JPS5926906A - Amorphous carbon material - Google Patents
Amorphous carbon materialInfo
- Publication number
- JPS5926906A JPS5926906A JP57136787A JP13678782A JPS5926906A JP S5926906 A JPS5926906 A JP S5926906A JP 57136787 A JP57136787 A JP 57136787A JP 13678782 A JP13678782 A JP 13678782A JP S5926906 A JPS5926906 A JP S5926906A
- Authority
- JP
- Japan
- Prior art keywords
- amorphous carbon
- carbon material
- hardness
- action
- properties
- 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
- 239000002194 amorphous carbon material Substances 0.000 title claims abstract description 29
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 6
- 230000005684 electric field Effects 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 abstract description 32
- 230000003287 optical effect Effects 0.000 abstract description 16
- 239000010409 thin film Substances 0.000 abstract description 15
- 229910003460 diamond Inorganic materials 0.000 abstract description 11
- 239000010432 diamond Substances 0.000 abstract description 11
- 238000000862 absorption spectrum Methods 0.000 abstract description 10
- 239000000758 substrate Substances 0.000 abstract description 10
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011521 glass Substances 0.000 abstract description 7
- 238000000151 deposition Methods 0.000 abstract description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002441 X-ray diffraction Methods 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 229910052710 silicon Inorganic materials 0.000 abstract description 4
- 239000010703 silicon Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 239000003575 carbonaceous material Substances 0.000 abstract 2
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 16
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 12
- 229910003481 amorphous carbon Inorganic materials 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 8
- 239000001294 propane Substances 0.000 description 6
- -1 acetylene hydrocarbons Chemical class 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000005484 gravity Effects 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 229910021417 amorphous silicon Inorganic materials 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000007373 indentation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000006748 scratching Methods 0.000 description 3
- 230000002393 scratching effect Effects 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 238000007542 hardness measurement Methods 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/16—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only elements of Group IV of the Periodic System
- H01L29/1604—Amorphous materials
Abstract
Description
【発明の詳細な説明】
本発明は、真空容器内において炭化水素糸物負（例えば
ＣＨ＝、 Ｃ＝）ｉ・、Ｃ［有］Ｈｏ・・・・・などメ
タン系炭化水素あるいはＣ，Ｈ４，Ｃ，Ｈ＝などエチレ
ン系炭化水累、アセチレン系炭化水素）をＲＦ高周波電
界ラジオ周波数）の作用のもとにプラズマ分解析出は）
プラズマＣＶＤという）して得られる発光特性ならびに
半導体特性を有しかつ高硬度なアモルファス炭３Ｆｉ：
月料に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to the production of methane-based hydrocarbons such as hydrocarbon threads (for example, CH=, C=) , C, H = ethylenic hydrocarbons, acetylene hydrocarbons) under the action of RF high frequency electric field (radio frequency).
Amorphous carbon 3Fi with high hardness and luminescent properties and semiconducting properties obtained by plasma CVD:
It concerns monthly charges.
プラズマＣＶＤ法によって得られたアモルファス炭素材
料は、淡黄色の透明物質で、次の２つの大きな特徴ある
物理的性質を有することが見出された。It has been discovered that the amorphous carbon material obtained by plasma CVD is a pale yellow transparent substance and has the following two major physical properties.
１つは、発光特性ならびに半導体特性を有することで、
水銀ランプの発する３６５／Ｘ７７７１−紫外線励起に
よって２．６ｅＶ に発光ピークを持つ青白色の明る
いフォトルミネッセンスが観察され、かつ３． ＯｅＶ
の光学ギャップを有する半導体特性を示した。One is that it has light emitting properties and semiconductor properties,
3. Bright blue-white photoluminescence with an emission peak at 2.6 eV was observed by excitation of 365/X7771-ultraviolet light emitted by a mercury lamp, and 3. OeV
It exhibited semiconductor properties with an optical gap of .
この性質は、実用面からは、青白色の発光ダイオードあ
るいは半導体レーザダイオードとしての可能性を有する
。From a practical standpoint, this property has the potential to be used as a blue-white light emitting diode or a semiconductor laser diode.
また青白色の螢光ランプへの応用も可能であり、青白色
の透明螢光ランプの実現の可能性もある。It is also possible to apply it to a blue-white fluorescent lamp, and there is a possibility of realizing a blue-white transparent fluorescent lamp.
さらに大きな光学ギャップを有することから、高効率太
陽電池への可能性も考えられる。Since it has an even larger optical gap, it is possible that it could be used as a high-efficiency solar cell.
他の価値ある特徴の１つは、ダイヤモンドに匹敵する極
めて高い硬度を有しているということである。One of its other valuable features is that it has extremely high hardness, comparable to diamond.
アモルファス炭素材料は、物質の表面に容易に膜状とし
て析出形成できることから、この極めて硬いという性質
を一般の物質に賦与して劇摩耗性の優れたものに改善で
きるという極め″′Ｃ有用な応用が考えられる。Since amorphous carbon materials can be easily formed as a film on the surface of materials, they have an extremely useful application in that they can impart this extremely hard property to ordinary materials and improve them to have excellent wear resistance. is possible.
例えばメガネレンズあるいは、腕時計のカバーガラスな
どはよく傷がつき見苦しくなる場合があるが、アモルフ
ァス炭素材料をこれらの上に析出被着させることによっ
て全く傷のつかないものに改善することは容易である。For example, eyeglass lenses and watch cover glasses often get scratched and become unsightly, but it is easy to make them completely scratch-free by depositing amorphous carbon material on them. .
本発明は、このように特異なかつ有用な物理的、機械的
性質を有するアモルファス炭素材料特にアモルファス炭
素薄膜材料に関して基本的かつ実用的に価値ある技術を
提供しようとするものである。The present invention aims to provide fundamental and practically valuable technology regarding amorphous carbon materials, particularly amorphous carbon thin film materials, which have such unique and useful physical and mechanical properties.
従来、アモルファス炭素材料は油煙（スス）として知ら
れているもので、その応用例は鉛筆の芯、墨汁などの他
、導電材料として摺動子接点制料など、また耐熱性を利
用した炉材などの炭素製品として実用に供されてきてい
る。Traditionally, amorphous carbon materials have been known as soot, and their applications include pencil lead, India ink, etc., as well as conductive materials such as slider contact materials, and furnace materials that take advantage of their heat resistance. It has been put into practical use as carbon products such as carbon products.
しかし、本発明において提供されるアモルファス炭素材
料のように半導体的１機械的にその特異な機能を賦与し
たものでこれまでに実用化された例はまだない。However, there has not yet been an example of an amorphous carbon material provided with a semiconductor-like or mechanically unique function that has been put into practical use like the amorphous carbon material provided in the present invention.
アモルファス炭素材料をアセチレンガスのグロー放電分
解゛法により初めて作成し、電気的、光学的性質を倹約
した例としてＡｎｄ６ｒｓｏｎ （英国）の報告がある
。There is a report by And6rson (UK) as an example in which an amorphous carbon material was created for the first time by the glow discharge decomposition method of acetylene gas, and its electrical and optical properties were economized.
また、その後アセチレンガスにホスフィン、ジボランな
どのガスを混入してアモルファス炭素材料を作成し、主
にその電気的特性について報告したものにＭｅｙｅｒＳ
Ｏｎ （英国）がイル。In addition, MeyerS.
On (UK) is IL.
さらに、■ｏｒａ（英国）らが、メタンをグロー放電分
解して立方晶の結晶構造を持つ擬ダイヤモンド膜を形成
せしめたとの報告を行なっているのみで、膜の電気的、
光学的性質については述べられていない。Furthermore, ORA (UK) et al. have only reported that a pseudodiamond film with a cubic crystal structure was formed by glow discharge decomposition of methane, but the electrical and
No mention is made of optical properties.
ごく最近、渡辺らは、エチレンガスのグロー放電分解に
より、析出形成したアモルファス炭素膜の発光特性を報
告したか光学ギャップ２．６ｅＶ、発光ピークエネルギ
ー２．ＯｅＶ程度と小さいものであった。Very recently, Watanabe et al. reported the luminescence properties of an amorphous carbon film precipitated by glow discharge decomposition of ethylene gas, with an optical gap of 2.6 eV and an emission peak energy of 2. It was as small as about OeV.
さらに、本発明にかかるアモルファス炭素材料と異なる
ものの、同様な発光特性、半導体特性を有するものとし
て大木らによりケイ累ターゲットを用いてプロパンガス
雰囲気で反応性スパッタリングすることによりアモルフ
ァス炭化ケイ素材料を。Furthermore, although different from the amorphous carbon material according to the present invention, it has similar luminescent properties and semiconducting properties.Oki et al. produced an amorphous silicon carbide material by reactive sputtering in a propane gas atmosphere using a silicon target.
又あるいは、テトラメチルシラン（ｓ ｔ （ＣＨ，）
４）をグロー放電分解することによりアモルファス炭
化ケイ素材料を膜状に析出形成した例が報告されている
。Alternatively, tetramethylsilane (s t (CH,)
An example has been reported in which an amorphous silicon carbide material was deposited in a film form by glow discharge decomposition of 4).
しかし、発光特性はおよそ２．０〜２．３ｅＶ であり
光学ギャップは２．５〜２．６ｅＶ とそれぞれ小さ
い値であることが報告されている程度に過ぎない。However, it has only been reported that the emission characteristics are approximately 2.0 to 2.3 eV and the optical gap is 2.5 to 2.6 eV, which are small values.
これらの結゛果に対し、本発明にかかるアモルファス炭
素薄膜材料の特徴は、２．６ ｅＶ と比較的短波長側
に発光ピークを持ち、さらに３．ＯｅＶと極めて大きな
光学ギャップを有すると共に極めて硬いという機械的強
度を伽えた物質であることである。In contrast to these results, the amorphous carbon thin film material according to the present invention is characterized by having an emission peak on the relatively short wavelength side of 2.6 eV, and 3. It is a material with outstanding mechanical strength, having an extremely large optical gap of OeV and being extremely hard.
以１に、本発明の効果を検証するため、後述の実施例１
に記載した条件でシリコン基板上ならびにスライドガラ
ス上にプロパンガスのプラズマＣＶＤにより分解析出し
て得られたアモルファス炭素薄膜材料の物理的、光学的
２機械的性負について軸べた結果について述べる。First, in order to verify the effects of the present invention, Example 1 described below will be described.
We will discuss the physical, optical, and mechanical properties of amorphous carbon thin film materials obtained by fractional deposition using propane gas plasma CVD on silicon substrates and glass slides under the conditions described in .
プロパンガスのプラズマＣＶＤにより得られたアモルフ
ァス炭素薄膜は、淡黄色の透明材料である。The amorphous carbon thin film obtained by propane gas plasma CVD is a pale yellow transparent material.
スライドガラス基板から剥離した膜の比重は浮遊法（薄
膜状物質の比重測定法の一つである）により測定したと
ころ１．１５〜１．１６ ｙｃＴＬ” であった。The specific gravity of the film peeled off from the slide glass substrate was 1.15 to 1.16 ycTL'' as measured by a floating method (one of the methods for measuring the specific gravity of thin film-like substances).
ダイヤモンドの比ｌはａ、 ５１ ｔ７ｃｒＸであり、
これよりはるかに小さな値であった。The ratio l of diamond is a, 51 t7crX,
The value was much smaller than this.
尚、上記浮遊法による比重の測定について述べれ測定に
用いた重液は臭化亜鉛（ＺｎＢｒｘ比ｋ ４．２１９）
でこれに膜を浮べ希釈液のエタノール（Ｃ−）１＝ＯＨ
比ｍ０．７９３）を加えながら重液の比重を変えて膜か
丁度沈降開始したときの液比ｌをもって、その膜の比重
とする。The measurement of specific gravity by the above-mentioned floating method is described. The heavy liquid used for the measurement was zinc bromide (ZnBrx ratio k 4.219).
Float the membrane on this and dilute the diluted ethanol (C-)1=OH
The specific gravity of the heavy liquid is changed while adding the ratio m0.793), and the liquid ratio 1 at which the membrane just starts to settle is taken as the specific gravity of the membrane.
作製した薄膜材料は、第１図のＸ線回折の結果よりアモ
ルファス構造であることを確認した。The produced thin film material was confirmed to have an amorphous structure from the X-ray diffraction results shown in FIG.
また第２図は、この薄膜の赤外吸収スペクトルを示して
いる。Moreover, FIG. 2 shows the infrared absorption spectrum of this thin film.
この図よりおよそ２９００ｃｍ−’ 、 １４６０ｃ
ＩｒＬ−、’ 。Approximately 2900cm-', 1460c from this figure
IrL-,'.
１３８０ ｃｍ−’にそれぞれＣ−Ｈ九の伸縮振動、Ｃ
−ＨｊＣ−出の変角振動による強い吸収が観察され、こ
れよりアモルファス炭素薄膜材料には水素が強く結合し
ていることが知られた。Stretching vibration of C-H9 at 1380 cm-', C
Strong absorption due to bending vibration of -HjC- was observed, and from this it was known that hydrogen was strongly bonded to the amorphous carbon thin film material.
その証拠として最高６００℃まで加熱焼鈍したが、これ
らの特性には何らの変化が認められなかった。As proof of this, the material was annealed at a maximum temperature of 600°C, but no change was observed in these properties.
これらの結果よりこのプロパンカスのプラズマＣＶＤに
より形成された薄膜は、主にＣ，Ｈ原子より構成された
アモルファス炭素材料であることが判明した。These results revealed that the thin film formed by plasma CVD of propane gas was an amorphous carbon material mainly composed of C and H atoms.
またこの膜の抵抗率ｙは、１０”ΩｃｒＩＬ程度であっ
た。Further, the resistivity y of this film was approximately 10'' ΩcrIL.
以上のような本発明にかかる水素を含有するアモルファ
ス炭素薄膜材料の第１の効果である発光特性についてま
ず詳述する。First, the light emitting property, which is the first effect of the hydrogen-containing amorphous carbon thin film material according to the present invention, will be described in detail.
水銀灯３６５？２ｍの紫外線励起による発光特性はスラ
イドガラス上に形成されたアモルファス炭素薄膜材料に
よって詭べられた。The luminescence characteristics caused by ultraviolet excitation from a 365-2m mercury lamp were studied using an amorphous carbon thin film material formed on a slide glass.
この結果は、第３図に示されている。The results are shown in FIG.
この図で３つの曲線は、基板温度を室温、１００℃。The three curves in this figure are for substrate temperatures of room temperature and 100°C.
１５０℃で作成された材料の発光特性を示している。It shows the luminescent properties of the material made at 150°C.
室温で作成した材料は発光ピークエネルギーが２．６
ｅＶで青白色の発光が観察された。The material created at room temperature has an emission peak energy of 2.6
Blue-white light emission was observed at eV.
また１００℃、１５０℃と作成温度の上昇とともに低エ
ネルギー側に発光ピークがシフトする傾向がみられた。Furthermore, as the production temperature increased to 100°C and 150°C, there was a tendency for the emission peak to shift to the lower energy side.
また第４図は、可視吸収スペクトルを示す図で、室温で
作成した膜では吸収端が３．ＯｅＶにある。Moreover, FIG. 4 is a diagram showing the visible absorption spectrum, and the absorption edge of the film prepared at room temperature is 3. It is in OeV.
これらの発光ピークエネルギー、光学ギャップは。What are their emission peak energies and optical gaps?
現在までに報告されているアモルファスケイ素。Amorphous silicon reported to date.
アモルファス炭化ケイ素材料を含めて最大の値であった
。This was the highest value including the amorphous silicon carbide material.
この発光特性および可視吸収スペクトルは、ブラズマＣ
ＶＤの分解析出の条件により多少変化し、例えは後述の
実施例２による場合には発光ピークが２・３ ｅＶ、可
視吸収スペクトルの光学ギャップが２．７ｅＶであった
。This emission characteristic and visible absorption spectrum are based on plasma C
It varies somewhat depending on the conditions of the VD separation, and for example, in the case of Example 2 described later, the emission peak was 2.3 eV and the optical gap of the visible absorption spectrum was 2.7 eV.
このことは、アモルファス炭素薄膜材料の製造条件によ
って光学的、半導体的性質の一部を適消変化させ、うる
ものであることを示唆している。This suggests that some of the optical and semiconductor properties can be appropriately changed depending on the manufacturing conditions of the amorphous carbon thin film material.
さて本発明にかかる第２の効果は極めて特異な問題でア
モルファス炭素材料がダイヤモンドに匹敵しつる高硬度
を持っているという材料物性で革命的特性の結果を検証
することである・
第５図は、各種の材料の硬さをそれぞれ大小関係で示し
た結果である。Now, the second effect of the present invention is to verify the revolutionary property of an amorphous carbon material in terms of material physical properties, which is a very unique problem and has a high hardness comparable to that of diamond. , which shows the hardness of various materials in terms of magnitude.
すなわち本発明によって得られたアモルファス炭素材料
について寺沢式マイクロビッカース硬度計（本硬度ｕ１
は、薄膜用硬度計として使用されているもので、敢低荷
ｉ０，１４ｎ高荷重が２００１まで測定が可能かもので
ある。）により硬さ測定を次の手順で行なった。That is, the amorphous carbon material obtained by the present invention was measured using a Terasawa micro-Vickers hardness tester (actual hardness u1).
is used as a hardness tester for thin films, and can measure low loads i0,14n and high loads up to 2001. ), the hardness was measured using the following procedure.
まず、アモルファス炭素材料は薄膜材料であることから
初めに０．１１の荷重の下で測定したところダイヤモン
ド圧子の圧痕は全く認められなかったＯ
次いで荷ｌを１ノ、５？、１０？・・・・と引き続き増
大して硬度測定を行なったが先と同様全くダイヤモンド
圧子の圧痕はつかず１００１に至って薄膜材料に十文字
状の亀裂が初めて確認できるにいたった。First, since the amorphous carbon material is a thin film material, when it was first measured under a load of 0.11, no indentation by the diamond indenter was observed. , 10? The hardness continued to increase and the hardness was measured, but as before, there was no indentation of the diamond indenter at all, and when it reached 1001, a cross-shaped crack in the thin film material could be observed for the first time.
しかし、なおかつ十文字状亀裂の中心に硬度値を与える
ダイヤモンド圧子の圧痕は確認できなかった。However, no indentation by the diamond indenter, which gives hardness values, could be observed at the center of the criss-cross crack.
この実験結果は、まさに本発明にかかるアモルファス炭
素材料がダイヤモンドに匹敵する尚い硬度値を有してい
ることの証明である。This experimental result proves that the amorphous carbon material according to the present invention has a hardness value comparable to that of diamond.
さらにこれを実証するためにモース硬度と呼ばれる硬度
測定の方法に従って、他種材料とそれぞれ引っ掻き方法
によって硬さの順位を比較して並べた結果が第５図であ
る。Furthermore, in order to prove this, according to a hardness measurement method called Mohs hardness, the hardness rankings of the materials are compared and arranged according to the scratching method with other materials, and the results are shown in FIG.
すなわちダイヤモンドとアモルファス炭素材料では互い
に傷をつけ合うことはできないが他の材料に対しては容
易に引っ掻き傷をつけうろことを確認した。In other words, it was confirmed that diamond and amorphous carbon materials cannot scratch each other, but they easily scratch other materials.
以上に本発明にかかるアモルファス炭素材料の物理的、
光学的１機械的性質について概略を説明したが以下では
実施例をもって詳細に説明する。As described above, the physical properties of the amorphous carbon material according to the present invention,
Although the optical and mechanical properties have been briefly explained, they will be explained in detail using examples below.
実施例１
銹導結合型のプラズマＣＶＤ装置（石英管５０醜ψ ）
においてまず真空容器を１０〜１０Ｔｏｒｒに真空排気
した後市販のプロパン（純度９８３％）ガスを４ ｇ
ｍＴｏｒｒになるように導入しＲＦｉ ３．５６ ＭＥ
（ｚ、 Ｎ力２０Ｗを投入しプラズマＣＶＤによってシ
リコン基板およびスライドガラス基板上にアモルファス
炭素材料を厚さ１０．Ｌ４？ｌＬ程度の膜状に析出形成
させた。Example 1 Plasma CVD device of galvanic coupling type (quartz tube 50 mm)
First, the vacuum container was evacuated to 10 to 10 Torr, and then 4 g of commercially available propane (983% purity) gas was added.
Introduced to become mTorr RFi 3.56 ME
(z, N power of 20 W was applied and an amorphous carbon material was deposited and formed into a film with a thickness of about 10.L4-1L on a silicon substrate and a slide glass substrate by plasma CVD.
基板温度は室温、１００℃、１５０’Ｃの３種類で杓う
た。Three types of substrate temperature were used: room temperature, 100°C, and 150'C.
また堆積速度は１００〜ｚｏｏｉ−であり堆積速度は基
板温度の上昇とともに若干減少する傾向があった。Further, the deposition rate was 100 to zooi-, and the deposition rate tended to decrease slightly as the substrate temperature increased.
得られた膜の構造は第１図のＸ線回折の結果からもわか
るように炭素の回折線はみられずアモルファスであるこ
とが＠誌された。It was reported that the structure of the obtained film was amorphous, with no carbon diffraction lines seen, as can be seen from the X-ray diffraction results shown in Figure 1.
スライドガラス基板上に堆積した膜について水銀灯３６
５ｖｒＬ紫外線励起により発光特性を調べた結果は第３
図に示されている。Mercury lamp 36 for films deposited on slide glass substrates
The results of investigating the luminescence characteristics by 5vrL ultraviolet excitation are as follows.
As shown in the figure.
また可視吸収スペクトルを調べた結果は第４図で示され
ている。Further, the results of examining the visible absorption spectrum are shown in FIG.
すなわち塞流で形成されたアモルファス炭素材料は２，
６ｅＶにピークを持つ発光特性を有し、かつ光学ギャッ
プ３．ＯｅＶ の半導体性負な有する物質であることが
わかる。In other words, the amorphous carbon material formed by blockage is 2,
It has light emission characteristics with a peak at 6 eV, and has an optical gap 3. It can be seen that the material has a negative semiconducting property of OeV.
さらに基板＠度の上昇に伴い発光特性、ならびに光学ギ
ャップは低エネルギー側にそれぞれ移動した、
また、その発光強度は、この３つの間で同等であった。Furthermore, as the substrate temperature increased, the emission characteristics and the optical gap shifted to the lower energy side, and the emission intensity was equivalent among the three.
なおこの物・債をマイクロビッカース硬度針によって硬
度測定を行なったところダイヤモンド圧子の庄成はみら
れず測定不可能であった。When the hardness of this product/bond was measured using a micro Vickers hardness needle, no hardening of the diamond indenter was observed and measurement was impossible.
この膜で他物質に傷をつけたところ第５図に示すような
硬さの順位が得られた。When this film was used to scratch other materials, the hardness rankings shown in Figure 5 were obtained.
すなわちこの膜物質はダイヤモンドと同程度の硬さを有
していることが知られた。In other words, it is known that this film material has a hardness comparable to that of diamond.
これらの膜を２００℃、４００℃、６００℃の各温度で
３０分間真空焼鈍して物理的、光学的。These films were vacuum annealed at 200°C, 400°C, and 600°C for 30 minutes to improve physical and optical properties.
機械的緒特性を同様な方法で測定したが焼鈍以前の膜と
比較して何らの変化もみられなかった。Mechanical properties were measured using the same method, but no changes were observed compared to the film before annealing.
実施例２
上記の装置において市販のプロパンガスを５簿Ｔｏｒｒ
となしプラズマＣＶＤ法により先と同様分解析出して得
られた膜の発光特性は２．３ｅＶにピークを持ち可視吸
収スペクトルの吸収端は２．７ｅＶであった。Example 2 In the above apparatus, commercially available propane gas was heated to 5 Torr.
The luminescent properties of the film obtained by fractional analysis using the Tonashi plasma CVD method in the same manner as before had a peak at 2.3 eV, and the absorption edge of the visible absorption spectrum was 2.7 eV.
一方マイクロビッカース硬度計による硬度測定は、先と
同様に不用能であった。On the other hand, hardness measurement using a micro-Vickers hardness meter was, as before, useless.
また・、お互いの引っ掻き偽による相対的硬度比較は第
５図と同じ結果であった。In addition, a comparison of the relative hardness between the scratches and the scratches yielded the same results as shown in FIG.
以上のように本発明にかかるアモルファス炭素材料は、
その発光特性、半導体特性および機械特性などにおいて
従来の物質とは、まったく比肩しえない稀なる特性を有
するものでその応用的価値は極めて犬であるといえる。As described above, the amorphous carbon material according to the present invention is
It has rare properties that are completely incomparable to conventional materials in terms of luminescent properties, semiconductor properties, mechanical properties, etc., and it can be said that its application value is extremely unique.
第１図は、アモルファス炭素材料のＸ線回折を示す図、
第２図は、アモルファス炭素材料の赤外吸収スペクトル
を示す図、第３図は、アモルファス炭素材料の水銀灯励
起による発光特性を示す図、第４図は、アモルファス炭
素材料の可視吸収スペクトルを示す図、第５図は、アモ
ルファス炭素材料の硬さを相対的に比較した図である。
昭和５７年８月 ５ 日
出願人 −ノ 瀬 幸 １６雄発明者 下
川 房 男
７／浦
２θ （龜８）
７２弗
＋ｖＱＶ＠１ｌｕｌｌｌｏａｒ １ｃｌｎ’１】Ｚ
佃
手続補正書（加０
昭和５７年１２４ ｐ Ｂ
特許庁長官若杉和夫 殿
１、事件の表示
アモルファス炭素材料
３ 補正をする者
事′件との関係 特許出願人
−）瀬 幸 雄
４、代理人
５、補正命令の日付 昭和５７年１１月１２日特願
昭５７−１３６７８７号手続補正書本願（＝関し明細
曹中下記の箇所を補正する。
記
１ 第１１頁第１２行目から第１３行目の「第５図は、
・・−・結果である。」とあるを削除する・
２ 第１３頁第７行目から第８行目の「引っ掻き方法・
・・・第５図である。」とあるを次のよう菟二補正する
。
［引っ掻き方法（二よって硬さの順位を比較して並べる
と、
タイヤモンドゴアモ乞σメ炭素〉超硬工具〉石英〉ガラ
ス〉軟鋼〉銅となった。」
３ 第１７頁第６行目から第７行目の「お互いの・・Φ
・結果であった。」とあるを次のように補正する。
「お互いの引っ掻き傷による相対的硬度比較＃ま前肝己
の、
タイヤセンド２ア七ηアス炭素〉超硬工具〉石英〉カス
〉軟鋼〉銅と同じ結果であった。」
４ 第１８頁第３行目から第５行目の「第４図は。
・・φ・図である。」とあるを次のように補正する。
ｒ＊４図は、アモルファス炭素材料の同視吸収スペクト
ルを示す図である。」
５ 第１６頁第５行目から第６行目の「この膜で・・・
・得られた。」とあるを次のよう（＝補正する。
「この膜で他物質４二傷をつけたところ、灯ヤモンド２
）ファス炭素〉超硬工具〉石英〉カス〉軟鋼〉銅のよう
な硬さの順位が得られた。」FIG. 1 is a diagram showing X-ray diffraction of an amorphous carbon material,
Figure 2 shows the infrared absorption spectrum of the amorphous carbon material, Figure 3 shows the emission characteristics of the amorphous carbon material when excited by a mercury lamp, and Figure 4 shows the visible absorption spectrum of the amorphous carbon material. , FIG. 5 is a diagram showing a relative comparison of the hardness of amorphous carbon materials. August 5, 1981 Applicant - Nose Yuki 16 Male Inventor Fusa Shimokawa 7/Ura 2θ (8) 72 弗+vQV@1lulloar 1cln'1]Z
Tsukuda Procedural Amendment (K0 1981 124 p B Kazuo Wakasugi, Commissioner of the Japan Patent Office 1, Indication of the case Amorphous carbon material 3 Person making the amendment Relationship with the case Patent applicant -) Yukio Se 4, Agent 5. Date of amendment order: November 12, 1980 Patent application No. 136787/1987 Procedural amendment main application (=The following parts of the detailed description are amended. Note 1 Page 11, lines 12 to 13 The fifth figure of the eye is
...--This is the result. 2 Delete "Scratching method" from line 7 to line 8 on page 13.
...Figure 5. '' is amended by Soji as follows. [Scratching method (2) Comparing and arranging the hardness rankings, the results were: carbon, carbide tools, quartz, glass, mild steel, and copper.'' 3 Page 17, line 6 In line 7, “each other’s...Φ
・It was a result. ” should be corrected as follows. "A comparison of relative hardness based on mutual scratches. The results were the same as those of Tire Send 2A, Carbon, Carbide Tools, Quartz, Scum, Mild Steel, and Copper." 4 Page 18 In the third to fifth lines, the statement ``Figure 4 is . The r*4 diagram is a diagram showing an isotropic absorption spectrum of an amorphous carbon material. ” 5 Page 16, lines 5 to 6, “With this membrane...
・Obtained. ” is corrected as follows (=corrected. “When I made 42 scratches on other substances with this film, Toriyamond 2
) Hardness rankings were obtained such as Fas carbon, carbide tools, quartz, scum, mild steel, and copper. ”
Claims (1)
作用によりプラズマ状となし、その作用によって分解、
析出形成せられた発光特性ならびに半導体特性を有し、
かつ高硬度なアモルファス炭素材料。In a vacuum container, hydrocarbons are turned into a plasma by the action of an RF high-frequency electric field, and decomposed by that action.
It has precipitated luminescent properties and semiconducting properties,
Amorphous carbon material with high hardness.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57136787A JPS5926906A (en) | 1982-08-05 | 1982-08-05 | Amorphous carbon material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57136787A JPS5926906A (en) | 1982-08-05 | 1982-08-05 | Amorphous carbon material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS5926906A true JPS5926906A (en) | 1984-02-13 |
Family
ID=15183503
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57136787A Pending JPS5926906A (en) | 1982-08-05 | 1982-08-05 | Amorphous carbon material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5926906A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62265113A (en) * | 1986-05-09 | 1987-11-18 | Yasunobu Akimoto | Production of hard carbon thin sheet |
| GR880100402A (en) * | 1987-08-03 | 1989-05-25 | Siemens Ag | New basic material for semiconductors conrtuction |
| AU614090B2 (en) * | 1987-08-03 | 1991-08-22 | Siemens Aktiengesellschaft | Semiconductor base material |
| US5135808A (en) * | 1990-09-27 | 1992-08-04 | Diamonex, Incorporated | Abrasion wear resistant coated substrate product |
| US5527596A (en) * | 1990-09-27 | 1996-06-18 | Diamonex, Incorporated | Abrasion wear resistant coated substrate product |
| US5637353A (en) * | 1990-09-27 | 1997-06-10 | Monsanto Company | Abrasion wear resistant coated substrate product |
| US5643423A (en) * | 1990-09-27 | 1997-07-01 | Monsanto Company | Method for producing an abrasion resistant coated substrate product |
| EP0787070A1 (en) * | 1994-08-31 | 1997-08-06 | Mobil Oil Corporation | Protective coating for pressure-activated adhesives |
| US5827522A (en) * | 1996-10-30 | 1998-10-27 | Troy Corporation | Microemulsion and method |
-
1982
- 1982-08-05 JP JP57136787A patent/JPS5926906A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62265113A (en) * | 1986-05-09 | 1987-11-18 | Yasunobu Akimoto | Production of hard carbon thin sheet |
| GR880100402A (en) * | 1987-08-03 | 1989-05-25 | Siemens Ag | New basic material for semiconductors conrtuction |
| AU614090B2 (en) * | 1987-08-03 | 1991-08-22 | Siemens Aktiengesellschaft | Semiconductor base material |
| US5055421A (en) * | 1987-08-03 | 1991-10-08 | Siemens Aktiengesellschaft | Method for the plasma deposition of hydrogenated, amorphous carbon using predetermined retention times of gaseous hydrocarbons |
| US5635245A (en) * | 1990-09-27 | 1997-06-03 | Monsanto Company | Process of making abrasion wear resistant coated substrate product |
| US5527596A (en) * | 1990-09-27 | 1996-06-18 | Diamonex, Incorporated | Abrasion wear resistant coated substrate product |
| US5135808A (en) * | 1990-09-27 | 1992-08-04 | Diamonex, Incorporated | Abrasion wear resistant coated substrate product |
| US5637353A (en) * | 1990-09-27 | 1997-06-10 | Monsanto Company | Abrasion wear resistant coated substrate product |
| US5643423A (en) * | 1990-09-27 | 1997-07-01 | Monsanto Company | Method for producing an abrasion resistant coated substrate product |
| US5844225A (en) * | 1990-09-27 | 1998-12-01 | Monsanto Company | Abrasion wear resistant coated substrate product |
| EP0787070A1 (en) * | 1994-08-31 | 1997-08-06 | Mobil Oil Corporation | Protective coating for pressure-activated adhesives |
| EP0787070A4 (en) * | 1994-08-31 | 1998-12-02 | Mobil Oil Corp | Protective coating for pressure-activated adhesives |
| US5827522A (en) * | 1996-10-30 | 1998-10-27 | Troy Corporation | Microemulsion and method |
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