JPH01301506A - Production of hydrogenated amorphous carbon thin film - Google Patents
Production of hydrogenated amorphous carbon thin filmInfo
- Publication number
- JPH01301506A JPH01301506A JP63133206A JP13320688A JPH01301506A JP H01301506 A JPH01301506 A JP H01301506A JP 63133206 A JP63133206 A JP 63133206A JP 13320688 A JP13320688 A JP 13320688A JP H01301506 A JPH01301506 A JP H01301506A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- film
- film thickness
- hydrocarbon
- thin 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.)
- Pending
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 30
- 229910003481 amorphous carbon Inorganic materials 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000007789 gas Substances 0.000 claims abstract description 88
- 239000010408 film Substances 0.000 claims abstract description 79
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 29
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 29
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 3
- 238000013461 design Methods 0.000 abstract description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 31
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 13
- 239000005977 Ethylene Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 239000000758 substrate Substances 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 5
- 238000010884 ion-beam technique Methods 0.000 description 4
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000007847 structural defect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- -1 for example Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000007723 transport mechanism Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
Ａ、産業上の利用分野
本発明は、水素化アモルファス炭素薄膜の製造方法に関
するものである。DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention relates to a method for producing hydrogenated amorphous carbon thin films.
Ｂ９発明の概要
本発明は、炭化水素ガスと水素ガスとの混合ガスを真空
容器内に導入して、プラズマ化学的蒸着法により水素化
アモルファス炭素薄膜を製造する方法において、
例えばメタンガスを用いて、製造開始時から、膜厚の大
きさにより例えば抵抗率が変化しない臨界膜厚が得られ
るまでの時間Ｔ。を予め求めておき、メタンガスよりも
分解効率の高い例えばエチレンガスをメタンガスと混合
して、その混合ガスを製膜開始時に導入し、その後エチ
レンガスの導入量を時間Ｔ。またはその付近にて零にな
るようにコントロールすることによって、
膜厚が小さくてら、大きな膜厚の薄膜特性を得ることが
でき、これによりデバイス設計を容易にしたものである
。B9 Summary of the Invention The present invention provides a method for producing a hydrogenated amorphous carbon thin film by a plasma chemical vapor deposition method by introducing a mixed gas of hydrocarbon gas and hydrogen gas into a vacuum container, using, for example, methane gas. The time T required from the start of production until a critical film thickness is obtained at which the resistivity does not change depending on the film thickness. is determined in advance, for example, ethylene gas, which has a higher decomposition efficiency than methane gas, is mixed with methane gas, the mixed gas is introduced at the start of film formation, and then the amount of ethylene gas introduced is determined by the time T. By controlling the film so that it becomes zero at or around that point, it is possible to obtain thin film characteristics with a large film thickness even if the film thickness is small, thereby facilitating device design.
Ｃ１従来の技術
ダイヤモンド状炭素薄膜もしくは水素化アモルファス炭
素薄膜の製造法としては、イオンビーム法、スパッタ法
、ＣＶＤ法（化学的蒸着法）などが知られている。C1 Prior Art Known methods for producing diamond-like carbon thin films or hydrogenated amorphous carbon thin films include ion beam method, sputtering method, and CVD method (chemical vapor deposition method).
イオンビーム法は基板にイオンビームを照射するため、
界面に構造欠陥が生じやすく、また有機材料や半導体な
どイオンビームに侵されやすい材質に対しては膜を形成
しにくいという欠点がある。The ion beam method irradiates the substrate with an ion beam, so
It has the disadvantage that structural defects tend to occur at the interface, and it is difficult to form a film on materials that are easily attacked by ion beams, such as organic materials and semiconductors.
スパッタ法は、スパッタガス種等の製膜因子の変化によ
り各種の特性を引き出すことができて、イオンダメージ
、構造欠陥の少ない膜を作製出来るが、ＣＶＤ法に較べ
て製膜速度が遅く、水素ガス中のスパッタでは水素が比
較的過剰に入りやすいという欠点が生じやすい。The sputtering method can bring out various properties by changing film-forming factors such as the sputtering gas type, and can produce films with less ion damage and structural defects, but the film-forming speed is slower than the CVD method, and hydrogen Sputtering in gas tends to have the disadvantage that hydrogen tends to enter in a relatively excessive amount.
ＣＶＤ法には、熱、光、プラズマＣＶＤ法等があり、水
素化アモルファス炭素薄膜は主にプラズマＣＶＤ法によ
り作製されている。CVD methods include heat, light, and plasma CVD methods, and hydrogenated amorphous carbon thin films are mainly produced by plasma CVD methods.
Ｄ６発明が解決しようとする課題
ところで最近高性能デバイス作製のために他のアモルフ
ァス物質（アモルファスＳｉ、アモルファスＳｉＣ等）
において超格子など原子層単位の極めて膜厚の小さい薄
膜について特性を制御する必要性が出て来た。プラズマ
ＣＶＤ法は、製膜速度が速く工業生産向きであり、製膜
因子数も多いため、特性も他の製膜法に比較して多様な
ものを作製しやすい長所があるが、アモルファスは研究
の歴史も浅いため、プラズマ状態記述の物性値に対して
制御可能なパラメータが少ないこと及び製膜機構が明確
になっていないことから、プラズマ状態の変動による膜
特性の膜厚依存性等が生じ、このため均質でかつ目的特
性の膜を作製することが困難であり、ｌ ００ ｎｍ以
下の膜厚の薄膜を設計する場合、設計通りのデバイスを
作製出来ないという問題点があった。アモルファスＳｔ
、ＳｉＣ等に見られたこれらの問題点がプラズマＣＶＤ
法で作製した水素化アモルファス炭素薄膜にも生じてい
ることが判明し、例えば第７図に示すように光吸収測定
においても同一の作製条件でありなから膜厚により図の
ような違いが見られる。このようなことからデバイス作
製上、特に膜厚が５０ｎｍ以下の薄膜の製作において支
障をきたしている。D6 Problems to be solved by the invention Recently, other amorphous materials (amorphous Si, amorphous SiC, etc.) have been used for the production of high-performance devices.
In recent years, it has become necessary to control the properties of thin films such as superlattices, which have extremely small thicknesses on the order of atomic layers. The plasma CVD method has a fast film forming speed and is suitable for industrial production, and has a large number of film forming factors, so it has the advantage of being able to easily produce products with a variety of properties compared to other film forming methods. Since the history of plasma processing is short, there are few parameters that can be controlled with respect to the physical property values that describe the plasma state, and the film forming mechanism is not clear, so film properties may depend on film thickness due to fluctuations in plasma state. Therefore, it is difficult to produce a film that is homogeneous and has the desired characteristics, and when designing a thin film with a thickness of 1 00 nm or less, there is a problem that a designed device cannot be produced. Amorphous St
, SiC, etc., these problems have been solved by plasma CVD.
It has been found that this phenomenon also occurs in hydrogenated amorphous carbon thin films prepared by the method, and for example, as shown in Figure 7, even in optical absorption measurements, differences can be seen depending on the film thickness even though the manufacturing conditions are the same. It will be done. This poses a problem in manufacturing devices, especially in manufacturing thin films with a thickness of 50 nm or less.
本発明の目的は、膜厚が小さくても大きな膜厚の薄膜特
性を得ることができ、これによりデバイス設計を容易に
することにある。An object of the present invention is to obtain thin film characteristics with a large thickness even if the film thickness is small, thereby facilitating device design.
Ｅ０課題を解決するための手俊
本発明は、電力印加開始時からしばらくの間はプラズマ
状態が不安定であり、そのため従来の製法、即ちプラズ
マ状態の不安定、安定の時期にかかわらず同一の条件で
製造する方法では、膜厚か小さい場合にはプラズマ状態
の不安定性の影響を受け、この結果膜厚の大きさによっ
て特性にばらつきがある点に着眼して成されたものであ
り、具体的には一種類の炭化水素ガスと水素ガスとの混
合ガスを用いて得られる前記薄膜について、膜厚と薄膜
の特性との関係を予め調べることにより、膜厚の大きさ
によって薄膜の特性が変化しない臨界膜厚を求めると共
に、製膜開始時から膜厚か前記臨界膜厚になるまでの時
間Ｔ。を求めておき、面記一種類の炭化水素ガス及び当
該炭化水素ガスよりも分解効率の高い他の種類の炭化水
素ガスの混合炭化水素ガスと水素ガスとの混合ガスを真
空容器内に導入して製膜を開始し、その後炭化水素ガス
と水素ガスとの体積比を固定したまま、前記他の種類の
炭化水素ガスの導入量を前記時間Ｔｏ経過後またはその
付近にて零になるように減少させることを特徴とする。To solve the E0 problem, the present invention has the advantage that the plasma state is unstable for a while from the start of power application, and therefore the conventional manufacturing method, that is, the same process regardless of the period of instability or stability of the plasma state. This method was developed based on the fact that when the film thickness is small, the plasma state is affected by instability, and as a result, the characteristics vary depending on the film thickness. Specifically, for the thin film obtained using a mixed gas of one type of hydrocarbon gas and hydrogen gas, by investigating the relationship between the film thickness and the properties of the thin film in advance, it is possible to determine the properties of the thin film depending on the size of the film thickness. In addition to determining the critical film thickness that does not change, the time T from the start of film formation until the film thickness reaches the critical film thickness. A mixture of one type of hydrocarbon gas and another type of hydrocarbon gas whose decomposition efficiency is higher than that of the hydrocarbon gas and hydrogen gas is introduced into a vacuum container. After that, while keeping the volume ratio of hydrocarbon gas and hydrogen gas fixed, the amount of the other type of hydrocarbon gas introduced is made to become zero after or near the elapse of the time To. It is characterized by decreasing.
Ｆ、実施例
本発明方法は、例えば第２図及び第３図に夫々示す製造
装置及び制御系を用いることにより実行される。第２図
に示すＣＶＤ装置は３槽分離真空槽１．〜Ｉ３を連設し
て成り、水素化アモルファス炭素薄膜（以下ｒａ−ｃ膜
」という）を得るためには、先ず真空槽１．内を１．３
３Ｘ１０−’Ｐａ（ＩＸＩＯ−’Ｔｏｒｒ）まで減圧し
た後、炭化水素ガス例えばメタン（ＣＨ４）ガスを適度
の水素ガスで希釈した混合ガスを真空槽１．内に導入ル
、電極を兼ねたサセプタ２１上の基板３をヒータ４１で
適時！５０〜３００℃に加熱した後所定の圧力に槽内を
調節し、次いで平面方向のムラをなくすためにサセプタ
２１を回転させながら、電極５１゜サセプタ２１間に高
周波電源Ｅ、から１３．５６Ｍ１−１ ｚの高周波電力
２０〜３００Ｗを加え、プラズマを発生させて基板３１
上に膜を形成する。６．は排気口である。真空槽１１内
の圧力については、第３図に示すように真空計７よりの
検出値に基づいてコンピュータ８により排気ロエアー弁
スイッチ９及びマスフローコントローラ用電源ＩＯを制
御することによって行われ、また電極への印加重力（人
力電力）については高周波電源１１を制御することによ
って行われる。更にガス流量、ガス混合比もこの制御系
によって随時微妙に制御される。F. EXAMPLE The method of the present invention is carried out, for example, by using the manufacturing apparatus and control system shown in FIGS. 2 and 3, respectively. The CVD apparatus shown in FIG. 2 has three separate vacuum tanks: 1. In order to obtain a hydrogenated amorphous carbon thin film (hereinafter referred to as "RA-C film"), first, a vacuum chamber 1. 1.3 inside
After reducing the pressure to 3X10-'Pa (IXIO-'Torr), a mixed gas prepared by diluting a hydrocarbon gas, such as methane (CH4) gas with an appropriate amount of hydrogen gas, is placed in a vacuum chamber 1. Introduce the substrate 3 on the susceptor 21, which also serves as an electrode, with the heater 41 at the appropriate time! After heating to 50 to 300°C, adjust the pressure inside the tank to a predetermined pressure, and then, while rotating the susceptor 21 to eliminate unevenness in the plane direction, a high frequency power source E, 13.56M1- is applied between the electrode 51° and the susceptor 21. 1z high frequency power of 20 to 300 W is applied to generate plasma and heat the substrate 31.
Form a film on top. 6. is an exhaust port. The pressure inside the vacuum chamber 11 is controlled by the computer 8 controlling the exhaust lower air valve switch 9 and the mass flow controller power supply IO based on the detected value from the vacuum gauge 7, as shown in FIG. The applied force (human power) is applied by controlling the high frequency power source 11. Furthermore, the gas flow rate and gas mixture ratio are also finely controlled by this control system.
他の真空槽Ｉｔ、Ｉｓは前記真空槽！、と同一構造に設
計されており、２−．２３はサセプタ、４．。The other vacuum chambers It and Is are the vacuum chambers! , is designed to have the same structure as 2-. 23 is a susceptor; 4. .
４３はヒータ、５．．５．は電極、６．．６．は排気口
である。真空槽１１〜鳳８間には図示しな、い基板搬送
機構が装着されており、ロック弁ＶＡ、ＶＢを開閉する
ことにより真空状態を維持したまま基板を真空槽ｌ、〜
１１間を移動させることができる。43 is a heater; 5. ．． 5. is an electrode, 6. ．． 6. is an exhaust port. A substrate transport mechanism (not shown) is installed between the vacuum chambers 11 and 8, and by opening and closing lock valves VA and VB, the substrates are transferred to the vacuum chambers 1 and 8 while maintaining the vacuum state.
It is possible to move between 11.
従って６槽にて独立に所望の特性の薄膜を作製すること
が可能であり、例えばＰ型半導体層、ｎ型半導体層及び
真性半導体層を汚染されることなく順次に積層したもの
を作製することができる。Therefore, it is possible to independently produce thin films with desired characteristics in six tanks. For example, it is possible to produce a thin film with desired characteristics, for example, by sequentially stacking a P-type semiconductor layer, an n-type semiconductor layer, and an intrinsic semiconductor layer without contamination. I can do it.
本発明方法はこれら真空槽！１〜１．のいずれの製膜プ
ロセスにおいても適用することができ、本発明方法を実
行するためには、先ず従来法によって臨界膜厚を求めて
おく。例えばメタンガスを炭化水素ガスとして用い、膜
厚が１１００ｎ以下であっても’ｌ ００ ｎｍの膜厚
と同程度の特性をもった薄膜を作製しようとする場合、
メタンガスを水素ガスによって５０％に希釈した混合ガ
スを真空槽内に導入した後電力を印加し、製膜時間を変
えて種々の膜厚のａ−Ｃ膜を予め作製しておく。そして
これらについて例えば抵抗率を調べ、膜厚の大きさによ
って抵抗率が変化しない臨界膜厚を求めると共に、電力
印加時から膜厚が臨界膜厚になるまでの時間Ｔ。を求め
ておく。第４図は抵抗率と膜厚との関係を示す測定デー
タであり、この図かられかるように抵抗率は膜厚が小さ
い程高く、略４０ｎｍ（４００人）を越えると膜厚増加
に対して飽和している。従ってこの場合臨界膜厚は４０
ｎｍとなる。なおこの例では、基板直径２０Ｃｆｆ、基
板温度１５０℃、槽内圧力！３．３Ｐａ。The method of the present invention uses these vacuum chambers! 1-1. It can be applied to any film forming process, and in order to carry out the method of the present invention, the critical film thickness is first determined by a conventional method. For example, when trying to create a thin film using methane gas as a hydrocarbon gas and having the same properties as a film with a thickness of 100 nm, even if the film thickness is 1100 nm or less,
After a mixed gas of methane gas diluted to 50% with hydrogen gas is introduced into a vacuum chamber, electric power is applied, and a-C films of various thicknesses are prepared in advance by changing the film forming time. Then, for example, the resistivity of these is investigated, and the critical film thickness where the resistivity does not change depending on the film thickness is determined, and the time T from when power is applied until the film thickness reaches the critical film thickness. Let's find out. Figure 4 shows measurement data showing the relationship between resistivity and film thickness.As can be seen from this figure, the resistivity increases as the film thickness decreases, and when it exceeds approximately 40 nm (400 nm), the resistivity increases with increasing film thickness. It's saturated. Therefore, in this case, the critical film thickness is 40
nm. In this example, the substrate diameter is 20Cff, the substrate temperature is 150°C, and the pressure inside the tank is ! 3.3Pa.
人力電力２０Ｗ、電極間距離２ＣＪＩとしている。The human power was 20W and the distance between the electrodes was 2CJI.
ところで炭化水素ガスとして用いるガス種と臨界膜厚と
の関係を調べたところ第５図に示すように、臨界膜厚は
ガス種の分解効率、即ち製膜速度と略比例していること
がわかった。このことから電力印加時から一定時間内に
おいて製膜された薄膜は膜厚の影響を受け、その原因は
プラズマ状態が電力印加開始時から一定時間内は不安定
であり、時間経過と共に安定状態に向かっていくためで
あると推察される。このように考えれば、プラズマ状態
が不安定な時間帯は前記時間Ｔ。に対応する。By the way, when we investigated the relationship between the gas species used as hydrocarbon gas and the critical film thickness, we found that the critical film thickness is approximately proportional to the decomposition efficiency of the gas species, that is, the film formation rate, as shown in Figure 5. Ta. From this, a thin film formed within a certain period of time from the time of power application is affected by the film thickness, and the reason for this is that the plasma state is unstable within a certain time from the start of power application, and becomes stable over time. It is surmised that this is because they are heading towards the area. Considering this, the time period when the plasma state is unstable is the above-mentioned time T. corresponds to
そこで本発明では、製膜開始時即ち電力印加時にはメタ
ンガスよりも高い例えばエチレンガス（ｃｔＨ＊ガス）
をメタンガスと混合し、プラズマ状態が安定するに従っ
て、エチレンガス及びメタンガスの混合ガスと水素ガス
との体積比を固定したままエチレンガスの導入虫を減少
させる。具体的にはエチレンガス及びメタンガスよりな
る混合ガスに対するエチレンガスのガス濃度Ｇの初期値
をＧ。とすると、第６図に示すようにガス濃度Ｇをコン
トロールして製膜する。この例では時間ｔとガス濃度Ｇ
との関係は次式で表される。Therefore, in the present invention, at the start of film formation, that is, when electric power is applied, a gas higher than methane gas, for example, ethylene gas (ctH* gas) is used.
is mixed with methane gas, and as the plasma state stabilizes, the volume ratio of the mixed gas of ethylene gas and methane gas to hydrogen gas is kept fixed and the number of insects introduced into the ethylene gas is reduced. Specifically, G is the initial value of the gas concentration G of ethylene gas for a mixed gas consisting of ethylene gas and methane gas. Then, the film is formed by controlling the gas concentration G as shown in FIG. In this example, time t and gas concentration G
The relationship with is expressed by the following equation.
Ｇ ”ＧＯＸ （ｔ ＴＯ） ”／Ｔｏ”そしてＧ。G “GOX (t TO)”/To” and G.
を種々変えて特性を調べたところ、膜厚がｌ ＯＯｎｍ
以下のａ−ｃ膜について、メタンガス菫００％を炭化水
素ガスとして用いて作製した２ ００ ｎ ｍ （各種
の特性が測定できる典型的厚さ）の膜厚を有するａ−ｃ
膜と同等の特性を得るためには、Ｇｏが１０〜６０％で
あった。１０％以下では、分解効率の高いガスを混合し
た効果が少ないので、膜厚の大きさによってばらついて
しまう。一方第７図に示すようにガス種によって光学的
バンドギャップの大きさが異なるため、６０％を越える
と光学的バンドギャップが低下してしまう。Ｇｏか１０
〜６０％の場合には、光吸収プロファイル、抵抗率につ
いて上記の２００ｎｍの膜厚のものと一致した。When we investigated the characteristics by changing various values, we found that the film thickness was lOOnm.
The following a-c film has a film thickness of 200 nm (typical thickness at which various properties can be measured) and was prepared using 00% methane gas as a hydrocarbon gas.
In order to obtain properties equivalent to the membrane, Go was 10-60%. If it is less than 10%, the effect of mixing a gas with high decomposition efficiency will be small, and the thickness will vary depending on the size of the film. On the other hand, as shown in FIG. 7, the size of the optical bandgap varies depending on the gas species, so if it exceeds 60%, the optical bandgap will decrease. Go or 10
In the case of ~60%, the light absorption profile and resistivity matched those of the above film thickness of 200 nm.
本発明では、メタンガスに限らず例えばエチレンガス１
００％を炭化水素ガスとして用いた薄膜特性を得る場合
にも適用することができ、この場合にはエチレンガス及
びアセヂレンガス（Ｃ，Ｈ。In the present invention, not only methane gas but also ethylene gas 1
It can also be applied to obtain thin film properties using 00% hydrocarbon gas, in which case ethylene gas and acetylene gas (C,H) are used.
ガス）よりなる混合ガスに対するアセチレンガス濃度の
初期値Ｇ。を１０〜５０％に設定して、第６図に示すよ
うにＧをコントロールすれば、膜厚か１１００ｎ以下の
ａ−Ｃ膜について、エチレンガスｌＯＯ％を炭化水素ガ
スとして用いて作製した２００ｎｍの膜厚を有するａ−
ｃ膜と同等の特性を得ることができる。Initial value G of acetylene gas concentration for a mixed gas consisting of By setting G to 10 to 50% and controlling G as shown in Figure 6, for an a-C film with a film thickness of 1100 nm or less, a 200 nm film made using 100% ethylene gas as a hydrocarbon gas can be obtained. a- with film thickness
It is possible to obtain properties equivalent to those of c-film.
Ｇ９発明の効果
本発明では、電力印加開始時からしばらくの間は従来の
条件では十分なプラズマ状態が得られず、これに起因し
て膜厚が小さい場合には特性にばらつきがあるという点
に着目し、例えばメタンガス１００％に対応するａ−ｃ
膜を得る場合、製造開始時即ち電力印加開始時にはメタ
ンガスよりも分解効率の高い例えばエチレンガスをメタ
ンガスと混合し、プラズマ状態が安定にするに従ってエ
チレンガスの導入量を減少させているため、例えばメタ
ンガスｌＯＯ％あるいはエチレンガス１００％で製膜し
た、アモルファス超格子等でよく用いられる２〜２０
ｎ ｍ （２０〜２００人）の膜厚のａ−ｃ膜を得た場
合、２００ ｎ ｍ （２０００人）の膜厚程度のもの
と同一の特性を得ることができ、従ってデバイス設計が
簡単になる。G9 Effects of the Invention The present invention has an advantage in that a sufficient plasma state cannot be obtained under conventional conditions for a while from the start of power application, and due to this, there are variations in characteristics when the film thickness is small. Focusing on, for example, a-c corresponding to 100% methane gas
When obtaining a film, at the start of production, that is, when power is applied, for example, ethylene gas, which has a higher decomposition efficiency than methane gas, is mixed with methane gas, and as the plasma state stabilizes, the amount of ethylene gas introduced is reduced. 2 to 20, which is often used in amorphous superlattice films formed with lOO% or 100% ethylene gas.
If an a-c film with a thickness of 20 nm (20 to 200 people) is obtained, it is possible to obtain the same characteristics as a film with a thickness of about 200 nm (2000 people), which simplifies device design. Become.
第１図は本発明の実施例に係るガス濃度パターンを示す
グラフ、第２図は製造装置の一例を示す構成図、第３図
は制御系を示すブロック図、第４図は抵抗率と膜厚との
関係を示すグラフ、第５図はガス種毎の臨界膜厚及び製
膜速度を示すグラフ、第６図は光学的バンドギャップと
ガス種との関係を示すグラフ、第７図は光吸収特性を示
すグラフである。
！１〜ｌ、・・・真空槽、２Ｉ〜２３・・・サセプタ、
３・・・基板、４．〜４．・・・ヒータ、５１〜５３・
・・電極、６１〜６．・・排気口。
第１図
ブス薬事へ゛ターン図
Ｔ。
畔 間 （ｓｅｃ）
拡杭手 （Ω・ａｍ）
第５図
でス糎毎のテ゛°−り図
ＣＨｂ ＣｔＨｈ ＣｚＨｚブス糎
第６図
代２す宜勺ノ＼゛ンドギ黛ヅフ゛に７７”ス糎ヒの閘イ
示訝りＣＨ４Ｃ２Ｈ４Ｃ２Ｈ２Fig. 1 is a graph showing a gas concentration pattern according to an embodiment of the present invention, Fig. 2 is a configuration diagram showing an example of a manufacturing device, Fig. 3 is a block diagram showing a control system, and Fig. 4 is a graph showing resistivity and film. Figure 5 is a graph showing the critical film thickness and film forming rate for each gas type. Figure 6 is a graph showing the relationship between optical band gap and gas type. Figure 7 is a graph showing the relationship between optical band gap and gas type. It is a graph showing absorption characteristics. ! 1 to l,... vacuum chamber, 2I to 23... susceptor,
3...Substrate, 4. ~4. ... Heater, 51-53.
...Electrode, 61-6. ··exhaust port. Figure 1 Turn diagram T to Busu Pharmaceutical Affairs. Pile width (sec) Pile expansion (Ω・am) In Fig. 5, there are 77” squares for each thread in Fig. 6. Glue lock indication CH4C2H4C2H2
Claims (1)
内に導入して、プラズマ化学的蒸着法により水素化アモ
ルファス炭素薄膜を製造する方法において、 一種類の炭化水素ガスと水素ガスとの混合ガスを用いて
得られる前記薄膜について、膜厚と薄膜の特性との関係
を予め調べることにより、膜厚の大きさによって薄膜の
特性が変化しない臨界膜厚を求めると共に、製膜開始時
から膜厚が前記臨界膜厚になるまでの時間Ｔ＿０を求め
ておき、前記一種類の炭化水素ガス及び当該炭化水素ガ
スよりも分解効率の高い他の種類の炭化水素ガスの混合
炭化水素ガスと水素ガスとの混合ガスを真空容器内に導
入して製膜を開始し、その後炭化水素ガスと水素ガスと
の体積比を固定したまま、前記他の種類の炭化水素ガス
の導入量を前記時間Ｔ＿０経過後またはその付近にて零
になるように減少させることを特徴とする水素化アモル
ファス炭素薄膜の製造方法。(1) In a method for producing a hydrogenated amorphous carbon thin film by plasma chemical vapor deposition by introducing a mixed gas of hydrocarbon gas and hydrogen gas into a vacuum container, one type of hydrocarbon gas and hydrogen gas are mixed. For the thin film obtained using a mixed gas, by examining the relationship between film thickness and thin film properties in advance, we can determine the critical film thickness at which the properties of the thin film do not change depending on the size of the film thickness. The time T_0 required for the film thickness to reach the critical film thickness is determined, and a mixed hydrocarbon gas of the one type of hydrocarbon gas and another type of hydrocarbon gas whose decomposition efficiency is higher than that of the hydrocarbon gas and hydrogen are determined. A mixed gas with gas is introduced into a vacuum container to start film formation, and then, while keeping the volume ratio of hydrocarbon gas and hydrogen gas fixed, the amount of the other type of hydrocarbon gas introduced is changed over the time T_0. 1. A method for producing a hydrogenated amorphous carbon thin film, which comprises reducing the amount to zero after a certain period of time or around the same time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63133206A JPH01301506A (en) | 1988-05-31 | 1988-05-31 | Production of hydrogenated amorphous carbon thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63133206A JPH01301506A (en) | 1988-05-31 | 1988-05-31 | Production of hydrogenated amorphous carbon thin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01301506A true JPH01301506A (en) | 1989-12-05 |
Family
ID=15099212
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63133206A Pending JPH01301506A (en) | 1988-05-31 | 1988-05-31 | Production of hydrogenated amorphous carbon thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01301506A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0617997A1 (en) * | 1993-03-23 | 1994-10-05 | Rotem Industries Ltd. | Method of improving the selectivity of carbon membranes by chemical carbon vapor deposition |
| US5413773A (en) * | 1990-10-09 | 1995-05-09 | General Motors Corporation | Method for forming carbon filters |
| JP2009235495A (en) * | 2008-03-27 | 2009-10-15 | Ngk Insulators Ltd | Method for forming amorphous carbon film |
| JP2009242879A (en) * | 2008-03-31 | 2009-10-22 | Ngk Insulators Ltd | Dlc film deposition method |
| CN102659094A (en) * | 2012-01-03 | 2012-09-12 | 西安电子科技大学 | Method for preparing graphene on SiC substrate based on annealing of Cu film and C12 reaction |
| CN103553029A (en) * | 2013-10-31 | 2014-02-05 | 中国科学院上海微***与信息技术研究所 | Method for preparing vertical graphene-based thermal material |
-
1988
- 1988-05-31 JP JP63133206A patent/JPH01301506A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5413773A (en) * | 1990-10-09 | 1995-05-09 | General Motors Corporation | Method for forming carbon filters |
| EP0617997A1 (en) * | 1993-03-23 | 1994-10-05 | Rotem Industries Ltd. | Method of improving the selectivity of carbon membranes by chemical carbon vapor deposition |
| US5695818A (en) * | 1993-03-23 | 1997-12-09 | Rotem Industries Ltd. | Method of improving the selectivity of carbon membranes by chemical carbon vapor deposition |
| JP2009235495A (en) * | 2008-03-27 | 2009-10-15 | Ngk Insulators Ltd | Method for forming amorphous carbon film |
| JP2009242879A (en) * | 2008-03-31 | 2009-10-22 | Ngk Insulators Ltd | Dlc film deposition method |
| CN102659094A (en) * | 2012-01-03 | 2012-09-12 | 西安电子科技大学 | Method for preparing graphene on SiC substrate based on annealing of Cu film and C12 reaction |
| CN103553029A (en) * | 2013-10-31 | 2014-02-05 | 中国科学院上海微***与信息技术研究所 | Method for preparing vertical graphene-based thermal material |
| CN103553029B (en) * | 2013-10-31 | 2015-07-01 | 中国科学院上海微***与信息技术研究所 | Method for preparing vertical graphene-based thermal material |
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