JPH0558068B2 - - Google Patents
Info
- Publication number
- JPH0558068B2 JPH0558068B2 JP61147514A JP14751486A JPH0558068B2 JP H0558068 B2 JPH0558068 B2 JP H0558068B2 JP 61147514 A JP61147514 A JP 61147514A JP 14751486 A JP14751486 A JP 14751486A JP H0558068 B2 JPH0558068 B2 JP H0558068B2
- Authority
- JP
- Japan
- Prior art keywords
- diamond
- hydrogen
- thermal conductivity
- carbon
- carbon film
- 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 - Lifetime
Links
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 238000000034 method Methods 0.000 description 9
- 229910003460 diamond Inorganic materials 0.000 description 7
- 239000010432 diamond Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005001 rutherford backscattering spectroscopy Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、気相から室温の基板上に析出させる
ことのできる高熱伝導性ダイヤモンド状カーボン
膜に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to highly thermally conductive diamond-like carbon films that can be deposited from the gas phase onto a substrate at room temperature.
（従来の技術と発明が解決しようとする問題点）
気相からのダイヤモンドないしはダイヤモンド
状カーボン膜の合成方法として、約2000℃に加熱
したフイラメントを触媒とする方法、放電（直
流、高周波、マイクロ波等）を利用した方法、イ
オンビーム法、スパツタ法等が知られている。こ
れらの方法の多くは、基板を約800℃に加熱しな
ければならない欠点を有している。また結晶ダイ
ヤモンド粒子の密集化により膜状にするには、長
時間かかり、その表面も荒い欠点を有している。(Problems to be solved by the prior art and the invention) Methods for synthesizing diamond or diamond-like carbon films from the gas phase include methods using a filament heated to about 2000°C as a catalyst, electric discharge (direct current, high frequency, microwave etc.), ion beam method, sputter method, etc. are known. Many of these methods have the disadvantage that the substrate must be heated to about 800°C. Furthermore, due to the density of the crystalline diamond particles, it takes a long time to form a film, and the surface thereof also has the disadvantage of being rough.
室温付近でダイヤモンド状カーボン膜を合成し
た例として、1980年発行のジヤーナル・オブ・ノ
ンクリスタリン、ソリツズ誌（Journal of Non
−Crystalline Solids）第35＆36巻第435ページ記
載の論文でガラスないしはモリブデンをガラス上
の蒸着したものを基板に用い、アセチレンを直流
グロー放電により分解し、硬質カーボン膜を合成
したことを報告している。しかしながら、熱伝導
性については延べられていない。また、従来の報
告では、水素含有率と熱伝導性の関係を明らかに
したものではなく、水素含有量は制御されていな
い。 An example of synthesizing a diamond-like carbon film near room temperature is given in the Journal of Noncrystallines, published in 1980.
-Crystalline Solids) Vol. 35 & 36, page 435, reports that a hard carbon film was synthesized by using glass or molybdenum vapor-deposited on glass as a substrate and decomposing acetylene by direct current glow discharge. . However, thermal conductivity is not discussed. In addition, conventional reports do not clarify the relationship between hydrogen content and thermal conductivity, and the hydrogen content is not controlled.
ところで近年のエレクトロニクス技術の進歩は
極めて著るしいものがあり、高硬度で高絶縁性か
つ高熱伝導性材料が種々の分野例えば磁気記録媒
体表面コーテイング、磁気ヘツドの表面コーテイ
ング、ICやLSIなどの電子デバイスの表面保護膜
や多層配線間絶縁膜などの用途のために、必要と
されている。従来の炭素膜は抵抗が低かつたり、
高抵抗であつても硬度が1000Kg／mm2以下と小さか
つたり、熱伝導度は100w／ｗ・ｋ以下と小さか
つたり、成膜温度が約500℃以下では性能の優れ
た膜が製作できないという種々の欠点を有してい
た。 By the way, the progress in electronics technology in recent years has been extremely remarkable, and materials with high hardness, high insulation properties, and high thermal conductivity are being used in various fields such as surface coatings for magnetic recording media, surface coatings for magnetic heads, and electronic devices such as ICs and LSIs. It is needed for applications such as device surface protection films and multilayer wiring insulating films. Conventional carbon films have low resistance and
Even if it has high resistance, the hardness is small at less than 1000Kg/ mm2 , the thermal conductivity is small at less than 100w/w・k, and it is not possible to produce a film with excellent performance at a film formation temperature of about 500℃ or less. It had various drawbacks.
本発明の目的は、このような従来の欠点を除去
せしめて、室温で合成できる高熱伝導性ダイヤモ
ンド状カーボン膜を提供することにある。 An object of the present invention is to eliminate such conventional drawbacks and provide a highly thermally conductive diamond-like carbon film that can be synthesized at room temperature.
（問題点を解決するための手段）
本発明によれば、水素含有量を20原子％〜30原
子％とすることによつて、高熱伝導性ダイヤモン
ド状カーボン膜が得られる。(Means for Solving the Problems) According to the present invention, a highly thermally conductive diamond-like carbon film can be obtained by controlling the hydrogen content to 20 at % to 30 at %.
気相からのダイヤモンドないし非晶質のダイヤ
モンド状カーボンの合成過程では、熱力学的に準
安定な相を安定化せしめる人工的操作を要求され
る。特に室温付近での合成の場合、内部エネルギ
ーの高いプラズマを利用したり、イオンを加速し
て基板に衝突させる等の工夫が必要となる。更に
非晶質状態でダイヤモンドの特性を得ようとする
場合には、カーボン膜中に炭素と水素の結合を積
極的に利用する方法がとられる。本発明者らは、
よりダイヤモンドに近い性質を得るために製造条
件を種々検討した結果、水素含有量に最適の値が
存在することを見出し本発明に到つた。水素の役
割としては、ダイヤモンド状カーボンを安定化せ
しめるのではなく、存在するダングリングボンド
を補障することによつて、フオノンの散乱を防止
し、熱伝導率を増加するものと考えられる。 The process of synthesizing diamond or amorphous diamond-like carbon from the gas phase requires artificial manipulations to stabilize the thermodynamically metastable phase. In particular, in the case of synthesis near room temperature, it is necessary to take measures such as using plasma with high internal energy or accelerating ions to collide with the substrate. Furthermore, when attempting to obtain the characteristics of diamond in an amorphous state, a method is used that actively utilizes the bonds between carbon and hydrogen in the carbon film. The inventors
As a result of examining various manufacturing conditions in order to obtain properties closer to those of diamond, it was discovered that an optimum value exists for the hydrogen content, and the present invention was achieved. The role of hydrogen is not to stabilize diamond-like carbon, but to compensate for existing dangling bonds, thereby preventing phonon scattering and increasing thermal conductivity.
実施例 １
反応ガスとして、水素とメタンの混合ガスを用
い、第１図の直流グロー放電装置を用い、室温の
シリコン基板状に２ミクロンのダイヤモンド状カ
ーボン膜を合成した。第１図で１はアノード、２
はカソード、３は直流電源、４は基板である。水
素含有量は、圧力を変えることによつても制御で
きるが、この実験では、全圧を２トールと一定に
保ちメタンと水素の混合比を変えて水素含有量を
制御している。第２図に合成したダイヤモンド状
カーボン膜の熱伝導率の水素の含有量との関係を
示す。第２図より、水素含有量が20〜30原子パー
セントの時熱伝導率が大きく、最大で銅と同程度
まで上昇していることが判明した。この条件での
特性は、析出速度が毎分100オングストローム、
電気抵抗は、1013Ω・cmと高絶縁性で、酸・アル
カリに耐して不活性であり、硬度も約3000ビツカ
ース硬度と硬い膜である。更に膜表面は、非常に
平滑で鏡面状態でくもりのない良好なものであつ
た。Example 1 A diamond-like carbon film of 2 microns was synthesized on a silicon substrate at room temperature using a mixed gas of hydrogen and methane as a reactive gas and using the direct current glow discharge apparatus shown in FIG. In Figure 1, 1 is the anode, 2
is a cathode, 3 is a DC power supply, and 4 is a substrate. The hydrogen content can also be controlled by changing the pressure, but in this experiment, the total pressure was kept constant at 2 Torr and the hydrogen content was controlled by changing the mixing ratio of methane and hydrogen. FIG. 2 shows the relationship between the thermal conductivity of the synthesized diamond-like carbon film and the hydrogen content. From Figure 2, it was found that when the hydrogen content was 20 to 30 atomic percent, the thermal conductivity was high, reaching a maximum of the same level as copper. The characteristics under this condition are that the deposition rate is 100 angstroms per minute,
It is highly insulating with an electrical resistance of 10 13 Ωcm, is resistant to acids and alkalis, is inert, and has a hardness of approximately 3000 Vickers hardness. Furthermore, the film surface was very smooth, mirror-like, and free of cloudiness.
実施例 ２
第３図に示す直流グロー放電装置を用い、実施
例１と同じ条件でダイヤモンド状カーボン膜を合
成し、熱伝導率を評価した所、実施例１と同様な
傾向を得た。ただし、この膜の硬度は約10000ビ
ツカース硬度とほぼダイヤモンド相当の値を示す
ので、熱伝導率も最大で600w／ｍ・ｋとダイヤ
モンドに近い値が得られた。Example 2 A diamond-like carbon film was synthesized using the DC glow discharge device shown in FIG. 3 under the same conditions as in Example 1, and the thermal conductivity was evaluated, and the same trends as in Example 1 were obtained. However, the hardness of this film is about 10,000 Vickers hardness, which is almost equivalent to diamond, and the thermal conductivity was also close to that of diamond, at a maximum of 600 w/m·k.
なお実施例１、２において水素量の定量分析
は、カーボン原子数をラザフオード・バツクスキ
ヤツタリング法で、水素原子をプロトン・リコイ
ル・デイテクシヨン法で分析し、カーボン原子に
対する水素原子比で求めた。更に、赤外吸収スペ
クトルに現れる2900cm-1当りのＣ−Ｈ伸縮モード
によるピークの積分強度より、水素量を確認し
た。 In Examples 1 and 2, the amount of hydrogen was quantitatively analyzed by analyzing the number of carbon atoms using the Rutherford back scattering method and analyzing the hydrogen atoms using the proton recoil detection method, and determining the hydrogen atomic ratio to carbon atoms. Further, the amount of hydrogen was confirmed from the integrated intensity of the peak due to the C--H stretching mode per 2900 cm -1 appearing in the infrared absorption spectrum.
（発明の効果）
本発明により、高熱伝導性ダイヤモンド状カー
ボン膜を室温の基板に析出させることができる。
水素含有量が20原子パーセント以下かないしは30
原子パーセント以上のカーボン膜では非常に低い
熱伝導性を示し、本発明の効果は非常に大きい。
更に、水素を含有しないアモルフアスカーボン膜
に比べると２桁大きい。(Effects of the Invention) According to the present invention, a highly thermally conductive diamond-like carbon film can be deposited on a substrate at room temperature.
Hydrogen content less than 20 atomic percent or 30 atomic percent
A carbon film of atomic percent or more exhibits very low thermal conductivity, and the effects of the present invention are very large.
Furthermore, it is two orders of magnitude larger than an amorphous carbon film that does not contain hydrogen.
第１図及び第３図は、本発明の方法に直接使用
する装置の概略図。第２図は、ダイヤモンド状カ
ーボン膜の熱伝導率と水素の含有量の関係を示す
図。
図において、１はアノード、２はカソード、３
は直流電源、４はスクリーンメツシユである。
1 and 3 are schematic diagrams of equipment used directly in the method of the invention. FIG. 2 is a diagram showing the relationship between the thermal conductivity and hydrogen content of a diamond-like carbon film. In the figure, 1 is an anode, 2 is a cathode, 3
is a DC power supply, and 4 is a screen mesh.
Claims (1)
ーセント以下であることを特徴とするダイヤモン
ド状カーボン膜。1. A diamond-like carbon film characterized by having a hydrogen content of 20 atomic percent or more and 30 atomic percent or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61147514A JPS634068A (en) | 1986-06-23 | 1986-06-23 | Diamondlike carbon film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61147514A JPS634068A (en) | 1986-06-23 | 1986-06-23 | Diamondlike carbon film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS634068A JPS634068A (en) | 1988-01-09 |
| JPH0558068B2 true JPH0558068B2 (en) | 1993-08-25 |
Family
ID=15432060
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61147514A Granted JPS634068A (en) | 1986-06-23 | 1986-06-23 | Diamondlike carbon film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS634068A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2728918B2 (en) * | 1988-11-30 | 1998-03-18 | 株式会社リコー | Liquid jet recording head |
| EP1197581B1 (en) * | 1999-05-19 | 2006-10-25 | Mitsubishi Shoji Plastics Corporation | Dlc film, dlc-coated plastic container, and method and apparatus for manufacturing dlc-coated plastic container |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5842473A (en) * | 1981-09-07 | 1983-03-11 | Semiconductor Energy Lab Co Ltd | Manufacture of thermal head |
| JPS5842472A (en) * | 1981-09-07 | 1983-03-11 | Semiconductor Energy Lab Co Ltd | Thermal head |
| JPS60157725A (en) * | 1984-01-26 | 1985-08-19 | Denki Kagaku Kogyo Kk | Magnetic storage medium |
| JPS60195092A (en) * | 1984-03-15 | 1985-10-03 | Tdk Corp | Method and apparatus for production of carbon thin film |
-
1986
- 1986-06-23 JP JP61147514A patent/JPS634068A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5842473A (en) * | 1981-09-07 | 1983-03-11 | Semiconductor Energy Lab Co Ltd | Manufacture of thermal head |
| JPS5842472A (en) * | 1981-09-07 | 1983-03-11 | Semiconductor Energy Lab Co Ltd | Thermal head |
| JPS60157725A (en) * | 1984-01-26 | 1985-08-19 | Denki Kagaku Kogyo Kk | Magnetic storage medium |
| JPS60195092A (en) * | 1984-03-15 | 1985-10-03 | Tdk Corp | Method and apparatus for production of carbon thin film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS634068A (en) | 1988-01-09 |
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