JP2013115096A - Diamond-containing heat sink material and manufacturing method thereof - Google Patents
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- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 80
- 239000010432 diamond Substances 0.000 title claims abstract description 79
- 239000000463 material Substances 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000002245 particle Substances 0.000 claims abstract description 60
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000007769 metal material Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000011159 matrix material Substances 0.000 claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000002844 melting Methods 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- 239000011812 mixed powder Substances 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 239000010410 layer Substances 0.000 claims description 26
- 229910052802 copper Inorganic materials 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 239000011247 coating layer Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 150000001247 metal acetylides Chemical class 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 20
- 239000010949 copper Substances 0.000 description 18
- 150000003839 salts Chemical class 0.000 description 12
- 239000010936 titanium Substances 0.000 description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005498 polishing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- -1 titanium carbide Chemical compound 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- MPUPIFAINMLUSG-UHFFFAOYSA-L copper;formaldehyde;sulfate Chemical compound [Cu+2].O=C.[O-]S([O-])(=O)=O MPUPIFAINMLUSG-UHFFFAOYSA-L 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- BUKHSQBUKZIMLB-UHFFFAOYSA-L potassium;sodium;dichloride Chemical compound [Na+].[Cl-].[Cl-].[K+] BUKHSQBUKZIMLB-UHFFFAOYSA-L 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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- Cooling Or The Like Of Electrical Apparatus (AREA)
- Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
Abstract
Description
本発明は、ダイヤモンド含有ヒートシンク材、特に放熱性の改良されたヒートシンク材及びその製造方法に関する。 The present invention relates to a diamond-containing heat sink material, in particular, a heat sink material with improved heat dissipation and a method for manufacturing the same.
電子機器に装着されている半導体素子の、自己又は周囲部材の発熱による劣化の回避を目的としたヒートシンク材料として、銅の2倍以上の熱伝導率を有する、ダイヤモンド(粒子)と銅または銀との複合材料が注目されている。 As a heat sink material for the purpose of avoiding deterioration due to heat generation of self or surrounding members of semiconductor elements mounted on electronic devices, diamond (particles) and copper or silver having a thermal conductivity more than twice that of copper These composite materials are attracting attention.
共に熱伝導率の高い物質であるこれらの両料材の配合比を制御することにより、熱膨張率を半導体素子に合わせることができるのもこの材料の大きな特徴である。しかし、ダイヤモンドの銅または銀との濡れの悪さによって生じる接合部における不連続が、期待した熱伝導率が得られない原因になっている。このような欠点の解消のために、接合部に、ダイヤモンドと銅または銀との両方に化学結合性を有する金属炭化物、例えば炭化チタンを介在させる技術が公知である。 It is a major feature of this material that the thermal expansion coefficient can be matched to that of the semiconductor element by controlling the blending ratio of these two materials, both of which have high thermal conductivity. However, the discontinuity at the joint caused by the poor wettability of diamond with copper or silver causes the expected thermal conductivity not to be obtained. In order to eliminate such drawbacks, a technique is known in which a metal carbide having a chemical bonding property to both diamond and copper or silver, such as titanium carbide, is interposed in the joint.
ダイヤモンド表面にチタンなどの金属炭化物を配置することは、メタルボンドダイヤモンド工具の製造において、チタン粉末の添加やチタン蝋の適用という形で、従来から用いられている技術である。一般にＳi、Ｔi、Ｚr、Ｈf、Ｖ、Ｎb、Ｔa、Ｃr、Ｍo、Ｗの諸金属を含む金属炭化物は、ダイヤモンド(カーボン) に比べると、銅族金属に対する濡れ性が良く、炭化物被膜を介してダイヤモンドと銅族金属との化学的な結合が期待できる。 Placing a metal carbide such as titanium on the diamond surface is a technique conventionally used in the manufacture of metal bond diamond tools in the form of addition of titanium powder or application of titanium wax. In general, metal carbides containing various metals such as Si, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W have better wettability with respect to copper group metals than diamond (carbon). Therefore, chemical bonding between diamond and copper group metal can be expected.
この際、焼結に先立ってチタン蝋の利用による金属炭化物層をダイヤモンド表面に形成する技術も公知である。 At this time, a technique for forming a metal carbide layer on the diamond surface by using titanium wax prior to sintering is also known.
これらの各手法では、加熱下で、炭素(ダイヤモンド)に対する親和力の大きな炭化物形成金属とダイヤモンドとの反応が先行し、生成した炭化物層を介してダイヤモンドとマトリックス金属との強固な接合が可能になるものと理解されている。 In each of these methods, the reaction between the carbide-forming metal having a high affinity for carbon (diamond) and diamond precedes the reaction under heating, and the diamond and the matrix metal can be strongly bonded via the generated carbide layer. It is understood.
金属炭化物自体の熱伝導率は銅または銀に比して一桁低いことから、炭化物の被覆層は可能な限り薄くすることが望まれる。しかしながら、上記のように炭化物形成金属を粉末としてマトリックス金属に添加し、加熱焼結の際にダイヤモンド表面への金属炭化物形成を期待する従来方法では、ダイヤモンド表面に形成される炭化物被覆層厚さの均一化、また厚さ自体をを厳密に制御することは困難である。 Since the thermal conductivity of metal carbide itself is an order of magnitude lower than that of copper or silver, it is desirable to make the carbide coating layer as thin as possible. However, in the conventional method in which the carbide forming metal is added to the matrix metal as a powder as described above and metal carbide is formed on the diamond surface during the heating and sintering, the thickness of the carbide coating layer formed on the diamond surface is reduced. It is difficult to make uniform and to strictly control the thickness itself.
一方、加熱焼結に先立ってダイヤモンド粒子表面に炭化物被覆を予め設定しておく手段として、スパッタリング、蒸着、ＣＶＤ、溶射などの手法が知られているが、これらにおいても被覆層の厚さの均一化を厳密に制御することは困難である。 On the other hand, methods such as sputtering, vapor deposition, CVD, and thermal spraying are known as means for preliminarily setting the carbide coating on the diamond particle surface prior to heating and sintering. Even in these methods, the coating layer has a uniform thickness. It is difficult to strictly control the conversion.
従って、本発明は従来のマトリックス金属材とダイヤモンド粒子との複合ヒートシンク材における前記問題を解消した、熱伝導性に優れたヒートシンク用の素材を提供することを課題とする。 Accordingly, an object of the present invention is to provide a heat sink material excellent in thermal conductivity, which solves the above-mentioned problems in the conventional composite heat sink material of matrix metal material and diamond particles.
このような問題は本発明においては、ダイヤモンドとマトリックス金属との確実な接合を実現しながら、熱伝導率の低い接合中間層の厚さを極力小さくすることにより、可能な最高の熱伝導性材料を創製することによって解決される。 In the present invention, such a problem is achieved by reducing the thickness of the bonding intermediate layer having low thermal conductivity as much as possible while realizing reliable bonding between diamond and the matrix metal. It is solved by creating.
本発明のヒートシンク材は、整粒されかつ粒子の全表面に被覆厚さが制御された金属炭化物層を有する被覆ダイヤモンド粒子を、高い熱伝導性を有するマトリックス金属材中に、該金属材と密に接触して分散されていることを特徴とする。 The heat sink material of the present invention comprises coated diamond particles having a metal carbide layer that is sized and whose coating thickness is controlled on the entire surface of the particles in a matrix metal material having high thermal conductivity. It is characterized by being dispersed in contact with
本発明においては、ダイヤモンド粒子と金属材との接合中間層の形成には、熔融塩中に溶け出した炭化物形成金属とダイヤモンド(炭素)表面との反応を用いる。これはパイロゾル法と呼ばれる手法で、古くから金属チタンの回収などに利用されている。 In the present invention, the reaction between the carbide-forming metal dissolved in the molten salt and the diamond (carbon) surface is used to form the bonding intermediate layer between the diamond particles and the metal material. This is a method called a pyrosol method, which has been used for a long time to recover metallic titanium.
かかるヒートシンク材は、本発明の要旨をなす次の各工程を有する方法によって、効果的に製造される：
(1) 整粒されたダイヤモンド粒子の全表面に、パイロゾル法によって金属炭化物層を形成することによって被覆ダイヤモンド粒子を得る工程、
(2) 前記被覆ダイヤモンド粒子とマトリックス金属材の粉末とを密に混合して混合粉とし、焼結反応容器内に充填する工程、
(3) 前記混合粉を還元性雰囲気中で加熱することによって酸素を除去する工程、及び
(4) 前記反応容器をマトリックス金属材の融点以上の加熱温度及び100ＭＰa以上の焼結圧力に供し、該金属材を溶融して被覆ダイヤモンド粒子間の空隙に流入・充填し、金属炭化物層を介してダイヤモンド粒子及び金属材を一体化させる工程。
Such a heat sink material is effectively manufactured by a method having the following steps forming the gist of the present invention:
(1) A step of obtaining coated diamond particles by forming a metal carbide layer by a pyrosol method on the entire surface of the sized diamond particles,
(2) A step of intimately mixing the coated diamond particles and the matrix metal material powder to form a mixed powder, and filling the sintered reaction vessel,
(3) removing oxygen by heating the mixed powder in a reducing atmosphere; and
(4) The reaction vessel is subjected to a heating temperature equal to or higher than the melting point of the matrix metal material and a sintering pressure equal to or greater than 100 MPa, and the metal material is melted to flow into and fill the voids between the coated diamond particles, through the metal carbide layer. Integrating diamond particles and metal material.
本発明において、炭化物形成金属とダイヤモンドとの反応によって形成された金属炭化物層は一般に緻密であって、この層を経由する金属の拡散速度は格段に小さくなる。従って未反応箇所における反応が優先することとなり、結果としてダイヤモンド粒子全表面にわたってほぼ均一厚さの炭化物被膜が形成される。さらにダイヤモンドに対する炭化物形成金属の添加量を予め設定しておくことにより、要望に応じて制御された厚さを持つ炭化物層をダイヤモンド粒子表面に形成することが可能である。 In the present invention, the metal carbide layer formed by the reaction between the carbide-forming metal and diamond is generally dense, and the diffusion rate of the metal passing through this layer is remarkably reduced. Accordingly, the reaction at the unreacted portion is given priority, and as a result, a carbide coating having a substantially uniform thickness is formed over the entire surface of the diamond particles. Furthermore, by setting in advance the amount of carbide-forming metal added to diamond, it is possible to form a carbide layer having a controlled thickness on the diamond particle surface as desired.
本発明のヒートシンクにおける基材としてのダイヤモンド粒子には、通常の研削・研磨材用の整粒された粒子を用いることができる。 As the diamond particles as the base material in the heat sink of the present invention, regular sized particles for grinding and polishing materials can be used.
ヒートシンク素材は切断、表面研磨などの後加工を必要とする。従って、境界面積の減少による熱伝導特性向上には有利であっても加工が困難な粗いダイヤモンド粒子の含有は好ましくない。熱伝導特性と加工性との兼ね合いから、ダイヤモンド粒子としては平均粒径100μｍ以下、特に50μｍ以下のものが好適である。 The heat sink material requires post-processing such as cutting and surface polishing. Therefore, it is not preferable to contain rough diamond particles which are advantageous for improving heat conduction characteristics by reducing the boundary area but are difficult to process. In view of the balance between thermal conductivity and workability, diamond particles having an average particle size of 100 μm or less, particularly 50 μm or less are suitable.
本発明における炭化物層形成反応は熔融塩中で実施されることから、サブミクロンサイズのダイヤモンド粒子についても孤立粒子としての被覆が可能である。しかし境界面積が増し熱伝導特性の面から不利であるので、最小限平均粒径が10μｍ程度以上のものを用いるのが好ましい。 Since the carbide layer forming reaction in the present invention is carried out in a molten salt, it is possible to coat submicron-sized diamond particles as isolated particles. However, since the boundary area increases and this is disadvantageous from the viewpoint of heat conduction characteristics, it is preferable to use one having a minimum average particle size of about 10 μm or more.
炭化物層形成反応に用いる熔融塩としては、チタンの溶融塩電解に用いられる塩浴組成をそのまま用いることができる。即ちＮaＣl−ＫＣl共晶組成をベースとし、さらにＣaＣl2、ＭgＣl2などの添加により、熔融温度を600℃程度に低下させた混合塩が好適である。 As the molten salt used for the carbide layer forming reaction, the salt bath composition used for molten salt electrolysis of titanium can be used as it is. That is, a mixed salt based on the NaCl-KCl eutectic composition and having the melting temperature lowered to about 600 ° C. by addition of CaCl 2 , MgCl 2 or the like is preferable.
操作温度は、実質的に均一厚さの炭化物層をダイヤモンド表面に形成させるために、炭化物層形成反応を混合塩の熔融温度より100℃以上高く設定し、塩浴の粘度を低く保つことにより、金属の移動を容易にする必要がある。一方800℃を超える温度に合成ダイヤモンドを長時間曝すと、ダイヤモンド粒子自体の強度が次第に低下することが知られていることから、炭化物層形成反応は800℃を超えない温度で実施することが望ましい。 In order to form a carbide layer having a substantially uniform thickness on the diamond surface, the operation temperature is set to 100 ° C. or more higher than the melting temperature of the mixed salt, and the viscosity of the salt bath is kept low. It is necessary to facilitate the movement of the metal. On the other hand, when synthetic diamond is exposed to a temperature exceeding 800 ° C. for a long time, it is known that the strength of the diamond particles gradually decreases. Therefore, the carbide layer forming reaction is preferably performed at a temperature not exceeding 800 ° C. .
ダイヤモンド表面に形成する炭化物層は、ダイヤモンド(炭素)と高熱伝導性金属(銅または銀)との化学的結合を目指した接合層であって、炭化物層自体の熱伝導性は接合される両材質に比べて良好といえないことから、極端には数原子層の厚さで十分であり、制御可能な範囲内でできるだけ薄くすることが望ましい。 The carbide layer formed on the diamond surface is a bonding layer aimed at chemical bonding between diamond (carbon) and a high thermal conductivity metal (copper or silver), and the thermal conductivity of the carbide layer itself is the material to be bonded. Therefore, the thickness of several atomic layers is sufficient, and it is desirable to make it as thin as possible within a controllable range.
炭化物層形成反応においては、ダイヤモンド、炭化物形成金属粉末、混合塩をそれぞれ秤量し、混合して反応容器へ仕込むという通常の手法が利用できることから、炭化物形成金属粉末はダイヤモンドに対して質量比で 0.1％ とすることも可能である。この場合反応済みのダイヤモンドは原料のダイヤモンドと形状、透明度には顕著な差は認められないものの、若干灰色に着色していることが認められる。ダイヤモンド粒子表面のＸ線回折による炭化物の検出は困難であるが、蛍光Ｘ線分析によっては炭化物形成金属の存在を確認することができる。 In the carbide layer forming reaction, diamond, carbide-forming metal powder, and mixed salt can be weighed, mixed, and charged into a reaction vessel. % Can also be used. In this case, the reacted diamond is slightly colored in gray, although there is no significant difference in shape and transparency from the starting diamond. Although it is difficult to detect carbides by X-ray diffraction on the surface of diamond particles, the presence of carbide-forming metals can be confirmed by fluorescent X-ray analysis.
本発明における炭化物形成金属としては、広く用いられているチタンと共に、クロム、モリブデン、タングステンも好適である。これらの炭化物は銅への濡れ性が他の金属炭化物よりも良好であることが知られている。 As the carbide-forming metal in the present invention, chromium, molybdenum and tungsten are also suitable as well as titanium which is widely used. These carbides are known to have better wettability to copper than other metal carbides.
金属炭化物層を表面に有するダイヤモンド粒子は、銅粉または銀粉と共に混合して焼結用のカプセルへ充填してもよいが、炭化物層の表面に銅めっきを施しておくことによって、マトリックス材料の銅との接合をより確実にすることができる。 Diamond particles having a metal carbide layer on the surface may be mixed together with copper powder or silver powder and filled into a capsule for sintering. However, if the surface of the carbide layer is plated with copper, the matrix material copper Can be more reliably joined.
さらに上記のめっきにおいて、析出する金属の量としてマトリックスの組成に適した分量を使用することにより、マトリックス中におけるダイヤモンド粒子の分散の均一化を図ることも可能である。銅めっき方法としては化学めっき法が簡便であるが、炭化物層に導電性があることから、電気めっき法も用いることができる。 Furthermore, in the above plating, it is possible to make the dispersion of diamond particles uniform in the matrix by using an amount suitable for the composition of the matrix as the amount of the deposited metal. As the copper plating method, a chemical plating method is simple, but since the carbide layer is conductive, an electroplating method can also be used.
高熱伝導材のダイヤモンドとマトリックス材の銅とで構成されたヒートシンク素材の製作に際して、銅ならびに被覆材の炭化物の酸化は熱伝導率と接合力との低下の原因になるので、極力排除する必要があり、酸素を焼結反応に先立って反応系から除いておかねばならない。この目的で反応材料は予め水素雰囲気中において600℃以上の加熱処理を施すことが望ましい。 When manufacturing a heat sink material composed of high thermal conductivity diamond and matrix copper, the oxidation of copper and the carbide of the coating material causes a decrease in thermal conductivity and bonding strength, so it must be eliminated as much as possible. Yes, oxygen must be removed from the reaction system prior to the sintering reaction. For this purpose, it is desirable that the reaction material is previously subjected to a heat treatment at 600 ° C. or higher in a hydrogen atmosphere.
焼結にはホットプレス、ＨＩＰ、放電加圧焼結、超高圧力焼結といった、加圧下において銅の融点以上の温度を加える、加圧加熱焼結方法が用いられ、熔融した銅によってダイヤモンド粒子の隙間が埋められる。ダイヤモンドがグラファイトへ転移する可能性を避けるため、圧力はダイヤモンドが熱力学的に安定な領域の圧力を用いるのが望ましいが、非酸化雰囲気中における短時間加熱では、ダイヤモンドのグラファイト化を実質的に無視できるので、100 ＭＰa程度の圧力を付加するホットプレス焼結も用いることができる。 Sintering uses pressure-heated sintering methods such as hot pressing, HIP, electric discharge pressure sintering, and ultra-high pressure sintering that apply a temperature above the melting point of copper under pressure. The gap is filled. In order to avoid the possibility of diamond transitioning to graphite, it is desirable to use a pressure in a region where diamond is thermodynamically stable. Since it can be ignored, hot press sintering which applies a pressure of about 100 MPa can also be used.
金属炭化物自体の熱伝導率は銅または銀に比して一桁低いことから、被膜厚さは可能な限り薄く、特にナノメートルのオーダーする必要がある。例えば粒径100μｍのダイヤモンド粒子に対しては質量比で0.5 ％(被覆層厚さ換算で約58nm)以下、粒径10μｍのダイヤモンド粒子に対しては質量比で1.0％(被覆厚さ換算で約11nm)以下とするのが好ましい。 Since the thermal conductivity of the metal carbide itself is an order of magnitude lower than that of copper or silver, the film thickness needs to be as thin as possible, particularly on the order of nanometers. For example, for diamond particles with a particle size of 100 μm, the mass ratio is 0.5% (approx. 58 nm in terms of coating layer thickness) or less, and for diamond particles with a particle size of 10 μm, the mass ratio is 1.0% (approx. 11 nm) or less.
但し上記被覆厚さは、ダイヤモンド粒子を球と仮定した便宜上の計算値に過ぎない。一般の研削・研磨に用いられているダイヤモンド粒子は複雑な形状を呈していることから、粒子サイズの表示においては、すべての粒子が球状を呈していると仮定して扱われる場合が多い。本発明においても便宜上球換算径で表示するが、球換算で得られる見掛けの比表面積値に対して、ＢＥＴ法で測定した実際の比表面積値は、常に4〜5倍の値となっていることから、実際の被覆厚さの平均値は、上記計算値の1/5程度と見積もる必要がある。
次に本発明を実施例によって説明する。
However, the above-mentioned coating thickness is only a calculated value for convenience assuming that the diamond particle is a sphere. Since diamond particles used for general grinding / polishing have a complicated shape, in the display of particle size, it is often handled assuming that all particles are spherical. In the present invention, it is displayed as a sphere equivalent diameter for the sake of convenience, but the actual specific surface area value measured by the BET method is always 4 to 5 times the apparent specific surface area value obtained in sphere equivalent. Therefore, it is necessary to estimate the actual average value of the coating thickness as about 1/5 of the calculated value.
Next, the present invention will be described by way of examples.
ＩＲＭ 40-60(トーメイダイヤ(株)製の商品名。Ｍicrotrac ＵＰＡによる測定で平均粒径35μｍ)のダイヤモンド粒子に、 Ｔi粉をダイヤモンドに対して質量比で0.2％添加し、Ａr雰囲気内、ＮaＣl-ＫＣlの等モル混合物による熔融塩中で800℃に2時間保持し、ダイヤモンド粒子上にＴiＣ被覆層の形成反応を行った。反応後における塩浴除去の湿式処理において、未反応のチタンがないことを、塩酸溶解液の無着色で確認した。 To a diamond particle of IRM 40-60 (trade name, manufactured by Tomei Dia Co., Ltd., average particle diameter of 35 μm as measured by Microtrac UPA), 0.2% of Ti powder is added to the diamond in a mass ratio. The mixture was kept at 800 ° C. for 2 hours in a molten salt of an equimolar mixture of —KCl to form a TiC coating layer on the diamond particles. In the wet treatment for removing the salt bath after the reaction, the absence of unreacted titanium was confirmed by no coloring of the hydrochloric acid solution.
得られた被覆ダイヤモンドは、顕微鏡観察により、各ダイヤモンド粒子の全表面がＴiＣの薄膜で覆われていることが認められた。ダイヤモンド粒子を球と仮定した計算による被覆層の平均厚さは、添加チタン量から約0.008μｍと見積もられ、被覆層厚さとしては約2nmに相当した。 In the obtained coated diamond, it was confirmed by microscopic observation that the entire surface of each diamond particle was covered with a thin film of TiC. The average thickness of the coating layer calculated from the assumption that the diamond particles were spheres was estimated to be about 0.008 μm from the amount of added titanium, and the coating layer thickness was equivalent to about 2 nm.
得られたＴiＣ被覆ダイヤモンド80％(質量比。以下同様)と、呼称45μｍの電解銅粉20％とを十分に混合してＴa薄板製の焼結カプセルに充填し、4ＧＰa、1100℃、保持時間10分間の条件で焼結を行い、直径63mm、厚さ8mmの円板状焼結体を得た。得られた焼結体の密度は4.26g/cm3、レーザーフラッシュ法によって決定した熱伝導率は510Ｗ/ｍ・Ｋであった。 The obtained TiC-coated diamond 80% (mass ratio; the same applies hereinafter) and 20% electrolytic copper powder with a nominal value of 45 μm are mixed thoroughly and filled into a sintered Ta thin capsule, 4 GPa, 1100 ° C., holding time Sintering was performed for 10 minutes to obtain a disk-shaped sintered body having a diameter of 63 mm and a thickness of 8 mm. The density of the obtained sintered body was 4.26 g / cm 3 , and the thermal conductivity determined by the laser flash method was 510 W / m · K.
前記のＴiＣ被覆ダイヤモンド粒子上に、硫酸銅−ホルムアルデヒド系浴を用いて無電解銅めっきを行い、ダイヤモンド粒子に対して20％(質量比)のＣuをＴiＣ被覆層上に析出させた。得られたＴiＣ-Ｃu被膜ダイヤモンド粒子に対して10％の電解銅粉を添加し、十分に混合してからＴa製の容器に充填し、全体を水素雰囲気中にて100ＭＰa及び1150℃の一定条件下に10分間保持することによって加圧焼結し、熱伝導率450Ｗ/ｍ・Ｋの焼結品を得た。 Electroless copper plating was performed on the TiC-coated diamond particles using a copper sulfate-formaldehyde bath, and 20% (mass ratio) of Cu was deposited on the TiC coating layer. Add 10% electrolytic copper powder to the resulting TiC-Cu coated diamond particles, mix thoroughly, and then fill into a Ta container. The whole is kept at 100 MPa and 1150 ° C under hydrogen atmosphere. Under pressure holding by holding for 10 minutes, a sintered product having a thermal conductivity of 450 W / m · K was obtained.
以下に示すとおり異なる構成を有するヒートシンク材を作成した。各例において、ダイヤモンド粒子の品種はすべてＩＲＭ(トーメイダイヤ株式会社製)とし、サイズは研磨剤業界の呼称で示し、ダイヤモンド基体への炭化物被覆層形成のための添加金属量、炭化物被覆量及びＣu被覆量は、それぞれダイヤモンドに対する質量％で表示した。炭化物形成反応のための(溶融塩)温度は800℃、炭化物形成反応の保持時間は2時間に固定した。マトリックス素材として呼称45μｍの電解銅粉を用い、焼結は一定の圧力・温度条件5ＧＰa及び1100℃を10分間保持して行った。
本発明のヒートシンク用素材は従来技術製品に比べて熱伝導性に優れ、より効率的なヒートシンク材の製造に利用可能である。
The heat sink material of the present invention is superior in thermal conductivity as compared with the prior art products and can be used for more efficient heat sink material production.
Claims (10)
(1) 整粒されたダイヤモンド粒子の全表面に、パイロゾル法によって金属炭化物層を形成することによって被覆ダイヤモンド粒子を得る工程、
(2) 前記被覆ダイヤモンド粒子とマトリックス金属材の粉末とを密に混合して混合粉とし、焼結反応容器内に充填する工程、
(3) 前記混合粉を還元性雰囲気中で加熱することによって酸素を除去する工程、及び
(4) 前記反応容器をマトリックス金属材の融点以上の加熱温度及び100ＭＰa以上の焼結圧力に供し、該金属材を溶融して被覆ダイヤモンド粒子間の空隙に流入・充填し、金属炭化物層を介してダイヤモンド粒子及び金属材を一体化させる工程。 The manufacturing method of the heat sink material of Claim 1 which has each following process:
(1) A step of obtaining coated diamond particles by forming a metal carbide layer by a pyrosol method on the entire surface of the sized diamond particles,
(2) A step of intimately mixing the coated diamond particles and the matrix metal material powder to form a mixed powder, and filling the sintered reaction vessel,
(3) removing oxygen by heating the mixed powder in a reducing atmosphere; and
(4) The reaction vessel is subjected to a heating temperature equal to or higher than the melting point of the matrix metal material and a sintering pressure equal to or greater than 100 MPa, and the metal material is melted to flow into and fill the voids between the coated diamond particles, through the metal carbide layer. Integrating diamond particles and metal material.
The method for producing a heat sink material according to claim 7, wherein a metal Cu coating layer is further formed on the surface of the coated diamond particles in the step (1).
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