JPS62227089A - Method and device for treating surface - Google Patents
Method and device for treating surfaceInfo
- Publication number
- JPS62227089A JPS62227089A JP6964686A JP6964686A JPS62227089A JP S62227089 A JPS62227089 A JP S62227089A JP 6964686 A JP6964686 A JP 6964686A JP 6964686 A JP6964686 A JP 6964686A JP S62227089 A JPS62227089 A JP S62227089A
- Authority
- JP
- Japan
- Prior art keywords
- discharge
- plasma
- substrate
- lte
- surface treatment
- 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
- 238000000034 method Methods 0.000 title claims description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 238000004381 surface treatment Methods 0.000 claims abstract description 25
- 238000011282 treatment Methods 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims description 41
- 239000002245 particle Substances 0.000 claims description 15
- 230000005469 synchrotron radiation Effects 0.000 claims description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 10
- 230000008878 coupling Effects 0.000 claims description 4
- 238000010168 coupling process Methods 0.000 claims description 4
- 238000005859 coupling reaction Methods 0.000 claims description 4
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 230000001939 inductive effect Effects 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 claims 1
- 150000004756 silanes Chemical class 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 41
- 230000015572 biosynthetic process Effects 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 8
- 238000005530 etching Methods 0.000 abstract description 5
- 239000012495 reaction gas Substances 0.000 abstract description 5
- 230000002349 favourable effect Effects 0.000 abstract 1
- 210000002381 plasma Anatomy 0.000 description 71
- 239000010408 film Substances 0.000 description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 229910052739 hydrogen Inorganic materials 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 239000001257 hydrogen Substances 0.000 description 14
- 238000012545 processing Methods 0.000 description 13
- 239000010453 quartz Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 230000001965 increasing effect Effects 0.000 description 7
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- MXCPYJZDGPQDRA-UHFFFAOYSA-N dialuminum;2-acetyloxybenzoic acid;oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3].CC(=O)OC1=CC=CC=C1C(O)=O MXCPYJZDGPQDRA-UHFFFAOYSA-N 0.000 description 5
- -1 hydrogen radicals Chemical class 0.000 description 5
- 238000004020 luminiscence type Methods 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000004993 emission spectroscopy Methods 0.000 description 4
- 150000002431 hydrogen Chemical group 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 150000002831 nitrogen free-radicals Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
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- 238000010894 electron beam technology Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（イ）産業上の利用分野
この発明は、所定の放射光および活性種を作成し、これ
を利用することによって、殊に半導体デバイスの絶縁体
膜、半導体膜、金属膜の膜生成、エツチング、表面クリ
ーニング、表面改質等の表面処理を行なう表面処理方法
およびその装置に関する。DETAILED DESCRIPTION OF THE INVENTION (a) Industrial application field The present invention creates a predetermined synchrotron radiation and active species, and uses them to improve the production of insulator films, semiconductor films, and metals of semiconductor devices, in particular. The present invention relates to a surface treatment method and apparatus for surface treatment such as film formation, etching, surface cleaning, and surface modification.
（ロ）従来の技術
気体を光化学反応または活性種を用いる反応により活性
化し、基体表面に目的とする物質を堆積させ薄膜化した
り、エツチング、表面改質等の処理をする方法は、処理
が低温で可能であること、荷電粒子の衝撃による損傷が
ないこと、光化学的選択性または活性種による選択性に
より従来にない処理が可能となること、反応過程の選択
及び成膜の制御が容易であることなどから近年急速な進
展をみせている。(b) Conventional technology The method of activating gas by photochemical reaction or reaction using active species, depositing the target substance on the surface of the substrate to form a thin film, etching, surface modification, etc. There is no damage due to the impact of charged particles, unprecedented processing is possible due to photochemical selectivity or active species selectivity, and it is easy to select the reaction process and control film formation. Due to this, rapid progress has been made in recent years.
従来から知られている光化学的表面処理方法は、大別し
て２つに分けられる。一つは光源として放電ランプを用
いる方法であり、他の一つは光源としてレーザーを用い
る方法である。しかし放電ランプを用いる方法では、一
般的に放射光の輝度が小さく、レーザーを用いる方法で
は、レーザ一本体が高価につく。Conventionally known photochemical surface treatment methods can be roughly divided into two types. One method uses a discharge lamp as a light source, and the other method uses a laser as a light source. However, in the method using a discharge lamp, the luminance of the emitted light is generally low, and in the method using a laser, the laser itself is expensive.
また通常の場合、処理装置は光源と処理室が窓によっ、
で分離されており、特に光ＣＶＤ等の場合にはこの窓上
に異物が堆積し、こ＼で放射光が減衰する問題が生じる
。In addition, in normal cases, the processing equipment has a light source and a processing chamber with a window.
Particularly in the case of optical CVD, etc., foreign matter accumulates on this window, causing a problem in which the emitted light is attenuated.
これを改善する発明として、特開昭５９−１６９６６号
公報所載の発明と特開昭６０−２４３７３の発明が存在
する。前者の発明は、光源部と処理部とを同一容器内に
設置し、光源としてその明細書より推量されるように、
熱陰極放電あるいはＡＣ放電または直流放電によるグロ
ー放電光を用い、放電用電極の周囲に電極の保護のため
の保護用ガスを供給し、放電の安定化すなわち光源の安
定化をはかる内容となっている。しかしこの構成は装置
の構造を複雑にするとともに表面処理に直接関係のない
気体を処理系内に導入することになるため、これが表面
処理の種類を制限し又は処理に悪影響をあたえるという
欠点を生んでいる。As inventions for improving this, there are the invention disclosed in Japanese Patent Application Laid-Open No. 59-16966 and the invention disclosed in Japanese Patent Application Laid-Open No. 60-24373. In the former invention, a light source section and a processing section are installed in the same container, and as a light source, as inferred from the specification,
Using glow discharge light from hot cathode discharge, AC discharge, or DC discharge, a protective gas is supplied around the discharge electrode to protect the electrode, thereby stabilizing the discharge, that is, stabilizing the light source. There is. However, this configuration complicates the structure of the device and introduces gases that are not directly related to surface treatment into the treatment system, which has the disadvantage of limiting the types of surface treatment or adversely affecting the treatment. I'm reading.
後者の発明は、中空陰極放電の放電光を光源として活用
するもので本願の出願人の出願になるものであり、その
明細書に記載の通り極めて良質のアモルファス水素化シ
リコン膜を生むなどの大きい効果があるが、その反面、
成膜速度などの処理速度が極端に遅く、そのため到底こ
れを実用に供することができないことがその後の実験で
判明している。The latter invention utilizes the discharge light of a hollow cathode discharge as a light source and is filed by the applicant of the present application, and as described in the specification, it produces a large amorphous hydrogenated silicon film of extremely high quality. It is effective, but on the other hand,
Subsequent experiments have revealed that the processing speed, such as the film formation speed, is extremely slow, and as a result, it cannot be put to practical use.
また、一般に活性種は、物質に光あるいは電子等を照射
することによって作成することができるが、光によって
作成される活性状態は、光遷移が禁止されていない活性
状態が、その禁止されていない活性状態から項間交差あ
るいは緩和によって生じた活性状態のみであるのに対し
、プラズマ内部や電子ビームなどで粒子の衝突により生
じる活性状態は上記に限定さ九ず、光遷移が禁止されて
いる活性状態へも容易に遷移が拡大し、光の場合とは異
って雑多な、有害で不純物を含んだ活性種を作り出す。In addition, active species can generally be created by irradiating a substance with light or electrons, but the active state created by light is the active state in which phototransition is not prohibited. Only active states are generated by intersystem crossing or relaxation from an active state, whereas active states generated by particle collisions in plasma or electron beams are not limited to the above, and active states in which optical transition is prohibited. The transition easily extends to other states, and unlike in the case of light, it creates active species that are miscellaneous, harmful, and contain impurities.
プラズマによって成膜を行なう従来の技術の殆んどは、
プラズマに基体が直接接するものであるためプラズマ中
のこれら有害な活性種や荷電粒子が基体に衝撃を与えて
損傷を生じ、基体に不純物を添加して１例えばこの基体
上に作られた半導体デバイスの電気的特性を劣化させる
など欠点がある。このような劣化は、たとえばＭ。Most of the conventional technologies that deposit films using plasma are
Since the substrate is in direct contact with the plasma, these harmful active species and charged particles in the plasma impact the substrate and cause damage, and impurities are added to the substrate, resulting in a semiconductor device being fabricated on this substrate. There are drawbacks such as deterioration of the electrical characteristics of the Such deterioration is caused by, for example, M.
Ｓ型半導体デバイスではｖｔｈの変動、バイボーラ型半
導体デバイスではｈｆａの変動等に強く表われる。そし
て、昨今のように半導体デバイスの集積度が極めて大き
いものになると、微少の荷電粒子の衝撃等によっても著
しい電気的特性の劣化を招くことになるため、不純物の
少い活性種を使用したり、衝撃のない光を利用したりす
る無損傷プロセスの開発が特に望まれるようになってい
る。In S-type semiconductor devices, this phenomenon is strongly manifested in vth fluctuations, and in bibolar-type semiconductor devices, it is strongly manifested in hfa fluctuations. As the degree of integration of semiconductor devices becomes extremely large these days, even the impact of minute charged particles can cause significant deterioration of electrical characteristics, so it is necessary to use active species with fewer impurities. The development of damage-free processes, such as the use of non-impact light, has become particularly desirable.
（ハ）発明の目的
この発明は、表面処理に有用で純度の高い１強力な放射
光又は活性種を安定して作成し、これを用いることによ
って、工業的に利用可能な程の充分な速度で、良質で有
効的な表面処理を行なうことのできる。新規な表面処理
方法およびその装置の提供を目的とする。(c) Purpose of the Invention This invention stably produces a powerful synchrotron radiation or active species that is useful for surface treatment and has high purity. This allows for high quality and effective surface treatment. The purpose of this invention is to provide a novel surface treatment method and device.
（ニ）発明の構成
本願の第１の発明は、交番電力の印加された空間に所定
の気体を導入することによってＬＴＥ放電を発生せしめ
、このＬＴＥ放電のプラズマに生ずる放射光又は活性種
を、該ＬＴＥ放電の外に置かれた基体の表面に導くこと
によって、該基体の表面に所定の処理を施す表面処理方
法によって前記目的を達成したものである。(d) Structure of the Invention The first invention of the present application generates LTE discharge by introducing a predetermined gas into a space to which alternating power is applied, and uses synchrotron radiation or active species generated in the plasma of this LTE discharge to The above objective is achieved by a surface treatment method in which a predetermined treatment is performed on the surface of a base by guiding the LTE discharge to the surface of the base placed outside the LTE discharge.
また本願の第二の発明は、この第一の発明の方法を用い
て、工業的に十分に利用可能な装置を次の構成によって
実現するものである。即ちそれは、被処理基体を収容す
る反応室と、交番電力電源と、誘導結合、容量結合はま
たは空胴共振によって前記電源の交番電力が印加される
放電用空間をそなえた放電室と、
前記放電用空間に所定の気体を導入する手段と、前記放
電用空間の放電プラズマに生じた放射光又は活性種を、
前記反応室の前記被処理基体の表面に導く照射手段とを
そなえ。Further, the second invention of the present application uses the method of the first invention to realize an apparatus that can be fully used industrially with the following configuration. That is, it includes a reaction chamber that accommodates a substrate to be processed, an alternating power source, a discharge chamber equipped with a discharge space to which alternating power of the power source is applied by inductive coupling, capacitive coupling, or cavity resonance, and the discharge chamber. means for introducing a predetermined gas into the discharge space, and synchrotron radiation or active species generated in the discharge plasma in the discharge space;
and irradiation means for guiding the surface of the substrate to be processed in the reaction chamber.
前記交番電力電源が前記放電用空間内にＬＴＥ放電を生
むに充分な大きさの電力容量をそなえるとともに、
〔前記交番電力電源の電力容量〕を〔前記放電用空間が
前記基体に向って開く開口面積〕で割った値が２ Ｗ／
ａ＃以上であるような構成の装置で、前記方法を装置化
したものである。The alternating power source has a power capacity large enough to generate LTE discharge in the discharge space, and [the power capacity of the alternating power source] has an opening in which the discharge space opens toward the base body. The value divided by [area] is 2 W/
This is an apparatus having a configuration such that the number of points is greater than or equal to a#, and is an apparatus of the above-mentioned method.
（ホ）実施例
第１図は、この発明の実施例の表面処理装置を示したも
のである。１０は放電室であり、２０は反応室である。(E) Embodiment FIG. 1 shows a surface treatment apparatus according to an embodiment of the present invention. 10 is a discharge chamber, and 20 is a reaction chamber.
放電室１０は高周波（数ＫＨｚ〜数百Ｍ Ｈｚ ）の電
源１、コイル２及び放電管６で構成されており、電源１
から発する高周波電圧がコイル２に印加されると、放電
管６の内部の高周波誘導結合された放電用空間６０に放
電が生じる。The discharge chamber 10 is composed of a high frequency (several KHz to several hundred MHz) power source 1, a coil 2, and a discharge tube 6.
When a high frequency voltage emitted from the coil 2 is applied to the coil 2, a discharge occurs in the discharge space 60 which is inductively coupled to the high frequency inside the discharge tube 6.
これは、コイル２の代りに、放電管６をはさむ一対の板
状電極を設け、これに電力を印加して容量結合された放
電用空間６０を作るのでもよい。高周波としてマイクロ
波領域（Ｇ Ｈｚオーダー）の周波数を用いる場合は、
マイクロ波キャビティをコイル２の代りに放電管６をと
り囲む様に設置する。このときは空胴共振の放電用空間
６０を利用することになる。そして、上記のように放電
が生じた放電管６の内部に放電用ガスを流れ５の方向か
らバルブ４を介して導入する６放電管６は通常絶縁物で
作成され、その材質としては石英ガラス。This may be done by providing a pair of plate-shaped electrodes sandwiching the discharge tube 6 in place of the coil 2, and applying electric power to these to create a capacitively coupled discharge space 60. When using a frequency in the microwave region (GHz order) as the high frequency,
A microwave cavity is installed so as to surround the discharge tube 6 instead of the coil 2. At this time, the cavity resonance discharge space 60 is used. Then, the discharge gas is introduced into the discharge tube 6 from the direction of the flow 5 through the bulb 4 into which the discharge has occurred as described above.The discharge tube 6 is usually made of an insulating material, and its material is quartz glass. .
サファイヤまたはセラミクス等が有能である。石英ガラ
スを用いた場合は放電プラズマの高温化によって石英ガ
ラスが溶融するおそれがあるため、放電管６を石英ガラ
スの２重管とし、内外２つの管の間に冷却水を流すこと
がある。Sapphire or ceramics are possible. If quartz glass is used, there is a risk that the quartz glass will melt due to the high temperature of the discharge plasma, so the discharge tube 6 may be a double tube of quartz glass, and cooling water may be flowed between the two tubes, the inner and outer tubes.
印加する高周波電力を大きくしてゆくにしたがって先づ
高周波グロー放電を生じるが、さらに大きい電力を加え
るときはプラズマからの発光が飛がｗｔ察される。ＬＴ
Ｅプラズマ３の発生は多くの場合ヒステリシス的である
。このプラズマ３は非常に輝度が高く多くの場合通常の
直流グロー放電とは異ったスペクトルパターンを示す。As the applied high-frequency power is increased, high-frequency glow discharge occurs first, but when even higher power is applied, it is observed that the emission of light from the plasma is significantly reduced. LT
The generation of E plasma 3 is often hysteretic. This plasma 3 has very high brightness and often exhibits a spectral pattern different from that of a normal DC glow discharge.
たとえば前記した導入ガスが水素であったとして、水素
の場合で述べると、通常の直流グロー放電あるいは高周
波グロー放電のときには先づ水素分子に起因する可視光
域から紫外光域に達する連続スペクトルが存在し、これ
に加えた形で、水素原子に起因するバルマー系列および
ライマン系列の発光を観測することができる。しかしこ
のときのこれら系列の発光は比較的弱くそのため放射光
の色は白票色となっている。For example, assuming that the gas introduced above is hydrogen, in the case of hydrogen, during normal DC glow discharge or high frequency glow discharge, there is a continuous spectrum that first reaches from the visible light region to the ultraviolet light region due to hydrogen molecules. However, in addition to this, it is also possible to observe Balmer series and Lyman series emissions caused by hydrogen atoms. However, the luminescence of these series at this time is relatively weak, so the color of the emitted light is white.
ところが、Ｌ Ｔ’Ｅプラズマ３を生じたときは、放射
光の色は目視では輝度の非常に高い赤色となっていて、
それは水素原子の発光のバルマー系の輝度が非常に高く
なった結果であることを知る。However, when L T'E plasma 3 was generated, the color of the synchrotron radiation was red with very high brightness when visually observed.
We know that this is the result of the extremely high brightness of the Balmer system of hydrogen atom light emission.
同時に可視部にないため直接口には見えないが、ライマ
ン系の輝度も非常に高くなっているのが測定で確認でき
る。この輝度の高まる様子を図示すると第２図のように
なる。（ＬＴＥ放電を発生せしめたときの最大の特徴の
１つである発光の波長は、プラズマ発生に用いた気体の
種類によって定まる。）
ライマンα光は１２１．６ｎｍの波長を持っており、周
知のようにこの波長の光を用いるときはシラン、ジシラ
ンの直接分解が可能である。その上、この光の場合は、
Ｍ ｇ Ｆ ｚ ｅ Ｌ ｘ Ｆ等の光学透過材料およ
びＭｇＦ２コーティングのＡＱリフレクタ−が使用でき
る長所もあり、光学系を組むことが極めて容易になって
非常に有用である。これまでは、このライマンα光の高
輝度のものを取り出すことのできる良い光源がなかった
ために、この波長光はあまり利用されていなかったもの
である。上記した高周波ＬＴＥプラズマ光は、この意味
で光源として貴重である。At the same time, although it cannot be seen directly in the mouth because it is not in the visible region, measurements confirm that the Lyman luminance is also extremely high. The manner in which this brightness increases is illustrated in FIG. 2. (The wavelength of the emitted light, which is one of the most important characteristics when generating an LTE discharge, is determined by the type of gas used to generate plasma.) Lyman-α light has a wavelength of 121.6 nm, and the well-known When using light of this wavelength, it is possible to directly decompose silane and disilane. Moreover, in the case of this light,
There is also the advantage that optically transparent materials such as MgFzeLxF and AQ reflectors coated with MgF2 can be used, making it extremely easy to assemble an optical system, which is very useful. Until now, this wavelength of light has not been utilized much because there has been no good light source that can extract high-intensity Lyman alpha light. The high frequency LTE plasma light described above is valuable as a light source in this sense.
なお上記の導入ガスとしては水素のほかに窒素、アルゴ
ン、ヘリウム、水銀等の気体およびこれらの混合気体も
有能で、高輝度の有用光を放射するＬＴＥ放電プラズマ
を生じうる。In addition to hydrogen, gases such as nitrogen, argon, helium, mercury, and mixtures thereof can also be used as the introduced gas, and LTE discharge plasma that emits high-intensity useful light can be generated.
更に続けると、上記の導入ガスが水素の場合には、ＬＴ
Ｅプラズマ内には、通常の高周波グロー放電と比較して
極めて多量の水素原子および水素分子の励起状態、水素
ラジカル、イオン等の活性種の存在するのが発光分光分
析で確認できる。ＬＴＥ放電プラズマで多量の活性種の
生れることは、他のガス、例えば窒素の場合も同じてあ
って、第３図及び第４図は、窒素の真空紫外発光分光分
析の結果を示したものである。第３図は、ＬＴＥプラズ
マの発光分析、第４図は高周波グロープラズマの発光分
析である。両プラズマは同じ装置を使ってともに１３
、５６ ＭＨｚ、 ２ 、５ｋＷ、圧カフ。Continuing further, when the above introduced gas is hydrogen, LT
It can be confirmed by emission spectroscopy that in the E plasma, compared to a normal high-frequency glow discharge, there are extremely large amounts of hydrogen atoms, excited states of hydrogen molecules, hydrogen radicals, active species such as ions, and the like. The generation of large amounts of active species in LTE discharge plasma is also true for other gases, such as nitrogen, and Figures 3 and 4 show the results of vacuum ultraviolet emission spectrometry analysis of nitrogen. It is. FIG. 3 shows the emission analysis of LTE plasma, and FIG. 4 shows the emission analysis of high-frequency glow plasma. Both plasmas were generated using the same equipment.
, 56 MHz, 2, 5 kW, pressure cuff.
ＯｍＴｏｒｒ、Ｎ２流量３０ｓｃｃｍの条件下で太られ
たものである。この装置のこの作成条件では１丁度、Ｌ
ＴＥと高周波グローの二つの状態が、互に他にヒステリ
シス的に移行するため、同一条件でＬＴＥと高周波グロ
ーの二つの状態を作り出し比較することができる。発光
強度を示す縦軸は、両図とも任意単位となっているが、
ＬＴＨのグラフの縦軸の目盛は、グロー放電のグラフの
縦軸の目盛１００倍近くにまで目盛が強度に縮められて
おり１２０ｎｍの光の強度で比較すると、ＬＴＥの方が
高周波グローに比較して１２０倍の発光強度がある。そ
して先述の水素の場合と同様にこの窒素の場合でもＬＴ
Ｅプラズマは短波長光の輝度が強く、そのスペクトルは
、窒素原子からの発光に属することから、ＬＴＥプラズ
マの内部に活性種、特に窒素ラジカルを多く含まれるこ
とが明らかである。It was thickened under the conditions of OmTorr and N2 flow rate of 30 sccm. Under this production condition of this device, exactly 1 L
Since the two states of TE and high-frequency glow transition from each other in a hysteretic manner, it is possible to create and compare the two states of LTE and high-frequency glow under the same conditions. The vertical axis showing the luminescence intensity is in arbitrary units in both figures, but
The scale on the vertical axis of the LTH graph has been reduced in intensity to nearly 100 times the scale on the vertical axis of the glow discharge graph, and when comparing the intensity of 120 nm light, LTE is higher than high-frequency glow. It has 120 times the luminous intensity. And as in the case of hydrogen mentioned above, in the case of nitrogen as well, LT
Since E plasma has a strong short wavelength light and its spectrum belongs to light emission from nitrogen atoms, it is clear that LTE plasma contains many active species, especially nitrogen radicals.
なお水素、窒素のみならず酸素やそのほかのガスについ
ても同様な結果が得られる。Note that similar results can be obtained not only for hydrogen and nitrogen but also for oxygen and other gases.
高周波グロー放電と高周波ＬＴＥプラズマ放電を比較す
ると、両者の間には、次のような違いがあり、次の条件
の−、二を欠く場合でも両者は容易に判然と区別できる
。When high-frequency glow discharge and high-frequency LTE plasma discharge are compared, there are the following differences between the two, and even if the following conditions - and -2 are lacking, the two can be easily distinguished.
（ａ）高周波グロー放電は発光部が広がる傾向にあり、
高周波ＬＴＥプラズマ放電では逆に発光部が局所に集ま
る傾向にある。(a) In high-frequency glow discharge, the light emitting part tends to spread,
In high frequency LTE plasma discharge, on the contrary, the light emitting parts tend to gather locally.
（ｂ）ＬＴＥプラズマ発生用の面放電の発光はそのスペ
クトルパターンが異なっている。このスペクトルの相異
によっても、電子状態に相違のあることが判然とする。(b) The light emission of the surface discharge for LTE plasma generation has different spectral patterns. This difference in spectra also reveals that there is a difference in electronic state.
該ガスが多原子分子の場合には、高周波ＬＴＥプラズマ
放電では、高周波グロー放電で見られなかった振動およ
び回転モードの励起がしばしばａ測される。When the gas is a polyatomic molecule, excitation of vibrational and rotational modes not seen in high frequency glow discharge is often observed in high frequency LTE plasma discharge.
（ｃ）高周波グロー放電状態と高周波ＬＴＥプラズマ放
電状態とは、前記したように、放電電力。(c) The high frequency glow discharge state and the high frequency LTE plasma discharge state refer to the discharge power as described above.
放電圧力等をパラメータとして、しばしばヒステリシス
ループをえかいて互に他に遷移し、放電インピーダンス
は面放電間で大きく異なる。Using discharge pressure and other parameters as parameters, the discharge impedance varies greatly between surface discharges, often with a hysteresis loop.
この遷移は電源から放電室に投入される放電電力の強度
に最も大きく依存する。これに関しては更に後述する。This transition is most dependent on the intensity of the discharge power input from the power source into the discharge chamber. This will be discussed further later.
（ｄ）高周波ＬＴＥプラズマ放電は高周波グロー放電プ
ラズマに較べて非常に輝度が高い。その差は格段である
。(d) High frequency LTE plasma discharge has much higher brightness than high frequency glow discharge plasma. The difference is significant.
例えばヘリウム等のようなガスの場合は、放電インピー
ダンスがヒステリシス的に変化せずそのためインピーダ
ンスのみからは高周波グロー放電と高周波ＬＴＥプラズ
マの間の移行を判別し難いが、高周波ＬＴＥプラズマ放
電状態になると高輝度のプラズマが局在化されるのが認
められ、目視によって面放電を識別することができる。For example, in the case of a gas such as helium, the discharge impedance does not change in a hysteretic manner, so it is difficult to distinguish between high-frequency glow discharge and high-frequency LTE plasma from impedance alone. A bright plasma was observed to be localized, and a surface discharge could be visually identified.
次に反応室２０について説明すると１反応室２０は、必
要ならば気密に保つことができる反応容器７とその中に
設けられた反応気体を導入するための導入リング１３．
基体１６を設置するための基体ホルダ８で構成されてい
る。Next, the reaction chamber 20 will be explained.The reaction chamber 20 consists of a reaction container 7 that can be kept airtight if necessary, and an introduction ring 13 provided therein for introducing a reaction gas.
It consists of a base holder 8 for installing a base 16.
そして反応室２０と放電室１０の間には、放電室１ｏ内
に発生したＬＴＥプラズマ３からの活性種１８または放
射光１７を反応室２０の基板１６の表面上に導入するメ
ツシュ状の電極３０が設けられでいる。所定の反応ガス
はバルブ１１を介して流れの方向１２から中空の導入リ
ング１３内に導かれ、リングの内側に多数設けられた小
孔１３０から基体１６の表面に吹き出されることで反応
容器７の内部に供給される。基体ホルダー８には温度コ
ントローラー９が設置されており必要に応じて基体１Ｇ
の温度を調節できる。Between the reaction chamber 20 and the discharge chamber 10, there is a mesh-like electrode 30 that introduces active species 18 or radiation light 17 from the LTE plasma 3 generated in the discharge chamber 1o onto the surface of the substrate 16 of the reaction chamber 20. is provided. A predetermined reaction gas is introduced into the hollow introduction ring 13 from the flow direction 12 through the valve 11, and is blown out onto the surface of the substrate 16 from a large number of small holes 130 provided inside the ring, thereby forming the reaction vessel 7. is supplied inside. A temperature controller 9 is installed on the substrate holder 8, and the substrate 1G is adjusted as necessary.
temperature can be adjusted.
前記した放電室の導入ガスおよび反応室に導かれる反応
ガスはバルブ１４を介してガスの流れ１５の方向に排気
される。放電室１ｏおよび反応室２０を大きく連通させ
た場合には、圧力が数Ｔａｒｒ以下の領域では、高周波
ＬＴＥプラズマの周囲に広がるグロー状プラズマがしば
しば反応室７の内部にまで広がってくる。上記のメツシ
ュ状電極３０には、これを防止するとか、これを助長す
るなどの調整機能をもたせることができる。The gas introduced into the discharge chamber and the reaction gas introduced into the reaction chamber are exhausted through the valve 14 in the direction of the gas flow 15. When the discharge chamber 1o and the reaction chamber 20 are largely communicated with each other, the glow-like plasma that spreads around the high-frequency LTE plasma often spreads into the inside of the reaction chamber 7 in a region where the pressure is several Tarr or less. The mesh-like electrode 30 described above can be provided with an adjustment function to prevent or encourage this.
なお、この電極３０の構造・形状・材質は、グロー状プ
ラズマが反応室２０内に広がるのを調整するとか、前記
したように活性種１８または放射光１７を基板１６の表
面に導入することができるものであれば良く、必ずしも
メツシュ状のもの等に限定されるものではない。この電
極３０に電圧を印加することでプラズマのシールド効果
を高めたり、逆にプラズマから荷電粒子を反応室２０内
部に引き出して荷電粒子を表面処理に積極的に利用した
りの調整ができる。The structure, shape, and material of this electrode 30 are designed to adjust the spread of the glow plasma within the reaction chamber 20 or to introduce the active species 18 or the synchrotron radiation 17 to the surface of the substrate 16 as described above. Any material that can be used may be used, and is not necessarily limited to a mesh-like material. By applying a voltage to this electrode 30, it is possible to enhance the shielding effect of the plasma, or conversely, draw charged particles from the plasma into the reaction chamber 20 to actively utilize the charged particles for surface treatment.
また電極３０と接地電位との間に適宜の容量のコンデン
サーを設置し、高周波的には接地電位とし直流的には浮
遊電位とすることもできる。この場合には異常放電を少
なくしてシールド効果が大きくなる。同様に電極３０と
接地電位との間にバンドパスフィルターを用いても良い
。Further, a capacitor of an appropriate capacity may be installed between the electrode 30 and the ground potential, and the potential may be set to the ground potential in terms of high frequency and floating potential in terms of direct current. In this case, abnormal discharge is reduced and the shielding effect is increased. Similarly, a bandpass filter may be used between the electrode 30 and the ground potential.
また電極３０のかわりに二Ｎに磁場を設定して同様の荷
電粒子調整効果をもたせることも可能である。第７図は
その実施例を示すもので、導波管３０１、マイクロ波導
入窓３０２を通って、電磁コイル３０４の作る磁場Ｂ内
に設けられた空胴共振器３０５に注入されるマイクロ波
電力は、この空胴内にＬＴＥプラズマ３を作り、以上が
放電室１０を形成する。ＬＴＥプラズマ３内の荷電粒子
は、磁場Ｂの発散部で加速されて基体１６上にそ＼がれ
ることになる。It is also possible to provide a similar charged particle adjustment effect by setting a magnetic field at 2N instead of the electrode 30. FIG. 7 shows an example of this, in which microwave power is injected into a cavity resonator 305 installed in a magnetic field B generated by an electromagnetic coil 304 through a waveguide 301 and a microwave introduction window 302. creates LTE plasma 3 within this cavity, and the above forms a discharge chamber 10. Charged particles within the LTE plasma 3 are accelerated by the divergent portion of the magnetic field B and are scattered onto the base 16.
なお電極３０を除去して、反応室２０内に広がってくる
グロー状プラズマを積極的に利用することもできる。Note that it is also possible to remove the electrode 30 and actively utilize the glow-like plasma that spreads within the reaction chamber 20.
第１図の装置を使用し、放電室１０の導入ガスとして窒
素を用い、反応室２０に導入するガスとしてシランガス
を用いたとき、基体１６の上にＳｉＮ膜が作成できた。When the apparatus shown in FIG. 1 was used, nitrogen was used as the gas introduced into the discharge chamber 10, and silane gas was used as the gas introduced into the reaction chamber 20, a SiN film was formed on the substrate 16.
このときの条件は、基体温度２００℃、圧カフ ００
ｍＴｏｒｒｔ ＳｉＨ４流量２５ｓｅｃｍ、 Ｎ２流量
２００ ｓｅｃｍ、電力３．５ｋＷ （１３，５６ＭＨ
，）である。The conditions at this time were: substrate temperature 200°C, pressure cuff 00°C.
mTorrt SiH4 flow rate 25sec, N2 flow rate 200sec, power 3.5kW (13,56MH
,).
同じく第１図の装置を使用し、放電室１０の導入ガスと
して水素を用い、反応室２０の導入ガスとしてシランガ
スまたはジシランガスを用いたとき、基体１６の表面に
ａ−８ｉ：Ｈ膜を作成できた。この反応は、ＬＴＥプ
ラズマから発生するライマン系列の短波長光によりシラ
ンまたはジシランが分解され（この反応にＬＴＥプラズ
マからの水素ラジカルが補助的な役割を果させることが
できる）、ａ−３ｉ： Ｈ膜の作成を促進していると考
えられる。Similarly, when using the apparatus shown in FIG. 1 and using hydrogen as the gas introduced into the discharge chamber 10 and silane gas or disilane gas as the gas introduced into the reaction chamber 20, an a-8i:H film could be formed on the surface of the substrate 16. Ta. In this reaction, silane or disilane is decomposed by Lyman series short wavelength light generated from LTE plasma (hydrogen radicals from LTE plasma can play an auxiliary role in this reaction), and a-3i: H It is thought that this promotes the formation of a film.
更にまた同じく第１図の装置を用いて、放電室１０の導
入ガスとして酸素を用い、酸素ラジカルおよびオゾン等
をＬＴＥプラズマを用いて作成し、酸素の短波長光又は
酸素ラジカルまたはオゾンを用いることによって基体表
面の有機物を水と二酸化炭素に分解し、基体表面の表面
クリーニングをすることができる。この場合は反応室の
導入ガスは必要なく、従って導入リング１３等は不用で
ある。Furthermore, using the same apparatus shown in FIG. 1, oxygen is used as the gas introduced into the discharge chamber 10, oxygen radicals, ozone, etc. are created using LTE plasma, and short wavelength light of oxygen or oxygen radicals or ozone is used. The organic matter on the surface of the substrate can be decomposed into water and carbon dioxide, and the surface of the substrate can be cleaned. In this case, no gas is required to be introduced into the reaction chamber, and therefore the introduction ring 13 and the like are unnecessary.
第８図は、ＬＴＥプラズマ３の放射光だけを利用する１
本発明の別の実施例を示す。放電室１０の導入ガスは、
矢印２１で示すように１反応室２０に至る前に排出され
、ＬＴＥプラズマ３内の活性種は基板１６の処理に参加
しない。Figure 8 shows 1 which uses only the synchrotron radiation of LTE plasma 3.
Another embodiment of the invention is shown. The gas introduced into the discharge chamber 10 is
As shown by arrow 21, the active species in LTE plasma 3 are discharged before reaching one reaction chamber 20 and do not participate in the processing of substrate 16.
第１１図は、その活性種の不参加を一層厳重にするもの
で、放電室１０と反応室２０の境に光学窓２２が設けら
れている。光ＣＶＤの場合は光学窓２２の曇りが問題に
なるが、光エッチング、光クリーニング等の処理では問
題を生じない。In FIG. 11, an optical window 22 is provided at the boundary between the discharge chamber 10 and the reaction chamber 20 to further prevent the active species from participating. In the case of optical CVD, clouding of the optical window 22 is a problem, but this does not occur in treatments such as optical etching and optical cleaning.
第１０図は、第７図に示したのと同種のマイクロ波電力
を使用する放電室１０と、反応室２ｏとの境に、ＬＴＥ
プラズマ３の活性種１７だけを通過させる遮光網１２１
，１２２を設けたものである。放電用ガスとしてＡｒを
用い、ＬＴＥプラズマ３ではゾ１１．５〜１１．７ｅＶ
のエネルギーをもつ、Ａｒの活性種を作り、これを反応
室１ｏに導入し、このエネルギーを使って反応ガス５ｉ
Ｈ４（活性化エネルギー約６０ｅＶ）、５ｉ２Ｈ，を解
離して基体１６上にアモルファスシリコン膜を堆積させ
るものである。FIG. 10 shows a discharge chamber 10 that uses the same type of microwave power as shown in FIG.
Shading net 121 that allows only active species 17 of plasma 3 to pass through
, 122 are provided. Ar is used as the discharge gas, and in LTE plasma 3 the voltage is 11.5 to 11.7 eV.
Active species of Ar with energy of
An amorphous silicon film is deposited on the substrate 16 by dissociating H4 (activation energy about 60 eV) and 5i2H.
また第１０図の装置ではＡｒのみならずＨｅの活性種を
用いても良い。また放電用ガスとしてＨ２を用いた場合
にはＬＴＥプラズマによりＨ２が解離して多量のＨＪＭ
子およびＨ，Ｈ，の励起種が生じる。このことはＨ２の
放電の色がＬＴＥプラズマでは「赤色」すなはちＨｇ子
の発光強度が非常に増大していることで明らかである。Furthermore, in the apparatus shown in FIG. 10, not only Ar but also He active species may be used. In addition, when H2 is used as the discharge gas, H2 is dissociated by LTE plasma and a large amount of HJM is generated.
excited species of H, H, and H, are produced. This is clear from the fact that the color of H2 discharge is "red" in LTE plasma, that is, the emission intensity of Hg particles is greatly increased.
このＨｇ子はＳ ｉ Ｈ４あるいは５ｉ２Ｈ，と反応し
て水素引き抜き反応を生じＳｉＨ４あるいは５１２ＨＧ
を分解する。この反応を利用すると基体温度が約５００
℃以下ではａ−８ｉ膜を、約５００℃以上ではポリクリ
スタルＳｉ膜を作成できる。This Hg particle reacts with SiH4 or 5i2H, causing a hydrogen abstraction reaction and producing SiH4 or 512HG.
Disassemble. Using this reaction, the substrate temperature can be reduced to approximately 500
At temperatures below .degree. C., an a-8i film can be formed, and at temperatures above about 500.degree. C., a polycrystalline Si film can be formed.
また、放電用ガスとしてＮＨ３を用いるとＬＴＥプラズ
マ内部ではＮ原子とＨｇ子が多数生じる。Further, when NH3 is used as the discharge gas, a large number of N atoms and Hg atoms are generated inside the LTE plasma.
このことはＬＴＥプラズマからの発光分光分析によりＮ
原子の発光７４５．２ｎｍおよび８２１．３ｎｍ、Ｎ原
子の発光バルマー系の輝度が非常に大きい２ことより明
らかである。This was confirmed by emission spectroscopic analysis from LTE plasma.
This is clear from the fact that the luminescence of atoms at 745.2 nm and 821.3 nm and the luminance of the Balmer system of N atoms are extremely large2.
このＮ原子およびＮ原子を利用すると、５ｔＨ４゜Ｓ
ｉＨＧと反応して基体表面にＳｉＮ膜を作成することが
できる。Using these N atoms and N atoms, 5tH4゜S
A SiN film can be created on the surface of the substrate by reacting with iHG.
また、放電用ガスとしてＮ２０を用いるとＬＴＥプラズ
マ内部では０原子とＮ原子が多数生じる。Further, when N20 is used as the discharge gas, many zero atoms and N atoms are generated inside the LTE plasma.
この活性種を利用するとＳｉＨ４あるいはＳｉ、Ｈ。When this active species is used, SiH4 or Si, H can be produced.
と反応して良品質のＳｉｏ２膜（オージェ電子分光では
Ｎ原子の含有を観測できない。）を作成できる。A high-quality Sio2 film (containing N atoms cannot be observed by Auger electron spectroscopy) can be created by reacting with the above.
第５図は、この発明の他の実施例を示したものである。FIG. 5 shows another embodiment of the invention.
この装置は、第１図の放電室を１０，１０′の２個にし
て１両者を単一の反応室の単一の被処理基体１６に対置
したものである。This apparatus has two discharge chambers 10 and 10' shown in FIG. 1, and one and both chambers are placed opposite to a single substrate 16 to be processed in a single reaction chamber.
そして放電室１０による前述の動作の上に、放電室１０
′で生成されたＬＴＥプラズマ３′からの放射光１７′
又は活性種１８′も電極３０’ を介して反応室２０に
導入され、それらが別途反応室２０に導かれた所定の反
応ガスと反応する。And on top of the above-described operation by the discharge chamber 10, the discharge chamber 10
Synchrotron radiation 17' from LTE plasma 3' generated in '
Alternatively, the active species 18' are also introduced into the reaction chamber 20 via the electrode 30', and react with a predetermined reaction gas that is separately introduced into the reaction chamber 20.
第５図の装置で、放電室１０の導入ガスとして水素を用
い、放電室１０’の導入ガスとして窒素を用い、反応室
２０の導入ガスとしてシランガスまたはジシランガスを
用いた場合にも基板１６の表面上にＳｉＮ膜が生成でき
た。この成膜メカニズムは明確ではないが、放電室１ｏ
で生成されるＬＴＥプラズマの短波長光（水素原子のラ
イマン系列）と、放電室１０′で生成されるＬＴＥプラ
ズマからの窒素ラジカルがシランと反応しく必要のとき
は放電室１０にで生成されるＬＥＴプラズマからの水素
ラジカルも反応に関与させることが出来る）ＳｉＮ膜が
作られたものと考えられる。In the apparatus shown in FIG. 5, the surface of the substrate 16 is also A SiN film was formed thereon. This film formation mechanism is not clear, but the discharge chamber 1o
The short wavelength light (Lyman series of hydrogen atoms) of the LTE plasma generated in the discharge chamber 10' reacts with the nitrogen radicals from the LTE plasma generated in the discharge chamber 10', and when necessary, the nitrogen radicals are generated in the discharge chamber 10. Hydrogen radicals from the LET plasma can also participate in the reaction) It is thought that a SiN film was produced.
以上の実施例は本発明の方法及び装置で如何なる処理が
可能であるかを例示したものであるが、可能な処理の種
類は上記にとゾまらない。Although the above embodiments are illustrative of what kind of processing is possible with the method and apparatus of the present invention, the types of possible processing are not limited to the above.
ところで本発明と同構造のグロー放電を利用する装置（
プラズマＣＶＤ装置）は、従来も数多く存在しており、
それら装置の中には印加する電力量を増せば、それだけ
で直ちに、本発明の装置と化すものは可成りの数にのぼ
る６
では、或装置を、それが本発明の装置であると特定しろ
るその特徴は何か、と言うと、それは、これ速達べて来
たようにプラズマの発光強度である。そして発光強度増
大の主因は前述の装置本体に付加される電源の電力容量
である６より詳しくは、第１には、放電用空間の体積に
対する、そして第２には放電用空間が被処理基体に向っ
て開く開口面積に対する、電源の投入可能電力の大きさ
である。By the way, a device using glow discharge having the same structure as the present invention (
Many plasma CVD devices (plasma CVD equipment) have existed in the past.
There are quite a number of devices that can instantly become devices of the present invention simply by increasing the amount of electric power applied to them.6 Now, let us identify a certain device as a device of the present invention. What is its characteristic, as we have already seen, is the intensity of the plasma's light emission. The main cause of the increase in luminescence intensity is the power capacity of the power supply added to the device main body as described above.6 More specifically, the first factor is the volume of the discharge space, and the second factor is that the discharge space is larger than the substrate to be processed. This is the amount of power that can be turned on by the power supply relative to the opening area that opens toward.
以下では、特にこの点に関して、話を具体的にして説明
する。In the following, this point will be explained in detail.
ＳｉＮ膜は半導体デバイスの被覆用に極めて重要な膜で
あるが、堅牢緻密でしがも弾力性（耐クラツク性）に富
み、段差被覆性にもすぐれたＳｉＮ膜は容易には得られ
ない。その成膜工程では被処理基板に損傷を生じないこ
とが要求されるので困難は倍加する。しかしデバイスが
微細化するに従って、良質の膜の必要性は一層痛感され
ている。Although a SiN film is an extremely important film for coating semiconductor devices, it is not easy to obtain a SiN film that is robust and dense, yet has high elasticity (cracking resistance) and excellent step coverage. The film forming process is required not to cause damage to the substrate to be processed, which increases the difficulty. However, as devices become smaller, the need for high-quality membranes is becoming more acutely felt.
従来のＳｉＮ膜は、ＳｉＮ材料をターゲットに置くスパ
ッタリングか、シランガス、窒素ガスにアンモニアガス
を加味した混合ガスのグロー放電中に被処理基板を曝す
プラズマＣＶＤ法で得られているが、両者とも到底前記
の要求を満足するものではない。前者の方法による膜は
段差被覆性が劣悪で、損傷が大きいし、後者の方法でえ
られる膜には、アンモニアの分解で生じたＨが多量に含
有されていて品質上問題がある。Conventional SiN films have been obtained by sputtering using a SiN material as a target, or by plasma CVD, which exposes the substrate to be processed during a glow discharge of a mixture of silane gas, nitrogen gas, and ammonia gas, but both methods are difficult to obtain. This does not satisfy the above requirements. The film obtained by the former method has poor step coverage and is severely damaged, and the film obtained by the latter method contains a large amount of H produced by decomposition of ammonia, which poses a quality problem.
本願の発明者らは、上記の問題を解決する実験研究の過
程で、先づ極めて良質のＳｉＮ膜が、無損傷で、前記し
た方法および装置でえられることを見出したが、しかし
、如何に良質の膜でも、成膜に時間がかったのでは、役
に立たない。半導体デバイス製造の工程に組み入れるた
めには、然るべき成膜速度が必要である。（因みに、前
記したプラズマＣＶＤ法では、ガス中にアンモニアを加
えることで、漸く成膜速度を実用的なものにしている。In the course of experimental research to solve the above problem, the inventors of the present application first discovered that an extremely high quality SiN film could be obtained without any damage using the method and apparatus described above. Even a high-quality film is useless if it takes a long time to form. In order to incorporate it into the process of semiconductor device manufacturing, a suitable film formation rate is required. (Incidentally, in the plasma CVD method described above, the film formation rate is finally made practical by adding ammonia to the gas.
）
本願の発明者は次のステップとして、具体的に、〔少く
ともＳｉＮ膜を実用的な速度で作成できる装置〕を目標
にした。) As the next step, the inventor of the present application specifically aimed at [an apparatus that can at least create a SiN film at a practical speed].
そして〔実用的な速度〕としては（１００人／ｍｉｎ以
上〕を採用した。この［１００人／ｍｉｎ以上］は、１
バツチの被膜工程が１時間以内であることを工業上利用
の最低条件と考え、この間に通常のパッシベーション膜
厚６０００Å以上が得られなくてはならないとして得ら
れたものである。We adopted (100 people/min or more) as the [practical speed].This [100 people/min or more] is 1
It was obtained because it was considered that the minimum requirement for industrial use is that the batch coating process takes less than one hour, and that a passivation film thickness of 6000 Å or more, which is the usual thickness, must be obtained during this time.
さて、第１図の装置で、ＳｉＮ膜を作成せんとして、放
電室に窒素ガスを導入してＬＴＥプラズマを作るとき、
特に重要なのはＬＴＥプラズマの放電室の構造・形状と
印加電力の関係である。放電室が主に円筒形の石英管で
できている場合には石英管の内径と電力の関係がＬＴＥ
プラズマ作成条件に大きな意味を持っている。ＬＴＥ放
電についての石英管の内径（横軸）と注入電力体積密度
（〔注入電力〕／〔放電用空間の体積〕）（縦軸）との
関係を第６図のＡ−Ｂ、Ｃ−８曲線に示す。Now, when using the apparatus shown in Figure 1 to create an SiN film and introduce nitrogen gas into the discharge chamber to create LTE plasma,
Particularly important is the relationship between the structure and shape of the LTE plasma discharge chamber and the applied power. If the discharge chamber is mainly made of a cylindrical quartz tube, the relationship between the inner diameter of the quartz tube and the power is LTE.
This has great significance for plasma creation conditions. The relationship between the inner diameter of the quartz tube (horizontal axis) and the injected power volume density ([injected power]/[volume of discharge space]) (vertical axis) for LTE discharge is shown in A-B and C-8 in Figure 6. Shown in the curve.
第６図のＣ−８曲線は、グロー状態から電力を加えて行
った場合にＬＴＥ状態化する注入電力体積密度を示して
おり、Ａ−Ｂ［ｔｌｉｌ＠はＬＴＥ状態から電力を下げ
て行った場合にグロー状態化する注入電力体積密度を示
している。両曲線で囲まれた範囲内では面状態が安定し
て存在できる。このためＬＴＥプラズマを用いた装置は
、電源の電力容量としてＣ−８曲線以上の能力を所有し
ているが。The C-8 curve in Figure 6 shows the volume density of the injected power that changes to the LTE state when power is added from the glow state. The figure shows the volume density of the injected power that will cause a glow state in the case of a glow state. A surface state can stably exist within the range surrounded by both curves. For this reason, devices using LTE plasma have a power capacity of a power supply that exceeds the C-8 curve.
あるいは何らかのＬＴＥプラズマ発生用トリガ機構およ
びＡ−８曲線以上の電源電力容量をもっことが必要であ
る。Alternatively, it is necessary to have some kind of trigger mechanism for LTE plasma generation and a power supply capacity greater than the A-8 curve.
ヒ入テリシス現象は内径約７■以下の石英管を用いた場
合に生れ、内径１国の石英管の場合を列にとると、グロ
ー状態から電力を次第に印加して行くとき８２０Ｗ／ａ
ｄではじめて放電はＬＴＥ状態化するが、ＬＴＥ状態か
ら次第に電力を下げるときは４８０Ｗ／ｃｄまで下げな
ければグロー状態化しない。この４８０Ｗ／ｃｄと８２
０Ｗ／ａｄとの間では面状態が安定して存在できる。The hysteresis phenomenon occurs when a quartz tube with an inner diameter of about 7 mm or less is used, and if we take the case of a quartz tube with an inner diameter of 1 mm, when power is gradually applied from the glow state, 820 W/a
The discharge reaches the LTE state for the first time at d, but when the power is gradually lowered from the LTE state, the glow state does not occur unless the power is lowered to 480 W/cd. This 480W/cd and 82
A stable surface state can exist between 0 W/ad.
（従ってこのため電力密度、圧力、ガス流量等々の同じ
条件下でグロー状態とＬＴＥ状態は比較でき、成膜に必
要な短波長光、たとえば窒素原子の２ｓ２２ｐ２３ｓ
（’Ｐ）状態から２ｇ”２ｐ” （’Ｓ）状態への遷移
による１２００ｍの光の発光強度を比較すると、グロー
状態に対してＬＴＥ状態では約２桁の発光強度増大とい
う格段の向上が認められる。またＬＴＥ状態では窒素分
子が多数解離して窒素原子となっており、窒素原子濃度
が顕著に増大することが明らかになっている。）
石英管の内径が７ａｍ以上になると、ヒステリシス領域
は見当らなくなり、注入電力体積密度も低下する。石英
管内径が１５ｄｌになると必要な注入電力体積密度は０
．２Ｗ／ａｄ弱の値となる。実験によれば、これらＡ−
Ｂ、Ｃ−８曲線が示す注入電力体積密度は、放電用ガス
の流量によっては殆んど変化しない。ガスの圧力はどう
影響するかというと実用範囲と考えられる３ ０ Ｑｍ
Ｔｏｒｒから５Ｔ ｏｒｒの間で高々３０％変化するの
みである。従って、注入電力体積密度は、ＬＴＥ放電を
特徴づける最良のｔａｌｌとなるものである。(For this reason, the glow state and the LTE state can be compared under the same conditions such as power density, pressure, gas flow rate, etc.).
Comparing the emission intensity of light at 1200 m due to the transition from the ('P) state to the 2g"2p"('S) state, it was found that the luminescence intensity increased by about two orders of magnitude in the LTE state compared to the glow state. It will be done. Furthermore, it has been revealed that in the LTE state, many nitrogen molecules dissociate into nitrogen atoms, and the concentration of nitrogen atoms increases significantly. ) When the inner diameter of the quartz tube becomes 7 am or more, the hysteresis region disappears and the volume density of the injected power decreases. When the inner diameter of the quartz tube becomes 15 dl, the required injection power volume density is 0.
．． The value is a little less than 2W/ad. According to experiments, these A-
The injected power volume density shown by curves B and C-8 hardly changes depending on the flow rate of the discharge gas. As for how the gas pressure affects it, it is 30 Qm, which is considered to be within the practical range.
It only changes by at most 30% between Torr and 5 Torr. Therefore, the injected power volume density is the best tall characteristic of LTE discharge.
現有のプラズマＣＶＤを見渡すとき、大きい放電用空間
をそなえる大型の装置でも注入電力体積密度が０．ＩＷ
／ａｄを超えるものは見当らない。When looking at existing plasma CVD systems, even large devices with a large discharge space have an injected power volume density of 0. IW
I can't find anything beyond /ad.
ＬＴＥ放電を本発明のように利用する考えが完全になか
ったためである。石英管が小径の場合では第６図に見ら
れるように、本発明の装置との注入電力の比は数１０倍
から数１００倍もにのぼる。This is because there was no idea of using LTE discharge as in the present invention. When the quartz tube has a small diameter, as shown in FIG. 6, the ratio of the injected power to the device of the present invention is several tens to hundreds of times higher.
一方、第６図のＤ−Ｅ曲線は、〔１００人／ｌｌｌ１ｎ
以上〕の成膜速度を確保するに必要な、注入電力面積密
度即ち〔注入電力〕／〔放電用空間が被処理基体に向っ
て開く開口面積〕のグラフ（実験値）を示したものであ
る。Ａ−Ｂ、Ｃ−Ｂ両曲線が石英管内径の増大で急速に
低下するのに対しＤ−Ｅ曲線は石英管の内径が変化して
もはシ一定で２Ｗ／ｄあたりの値を示す。On the other hand, the DE curve in FIG.
This is a graph (experimental value) of the injected power areal density, that is, [injected power]/[opening area where the discharge space opens toward the substrate to be processed] necessary to ensure the above film formation rate. . While both the A-B and C-B curves rapidly decrease as the inner diameter of the quartz tube increases, the DE curve remains constant even if the inner diameter of the quartz tube changes and shows a value around 2 W/d.
このＤ−Ｅ曲線は円筒形の石英放電管について測定され
たものであるが、実験によって、被処理基体上の膜堆積
速度などの処理速度は、ＬＴＥプラズマからの光を用い
た場合には［単位面積当りの放射光量］にほぼ比例する
ことが明らかとなっている。また活性種のみを使用する
場合には処理速度はおおよそ次のような関係式で関係付
けられる。This D-E curve was measured for a cylindrical quartz discharge tube, but experiments have shown that the processing speed, such as the film deposition rate on the substrate, is [ It has been found that the amount of radiation per unit area is approximately proportional to the amount of radiation per unit area. Furthermore, when only active species are used, the processing speed is roughly related by the following relational expression.
［処理速度］匡［活性種の供給量］ｏｃ［活性種の生成
量］・［活性種の流速］
［開口面積］
［開口面積］
は明らかである。［活性種の生成量］り［単位面積当り
の放射光量］の点については説明を補足する。[Processing speed] oc [Amount of active species supplied] oc [Amount of active species produced] [Flow rate of active species] [Opening area] [Opening area] A supplementary explanation will be provided regarding the [amount of active species produced] and [amount of emitted light per unit area].
たとえば一つの例として、窒素のＬＴＥプラズマからの
発光ではしばしば１２０．０ｇｍ （Ｎ ３ｓ’Ｐ→２
ｐ’Ｓ） 、１４９．３止（Ｎ３ｓ”Ｐ→２Ｐ”Ｄ）、
１７４．４ｎｏ＋ （Ｎ３ｓ”Ｐ−＋２ｐ２Ｐ）からの
発光強度が通常のＮ２の発光強度に比較して非常に強く
なる。プラズマ内部では主に電子の衝突によりほぼ一定
の確率で発光種が生じ、この発光種ごとに定まったほぼ
一定の確率で失活する。For example, as an example, the emission from a nitrogen LTE plasma is often 120.0 gm (N 3s'P→2
p'S), 149.3 stop (N3s"P→2P"D),
The emission intensity from 174.4no+ (N3s"P-+2p2P) becomes extremely strong compared to the emission intensity from normal N2. Inside the plasma, luminescent species are generated with an almost constant probability mainly due to electron collisions, and this Each luminescent species loses its activity with an almost constant probability.
かつ、窒素の場合はＬＴＥプラズマ内部に生じているＮ
原子の量は多く、Ｎ原子の発光強度がＮ８分子の発光強
度に比較して充分大きい（約１００倍）第３図、第４図
。このため［単位面積当りの放射光量］を測定すること
により開口面に存在する活性種（Ｎ［子）の濃度を知る
ことができる。すなわち［活性種の生成量］は［単位面
積当りの放射光量］とほぼ比例関係にある。In addition, in the case of nitrogen, the N generated inside the LTE plasma
The amount of atoms is large, and the emission intensity of N atoms is sufficiently large (approximately 100 times) compared to the emission intensity of N8 molecules in Figures 3 and 4. Therefore, by measuring the amount of emitted light per unit area, it is possible to know the concentration of active species (N) present on the aperture surface. That is, the [amount of active species produced] is approximately proportional to the [amount of emitted light per unit area].
水素のＬＴＥプラズマや他の気体のＬＴＥプラズマでも
同様である。The same applies to LTE plasma of hydrogen and LTE plasma of other gases.
このように光のみを用いる場合のみならず、活性種のみ
を用いる場合においても処理速度は単位面積当りの放射
光量により表わされそのグラフは第６図のＤ−Ｅ曲線と
同じである。In this way, not only when only light is used, but also when only active species are used, the processing speed is expressed by the amount of emitted light per unit area, and the graph is the same as the DE curve in FIG. 6.
放電用空間が円筒形以外の場合にも、〔放電用空間が被
処理基体に向って開く開口面積〕は、その字句通りに解
釈し、面積を計測して計算に用いることができる。なお
放電用空間６０と被処理基体１６の間に、メツシュ電極
３０が存在して部分的に遮ぎられたり、またはこの間に
余りに長い路が存在してその間で放射光や活性種が無用
のまま強く失なわれたりするときには、注入電力はそれ
に見合うだけ増加されるべきである。Even when the discharge space is not cylindrical, the [opening area of the discharge space toward the substrate to be processed] can be interpreted literally, and the area can be measured and used for calculation. Note that the mesh electrode 30 may be present between the discharge space 60 and the substrate 16 to be processed, and may be partially blocked, or an excessively long path may exist between the discharge space 60 and the substrate 16 to be processed, and the emitted light and active species may remain useless. If there is a strong loss, the injected power should be increased accordingly.
活性種のみを用いる場合には特に活性種の流速も問題と
なってくるが、通常の場合処理の均一性を保つ点から活
性種の流速はほぼ一意的に定まり、活性種の生成量のみ
考えれば良い。When only active species are used, the flow rate of active species becomes a problem, but in general, the flow rate of active species is almost uniquely determined in order to maintain uniformity of treatment, and only the amount of active species produced is considered. Good.
従来のプラズマＣＶＤ装置で注入電力面積密度が高い値
をとるのは、石英管の内径が５Ｇ以下の、むしろ小型の
装置である。大型の装置ではこの値は次第に低値をとり
、１／１０以下にもなってゆく。In conventional plasma CVD apparatuses, the injected power area density takes a high value in a rather small apparatus in which the inner diameter of the quartz tube is 5G or less. In large-sized devices, this value gradually decreases to less than 1/10.
従って、本発明の装置は、この注入電力面積密度を用い
てもこれを特徴づけることができる。Therefore, the device of the present invention can also be characterized using this injected power areal density.
上述は専らＳｉＮ膜の作成で本発明の詳細な説明したが
、本発明の装置は良質のＳｉＮ膜作成以外にもａ−Ｓ
Ｌ： Ｈ膜等々極めて多くの可能性を秘めている。Although the detailed explanation of the present invention has been given above exclusively with respect to the production of SiN films, the apparatus of the present invention can also be used for a-S
It has many possibilities such as L:H film.
以上実施例は、主として膜生成を中心に述べて来た。し
かし、活性種に例えば塩素系やフッ素系の気体を用いれ
ば表面をエツチングすることができる。さらに、例えば
酸素系の気体を用いて表面を酸化させたり窒素系の気体
を用いて表面を窒化させるなど表面の改質を行うことも
できる。これらの膜生成、エツチング、表面改質は無機
物の分野のみに留まらず有機物の分野にも勿論応用でき
る。The embodiments described above have mainly focused on film formation. However, if a chlorine-based or fluorine-based gas is used as the active species, the surface can be etched. Furthermore, the surface can also be modified, such as by oxidizing the surface using an oxygen-based gas or nitriding the surface using a nitrogen-based gas. These film formation, etching, and surface modification can of course be applied not only to the field of inorganic materials but also to the field of organic materials.
以上は何ら限定的に意味を持つものではなく多数の変形
が可能であることは云う迄もない。例えば、利用する活
性種と反応しにくいような熱陰極を用いるプラズマ発生
法が使用できるなど従来知られている各種の技術を組み
たて本発明の実施を行うことができる。Needless to say, the above does not have any limited meaning and many variations are possible. For example, the present invention can be implemented by combining various conventionally known techniques, such as a plasma generation method using a hot cathode that does not easily react with the active species used.
また、本発明の装置で、例えばメツシュ電極３０に印加
する荷電粒子阻止電圧を控え目にして、被処理基体上に
までグロー放電プラズマを拡大させるときは、衝撃損傷
は増すもの＼処理の速度を大きく増大させることが可能
である。Furthermore, in the apparatus of the present invention, if the charged particle blocking voltage applied to the mesh electrode 30 is moderated and the glow discharge plasma is expanded onto the substrate to be processed, impact damage will increase, but the processing speed will be increased. It is possible to increase it.
用途によってこの方法を使用し効果をあげることができ
る。This method can be used to great effect depending on the application.
これに対し現有のプラズマＣＶＤ装置を見渡すとき、注
入電力面積密度が０ 、２ Ｗ／ｃｍ２以上の装置を見
出すことができない。On the other hand, when looking at existing plasma CVD apparatuses, it is impossible to find any apparatus with an injected power areal density of 0.2 W/cm2 or more.
（へ）発明の効果
本発明は、表面処理に有用で純度の高い、強力な放射光
および活性種を安定して作成し、これを用いることで、
工業的に利用可能な種の充分な速度で、良質で有効的な
表面処理およびその装置を提供することができる。(f) Effects of the invention The present invention stably produces highly pure and powerful synchrotron radiation and active species useful for surface treatment, and by using this,
Good quality and effective surface treatments and equipment can be provided at sufficient rates of industrial availability.
第１図及び第５．７，８，９．１０図は、本願発明の実
施例の実施に使用する装置の正面断面図であり、第２図
は水素のＬＴＥ放電の注入電力と発光強度の関係を示す
図。第３図は、ＬＴＥプラズマからの真空紫外発光分光
分析結果を示したグラフであり、第４図はグロープラズ
マからの真空紫外発光分光分析結果を示したグラフであ
る。第６図はＳｉＮ膜作成時の注入電力体積密度と注入
電力面積密度のグラフである。
３ 、３−−−−−− Ｌ Ｔ Ｅプラズマ７−−−−
−−反応容器
１０．１０’−一−−放電室
１６−−−−−−被処理基体
’ １７−−−−−−放射光
１８−−−−−一活性種
２０−−−−−一反応室
３０．３０’−−−−メツシュ状電極
６０−−−−−一放電用空間
特許出願人 日電アネルバ株式会社
代理人弁理士 村 上 健 次
；主入電力 （イ玉荒す等イ亘）
ＦＩＧ、２
波長（ｎｍ）
ｙ皮 長 （ｎｍ）
ＦＩＧ、５
５芙管 白を釜
ＦＩＧ、６
ＦＩＧ、７
ＦＩＣｒ、９Figure 1 and Figures 5.7, 8, and 9.10 are front cross-sectional views of the apparatus used to implement the embodiments of the present invention, and Figure 2 shows the relationship between the injection power and emission intensity of hydrogen LTE discharge. Diagram showing relationships. FIG. 3 is a graph showing the results of vacuum ultraviolet emission spectroscopy from LTE plasma, and FIG. 4 is a graph showing the results of vacuum ultraviolet emission spectroscopy from glow plasma. FIG. 6 is a graph of the volume density of the injected power and the areal density of the injected power when forming the SiN film. 3, 3------ LTE plasma 7------
---Reaction vessel 10.10'-1--Discharge chamber 16-----Processed substrate' 17-----Radiation light 18--Active species 20-----1 Reaction chamber 30.30'----Mesh-shaped electrode 60-----Discharge space Patent applicant Kenji Murakami, Patent attorney for Nichiden Anelva Co., Ltd.; Main input power (Input power, etc.) FIG, 2 Wavelength (nm) y skin length (nm) FIG, 5 5 tube White pot FIG, 6 FIG, 7 FICr, 9
Claims (8)
ることによってＬＴＥ放電を発生せしめ、該ＬＴＥ放電
のプラズマによって生ずる放射光又は活性種を、該ＬＴ
Ｅ放電外に置かれた基体の表面に導くことによって、該
基体の表面に所定の処理を施すことを特徴とする表面処
理方法。(1) LTE discharge is generated by introducing a predetermined gas into a space to which alternating power is applied, and the synchrotron radiation or active species generated by the plasma of the LTE discharge is transferred to the LT
A surface treatment method characterized in that a predetermined treatment is performed on the surface of a substrate by guiding the E discharge to the surface of the substrate placed outside the substrate.
、誘導結合、容量結合または空胴共振によって前記電源
の交番電力が印加される放電用空間をそなえた放電室と
、 前記放電用空間に所定の気体を導入する手段と前記放電
用空間の放電プラズマに生じた放射光又は活性種を、前
記反応室の前記被処理基体の表面に導く照射手段とをそ
なえた表面処理装置において、 前記交番電力電源が前記放電用空間内にＬＴＥ放電を生
むに充分な大きさの電力容量をそなえるとともに、 〔前記交番電力電源の電力容量〕を〔前記放電用空間が
前記基体に向って開く開口面積〕で割った値が２Ｗ／ｃ
ｍ＾２以上であることを特徴とする表面処理装置。(2) a reaction chamber that accommodates a substrate to be processed, an alternating power source, and a discharge chamber provided with a discharge space to which alternating power of the power source is applied by inductive coupling, capacitive coupling, or cavity resonance; A surface treatment apparatus comprising means for introducing a predetermined gas into a space, and irradiation means for guiding synchrotron radiation or active species generated in discharge plasma in the discharge space to the surface of the substrate to be treated in the reaction chamber, The alternating power source has a power capacity large enough to generate LTE discharge in the discharge space, and [the power capacity of the alternating power source] has an opening in which the discharge space opens toward the base body. The value divided by [area] is 2W/c
A surface treatment device characterized in that the surface treatment is m^2 or more.
もしくは促進する荷電粒子調整手段をそなえたことを特
徴とする特許請求の範囲第２項記載の表面処理装置。(3) The irradiation means prohibits or limits transmission of charged particles;
3. The surface treatment apparatus according to claim 2, further comprising a charged particle adjusting means for accelerating the treatment.
要素とすることを特徴とする特許請求の範囲第３項記載
の表面処理装置。(4) The surface treatment apparatus according to claim 3, wherein the charged particle adjusting means includes a mesh electrode as a component.
とする特許請求の範囲第３項記載の表面処理装置。(5) The surface treatment apparatus according to claim 3, wherein the charged particle adjusting means comprises a magnetic field.
配備されていることを特徴とする特許請求の範囲第２ま
たは３項記載の表面処理装置。(6) The surface treatment apparatus according to claim 2 or 3, wherein a plurality of the discharge spaces are provided for a single substrate to be treated.
入される気体が、互にその種類を異にすることを特徴と
する特許請求の範囲第６項記載の表面処理装置。(7) The surface treatment apparatus according to claim 6, wherein the gas introduced into each of the plurality of discharge spaces is of a different type.
れる気体がＮ＿２を含み、他の一つに導入される気体が
Ｈ＿２を含み、前記反応室には前記放電用空間を径由し
ないでモノシラン、ジシランもしくはシラン誘導体また
はそれらの混合物を含む気体が導入されて、前記基体の
表面にＳｉＮ膜を堆積させることを特徴とする特許請求
の範囲第７項記載の表面処理装置。(8) The gas introduced into one of the plurality of discharge spaces includes N_2, the gas introduced into the other one contains H_2, and the reaction chamber has a diameter of the discharge space. 8. The surface treatment apparatus according to claim 7, wherein a gas containing monosilane, disilane, a silane derivative, or a mixture thereof is introduced without causing the substrate to deposit an SiN film on the surface of the substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6964686A JPS62227089A (en) | 1986-03-27 | 1986-03-27 | Method and device for treating surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6964686A JPS62227089A (en) | 1986-03-27 | 1986-03-27 | Method and device for treating surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62227089A true JPS62227089A (en) | 1987-10-06 |
| JPH0558072B2 JPH0558072B2 (en) | 1993-08-25 |
Family
ID=13408817
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6964686A Granted JPS62227089A (en) | 1986-03-27 | 1986-03-27 | Method and device for treating surface |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62227089A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63166971A (en) * | 1986-12-27 | 1988-07-11 | Anelva Corp | Method and apparatus for surface treatment |
| US4919783A (en) * | 1986-12-05 | 1990-04-24 | Anelva Corporation | Apparatus for processing an object by gas plasma with a reduced damage |
| JPH0488174A (en) * | 1990-08-01 | 1992-03-23 | Anelva Corp | Method and device for surface treatment |
| JPH11279758A (en) * | 1998-03-30 | 1999-10-12 | Shincron:Kk | Formation of metallic compound thin film and film forming device |
| JPH11279757A (en) * | 1998-03-27 | 1999-10-12 | Shincron:Kk | Method and device for forming thin film of composite metal compound |
| JP2001011605A (en) * | 1999-06-30 | 2001-01-16 | Shincron:Kk | Method and equipment for forming compound thin film of multicomponent metal |
| JP2003080059A (en) * | 2001-09-10 | 2003-03-18 | Yaskawa Electric Corp | Method and apparatus for treating material using reactive gas |
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|---|---|---|---|---|
| US4232057A (en) * | 1979-03-01 | 1980-11-04 | International Business Machines Corporation | Semiconductor plasma oxidation |
| JPS55141729A (en) * | 1979-04-21 | 1980-11-05 | Nippon Telegr & Teleph Corp <Ntt> | Ion-shower device |
| JPS5779621A (en) * | 1980-11-05 | 1982-05-18 | Mitsubishi Electric Corp | Plasma processing device |
| JPS58193726A (en) * | 1982-05-08 | 1983-11-11 | Ushio Inc | Vapor deposition method |
| JPS59145530A (en) * | 1983-12-23 | 1984-08-21 | Hitachi Ltd | Plasma processing device |
| JPS60202928A (en) * | 1984-03-28 | 1985-10-14 | Toshiba Corp | Optical pumping reaction device |
| JPS6191377A (en) * | 1984-10-12 | 1986-05-09 | Anelva Corp | Surface treating device |
| JPS61222534A (en) * | 1985-03-28 | 1986-10-03 | Anelva Corp | Method and apparatus for surface treatment |
-
1986
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4232057A (en) * | 1979-03-01 | 1980-11-04 | International Business Machines Corporation | Semiconductor plasma oxidation |
| JPS55141729A (en) * | 1979-04-21 | 1980-11-05 | Nippon Telegr & Teleph Corp <Ntt> | Ion-shower device |
| JPS5779621A (en) * | 1980-11-05 | 1982-05-18 | Mitsubishi Electric Corp | Plasma processing device |
| JPS58193726A (en) * | 1982-05-08 | 1983-11-11 | Ushio Inc | Vapor deposition method |
| JPS59145530A (en) * | 1983-12-23 | 1984-08-21 | Hitachi Ltd | Plasma processing device |
| JPS60202928A (en) * | 1984-03-28 | 1985-10-14 | Toshiba Corp | Optical pumping reaction device |
| JPS6191377A (en) * | 1984-10-12 | 1986-05-09 | Anelva Corp | Surface treating device |
| JPS61222534A (en) * | 1985-03-28 | 1986-10-03 | Anelva Corp | Method and apparatus for surface treatment |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4919783A (en) * | 1986-12-05 | 1990-04-24 | Anelva Corporation | Apparatus for processing an object by gas plasma with a reduced damage |
| JPS63166971A (en) * | 1986-12-27 | 1988-07-11 | Anelva Corp | Method and apparatus for surface treatment |
| JPH0488174A (en) * | 1990-08-01 | 1992-03-23 | Anelva Corp | Method and device for surface treatment |
| JPH11279757A (en) * | 1998-03-27 | 1999-10-12 | Shincron:Kk | Method and device for forming thin film of composite metal compound |
| JPH11279758A (en) * | 1998-03-30 | 1999-10-12 | Shincron:Kk | Formation of metallic compound thin film and film forming device |
| JP2001011605A (en) * | 1999-06-30 | 2001-01-16 | Shincron:Kk | Method and equipment for forming compound thin film of multicomponent metal |
| JP2003080059A (en) * | 2001-09-10 | 2003-03-18 | Yaskawa Electric Corp | Method and apparatus for treating material using reactive gas |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0558072B2 (en) | 1993-08-25 |
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