の酸化を防ぐようにした。
加熱は所定温度到達後３時間保持した後、取出し放冷し
た。実験の割りつけと結果を表３に示した。ここで得ら
れた炭化けい素は耐火材用として使用可能な純度であ
る。As the carbon material, 200-mesh powder of petroleum coke having a fixed carbon content of 98% was used. After mixing the grinding mud and the coke powder in a predetermined ratio, the oil component was separated by a centrifugal separator to obtain a paste-like precipitate (hereinafter referred to as sludge), and the sludge was filled in a 500 cc capacity closed graphite container. . As the heating furnace, a muffle type electric furnace capable of raising the temperature to 1800 ° C. was used. After charging the graphite container into the furnace, the container was buried with granular graphite to prevent oxidation during heating.
Heating was maintained for 3 hours after reaching a predetermined temperature, and then taken out and allowed to cool. Table 3 shows the assignment and results of the experiment. The silicon carbide obtained here has a purity that can be used for refractory materials.
【００２８】[0028]
【表３】 [Table 3]
【００２９】実施例２ 研削泥廃スラリー１００部当り水１００部と脂肪酸エス
テル系界面活性剤３０部を加えて、攪拌を充分行ってス
ラリーの粘性低下処理を行い、５０００ガウスの篭形コ
アー磁選機中を通過させ鉄分を除去した。組成をＳｉＣ
に対するＦｅ、金属質Ｓｉの割合にて表４に示した。Example 2 100 parts of water and 30 parts of a fatty acid ester-based surfactant were added per 100 parts of waste slurry of grinding mud, and the mixture was sufficiently stirred to reduce the viscosity of the slurry. It was passed through to remove iron. The composition is SiC
Table 4 shows the ratios of Fe and metallic Si with respect to.
【００３０】[0030]
【表４】 [Table 4]
【００３１】このスラリーについて、金属質Ｓｉ １０
０部当り炭素分４４部となるような割合で石油コークス
粉２００メッシュ通過粉を混合した。この割合は、Ｓｉ
からＳｉＣを生成する理論炭素量の１．０２７倍の過剰
である。次いで遠心分離機にて液体分を分離した。この
研削泥を実施例１に記したと同様の加熱炉にて１５００
℃にて３時間処理した。結果は表５に示す如く、鉄分の
極めて少ない炭化けい素が得られた。This slurry was prepared using metallic Si 10
The 200-mesh petroleum coke powder was mixed at a ratio such that the carbon content was 44 parts per 0 parts. This ratio is
Is an excess of 1.027 times the theoretical amount of carbon that produces SiC from Next, the liquid component was separated by a centrifuge. This grinding mud was heated in the same heating furnace as described in Example 1 to 1500.
Treated at ℃ for 3 hours. As shown in Table 5, silicon carbide with extremely low iron content was obtained.
【００３２】[0032]
【表５】 [Table 5]
【００３３】実施例３ 実施例２と同一に処理し石油コークスを配合したスラリ
ーを容器にて３０時間静置し、上澄を全容の約５０％分
離した。一方、炭化けい素合成原料としてサイズ５〜１
mm、ＳｉＯ2 ９９％のけい砂とサイズ３mm以下でＣ９８
％の石油コークスを１００部対３６．５部に混合した。
この両者を固体部分の重量比が略１対１となるよう混合
し、研削泥１００kg相当量の混合原料をアチソン炉の発
熱体近傍の一部分に充填した。アチソン炉の諸元は次の
通りである。Example 3 A slurry treated in the same manner as in Example 2 and mixed with petroleum coke was allowed to stand in a container for 30 hours, and the supernatant was separated by about 50% of the total volume. On the other hand, size 5 to 1
mm, silica 98% of SiO 2 and C98 with size 3mm or less
% Petroleum coke was mixed into 100 parts to 36.5 parts.
The two were mixed so that the weight ratio of the solid portion was approximately 1 to 1, and a mixed raw material equivalent to 100 kg of grinding mud was filled in a portion near the heating element of the Acheson furnace. The specifications of the Acheson furnace are as follows.
【００３４】発熱体長・・・・・１５ｍ 電源トランス・・・４，０００KW 原料充填量・・・・１２０トンHeating element length: 15 m Power transformer: 4,000 kW Raw material filling: 120 tons
【００３５】３４００ＫＷの負荷にて５０時間通電後、
電気を切り放冷した後、ＳｉＣインゴットを取出した。
研削泥充填部はアチソン炉の特性から２３００℃以上に
加熱されたと考えられ、他の部分と遜色ない良質のα型
針状結晶乃至は再結晶組織であった。代表成分を表６に
示す。After energizing with a load of 3400 KW for 50 hours,
After the electricity was cut off and allowed to cool, the SiC ingot was taken out.
The grinding mud filling portion was considered to have been heated to 2300 ° C. or higher from the characteristics of the Acheson furnace, and had a high-quality α-type acicular crystal or recrystallized structure comparable to other portions. Table 6 shows representative components.
【００３６】[0036]
【表６】 [Table 6]
【００３７】実施例４ 実施例１にて得られた結晶体を用いてα−ＳｉＣ粒子の
分離を行った。試料についてＮｏ．１〜Ｎｏ．４を略同
量混合し、全体を９００ｇとした。振動ミルで試料を粉
砕した後、沈降法により各粗粉、微粉に分級した。Example 4 Using the crystal obtained in Example 1, α-SiC particles were separated. No. for the sample. 1 to No. 4 was mixed in substantially the same amount to make the whole 900 g. After pulverizing the sample with a vibration mill, each sample was classified into coarse powder and fine powder by a sedimentation method.
【００３８】振動ミルはポット容積 ２Ｌ スチールボール径 ８mm、ボール量４kg 試料装填量 ４００ｇ／１回The vibrating mill has a pot capacity of 2 L, a steel ball diameter of 8 mm, a ball quantity of 4 kg, and a sample loading of 400 g / time.
【００３９】[0039]
【表７】 [Table 7]
【００４０】ミル時間の増加により、粗粉、即ちα−Ｓ
ｉＣのＤ９０％粒径は細くなる傾向を示した。粗粉のＤ
１０％粒径は分級操作の都合であり、この値は上下に調
整可能である。Due to the increase in milling time, coarse powder, ie, α-S
The D90% particle size of iC showed a tendency to become thin. Coarse powder D
The 10% particle size is convenient for the classification operation, and this value can be adjusted up and down.
【００４１】結晶多形から３Ｃ（β−ＳｉＣ）が容易に
微粉化し、分離されていることが認められる。尚、粉砕
機として振動ミルが最適というわけではなく、目的に適
した装置を選択することができる。It is recognized that 3C (β-SiC) is easily pulverized and separated from the crystalline polymorph. Note that a vibration mill is not optimal as a crusher, and an apparatus suitable for the purpose can be selected.
【００４２】[0042]
【発明の効果】本発明によれば、従来廃棄処理されてい
た研削泥を経済的かつ性能面でそれぞれの用途において
遜色なく容易に研削材や耐火材用の炭化けい素結晶とし
て再利用できる。According to the present invention, the grinding mud conventionally discarded can be easily and economically and easily reused as a silicon carbide crystal for a refractory material in terms of performance and performance.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０４Ｂ 35/65 Ｃ０４Ｂ 35/56 １０１Ｐ // Ｈ０１Ｌ 21/02 35/65 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI C04B 35/65 C04B 35/56 101P // H01L 21/02 35/65
Claims (2)
含有する研削用スラリーを媒体としてワイヤソーを用い
て高純度シリコン塊からウエハーを切り出す際に発生す
る研削泥に、該研削泥中の金属けい素を炭化けい素に転
化するに必要な量の炭素を加え、非酸化条件下で１２０
０℃以上に加熱することを特徴とする炭化けい素結晶体
の製造法。1. A grinding slurry generated when a wafer is cut from a high-purity silicon lump using a wire saw with a grinding slurry containing silicon carbide grinding particles and a mineral oil or an aqueous solution as a medium. The amount of carbon required to convert silicon to silicon carbide is added and under non-oxidizing conditions 120
A method for producing a silicon carbide crystal, comprising heating to 0 ° C. or higher.
請求項１記載の炭化けい素結晶体の製造法。2. The method for producing a silicon carbide crystal according to claim 1, wherein the heating is performed in an Acheson furnace.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9281876A JPH11116227A (en) | 1997-10-15 | 1997-10-15 | Production of silicon carbide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9281876A JPH11116227A (en) | 1997-10-15 | 1997-10-15 | Production of silicon carbide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11116227A true JPH11116227A (en) | 1999-04-27 |
Family
ID=17645210
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9281876A Pending JPH11116227A (en) | 1997-10-15 | 1997-10-15 | Production of silicon carbide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11116227A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009527369A (en) * | 2006-02-24 | 2009-07-30 | イーファ ダイアモンド インダストリアル カンパニー リミテッド | CUTTING TIP FOR CUTTING TOOL, CUTTING TIP MANUFACTURING METHOD, AND CUTTING TOOL |
| WO2011019054A1 (en) * | 2009-08-13 | 2011-02-17 | 信越化学工業株式会社 | Method for producing silicon carbide |
-
1997
- 1997-10-15 JP JP9281876A patent/JPH11116227A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009527369A (en) * | 2006-02-24 | 2009-07-30 | イーファ ダイアモンド インダストリアル カンパニー リミテッド | CUTTING TIP FOR CUTTING TOOL, CUTTING TIP MANUFACTURING METHOD, AND CUTTING TOOL |
| US8360046B2 (en) | 2006-02-24 | 2013-01-29 | EWHA Diamond Industrial Co., Ltd. | Cutting tip, method for making the cutting tip and cutting tool |
| WO2011019054A1 (en) * | 2009-08-13 | 2011-02-17 | 信越化学工業株式会社 | Method for producing silicon carbide |
| JP2011037675A (en) * | 2009-08-13 | 2011-02-24 | Shin-Etsu Chemical Co Ltd | Method for producing silicon carbide |
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