JPH1081970A - Formation of thin coating - Google Patents
Formation of thin coatingInfo
- Publication number
- JPH1081970A JPH1081970A JP9094427A JP9442797A JPH1081970A JP H1081970 A JPH1081970 A JP H1081970A JP 9094427 A JP9094427 A JP 9094427A JP 9442797 A JP9442797 A JP 9442797A JP H1081970 A JPH1081970 A JP H1081970A
- Authority
- JP
- Japan
- Prior art keywords
- magnetic field
- substrate
- reaction chamber
- thin film
- forming
- 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
- 239000011248 coating agent Substances 0.000 title abstract 4
- 238000000576 coating method Methods 0.000 title abstract 4
- 230000015572 biosynthetic process Effects 0.000 title description 3
- 239000000758 substrate Substances 0.000 claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000003993 interaction Effects 0.000 claims abstract description 12
- 230000005684 electric field Effects 0.000 claims abstract description 9
- 239000010408 film Substances 0.000 claims description 28
- 239000010409 thin film Substances 0.000 claims description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims 1
- 239000007789 gas Substances 0.000 description 13
- 229910003460 diamond Inorganic materials 0.000 description 6
- 239000010432 diamond Substances 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005094 computer simulation Methods 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001475 halogen functional group Chemical group 0.000 description 2
- 229910021332 silicide Inorganic materials 0.000 description 2
- 241000894007 species Species 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 241001364096 Pachycephalidae Species 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- -1 aluminum compound Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Plasma Technology (AREA)
- Carbon And Carbon Compounds (AREA)
- Chemical Vapour Deposition (AREA)
- Drying Of Semiconductors (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はマイクロ波電界を加える
とともに、外部磁場を加え、それらの相互作用を利用し
て基板上にｉ−カーボン膜を形成する薄膜形成方法に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming an i-carbon film on a substrate by applying an external magnetic field while applying a microwave electric field and utilizing the interaction therebetween.
【０００２】[0002]
【従来の技術】従来、薄膜の形成手段としてＥＣＲ（電
子サイクロトロン共鳴）を用い、その発散磁場を利用し
てこの共鳴空間より「離れた位置」に基板を配設し、そ
こでの薄膜特にアモルファス構造を有する薄膜を形成す
る方法が知られている。2. Description of the Related Art Heretofore, ECR (Electron Cyclotron Resonance) has been used as a means for forming a thin film, and a substrate is disposed at a position "distant from the resonance space" by utilizing the diverging magnetic field. There is known a method of forming a thin film having the following.
【０００３】さらに一般的にはかかるＥＣＲ ＣＶＤ
（化学気相法）に加えて、反応性ガスを用いる薄膜形成
手段として数種類知られており、それらは熱ＣＶＤ、加
熱フィラメントＣＶＤ、化学輸送法、１３．５６ＭＨz
の周波数を用いるプラズマＣＶＤ法、マイクロ波のみを
用いるプラズマＣＶＤ法が知られている。特にＥＣＲＣ
ＶＤ法は活性種を磁場によりピンチングし、高エネルギ
化することにより電子エネルギを大きくし、効率よく気
体をプラズマ化させている。[0003] More generally, such ECR CVD
In addition to the (chemical vapor deposition) are known several kinds as a thin film formation means using a reactive gas, they heat CVD, heated filament CVD, chemical transport method, 13.56MH z
And the plasma CVD method using only microwaves are known. Especially ECRC
In the VD method, the active species are pinched by a magnetic field, and the energy is increased to increase the electron energy, thereby efficiently converting the gas into plasma.
【０００４】しかしプラズマ化させることにより、気体
が有する高エネルギにより基板の被形成面がスパッタ
（損傷）を受けることを防ぐため、このＥＣＲ条件を満
たした空間より「離れた位置」に基板を配設し、高エネ
ルギ条件下でのプラズマ状態を避けたイオンシャワー化
した反応性気体を到達させることにより薄膜形成を行っ
ていた。However, in order to prevent the surface on which the substrate is formed from being sputtered (damaged) by the high energy of the gas by generating the plasma, the substrate is disposed at a position "distant from" a space satisfying the ECR condition. And a thin film is formed by reaching a reactive gas in the form of an ion shower while avoiding a plasma state under high energy conditions.
【０００５】この装置によって形成された薄膜は、アモ
ルファス構造を有していた。また、イオン源で発生した
イオンシャワーを薄膜形成用基板まで到達させるため
に、反応圧力領域を低く（１０-4Ｔｏｒｒ台）する必要
があった。そのため、ダイヤモンド薄膜等高い結晶性を
必要とする被膜を形成することが困難であった。また、
反応圧力範囲が限られているため幅広い条件下での被膜
形成を行なえない問題があった。[0005] The thin film formed by this device had an amorphous structure. Further, in order to allow the ion shower generated by the ion source to reach the substrate for forming a thin film, it was necessary to lower the reaction pressure range (on the order of 10 -4 Torr). Therefore, it has been difficult to form a film requiring high crystallinity such as a diamond thin film. Also,
Due to the limited reaction pressure range, there was a problem that a film could not be formed under a wide range of conditions.
【０００６】本発明の薄膜形成方法は、磁場および電場
の相互作用を利用して基板上にｉ−カーボン膜を形成す
る薄膜形成方法において、プラズマ反応室へマイクロ波
を導入し、前記プラズマ反応室に磁場を印加することに
より、前記基板に対して略平行な等磁場面を形成し、前
記プラズマ反応室へ導入した炭化物気体を前記磁場およ
び電場の相互作用により活性化させ、前記基板上にｉ−
カーボン膜を形成することを特徴とする。The thin film forming method of the present invention is a thin film forming method for forming an i-carbon film on a substrate by utilizing the interaction between a magnetic field and an electric field. By applying a magnetic field to the substrate, an iso-magnetic surface is formed substantially parallel to the substrate, and the carbide gas introduced into the plasma reaction chamber is activated by the interaction between the magnetic field and the electric field. −
It is characterized in that a carbon film is formed.
【０００７】すなわち、本発明は従来より知られたマイ
クロ波を用いたプラズマＣＶＤ法に磁場を加え、さらに
マイクロ波の電場と磁場との相互作用、好ましくはＥＣ
Ｒ（エレクトロンサイクロトロン共鳴）条件又はホイッ
スラー共鳴条件を含む相互作用を利用して、幅広い圧力
範囲において高密度高エネルギのプラズマを発生させ
る。その共鳴空間での高エネルギ状態を利用して、例え
ば活性炭素原子を多量に発生させ、再現性にすぐれ、均
一な膜厚、均質な特性のｉ−カーボン膜の被膜の形成を
可能としたものである。また加える磁場の強さを任意に
変更可能な為、電子のみではなく特定のイオンのＥＣＲ
条件を設定することができる。That is, the present invention applies a magnetic field to a conventionally known plasma CVD method using a microwave, and furthermore, an interaction between a microwave electric field and a magnetic field, preferably an EC.
Utilizing interactions including R (electron cyclotron resonance) conditions or Whistler resonance conditions, a high-density, high-energy plasma is generated in a wide pressure range. Utilizing the high energy state in the resonance space, for example, a large amount of activated carbon atoms are generated, and it is possible to form an i-carbon film having excellent reproducibility, uniform film thickness, and uniform characteristics. It is. In addition, since the strength of the applied magnetic field can be changed arbitrarily, the ECR of specific ions as well as electrons
Conditions can be set.
【０００８】具体的には、ヘルムホルツ型コイルより発
生する第１の磁場と、該コイルに垂直方向に設けられた
Ｉｏｆｆｅ ｂａｒを構成する永久磁石により発生する
第２の磁場により、反応空間においてマイクロ波により
発生するプラズマを閉じ込めさらに、第１、第２の磁場
により高密度の磁場を実現して高密度、高エネルギーの
プラズマを発生させて、結晶性の非常に高い薄膜を基板
上に形成する。More specifically, a microwave is generated in a reaction space by a first magnetic field generated by a Helmholtz type coil and a second magnetic field generated by a permanent magnet constituting an Ioff bar provided in a direction perpendicular to the coil. And a high-density, high-energy plasma is generated by the first and second magnetic fields to generate a high-density, high-energy plasma, thereby forming a thin film having extremely high crystallinity on the substrate.
【０００９】また本発明の構成に付加して、マイクロ波
と磁場との相互作用により高密度プラズマを発生させた
後、基板表面上まで至る間に高エネルギを持つ光（例え
ば紫外光）を照射し、活性種にエネルギを与えつづける
と、高密度プラズマ発生領域より十分離れた位置におい
ても高エネルギ状態に励起された炭素原子が存在し、よ
り大面積にダイヤモンド、ｉ−カーボン膜を形成するこ
とも可能であった。[0009] In addition to the structure of the present invention, after generating high-density plasma by interaction of a microwave and a magnetic field, light having a high energy (for example, ultraviolet light) is irradiated to the surface of the substrate. However, when energy is continuously applied to the active species, carbon atoms excited to a high energy state exist even at a position sufficiently distant from the high-density plasma generation region, and a diamond or i-carbon film is formed in a larger area. Was also possible.
【００１０】さらに磁場とマイクロ波の相互作用により
発生する高エネルギ励起種に直流バイアス電圧を加え
て、基板側に多量の励起種が到達するようにすることは
成膜速度を向上させる効果があった。以下に実施例を示
し、さらに本発明を説明する。Further, applying a DC bias voltage to a high-energy excited species generated by the interaction between a magnetic field and a microwave so that a large amount of excited species reach the substrate side has an effect of improving the film forming speed. Was. Examples are shown below to further describe the present invention.
【００１１】[0011]
【実施例】図１に本発明の薄膜形成方法に用いる磁場印
加可能なマイクロ波プラズマＣＶＤ装置を示す。図１に
示すように、この装置は減圧反応室（１）、予備室
（８）、基板加熱装置を兼ねた基板ホルダー（３）、第
１の磁場を発生する電磁石（５）、第２の磁場を発生す
る永久磁石（６）、マイクロ波発振器（４）、マイクロ
波導波管（７）、マイクロ波導入窓（１２）、排気系
（９）、およびガス導入系（１０）、（１１）より構成
されている。FIG. 1 shows a microwave plasma CVD apparatus capable of applying a magnetic field used in the thin film forming method of the present invention. As shown in FIG. 1, this apparatus comprises a reduced-pressure reaction chamber (1), a preliminary chamber (8), a substrate holder (3) also serving as a substrate heating device, an electromagnet (5) for generating a first magnetic field, and a second Permanent magnet (6) for generating a magnetic field, microwave oscillator (4), microwave waveguide (7), microwave introduction window (12), exhaust system (9), and gas introduction system (10), (11) It is composed of
【００１２】まず、ｉ−カーボン膜形成用基板（２）を
基板ホルダー（３）上に設置する。この基板ホルダー
（３）は高熱伝導性を有し、かつマイクロ波をできるだ
け乱さないため、セラミックの窒化アルミニュームを用
いた。この基板ホルダー（３）により前記基板（２）を
例えば５００℃に加熱する。次に水素を１０ＳＣＣＭガ
ス系（１１）を通して減圧反応室（１）へと導入し、外
部より周波数２．４５ＧＨz のマイクロ波を５００Ｗの
強さで加える。First, an i-carbon film forming substrate (2) is placed on a substrate holder (3). Since the substrate holder (3) has high thermal conductivity and does not disturb microwaves as much as possible, ceramic aluminum nitride is used. The substrate (2) is heated to, for example, 500 ° C. by the substrate holder (3). Next, hydrogen is introduced into the reduced pressure reaction chamber (1) through the 10 SCCM gas system (11), and a microwave having a frequency of 2.45 GHz is applied from the outside at a power of 500 W.
【００１３】さらに、磁場を約２Ｋガウスを電磁石
（５）より印加し、さらに、第２の磁場を永久磁石
（６）より加え高密度プラズマを減圧反応室（１）にて
発生させる。この時減圧反応室（１）の圧力は０．１Ｐ
ａに保持されている。前記減圧反応室（１）にて発生し
た高密度プラズマ領域より高エネルギを持つ水素原子ま
たは電子が基板（２）上に到り、表面を洗浄にする。さ
らにこの水素気体の導入を中止し、ガス系（１１）より
炭化物気体、例えばアセチレン（Ｃ2 Ｈ2 ）、メタン
（ＣＨ4 ）を導入し水素気体の場合と同様に活性化せし
める。Further, a magnetic field of about 2K Gauss is applied from the electromagnet (5), and a second magnetic field is applied from the permanent magnet (6) to generate high-density plasma in the reduced pressure reaction chamber (1). At this time, the pressure in the reduced pressure reaction chamber (1) was 0.1 P
a. Hydrogen atoms or electrons having higher energy than the high-density plasma region generated in the reduced-pressure reaction chamber (1) reach the substrate (2) and clean the surface. Further, the introduction of the hydrogen gas is stopped, and a carbide gas, for example, acetylene (C 2 H 2 ) or methane (CH 4 ) is introduced from the gas system (11) and activated in the same manner as in the case of the hydrogen gas.
【００１４】そして高エネルギ状態に励起された炭素原
子が生成され、約５００℃加熱された基板（２）上に、
この炭素原子が堆積し、ダイヤモンドまたはｉ−カーボ
ン膜が形成された。この場合、第１の磁場を発生する手
段としては、２つのリング状の電磁石（５）を用いたヘ
ルムホルツ方式を採用し、第２の磁場を発生する手段と
しては、図１及び図２（ａ）の反応室付近の断面図より
明らかなように図２（ｂ）に示されるような減圧反応室
（１）に平行でかつ、リング状の電磁石（５）に垂直な
Ｉｏｆｆｅ ｂａｒを構成する永久磁石（６）を採用し
ている。ここで、第２の磁場発生手段として、永久磁石
を使用すると電力消費を少なくすることが可能となっ
た。Then, carbon atoms excited to a high energy state are generated, and on the substrate (2) heated at about 500 ° C.,
The carbon atoms were deposited, forming a diamond or i-carbon film. In this case, as a means for generating the first magnetic field, a Helmholtz method using two ring-shaped electromagnets (5) is adopted, and as means for generating the second magnetic field, FIGS. As is clear from the cross-sectional view of the vicinity of the reaction chamber of FIG. 2, a permanent bar constituting an Ioffbar parallel to the decompression reaction chamber (1) and perpendicular to the ring-shaped electromagnet (5) as shown in FIG. A magnet (6) is employed. Here, when a permanent magnet is used as the second magnetic field generating means, power consumption can be reduced.
【００１５】これら第１及び第２の磁場により減圧反応
室（１）内に形成される等磁場面の様子を図３に示す。
これは、図３に示す座標系に従って描かれた減圧反応室
（１）内での等磁場面である。縦軸Ｚは、減圧反応室
（１）の横方向（すなわちマイクロ波導入窓から基板方
向であり、横軸はリング状の電磁石（５）の直径方向で
ある。同図より明らかなように、減圧反応室内での磁場
密度は、第１及び第２の磁場により相当高められている
様子がわかる。FIG. 3 shows the state of the isomagnetic field formed in the reduced pressure reaction chamber (1) by the first and second magnetic fields.
This is an iso-magnetic field in the reduced pressure reaction chamber (1) drawn according to the coordinate system shown in FIG. The vertical axis Z is the horizontal direction of the reduced-pressure reaction chamber (1) (that is, the direction from the microwave introduction window to the substrate), and the horizontal axis is the diameter direction of the ring-shaped electromagnet (5). It can be seen that the magnetic field density in the reduced pressure reaction chamber is considerably increased by the first and second magnetic fields.
【００１６】比較例として、第１の磁場のみの場合の減
圧反応室（１）内での等磁場面を図４に示す。磁場が１
つの場合と２つの場合では、明らかに磁場の分布の様子
がちがっており、減圧反応室（１）内で対称な分布が得
られており、かつ明らかに第２の磁場により減圧反応室
（１）内の磁場の密度が高められていることがわかる。
なお、図中の数字は磁束密度〔Ｇａｕｓｓ〕を示す。As a comparative example, FIG. 4 shows an isomagnetic field in the reduced pressure reaction chamber (1) when only the first magnetic field is used. Magnetic field is 1
In the two cases, the distribution of the magnetic field is clearly different, a symmetric distribution is obtained in the reduced-pressure reaction chamber (1), and obviously, the second magnetic field causes the reduced-pressure reaction chamber (1). It can be seen that the density of the magnetic field in parentheses) is increased.
The numbers in the figure indicate the magnetic flux density [Gauss].
【００１７】このように、本発明は異なる種類の磁場を
減圧反応室（１）のまわりで発生させて、減圧反応室内
に磁場の密度の高い部分を発生させ、その高い密度の磁
場とマイクロ波による電場との相互作用により高密度、
高エネルギのプラズマを発生させるものであり、これに
よってより結晶性の高い薄膜を形成することが可能とな
ったものである。As described above, according to the present invention, different types of magnetic fields are generated around the reduced-pressure reaction chamber (1) to generate a high-density portion of the magnetic field in the reduced-pressure reaction chamber. High density due to interaction with the electric field,
This is to generate high-energy plasma, thereby making it possible to form a thin film having higher crystallinity.
【００１８】また比較のために同条件下で磁場を印加せ
ずに薄膜形成を行った。その時基板上に形成された薄膜
はグラファイト膜であった。さらに本実施例と同条件下
において基板温度を６５０℃以上とした場合ダイヤモン
ド薄膜を形成することが可能であった。本実施例にて形
成された薄膜の電子線回析像をとったところ低温では、
アモルファス特有のハローパターンとともにダイヤモン
ドのスポットがみられ、ｉ−カーボン膜となっていた。
さらに基板温度を上げて形成してゆくにしたがい、ハロ
ーパターンが少しずつ消えて行き６５０℃以上でダイヤ
モンドとなった。For comparison, a thin film was formed under the same conditions without applying a magnetic field. The thin film formed on the substrate at that time was a graphite film. Further, when the substrate temperature was set to 650 ° C. or higher under the same conditions as in this example, it was possible to form a diamond thin film. When an electron diffraction image of the thin film formed in this example was taken,
Diamond spots were observed together with the halo pattern peculiar to amorphous, and the film was an i-carbon film.
As the substrate temperature was further increased, the halo pattern gradually disappeared and diamond was formed at 650 ° C. or higher.
【００１９】この基板に形成された薄膜のラマンスペク
トルをとったところ、波数１５００ｃｍ-1付近にややゆ
るやかなピークを有していたが、波数１３３３ｃｍ-1付
近に鋭いピークを有しており、ダイヤモンドが析出して
いたことが確認できた。また基板加熱温度を１５０℃未
満とした場合、磁場を加えてもｉ−カーボン膜を形成す
ることはできなかった。When the Raman spectrum of the thin film formed on this substrate was taken, it had a slightly gentle peak near the wave number of 1500 cm -1 , but a sharp peak near the wave number of 1333 cm -1 , Was confirmed to have precipitated. When the substrate heating temperature was lower than 150 ° C., an i-carbon film could not be formed even when a magnetic field was applied.
【００２０】かかる方式において、基板上に炭化珪化物
気体（メチルシラン）を用い炭化珪素の多結晶膜を作る
ことができる。アルミニューム化物気体とアンモニアと
の反応により窒化アルミニューム被膜を作ることもでき
る。さらに、タングステン、チタン、モリブデンまたは
それらの珪化物の高融点導体を作ることもできる。In such a method, a silicon carbide polycrystalline film can be formed on the substrate by using silicide gas (methylsilane). An aluminum nitride film can be formed by a reaction between an aluminum compound gas and ammonia. In addition, high melting point conductors of tungsten, titanium, molybdenum or silicides thereof can be made.
【００２１】図５は、他の実施例を示している。図１に
示した装置との差は、マイクロ波を減圧反応室（１）に
導入させる位置が、ヘルムホルツコイル（５）の中心面
Ｃよりも基板（２）に近いという点だけである。この構
成によって反応空間での磁場は、基板（２）に向かって
プラズマガスを集める効果がある。図６は、前記Ｉｏｆ
ｆｅ ｂａｒの変形例である。ここでは磁石（６）のモ
ーメントの向きが径方向となっている。図７（Ａ）及び
（Ｂ）は、Ｉｏｆｆｅ ｂａｒの他の形態を示す図であ
る。ここでは、２個のコイル（６）、（６）が４本のｂ
ａｒを形成している。記号は電流の方向を示している。FIG. 5 shows another embodiment. The only difference from the apparatus shown in FIG. 1 is that the position where microwaves are introduced into the reduced pressure reaction chamber (1) is closer to the substrate (2) than the center plane C of the Helmholtz coil (5). With this configuration, the magnetic field in the reaction space has an effect of collecting the plasma gas toward the substrate (2). FIG. 6 shows the Iof
It is a modified example of fe bar. Here, the direction of the moment of the magnet (6) is the radial direction. FIGS. 7A and 7B are diagrams showing other forms of Ioffe bar. Here, two coils (6) and (6) are four b
ar. The symbols indicate the direction of the current.
【００２２】また、反応性気体に水、酸素等を添加し
て、より結晶性の高い被膜を作製することも可能であ
る。さらに、本実施例によってマイクロ波はマイクロ波
導入窓より減圧反応室内へ導入したが、他の方法によっ
て導入しても何ら本発明を阻害するものではない。ま
た、本発明の方法に適用したプラズマ処理は、膜形成に
限らず、ＮＦ3 等を用いたエッチング処理を行う場合に
も有効である。Further, it is also possible to form a film having higher crystallinity by adding water, oxygen and the like to the reactive gas. Further, according to the present embodiment, the microwave is introduced into the decompression reaction chamber through the microwave introduction window, but introduction by another method does not hinder the present invention. Further, the plasma treatment applied to the method of the present invention is not limited to film formation, but is also effective when performing an etching treatment using NF 3 or the like.
【００２３】[0023]
【発明の効果】本発明の構成を取ることにより、従来作
製されていた結晶性を少なくとも一部に有する被膜の作
製条件より幅広い条件下にて結晶性の高いｉ−カーボン
膜の作製が可能となった。また従来法に比べ大面積に均
一なｉ−カーボン膜を形成することが可能であった。さ
らに作製されたｉ−カーボン膜は引張、圧縮とも膜応力
をほとんど有さない良好な膜であった。By adopting the constitution of the present invention, it is possible to produce an i-carbon film having a high crystallinity under a wider range of conditions than those of a conventionally produced film having at least a part of crystallinity. became. Further, it was possible to form a uniform i-carbon film over a large area as compared with the conventional method. Furthermore, the produced i-carbon film was a good film having almost no film stress in both tension and compression.
【図１】本発明で用いる磁場・電場相互作用を用いたマ
イクロ波プラズマ装置の概略を示す。FIG. 1 schematically shows a microwave plasma apparatus using a magnetic field / electric field interaction used in the present invention.
【図２（Ａ）】本発明の装置の断面図を示す。FIG. 2 (A) shows a cross-sectional view of the device of the present invention.
【図２（Ｂ）】第２の磁場を発生するコイルを示す。FIG. 2 (B) shows a coil for generating a second magnetic field.
【図３】コンピュータシミュレイションによる磁場状態
を示す。FIG. 3 shows a magnetic field state by computer simulation.
【図４】コンピュータシミュレイションによる磁場状態
を示す。FIG. 4 shows a magnetic field state by computer simulation.
【図５】本発明による他のマイクロ波プラズマ装置を示
す。FIG. 5 shows another microwave plasma device according to the present invention.
【図６】図２のＩｏｆｆｅ ｂａｒの変形例を示す。FIG. 6 shows a modification of Ioffe bar in FIG.
【図７（Ａ）】Ｉｏｆｆｅ ｂａｒの他の例を示す。FIG. 7A shows another example of Ioffe bar.
【図７（Ｂ）】Ｉｏｆｆｅ ｂａｒの他の例を示す。FIG. 7B shows another example of Ioffe bar.
１・・減圧反応室 ２・・基板 ３・・基板加熱装置を
兼ねた基板ホルダ ４・・マイクロ波発振器 ５・・外部磁場発生器 ６・
・外部磁場発生器1. Decompression reaction chamber 2. Substrate 3. Substrate holder also serving as substrate heating device 4. Microwave oscillator 5. External magnetic field generator 6.
・ External magnetic field generator
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０１Ｌ 21/3065 Ｈ０１Ｌ 21/302 Ｂ Continued on the front page (51) Int.Cl. 6 Identification code Agency reference number FI Technical display location H01L 21/3065 H01L 21/302 B
Claims (3)
板上にｉ−カーボン膜を形成する薄膜形成方法におい
て、 プラズマ反応室へマイクロ波を導入し、 前記プラズマ反応室に磁場を印加することにより、前記
基板に対して略平行な等磁場面を形成し、 前記プラズマ反応室へ導入した炭化物気体を前記磁場お
よび電場の相互作用により活性化させ、 前記基板上にｉ−カーボン膜を形成することを特徴とす
る薄膜形成方法。1. A thin film forming method for forming an i-carbon film on a substrate by utilizing an interaction between a magnetic field and an electric field, wherein a microwave is introduced into a plasma reaction chamber, and a magnetic field is applied to the plasma reaction chamber. Forming an iso-magnetic field surface substantially parallel to the substrate, activating the carbide gas introduced into the plasma reaction chamber by the interaction between the magnetic field and the electric field, and forming an i-carbon film on the substrate. A method for forming a thin film, comprising:
セチレンまたはメタンであることを特徴とする薄膜形成
方法。2. A thin film forming method according to claim 1, wherein said carbide gas is acetylene or methane.
ーボン膜形成時に１５０℃以上に加熱していることを特
徴とする薄膜形成方法。3. The thin film forming method according to claim 1, wherein the substrate is heated to 150 ° C. or more when forming the i-carbon film.
Priority Applications (1)
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|---|---|---|---|
| JP9094427A JP2965935B2 (en) | 1997-03-31 | 1997-03-31 | Plasma CVD method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9094427A JP2965935B2 (en) | 1997-03-31 | 1997-03-31 | Plasma CVD method |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7242484A Division JP2715277B2 (en) | 1995-08-28 | 1995-08-28 | Thin film forming equipment |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10148566A Division JP2892347B2 (en) | 1998-05-29 | 1998-05-29 | Thin film formation method |
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| Publication Number | Publication Date |
|---|---|
| JPH1081970A true JPH1081970A (en) | 1998-03-31 |
| JP2965935B2 JP2965935B2 (en) | 1999-10-18 |
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ID=14109941
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| Application Number | Title | Priority Date | Filing Date |
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|---|---|---|---|---|
| US7132621B2 (en) | 2002-05-08 | 2006-11-07 | Dana Corporation | Plasma catalyst |
| US7189940B2 (en) | 2002-12-04 | 2007-03-13 | Btu International Inc. | Plasma-assisted melting |
| US7432470B2 (en) | 2002-05-08 | 2008-10-07 | Btu International, Inc. | Surface cleaning and sterilization |
| US7445817B2 (en) | 2002-05-08 | 2008-11-04 | Btu International Inc. | Plasma-assisted formation of carbon structures |
| US7465362B2 (en) | 2002-05-08 | 2008-12-16 | Btu International, Inc. | Plasma-assisted nitrogen surface-treatment |
| US7494904B2 (en) | 2002-05-08 | 2009-02-24 | Btu International, Inc. | Plasma-assisted doping |
| US7498066B2 (en) | 2002-05-08 | 2009-03-03 | Btu International Inc. | Plasma-assisted enhanced coating |
| US7497922B2 (en) | 2002-05-08 | 2009-03-03 | Btu International, Inc. | Plasma-assisted gas production |
| US7560657B2 (en) | 2002-05-08 | 2009-07-14 | Btu International Inc. | Plasma-assisted processing in a manufacturing line |
| US7638727B2 (en) | 2002-05-08 | 2009-12-29 | Btu International Inc. | Plasma-assisted heat treatment |
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1997
- 1997-03-31 JP JP9094427A patent/JP2965935B2/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7445817B2 (en) | 2002-05-08 | 2008-11-04 | Btu International Inc. | Plasma-assisted formation of carbon structures |
| US7497922B2 (en) | 2002-05-08 | 2009-03-03 | Btu International, Inc. | Plasma-assisted gas production |
| US7214280B2 (en) | 2002-05-08 | 2007-05-08 | Btu International Inc. | Plasma-assisted decrystallization |
| US7227097B2 (en) | 2002-05-08 | 2007-06-05 | Btu International, Inc. | Plasma generation and processing with multiple radiation sources |
| US7309843B2 (en) | 2002-05-08 | 2007-12-18 | Btu International, Inc. | Plasma-assisted joining |
| US7432470B2 (en) | 2002-05-08 | 2008-10-07 | Btu International, Inc. | Surface cleaning and sterilization |
| US7638727B2 (en) | 2002-05-08 | 2009-12-29 | Btu International Inc. | Plasma-assisted heat treatment |
| US7494904B2 (en) | 2002-05-08 | 2009-02-24 | Btu International, Inc. | Plasma-assisted doping |
| US7132621B2 (en) | 2002-05-08 | 2006-11-07 | Dana Corporation | Plasma catalyst |
| US7498066B2 (en) | 2002-05-08 | 2009-03-03 | Btu International Inc. | Plasma-assisted enhanced coating |
| US7465362B2 (en) | 2002-05-08 | 2008-12-16 | Btu International, Inc. | Plasma-assisted nitrogen surface-treatment |
| US7560657B2 (en) | 2002-05-08 | 2009-07-14 | Btu International Inc. | Plasma-assisted processing in a manufacturing line |
| US7592564B2 (en) | 2002-05-08 | 2009-09-22 | Btu International Inc. | Plasma generation and processing with multiple radiation sources |
| US7608798B2 (en) | 2002-05-08 | 2009-10-27 | Btu International Inc. | Plasma catalyst |
| US7189940B2 (en) | 2002-12-04 | 2007-03-13 | Btu International Inc. | Plasma-assisted melting |
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| Publication number | Publication date |
|---|---|
| JP2965935B2 (en) | 1999-10-18 |
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