JPH0365594A - Synthesis of diamond thin film from organic solution - Google Patents
Synthesis of diamond thin film from organic solutionInfo
- Publication number
- JPH0365594A JPH0365594A JP1199298A JP19929889A JPH0365594A JP H0365594 A JPH0365594 A JP H0365594A JP 1199298 A JP1199298 A JP 1199298A JP 19929889 A JP19929889 A JP 19929889A JP H0365594 A JPH0365594 A JP H0365594A
- Authority
- JP
- Japan
- Prior art keywords
- solution
- organic solution
- thin film
- diamond thin
- synthesis
- 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.)
- Granted
Links
- 239000010432 diamond Substances 0.000 title claims abstract description 21
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 21
- 239000010409 thin film Substances 0.000 title abstract description 11
- 230000015572 biosynthetic process Effects 0.000 title description 8
- 238000003786 synthesis reaction Methods 0.000 title description 8
- 238000010438 heat treatment Methods 0.000 claims abstract 2
- 239000000758 substrate Substances 0.000 claims description 16
- 238000001308 synthesis method Methods 0.000 claims description 3
- 239000010408 film Substances 0.000 abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052710 silicon Inorganic materials 0.000 abstract description 4
- 239000010703 silicon Substances 0.000 abstract description 4
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 abstract description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 abstract 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 abstract 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 abstract 1
- 238000010586 diagram Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
本発明は溶液中でダイヤモンド薄膜を合成する方法に関
するちりである。ダイヤモンドは硬度および熱伝導度が
最高の値を有し、耐食性、光学特性、電気的特性等極め
て優れた特性を有している。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for synthesizing diamond thin films in solution. Diamond has the highest values of hardness and thermal conductivity, and has extremely excellent properties such as corrosion resistance, optical properties, and electrical properties.
そのために、Ｎ膜状ダイヤモンドは半導体のヒートシン
ク、・半導体素子、切削工具の保Ｎ膜、その他電気電子
、機械、化学等各種の分野にその応用が期待されている
。For this reason, N film-like diamond is expected to be applied to semiconductor heat sinks, semiconductor elements, N retaining films for cutting tools, and various other fields such as electrical and electronic, mechanical, and chemical fields.
現在合成されているダイヤモンド薄膜は大気圧以下の気
相中で行われており、その合成法を大別すると、物理蒸
着（ＰＶＤ）法と化学蒸着（ＣＶＤ）法に分けられる。Diamond thin films currently synthesized are performed in a gas phase at a pressure below atmospheric pressure, and the synthesis methods can be roughly divided into physical vapor deposition (PVD) and chemical vapor deposition (CVD).
ＰＶＤ法では炭化水素ガスを３００℃〜４００℃に加熱
した基板に接触させて行われており、従って基板は３０
０℃〜４００℃の温度に耐えるものでなければならない
、また。In the PVD method, hydrocarbon gas is brought into contact with a substrate heated to 300°C to 400°C.
It must also be able to withstand temperatures between 0°C and 400°C.
ＣＶＤ法は炭化水素ガスの熱分解反応を利用しているた
め、基板の温度は更に高く、７００℃〜９００℃の高温
にさらされる。したがって、応用面から見ると、合成温
度に対して大きな問題が残されている。即ち、この程度
の高温に耐える基板は種類も限られ、工業的応用範囲も
極く限られたものになる。Since the CVD method utilizes a thermal decomposition reaction of hydrocarbon gas, the temperature of the substrate is even higher, and the substrate is exposed to a high temperature of 700°C to 900°C. Therefore, from an application point of view, a big problem remains regarding the synthesis temperature. That is, there are only a limited number of types of substrates that can withstand such high temperatures, and the range of industrial applications is also extremely limited.
そこで、もしこの問題が溶液等を用いた液相で。So, if this problem is in a liquid phase using a solution etc.
しかも基板温度が１００℃以下でダイヤモンドの薄膜合
成が可能となると、その応用範囲は急速に広がり、その
実用価（＋ｆｌは計り知れないものとなる事は明白であ
る１本発明は溶液を用いた低温に於けるダイヤモンド薄
膜合成に関するちりである。Moreover, if it becomes possible to synthesize a diamond thin film at a substrate temperature of 100°C or less, its range of applications will rapidly expand, and it is clear that its practical value (+fl) will be immeasurable.1 The present invention uses a solution. This is dust related to diamond thin film synthesis at low temperatures.
そこで、まずその発想につき説明する。現在薄膜の合或
は、一般に液相中で行われているものは気相中でも行わ
れており、また逆に、気相中で合成されている膜はほと
んど溶液中でも行われている。一方、ダイヤモンド薄膜
の合成は気相中で可能になってきた。したがって、液相
中でもダイヤモンド薄膜合成の可能性は充分存在する。Therefore, I will first explain the idea. Thin film synthesis, which is currently generally carried out in a liquid phase, is also carried out in a gas phase, and conversely, most films synthesized in a gas phase are also carried out in a solution. On the other hand, it has become possible to synthesize diamond thin films in the gas phase. Therefore, there is ample possibility of synthesizing diamond thin films even in the liquid phase.
問題はその手段にある。例えば有機溶液を使用した場合
、常温では電流密度が数μＡ／Ｃｍ２程度しか流れない
。一方、気相合成の方から眺めると、ダイヤモンド合成
に必要な電流密度は数ｍＡ／Ｃｍ２であることがわかっ
ている。したがって、有機溶液よりダイヤモンド合成を
行う場合、電流密度に着目すると１０００倍程度の電流
が流れなければならない。ここに問題の本質が含まれて
いる。以下その具体的解決方法につき説明する。The problem lies in the means. For example, when an organic solution is used, the current density is only about several μA/Cm2 at room temperature. On the other hand, from the perspective of vapor phase synthesis, it is known that the current density required for diamond synthesis is several mA/Cm2. Therefore, when diamond synthesis is performed using an organic solution, a current of about 1000 times as much must flow when looking at the current density. This contains the essence of the problem. A specific solution to this problem will be explained below.
第１図は溶液合成法の略図を示す。まず、１は有機溶液
でこれはエタノール（Ｃ２Ｈ５０Ｈ） 、アセトン（Ｃ
Ｈ３ＣＯＣＨ３０Ｈ）、ベンゼン（ＣａＨｅ）、）リク
ロロエチレン（ＣＩ ＣＨ： ＣＣｌ ２）＃酸メチー
ル（ＣＨ３ＣＯＯＣＨ３）等の溶液であるが、これらの
溶液中でエタノールの導電特性が良好であったため、以
下溶液はエタノールとして説明する。同図で、２は比抵
抗ｌ０００ｍ以上のシリコン基板で、を源５より負電圧
を印加している。FIG. 1 shows a schematic diagram of the solution synthesis method. First, 1 is an organic solution containing ethanol (C2H50H), acetone (C
H3COCH30H), benzene (CaHe), )lichloroethylene (CICH: CCl2) #methyl acid (CH3COOCH3), etc., but since the conductive properties of ethanol were good in these solutions, the following solutions were used. Explained as ethanol. In the figure, reference numeral 2 denotes a silicon substrate having a specific resistance of 1000 m or more, to which a negative voltage is applied from a source 5.
本方式は、まずエタノールの導電性を増す手段として、
溶液をヒーター３で加熱し、その沸点近く迄温度上昇を
行い熱的な解離を行っている。６は溶液の温度を計るた
めの熱電対温度計である。This method is first used as a means to increase the conductivity of ethanol.
The solution is heated with a heater 3 to raise the temperature to near its boiling point to perform thermal dissociation. 6 is a thermocouple thermometer for measuring the temperature of the solution.
さらに、電流密度を増加させるための手段として本装置
は電極１ｊに高電圧を印加している。４は正電極で、電
極材料には直径４Φのカーボン棒を使用し、負電極側の
シリコン基板２との距離は５〜１０ｍｍに保っている。Furthermore, as a means for increasing the current density, this device applies a high voltage to the electrode 1j. 4 is a positive electrode, a carbon rod with a diameter of 4Φ is used as the electrode material, and the distance from the silicon substrate 2 on the negative electrode side is maintained at 5 to 10 mm.
第２図は溶液の温度をパラメータとし、基板の電流密度
と印加電圧の関係を示す。基板電流は、印加電圧が数■
の時にはμＡ／Ｃｍ２であるが、電圧の増加と共にほぼ
直線的に増加し、数ｔｏｏｖでｍＡ／ｃｍ２の領域に入
る。さらに、この頒は溶液の温度によっても増加し、最
後は電極の放電と溶液の沸点によってその限界値がきま
る。FIG. 2 shows the relationship between the current density of the substrate and the applied voltage, using the temperature of the solution as a parameter. The substrate current depends on the applied voltage
At , it is μA/cm2, but it increases almost linearly as the voltage increases, and reaches the mA/cm2 region after several toov. Furthermore, this distribution also increases with the temperature of the solution, and its limit value is finally determined by the electrode discharge and the boiling point of the solution.
一方、電流は時間によっても変化する。この変化によっ
てダイヤモンドの絶縁膜がシリコン基板りに形成されて
いくことが分かる。第２図は通電後３時間経過したとき
の図である。On the other hand, current also changes with time. It can be seen that this change causes a diamond insulating film to be formed on the silicon substrate. FIG. 2 is a diagram 3 hours after energization.
基板電流の時間的変化の１例を第３図に示す。FIG. 3 shows an example of a temporal change in substrate current.
第４図は基板上に形成されたダイヤモンド膜の膜厚と通
電時間の１例を示す。図のように、膜厚は時間と共に増
加するが、膜厚の増加と共に電流は流れなくなり、１０
時間以上経過すると飽和状態を示すようになる。飽和す
る膜厚は現在３０００〜４０００λであるが、この限界
は合成条件によって変化する。FIG. 4 shows an example of the thickness of a diamond film formed on a substrate and the current application time. As shown in the figure, the film thickness increases with time, but as the film thickness increases, the current stops flowing, and 10
If more than a certain amount of time has passed, the state will become saturated. The saturated film thickness is currently 3000 to 4000λ, but this limit changes depending on the synthesis conditions.
合成された膜の結晶構造は電子線の透過像および回折像
より調べた。第５図はダイヤモンドと膜の面間隔を比較
したものである。また、膜の結晶粒は数１００Å以下の
微結晶で構成されているこ隔および面指数の関係を表し
たものである。The crystal structure of the synthesized film was investigated using electron beam transmission images and diffraction images. FIG. 5 compares the interplanar spacing between diamond and film. Further, the crystal grains of the film are composed of microcrystals of several hundred angstroms or less, and the relationship between the spacing and the plane index is shown.
特許帛願人
難波義捷
第１図は有機溶液中からダイヤモンド薄膜を合成する装
置の概略図であり、第２図は装置の電極間に電圧を印加
した場合に流れる基板電流密度を溶液の温度をパラメー
タとして表したグラフである。第３図は基板電流密度と
通電時間の関係を表したグラフ、第４図は基板上に形成
された膜の膜厚と時間の関係を示したグラフである。第
５図はダイヤモンドの格子と形成された膜の格子の而開
第工図
第３図
通電時間
（時）
第２図
００
００
００
００
印加型止
（Ｖ）
第４図
通電時間
（時）Patent applicant Namba Gisho Figure 1 is a schematic diagram of an apparatus for synthesizing a diamond thin film from an organic solution, and Figure 2 shows the substrate current density flowing when a voltage is applied between the electrodes of the apparatus as a function of the temperature of the solution. This is a graph showing parameters. FIG. 3 is a graph showing the relationship between the substrate current density and current application time, and FIG. 4 is a graph showing the relationship between the film thickness of the film formed on the substrate and time. Figure 5 is a diagram of the development of the diamond lattice and the formed film lattice Figure 3 Current application time (hours) Figure 2 00 00 00 00 Application mold stop (V) Figure 4 Current application time (hours)
Claims (1)
位面積当りｍＡ／ｃｍ＾２程度の電流を流し、溶液から
ダイヤモンドの薄膜合成を行うことを特長とする溶液ダ
イヤモンド合成法A solution diamond synthesis method characterized by heating an organic solution, applying a negative high voltage to the substrate, and passing a current of approximately mA/cm^2 per unit area to synthesize a thin diamond film from the solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1199298A JPH0633234B2 (en) | 1989-08-02 | 1989-08-02 | Diamond thin film manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1199298A JPH0633234B2 (en) | 1989-08-02 | 1989-08-02 | Diamond thin film manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0365594A true JPH0365594A (en) | 1991-03-20 |
| JPH0633234B2 JPH0633234B2 (en) | 1994-05-02 |
Family
ID=16405477
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1199298A Expired - Fee Related JPH0633234B2 (en) | 1989-08-02 | 1989-08-02 | Diamond thin film manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0633234B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023120569A1 (en) * | 2021-12-21 | 2023-06-29 | 捷 唐 | Production method for diamond particles |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100791790B1 (en) * | 2006-05-30 | 2008-01-03 | 고려대학교 산학협력단 | Method of Manufacturing Hexagonal Nanoplate Diamond |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58213612A (en) * | 1982-06-01 | 1983-12-12 | Shigeo Nishida | Preparation of artificial diamond |
| JPS593016A (en) * | 1982-06-30 | 1984-01-09 | Shigeo Nishida | Manufacture of diamond |
-
1989
- 1989-08-02 JP JP1199298A patent/JPH0633234B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58213612A (en) * | 1982-06-01 | 1983-12-12 | Shigeo Nishida | Preparation of artificial diamond |
| JPS593016A (en) * | 1982-06-30 | 1984-01-09 | Shigeo Nishida | Manufacture of diamond |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023120569A1 (en) * | 2021-12-21 | 2023-06-29 | 捷 唐 | Production method for diamond particles |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0633234B2 (en) | 1994-05-02 |
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