JPS62229827A - Formation of deposited film - Google Patents
Formation of deposited filmInfo
- Publication number
- JPS62229827A JPS62229827A JP7226986A JP7226986A JPS62229827A JP S62229827 A JPS62229827 A JP S62229827A JP 7226986 A JP7226986 A JP 7226986A JP 7226986 A JP7226986 A JP 7226986A JP S62229827 A JPS62229827 A JP S62229827A
- Authority
- JP
- Japan
- Prior art keywords
- deposited film
- gaseous
- film forming
- forming method
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 239000002243 precursor Substances 0.000 claims abstract description 35
- 239000000758 substrate Substances 0.000 claims abstract description 35
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 30
- 150000002367 halogens Chemical class 0.000 claims abstract description 30
- 239000000126 substance Substances 0.000 claims abstract description 28
- 239000007800 oxidant agent Substances 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 230000005281 excited state Effects 0.000 claims abstract description 10
- 239000000470 constituent Substances 0.000 claims abstract description 7
- 230000000737 periodic effect Effects 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims description 34
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- -1 linear silane compound Chemical class 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910000078 germane Inorganic materials 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims 1
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 claims 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims 1
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 claims 1
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- 229910021480 group 4 element Inorganic materials 0.000 claims 1
- 229910052743 krypton Inorganic materials 0.000 claims 1
- 229910052754 neon Inorganic materials 0.000 claims 1
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 claims 1
- 229910052704 radon Inorganic materials 0.000 claims 1
- 229910000083 tin tetrahydride Inorganic materials 0.000 claims 1
- 229910052724 xenon Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 3
- 230000014759 maintenance of location Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 125
- 239000007789 gas Substances 0.000 description 52
- 239000010410 layer Substances 0.000 description 44
- 239000004065 semiconductor Substances 0.000 description 16
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 229910021417 amorphous silicon Inorganic materials 0.000 description 8
- 238000000151 deposition Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 239000013626 chemical specie Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910001120 nichrome Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910004473 SiHF3 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- ATVLVRVBCRICNU-UHFFFAOYSA-N trifluorosilicon Chemical compound F[Si](F)F ATVLVRVBCRICNU-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、機能性膜、殊に半導体デバイス、電子写真用
の感光デバイス、光学的画像入力装置用の光入力センサ
ーデバイス等の電子デバイスの用途に有用な機能性堆積
膜の形成法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to functional films, particularly for electronic devices such as semiconductor devices, photosensitive devices for electrophotography, and optical input sensor devices for optical image input devices. This invention relates to a method for forming a functional deposited film useful for various applications.
従来、半導体膜、絶縁膜、光導電膜、磁性膜或いは金属
膜等の非晶質乃至多結品質の機能性膜は、所望される物
理的特性や用途等の観点から個々に適した成膜方法が採
用されている。Conventionally, functional films of amorphous or polycrystalline quality, such as semiconductor films, insulating films, photoconductive films, magnetic films, or metal films, have been formed using films that are individually suited from the viewpoint of desired physical properties and applications. method has been adopted.
例えば、必要に応じて、水素原子（Ｈ）やハロゲン原子
（Ｘ）等の補償剤で不対電子が補償された非晶質や多結
品質の非単結晶シリコン（以後ｒＮＯＮ−３ｔ （Ｈ、
Ｘ）Ｊと略記し、結晶質シリコンを示す場合にはｒｐｏ
Ｑｙ−３ｉ（Ｈ，Ｘ）Ｊ と記す）膜等のシリコン堆積
Ｓ （尚、俗に言う微結晶シリコンは、Ａ−Ｓｔ（Ｈ、
Ｘ）の範噂にはいることは断るまでもない）の形成には
、真空蒸着法、プラズマＣＶＤ法、熱ＣＶＤ法、反応ス
パッタリング法、イオンブレーティング法、光ＣＶＤ法
などが試みられており、一般的には、プラズマＣＶＤ法
が広く用いられ、企業化されている。For example, if necessary, amorphous or polycrystalline non-single crystal silicon (rNON-3t (H,
X) Abbreviated as J, rpo to indicate crystalline silicon
Qy-3i (H,
It goes without saying that X) falls into the category of X), and so on. Generally, the plasma CVD method is widely used and commercialized.
面乍ら゛、従来から一般化されているプラズマＣＶＤ法
によるシリコン系堆ａ膜の形成に於ての反応プロセスは
、従来のＣＶＤ法に比較してかなり複雑であり、その反
応機構も不明な点が少なくない、Ｘ、その堆ａ膜の形成
パラメータも多く（例えば、基体温度、導入ガスの流量
と比、形成時の圧力、高周波電力、電極構造、反応容器
の構造、排気の速度、プラズマ発生方式など）これらの
多くのパラメータの組み釡せによるため１時にはプラズ
マが不安定な状態になリ、形成された堆積膜に著しい悪
影響を与えることが少なくなかった。そのうえ、装置特
有のパラメータを装置ごとに選定しなければならず、し
たがって製造条件を一般化することがむずかしいという
のが実状であった。Of course, the reaction process for forming silicon-based deposits by the conventionally popular plasma CVD method is considerably more complex than that of the conventional CVD method, and the reaction mechanism is still unclear. There are quite a few points, Due to the combination of these many parameters (generation method, etc.), the plasma becomes unstable at one point, which often has a significant adverse effect on the deposited film formed. Moreover, it is necessary to select device-specific parameters for each device, making it difficult to generalize manufacturing conditions.
他方、シリコン系堆積膜として電気的、光学的特性を各
用途毎に十分に満足させ得るものを発現させるためには
、現状ではプラズマＣＶＤ法によって形成することが最
良とされている。On the other hand, in order to develop a silicon-based deposited film that satisfies the electrical and optical characteristics for each application, it is currently considered best to form it by plasma CVD.
面乍ら、シリコン系堆積膜の応用用途によっては、大面
積化、膜厚均一性、膜品質の均一性を十分満足させて再
現性のある量産化を図らねばならないため、プラズマＣ
ＶＤ法によるシリコン系堆積膜の形成においては、量産
装置に多大な設備投資が必要となり、またその量産の為
の管理項目も複雑になり、管理許容幅も狭く。However, depending on the application of the silicon-based deposited film, it is necessary to fully satisfy the requirements of large area, uniform film thickness, and uniform film quality for reproducible mass production.
In forming a silicon-based deposited film by the VD method, a large amount of capital investment is required for mass production equipment, and the management items for mass production are also complicated, and the tolerance for management is narrow.
装置の調整も微妙であることから、これらのことが、今
後改善すべき問題点として指摘されている。Since the adjustment of the device is also delicate, these have been pointed out as problems that should be improved in the future.
又、プラズマＣＶＤ法の場合には、成膜される基体の配
されている成膜空間に於いて高周波或いはマイクロ波等
によって直接プラズマを生成している為に、発生する電
子や多数のイオン種が成膜過程に於いて膜にダメージを
与え膜品質の低下、膜品質の不均一化の要因となってい
る。In addition, in the case of plasma CVD method, since plasma is directly generated by high frequency waves or microwaves in the film forming space where the substrate to be film is placed, the generated electrons and many ion species are This causes damage to the film during the film formation process, causing deterioration of film quality and non-uniformity of film quality.
この点の改良として提案されている方法には、間接プラ
ズマＣＶＤ法がある。An indirect plasma CVD method has been proposed as an improvement in this respect.
該間接プラズマＣＶＤ法は、主堆積膜形成物質を成膜空
間から離れた上流位置にてマイクロ波等によって主堆１
１ｉ膜形成物質の活性種を生成し、該活性種を成膜空間
まで輸送することで。In the indirect plasma CVD method, the main deposited film-forming substance is heated by microwaves or the like at an upstream position away from the film-forming space.
1i by generating active species of the film forming substance and transporting the active species to the film forming space.
成膜に使用出来る様に計ったものである。It was designed so that it could be used for film formation.
面乍ら、斯かるプラズマＣＶＤ法でも、活性種の輸送が
必須であることから、成膜に有効な活性種の寿命が長く
なければならず、自ずと使用するガス種が制限され、種
々の堆ｉｎ膜が得られないこと、及びプラズマを発生す
る為に多大なエネルギーを要すること、成膜に有効な化
学種の生成及び量が簡便な管理下に木質的に、置かれな
いこと等の問題点は成績している。However, since the plasma CVD method also requires the transport of active species, the lifetime of the active species effective in film formation must be long, which naturally limits the types of gases that can be used, and Problems include the inability to obtain an in-film, the need for a large amount of energy to generate plasma, and the fact that the generation and amount of chemical species effective for film formation cannot be easily controlled. The score is good.
プラズマＣＶＤ法に対して、光ＣＶＤ法は、成膜時に膜
品質にダメージを与えるイオン種や電子が発生しないと
いう点で有利ではあるが、光源にそれ程多くの種類がな
いこと、光源の波長も紫外に片寄っていること、工業化
する場合には大型の光源とその電源を要すること、光源
からの光をｒ＆膜空間に導入する窓が成膜時に被膜され
て仕舞う為に成膜中に光量の低下、ひいては、光源から
の光が成膜空間に入射されなくなるという問題点がある
。The photo-CVD method has an advantage over the plasma CVD method in that it does not generate ion species or electrons that damage film quality during film formation, but there are not as many types of light sources, and the wavelength of the light source is also limited. There is a bias towards ultraviolet light, a large light source and its power source are required for industrialization, and the window that introduces the light from the light source into the r&film space is covered with a film during film formation, so it is difficult to reduce the amount of light during film formation. There is a problem in that the light from the light source decreases, and as a result, light from the light source no longer enters the film forming space.
更に、プラズマＣＶＤ法におけるイオンダメージの問題
や、光ＣＶＤ法における光入射窓のくもりといった問題
のない新規な堆積膜形成法として堆積膜形成用の気体状
原料物質と該原料物質に酸化作用をする性質を有する気
体状ハロゲン系酸化剤とを、化学反応させ、堆積膜を形
成する方法が注目されているが、該形成方法は、価電子
制御剤によるドーピングに対して、一層の改善が望まれ
ている。Furthermore, as a new method for forming a deposited film that does not have the problems of ion damage in plasma CVD and clouding of the light incident window in photoCVD, the method uses an oxidizing effect on the gaseous raw material for forming the deposited film and the raw material. A method in which a deposited film is formed by chemically reacting with a gaseous halogen-based oxidizing agent having properties has been attracting attention. ing.
上述の如く、シリコン系堆積膜の形成に於ては、解決さ
れるべき点は、まだまだ残っており、その実用可能な特
性、均一性を維持させながら低コストな装置で省エネル
ギー化を計って量産化できる形成方法を開発することが
切望されている。殊に、ｐ型、ｎ型、ｉ型の伝導型の半
導体膜をドーピング率を高めながら成膜する場合に、上
記要求の度合は高い、これ等のことは、他の機能性膜１
例えば半導体性の、窒化シリコン膜、炭化シリコン膜、
酸化シリコン膜等のシリコン系の膜やゲルマニウム系の
膜のドーピング率を高める場合に於ても各々同様の解決
されるべき問題として挙げることが出来る。As mentioned above, there are still many issues to be solved regarding the formation of silicon-based deposited films, and it is important to mass-produce them using low-cost equipment and saving energy while maintaining practical properties and uniformity. There is a strong desire to develop a forming method that can In particular, when forming p-type, n-type, or i-type conductivity semiconductor films while increasing the doping rate, the above requirements are high.
For example, semiconductor silicon nitride film, silicon carbide film,
Similar problems to be solved can also be raised when increasing the doping rate of silicon-based films such as silicon oxide films or germanium-based films.
本発明の目的は、上述した堆積膜形成法の欠点を除去す
ると同時に、従来の形成方法によらない新規な堆積膜形
成法を提供するものである。An object of the present invention is to eliminate the drawbacks of the above-mentioned method for forming a deposited film, and at the same time to provide a new method for forming a deposited film that does not rely on conventional methods.
本発明の他の目的は、省エネルギー化を計ると同時に膜
品質の管理が容易で大面積に亘って均−特性の価電子制
御剤がドーピングされた半導体性の堆積膜が得られる堆
積膜形成法を提供するものである。Another object of the present invention is to provide a method for forming a deposited film that saves energy, allows easy control of film quality, and provides a semiconductor deposited film doped with a valence electron control agent having uniform characteristics over a large area. It provides:
本発明の更に別の目的は、生産性、量産性に優れ、高品
質で電気的、光学的、半導体的等の物理特性に優れた膜
が簡便に得られる堆積膜形成法を提供することでもある
。Still another object of the present invention is to provide a method for forming a deposited film that is highly productive and mass-producible, and can easily produce a film with high quality and excellent physical properties such as electrical, optical, and semiconductor properties. be.
上記目的を達成する本発明の堆積膜形成法は、塩８１膜
形成用の気体状にし得るＡａＨｂＸｃ（但°し、Ａは周
期律表第■族元素、Ｘはハロゲン元素、ａ、ｂ、ｃは０
でない整数）なる構造の原料物質と該原料物質に酸化作
用をする性質を有する気体状ハロゲン系酸化剤と、価電
子制御剤となる成分を構成要素として含む気体状物質（
Ｄ）と、を反応空間内に導入して接触させ、前記反応空
間内圧と前記導入ガス滞留時間の積が０．Ｏ１〜１００
（Ｔｏｒｒ＠５ｅｃ）なる範囲において°励起状態の
前駆体を含む複数の前駆体を生成し、これらの前駆体の
内少なくとも１つの前駆体を堆積膜構成要素の供給源と
して成膜空間内にある基体上に堆積膜を形成することに
ある。The method for forming a deposited film of the present invention which achieves the above object is to use AaHbXc, which can be made into a gas for forming a salt 81 film (where A is an element from group Ⅰ of the periodic table, X is a halogen element, a, b, c is 0
A gaseous substance containing as constituent elements a raw material having a structure of a raw material (not an integer), a gaseous halogen-based oxidizing agent having the property of oxidizing the raw material, and a component serving as a valence electron control agent (
D) is introduced into the reaction space and brought into contact, and the product of the reaction space internal pressure and the introduced gas residence time is 0. O1~100
A plurality of precursors including precursors in an excited state are generated in a range of (Torr @ 5ec), and at least one of these precursors is used as a source of a deposited film component in a deposition space. The purpose is to form a deposited film on a substrate.
上記の大発明の堆積膜形成法によれば、省エネルギー化
と同時に大面積化、膜厚均一性、 ＪＩＩ品買０均一性
を十分満足させて管理の簡素化と量産化を図り、量産装
置に多大な設備投資も必要とせず、またその量産の為の
管理項目も明確になり、管理許容幅も広く、装置の調整
も簡単になる。According to the deposited film forming method of the above-mentioned great invention, it is possible to save energy, increase the area, fully satisfy the film thickness uniformity, JII product quality uniformity, simplify management and mass production, and make it suitable for mass production equipment. It does not require large capital investment, the control items for mass production become clear, the control tolerance is wide, and equipment adjustment becomes easy.
本発明の堆積膜形成法に於いて、使用される堆積膜形成
用の気体状原料物質及び価電子制御剤となる成分を構成
要素として含む気体状物質（Ｄ）は、気体状ハロゲン系
酸化剤と化学反応を起こすものであり、目的とする堆積
膜の種類、特性、用途等によって所望に従って適宜選択
される。In the method for forming a deposited film of the present invention, the gaseous substance (D) containing as a component a gaseous raw material for forming a deposited film and a component serving as a valence electron control agent is a gaseous halogen-based oxidizing agent. It is selected as desired depending on the type, characteristics, intended use, etc. of the desired deposited film.
堆積膜形成用の原料物質とハロゲン系酸化剤が通常状態
の場合に液体又は固体である場合には、Ａｒ、Ｈｅ、Ｈ
２等のキャリアーガスを使用し、必要に応じては熱も加
えながらバブリングを行なって気体状態として反応空間
に導入する。When the raw material for forming a deposited film and the halogen-based oxidizing agent are liquid or solid under normal conditions, Ar, He, H
Using a carrier gas such as No. 2, bubbling is performed while adding heat if necessary, and the gas is introduced into the reaction space in a gaseous state.
また物質（Ｄ）が、通常状態の場合に液体又は固体であ
る場合には、Ａｒ、Ｈｅ、Ｈ２等のキャリアーガスを使
用し、必要に応じては熱も加えながらバブリングを行な
って気体状態として反応空間に導入する。In addition, if the substance (D) is liquid or solid in its normal state, use a carrier gas such as Ar, He, H2, etc., and perform bubbling while adding heat if necessary to convert it into a gaseous state. introduced into the reaction space.
この際、上記気体状物質（Ｄ）から生成した活性種及び
、気体状原料物質及び気体状ハロゲン系酸化剤の分圧及
び混合比は、キャリアーガスの波量あるいは、堆積膜形
成用の原料物質及び気体状ハロゲン系酸化剤の蒸気圧を
調節することにより設定される。At this time, the active species generated from the gaseous substance (D), the partial pressure and mixing ratio of the gaseous raw material and the gaseous halogen-based oxidizing agent are determined by the wave amount of the carrier gas or the raw material for forming the deposited film. and is set by adjusting the vapor pressure of the gaseous halogen-based oxidant.
本発明に於いて使用される堆積膜形成用の原料物質とし
ては、例えば、半導体性のシリコン系堆積膜やゲルマニ
ウム系堆積膜等のテトラヘドラル系の堆１１を膜を得る
のであれば、直鎖状、及び分岐状の鎖状ハロゲン化シラ
ン化合物、環状ハロゲン化シラン化合物、鎖状ハロゲン
化ゲルマニウム化合物等が有効なものとして挙げること
が出来る。As the raw material for forming the deposited film used in the present invention, for example, if a tetrahedral deposit 11 such as a semiconducting silicon-based deposited film or a germanium-based deposited film is to be obtained, linear Effective examples include branched chain halogenated silane compounds, cyclic halogenated silane compounds, and chain halogenated germanium compounds.
具体的には、直鎖状ハロゲン化シラン化合物としてはＳ
ｉ Ｈ２Ｆ ２およびＳｉＨＦ３．分岐状鎖状シラン
化合物としては、５ｉＨ３ＳｉＦ（Ｓ １Ｈ３）Ｓ ｔ
Ｈ２ｓｉＨ３、鎖状ゲルマン化合物としては、ＧｅＨＢ
ｒ３およびＧｅＨＢｒ３が挙げられる。Specifically, as the linear halogenated silane compound, S
i H2F 2 and SiHF3. As the branched chain silane compound, 5iH3SiF(S 1H3)S t
H2siH3, as a chain germane compound, GeHB
r3 and GeHBr3.
勿論、これ等のシリコン系化合物及びゲルマニウム系化
合物は１種のみならず２種以上混合して使用することも
出来る。Of course, these silicon-based compounds and germanium-based compounds can be used not only alone, but also as a mixture of two or more.
大発明に於いて使用されるハロゲン系酸化剤は、反応空
間内に導入される際気体状とされ、同時に反応空間内に
導入される堆積膜形成用の気体状原料物質に化学的接触
だけで効果的に酸化作用をする性質を有するもので、Ｆ
２゜Ｃｌ３．Ｂｒ２．’Ｉｚ等のハロゲンガス、発生期
状態の弗素、塩素、臭素等が有効なものとして挙げるこ
とが出来る。The halogen-based oxidizing agent used in the great invention is in a gaseous state when introduced into the reaction space, and at the same time it is brought into chemical contact with the gaseous raw material for forming a deposited film, which is introduced into the reaction space. It has the property of effectively oxidizing, and F
2°Cl3. Br2. Effective examples include halogen gas such as Iz, nascent fluorine, chlorine, and bromine.
これ等のハロゲン系酸化剤は気体状で前記の物質（Ｄ）
の活性種及び前記の堆積膜形成用の原料物質の気体と共
に所望の流量と供給圧を与えられて反応空間内に導入さ
れて、前記物質（Ｄ）の活性種及び前記原料物質と混合
衝突し化学反応することで、前記物質（Ｄ）の活性種及
び、前記原料物質に酸化作用をして励起状態の前駆体を
含む複数種の前駆体を効率的に生成する。生成される励
起状態の前駆体及び他の前駆体は、少なくともそのいず
れか１つが形成される堆積、膜の構成要素の供給源とし
て働く。These halogen-based oxidizing agents are gaseous and the above-mentioned substance (D)
The active species of the substance (D) and the gas of the raw material for forming the deposited film are introduced into the reaction space under a desired flow rate and supply pressure, and mix and collide with the active species of the substance (D) and the raw material. Through the chemical reaction, the active species of the substance (D) and the raw material are oxidized to efficiently generate a plurality of types of precursors including excited state precursors. The excited state precursors and other precursors produced serve as a source for the components of the deposited film of which at least one is formed.
生成される前駆体は分解して又は反応して別の励起状態
の前駆体又は別の励起状態にある前駆体になって、或い
は必要に応じてエネルギーを放出はするがそのままの形
態でｒ＆膜室空間配設された基体表面に触れることで三
次元ネットワーク構造の堆積膜が作成される。The generated precursor decomposes or reacts to become a precursor in another excited state or a precursor in another excited state, or it releases energy as needed but remains in the r & film. By touching the surface of the substrate placed in the chamber space, a deposited film with a three-dimensional network structure is created.
励起されるエネルギーレベルとしては、前記励起状態の
前駆体がより低いエネルギーレベルにエネルギー遷移す
る。又は別の化学種に変化する過程に於いて発光を伴う
エネルギーレベルであることが好ましい。斯かるエネル
ギーの遷移に発光を伴なう励起状態の前駆体を含め活性
化された前駆体が形成されることで本発明の堆積膜形成
プロセスは、より効率良く、より省エネルギーで進行し
、膜全面に亘って均一でより良好な物理特性を有する堆
積膜が形成される。As the energy level is excited, the excited state precursor undergoes an energy transition to a lower energy level. Alternatively, the energy level is preferably one that accompanies luminescence in the process of changing into another chemical species. By forming activated precursors including excited state precursors that are accompanied by light emission due to such energy transition, the deposited film forming process of the present invention proceeds more efficiently and with lower energy consumption. A deposited film is formed that is uniform over the entire surface and has better physical properties.
本発明に於いて使用される物質（Ｄ）としぞは、シリコ
ン系半導体膜及びゲルマニウム系半導体膜の場１合には
、ｐ型の価電子制御剤、所謂ｐ型不純物として働く周期
率表節■族Ａの元素、例えばＢ、ＡＭ、Ｇａ、Ｉｎ、Ｔ
９．等を含む化合物、及びｎ型の価電子制御剤、所謂ｎ
型不純物として働く周期率表第Ｖ族Ａの元素１例えばＮ
、Ｐ、Ａｓ、Ｓｂ、Ｂｉ等を含む化合物を挙げることが
出来る。In the case of silicon-based semiconductor films and germanium-based semiconductor films, the substance (D) used in the present invention is a periodic table member that acts as a p-type valence electron control agent, a so-called p-type impurity. ■ Group A elements, such as B, AM, Ga, In, T
9. and n-type valence electron control agents, so-called n
Element 1 of group V A of the periodic table that acts as a type impurity, e.g. N
, P, As, Sb, Bi, and the like.
具体的には、ＮＨ３，ＨＮ３．Ｎ２Ｈ５Ｎ３゜Ｎ２Ｈ４
，ＮＨ４Ｎ・３ 、 Ｐ Ｈ３、Ｐ ２ Ｈ４ｒＡｓＨ
３、Ｓ ｂＨ３、Ｂ ｉＨ３、Ｂ２Ｈ６。Specifically, NH3, HN3. N2H5N3゜N2H4
, NH4N・3, P H3, P 2 H4rAsH
3, S bH3, B iH3, B2H6.
Ｂ４Ｈ１０，Ｂ５Ｈ９，１３５１（１１，Ｂ６Ｈ１ｏ。B4H10, B5H9, 1351 (11, B6H1o.
Ｂ ｓ ＨＩ３ 、ＡＭ （ＣＨ３） ３ 、Ａ
文 （Ｃ２Ｈｓ）３、Ｇａ （ＣＨ３）３ 、Ｉ ｎ
（ＣＨ３）３等を有効なものとして挙げることが出来る
。B s HI3 , AM (CH3) 3 , A
Sentence (C2Hs)3, Ga (CH3)3, I n
(CH3)3 etc. can be mentioned as effective ones.
と記物質（Ｄ）の気体を反応空間内に導入するには、独
立した複数のガス供給源より導入することができる。In order to introduce the gas of the substance (D) into the reaction space, it can be introduced from a plurality of independent gas supply sources.
本発明に於いては、堆積膜形成プロセスが円滑に進行し
、高品質で所望の物理特性を有する膜が形成される可〈
、成膜因子としての堆積膜形成用の、原料物質、物質（
Ｄ）の活性種及びハロゲン系酸化剤の種類と組み合せ、
これ等の混合比、混合時の圧力、流量、成膜空間内圧。In the present invention, the deposited film formation process proceeds smoothly, and a film having high quality and desired physical properties can be formed.
, raw materials, substances (
D) types and combinations of active species and halogen-based oxidizing agents;
These mixing ratios, pressure during mixing, flow rate, and internal pressure in the film forming space.
ガスの波型、成膜温度（基体温度及び雰囲気温度）が所
望に応じて適宜選択される。これ等の成膜因子は有機的
に関連し、単独で決定されるものではなく相互関連の下
に夫々に応じて決定される０本発明に於いて、反応空間
に導入される堆積膜形成用の気体状原料物質と気体状ハ
ロゲン系酸化剤との暖の割合は、上記成膜因子の中間座
する成膜因子との関係に於いて適宜所望に従って決めら
れるが、導入流量比で、好ましくは、ｌ／２０〜１００
／１が適当であり、より好ましくはｌ／１０〜５０／ｌ
とされるのが望ましい。The waveform of the gas and the film forming temperature (substrate temperature and ambient temperature) are appropriately selected as desired. These film formation factors are organically related and are not determined independently but are determined in accordance with each other. The ratio of heating between the gaseous raw material and the gaseous halogen-based oxidizing agent is determined as desired in relation to the film-forming factor located in the middle of the above-mentioned film-forming factors, but is preferably determined by the introduction flow rate ratio. , l/20~100
/1 is suitable, more preferably l/10 to 50/l
It is desirable that this is done.
又気体状物質（Ｄ）の反応空間への導入量の割合は、前
記気体状原料物質の種類及び作成される堆積膜の所望さ
れる半導体特性に応じて適宜所望に従って設定されるが
、前記気体状原料物質に対して、好ましくは１／１００
００００〜ｌ／１，０．より好ましくは１／１００００
０〜ｌ／２０．最適には１／１０００００−１１５０と
されるのが望ましい。Further, the ratio of the amount of the gaseous substance (D) introduced into the reaction space is appropriately set as desired depending on the type of the gaseous raw material and the desired semiconductor properties of the deposited film to be created. Preferably 1/100 of the raw material
0000~l/1,0. More preferably 1/10000
0~l/20. The optimum value is 1/100000-1150.
反応空間に導入される際の混合時の圧力としては前記気
体状原料物質及び気体状物質（Ｄ）の活性種と前記気体
状ハロゲン系酸化剤との接触を確率的により高める為に
は、より高い方が良いが、反応性を考慮して適宜所望に
応じて最適値を決定するのが良い。前記混合時の圧力と
しては、上記の様にして決められるが、夫々の導入時の
圧力として、好ましくはｌＸｌ０−７気圧〜１０気圧、
より好ましくはＩ Ｘ １０−６気圧〜３気圧とされる
のが望ましい。The pressure at the time of mixing when introduced into the reaction space is set to be more than Although a higher value is better, it is better to take reactivity into consideration and determine the optimum value as desired. The pressure at the time of mixing is determined as described above, but the pressure at the time of each introduction is preferably lXl0-7 atm to 10 atm,
More preferably, it is I x 10-6 atm to 3 atm.
成膜空間の内圧力は、成膜空間が反応空間と開放的に連
続している場合には、堆積膜形成用の気体状原料物質と
前記物質（Ｄ）と気体状ハロゲン系酸化剤との反応空間
での導入圧及び流量との関連に於いて、例えば差動排気
或いは、大型の排気装置の使用等の工夫を加えて調整す
ることが出来る。When the film-forming space is open and continuous with the reaction space, the internal pressure of the film-forming space is determined by the pressure of the gaseous raw material for forming the deposited film, the substance (D), and the gaseous halogen-based oxidizing agent. In relation to the introduction pressure and flow rate in the reaction space, adjustments can be made by, for example, using differential exhaust or a large exhaust device.
或いは１反応室間と成膜空間の連結部のコンダクタンス
が小さい場合には、成膜空間に適当な排気装置を設け、
該装置の排気量を制御することで成膜空間の圧力を調整
することが出来る。Alternatively, if the conductance at the connection between one reaction chamber and the film-forming space is small, install an appropriate exhaust device in the film-forming space,
By controlling the exhaust volume of the device, the pressure in the film forming space can be adjusted.
又、反応空間と成膜空間が一体的になっていて、反応位
置と成膜位置が空間的に異なるだけの場合には、前述の
様に差動排気するか或いは、排気能力の充分ある大型の
排気装置を設けてやれば良い。In addition, if the reaction space and film-forming space are integrated and the reaction position and film-forming position are only spatially different, use differential pumping as described above or use a large-scale pump with sufficient exhaust capacity. It is best to install an exhaust system.
前記気体状原料物質と前記気体状ハロゲン系酸化剤との
接触により励起状態の前駆体（Ｅ）が生成し反応空間内
に配設された基体に堆積し順次、膜を形成する。堆積を
効率良く行ない良質の膜を得るためには成膜因子を好適
に管理することが必要条件である０本発明の堆積膜形成
法に於いては生成した前駆体が基体に輸送され基体から
適当な熱エネルギーを受は取って膜形成が行なわれるた
め、この機構の各段階を好適に制御することが必要であ
る。前駆体を効率良く、生成するためには前記原料物質
と前記酸化剤との接触する確率を多くすることが望まし
く、言い換えると反応空間内圧を高めることに相当する
。しかしながら、内圧を高め過ぎても目的とする反応が
起らなかったり、逆に反応が進行し過ぎて目的の前駆体
が堆積に寄与しないで他の前駆体に変化してしまうとい
う弊害が生じる。従って反応空間内圧は前駆体を生成す
るために好適な範囲を選ぶ必要がある。A precursor (E) in an excited state is generated by the contact between the gaseous raw material and the gaseous halogen-based oxidizing agent, and is deposited on the substrate disposed in the reaction space to sequentially form a film. In order to perform deposition efficiently and obtain a high-quality film, it is necessary to appropriately control the film-forming factors. In the deposited film forming method of the present invention, the generated precursor is transported to the substrate, Since film formation takes place by receiving and receiving appropriate thermal energy, it is necessary to appropriately control each step of this mechanism. In order to efficiently generate a precursor, it is desirable to increase the probability of contact between the raw material and the oxidizing agent, which corresponds to increasing the internal pressure of the reaction space. However, if the internal pressure is increased too much, the desired reaction may not occur, or conversely, the reaction may proceed too much, causing the desired precursor to change into another precursor without contributing to the deposition. Therefore, it is necessary to select a suitable range for the internal pressure of the reaction space to produce the precursor.
一方生成された前駆体はその寿命が限られたものであり
反応空間内にとどまる時間が前駆体の寿命よりも長いと
前駆体は成膜に有効に使われなくなる。すなわち導入さ
れるガスの滞留時間は前駆体の寿命にかんがみて好適に
制御されるべきものである。さらには接触確率と滞留時
間とは相補的な関係をもち、例えば内圧が低く接触確率
が低い時は前駆体の寿命が長くなり滞留時間を大きくす
ることができる。したがって、内圧と滞留時間の積を成
膜の因子として管理することが本発明の堆積法では必須
である。On the other hand, the generated precursor has a limited lifetime, and if the time spent in the reaction space is longer than the lifetime of the precursor, the precursor will not be used effectively for film formation. That is, the residence time of the introduced gas should be suitably controlled in view of the lifetime of the precursor. Furthermore, contact probability and residence time have a complementary relationship; for example, when the internal pressure is low and the contact probability is low, the lifetime of the precursor becomes longer and the residence time can be increased. Therefore, it is essential in the deposition method of the present invention to control the product of internal pressure and residence time as a factor in film formation.
具体的には（内圧）×（滞留時間）は０．０１〜１００
（Ｔｏｒｒ＊５ｅｃ）にあることが好ましく、より好ま
しくは０．１−１０（Ｔｏｒｒ・ｓｅｃ）であるように
決められる。Specifically, (internal pressure) x (residence time) is 0.01 to 100
(Torr*5 ec), more preferably 0.1-10 (Torr·sec).
ガスの流星に就いては１反応室間への前記堆積ＩＩ２形
成用の原料物質、物質（Ｄ）の活性種及びハロゲン系酸
化剤の導入の際にこれ等が均一に効率良く混合され、前
記前駆体（Ｅ）が効率的に生成され且つ成膜が支障なく
適切になされる様に、ガス導入口と基体とガス排気口と
の幾何学的配置を考慮して設計される必要がある。Regarding the gas meteor, when introducing the raw material for forming the deposit II2, the active species of substance (D), and the halogen-based oxidizing agent into one reaction chamber, these are uniformly and efficiently mixed, and the above-mentioned In order to efficiently generate the precursor (E) and to properly form a film without any trouble, it is necessary to take into account the geometrical arrangement of the gas inlet, the substrate, and the gas outlet when designing.
この幾何学的な配置の好適な例の１つが第１図に示され
る。One preferred example of this geometry is shown in FIG.
成膜時の基体温度（Ｔｓ）としては、使用されるガス種
及び形成される堆積膜の種類と要求される特性に応じて
１個々に適宜所望に従って設定されるが、非晶質の膜を
得る場合には好ましくは室温から４５０℃、より好まし
くは５０〜４００℃とされるのが望ましい、殊に半導体
性や光導電性等の特性がより良好なシリコン系堆積膜を
形成する場合には、基体温度（Ｔｓ）は７０〜３５０℃
とされるのが望ましい、また、多結晶の膜を得る場合に
は、好ましくは２００〜６５０℃、より好ましくは３０
０〜６００°Ｃとされるのが望ましい。The substrate temperature (Ts) during film formation is set as desired depending on the type of gas used, the type of deposited film to be formed, and the required characteristics. When forming a silicon-based deposited film with better properties such as semiconductor properties and photoconductivity, the temperature is preferably room temperature to 450°C, more preferably 50 to 400°C. , the substrate temperature (Ts) is 70 to 350°C
In addition, when obtaining a polycrystalline film, the temperature is preferably 200 to 650°C, more preferably 30°C.
The temperature is preferably 0 to 600°C.
成膜空間の雰囲気温度（Ｔａｔ）としては、生成される
前記前駆体（Ｅ）及び前記前駆体（Ｆ）が成膜に不適当
な化学種に変化せず、且つ効率良く前記前駆体（Ｅ）が
生成される様に基体温度（Ｔｓ）との関連で適宜所望に
応じて決められる。The atmospheric temperature (Tat) in the film forming space is set such that the precursor (E) and the precursor (F) to be produced do not change into chemical species unsuitable for film formation, and the precursor (E) is efficiently heated. ) is determined as desired in relation to the substrate temperature (Ts).
本発明に於いて使用される基体としては、形成される堆
積膜の用途に応じて適宜所望に応じて選択されるのであ
れば導電性でも電気絶縁性であっても良い、導電性基体
としては、例えば、Ｎ ｉ、 Ｃｒ ｔステアＬ／ス、
Ａｆｌ、Ｃｒ。The substrate used in the present invention may be electrically conductive or electrically insulating, as long as it is selected as desired depending on the use of the deposited film to be formed. , for example, N i, Cr t steer L/S,
Afl, Cr.
Ｍｏ、Ａｕ、Ｉｒ、Ｎｂ、Ｔａ、Ｖ、Ｔｉ。Mo, Au, Ir, Nb, Ta, V, Ti.
Ｐｔ、Ｐｄ等の金属又はこれ等の合金が挙げられる。Examples include metals such as Pt and Pd, and alloys thereof.
電気絶縁性基体としては、ポリエステル。Polyester is used as the electrically insulating substrate.
ポリエチレン、ポリカーボネート、セルローズアセテー
ト、ポリプロピレン、ポリ塩化ビニル、ポリ塩化ビニリ
デン、ポリスチレン、ポリアミド等の合成樹脂のフィル
ム又はシート。Films or sheets of synthetic resins such as polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, etc.
ガラス、セラミック、紙等が通常使用される。Glass, ceramic, paper, etc. are commonly used.
これらの電気絶縁性基体は、好適には少なくともその一
方の表面が導電処理され、該導電処理された表面側に他
の層が設けられるのが望ましい。Preferably, at least one surface of these electrically insulating substrates is subjected to a conductive treatment, and another layer is preferably provided on the conductive treated surface side.
例えば、ガラスであれば、その表面がＮｉＣｒ、Ａｉ、
Ｃｒ、Ｍｏ、Ａｕ、Ｉｒ’、Ｎｂ。For example, if it is glass, its surface may be NiCr, Al,
Cr, Mo, Au, Ir', Nb.
Ｔａ、Ｖ、Ｔｉ、Ｐｔ、Ｐｄ、Ｉｎ２Ｏ３＋５ｎ０２
、 ＩＴＯ（Ｉ ｎ２０３＋５ｎ０２）等の薄膜を設け
る事によって導電処理され、或いはポリエステルフィル
ム等の合成樹脂フィルムであれば、ＮｉＣｒ、Ａｉ、Ａ
ｇ、Ｐｂ、Ｚｎ。Ta, V, Ti, Pt, Pd, In2O3+5n02
, ITO (In203 + 5n02), etc., or if it is a synthetic resin film such as polyester film, NiCr, Ai, A
g, Pb, Zn.
Ｎｉ 、Ａｕ、Ｃｒ、Ｍｏ、Ｉｒ、Ｎｂ、Ｔａ。Ni, Au, Cr, Mo, Ir, Nb, Ta.
Ｖ、Ｔｉ、Ｐｔ等の金属で真空蒸着、電子ビーム蒸着、
スパッタリング等で処理し、Ｘは前記金属でラミネート
処理して、その表面が導電処理される。支持体の形状と
しては、円筒状。Vacuum evaporation, electron beam evaporation, etc. of metals such as V, Ti, and Pt.
Processing is performed by sputtering or the like, and X is laminated with the metal described above, and its surface is subjected to conductive processing. The shape of the support is cylindrical.
ベルト状、板状等、任意の形状とし得、所望によって、
その形状が決定される。It can be of any shape, such as a belt or a plate, depending on your needs.
Its shape is determined.
基体は、基体と膜との密着性及び反応性を考慮して上記
の中より選ぶのが好ましい、更に両者の熱膨張の差が大
きいと膜中に多量の歪が生じ、良品質の膜が得られない
場合があるので、両者の熱膨張の差が近接している基体
を選択して使用するのが好ましい。It is preferable to select the substrate from among the above in consideration of the adhesion and reactivity between the substrate and the film. Furthermore, if the difference in thermal expansion between the two is large, a large amount of distortion will occur in the film, making it difficult to obtain a good quality film. Therefore, it is preferable to select and use a substrate whose thermal expansion difference is close to that of the two substrates.
又、基体の表面状態は、膜の構造（配向）や錐状組織の
発生に直接関係するので、所望の特性が得られる様な膜
構造と膜組織となる様に基体の表面を処理するのが望ま
しい。In addition, the surface condition of the substrate is directly related to the structure (orientation) of the film and the occurrence of cone-shaped structures, so it is important to treat the surface of the substrate so that it has a film structure and structure that provides the desired properties. is desirable.
第１図は本発明の堆積膜形゛成性を具現するに好適な装
置の１例を示すものである。FIG. 1 shows an example of an apparatus suitable for realizing the deposited film forming property of the present invention.
第１図に示す堆積膜形成装置は、装置本体、排気系及び
ガス供給系の３つに大別される。The deposited film forming apparatus shown in FIG. 1 is roughly divided into three parts: an apparatus main body, an exhaust system, and a gas supply system.
装置本体には、反応空間及び成膜空間が設けられている
。The apparatus main body is provided with a reaction space and a film forming space.
１０１〜１０８は夫々、成膜する際に使用されるガスが
充填されているボンベ、１０１ａ〜１０８ａは夫々ガス
供給パイプ、１０１ｂ〜１０８ｂは夫々各ボンベからの
ガスの流量調整用のマスフローコントロー９−．１ｏｌ
ｃ〜１０８ｃはそれぞれガス圧力計、１０１ｄ〜１０８
ｄ及び１０１ｅ−１０８ｅは夫々バルブ、１ｏ１ｆ〜１
０８ｆは夫々対応するガスボンベ内の圧力を示す圧力計
である。101 to 108 are cylinders filled with gases used for film formation, 101a to 108a are gas supply pipes, and 101b to 108b are mass flow controllers 9- for adjusting the flow rate of gas from each cylinder. ．． 1ol
c to 108c are gas pressure gauges, 101d to 108, respectively.
d and 101e-108e are valves, 1o1f to 1
08f is a pressure gauge that indicates the pressure inside the corresponding gas cylinder.
１２０は真空チャンバーであって、上部にガス導入用の
配管が設けられ、配管の下流に反応空間が形成される構
造を有し、且つ該配管のガス排出口に対向して、基体１
１８が配置される様に基体ホールダー１１２が設けられ
た成膜空間が形成される構造を有する。ガス導入用の配
管は、三重同心円配置構造となっており、中よりガスボ
ンベ１０１，１０２よりのガスが導入される第１のガス
導入管１０９、ガスボンベ１０３〜１０５よりのガスが
導入される第２のガス導入管１１０、及びガスボンベ１
０６〜１０８よりのガスが導入される第３のガス導入管
１１１を有する。Reference numeral 120 denotes a vacuum chamber, which has a structure in which a pipe for introducing gas is provided at the upper part and a reaction space is formed downstream of the pipe.
It has a structure in which a film forming space is formed in which a substrate holder 112 is provided such that a substrate holder 18 is disposed. The gas introduction pipes have a triple concentric arrangement structure, with a first gas introduction pipe 109 into which gas from gas cylinders 101 and 102 is introduced, and a second gas introduction pipe into which gas from gas cylinders 103 to 105 is introduced. gas introduction pipe 110 and gas cylinder 1
It has a third gas introduction pipe 111 into which gases from 06 to 108 are introduced.
各ガス導入管の反応空間へのガス排出には、その位置が
内側の管になる程基体の表面位置より遠い位置に配され
る設計とされている。即ち、外側の管になる程その内側
にある管を包囲する様に夫々のガス導入管が配設されて
いる。Each gas introduction tube is designed to discharge gas into the reaction space so that the inner tube is located further away from the surface of the substrate. That is, the gas introduction pipes are arranged so that the outer pipes surround the inner pipes.
各導入管への管ボンベからのガスの供給は。Gas is supplied from a tube cylinder to each inlet tube.
ガス供給パイプライン１２３〜１２５によって夫々なさ
れる。are provided by gas supply pipelines 123-125, respectively.
各ガス導入管、各ガス供給パイプライン及び真空チャン
バー１２０は、メイン真空パルプ１１９を介して不図示
の真空排気装置により真空排気される。Each gas introduction pipe, each gas supply pipeline, and the vacuum chamber 120 are evacuated by a vacuum evacuation device (not shown) via the main vacuum pulp 119.
基体１１８は基体ホルダー１１２を上下に移動させるこ
とによって各ガス導入管の位置より適宜所望の距離に設
置される。The base body 118 is installed at a desired distance from the position of each gas introduction pipe by moving the base body holder 112 up and down.
本発明の場合、この基体とガス導入管のガス排出口の距
離は、形成される堆積膜の種類及びその所望される特性
、ガス流量、真空チャンバーの内圧等を考慮して適切な
状態になる様に決められるが、好ましくは、数ｍｍ〜２
０ｃｍ、より好ましくは、５ｍｍ〜１５ｃｍ程度とされ
るのが望ましい。In the case of the present invention, the distance between the substrate and the gas outlet of the gas inlet pipe is determined appropriately by taking into consideration the type of deposited film to be formed, its desired characteristics, gas flow rate, internal pressure of the vacuum chamber, etc. It can be determined as desired, but preferably several mm to 2
It is desirable that the length be 0 cm, more preferably about 5 mm to 15 cm.
１１３は、基体１１８を成膜時に適当な温度に加熱した
り、或いは、成膜前に基体１１８を予備加熱したり、更
には、成膜後、膜を７ニールする為に加熱する基体加熱
ヒータである。Reference numeral 113 denotes a substrate heater that heats the substrate 118 to an appropriate temperature during film formation, preheats the substrate 118 before film formation, and further heats the film for 7 anneals after film formation. It is.
基体加熱ヒータ１１３は、導線１１４により電源１１５
により電力が供給される。The base heater 113 is connected to a power source 115 by a conductor 114.
Power is supplied by
１１６は、基体温度（Ｔｓ）の温度を測定する為の熱電
対で温度表示装置１１７に電気的に接続されている。116 is a thermocouple for measuring the substrate temperature (Ts), and is electrically connected to the temperature display device 117.
以下、実施例に従って、本発明を具体的に説明する。Hereinafter, the present invention will be specifically explained according to Examples.
実施例１
第１図に示す成膜装置を用いて１次の様にし本発明の方
法による堆積膜を作成した。Example 1 A deposited film according to the method of the present invention was produced in the following manner using the film forming apparatus shown in FIG.
リンを高濃度にドープした非晶質シリコン層堆積にたあ
ってボンベ１０１に充填されているＳ ｉ Ｈ２Ｆ ２
ガスを流量２０ｓｅｃｍでガス導入管１０９より、ポン
ベ１０４に充填されているＢ２Ｈ６ガス（Ｈ２ガスで１
％に稀釈されている）を流量２ｓｅｃｍでガス導入管１
１０より、ボンベ１０６に充填されているＦ２ガスを流
量２０ ｓ ｅ ｃ ｍ、ポンベ１０７に充填されてい
るＨｅガスを流量１８０ ｓ ｅ ｃ ｍでガス導入管
１１１より真空チャンバー１０２内に導入した。S i H2F 2 is filled in the cylinder 101 while depositing an amorphous silicon layer doped with phosphorus at a high concentration.
B2H6 gas (H2 gas filled in 104
%) at a flow rate of 2 sec.
10, the F2 gas filled in the cylinder 106 was introduced into the vacuum chamber 102 at a flow rate of 20 sec m, and the He gas filled in the cylinder 107 was introduced into the vacuum chamber 102 at a flow rate of 180 sec m.
このとき、真空チャン／＜−１２０内の圧力を真空パル
プ１１９の開閉度を調整して３００ｍＴｏｒｒにした。At this time, the pressure in the vacuum chamber /<-120 was adjusted to 300 mTorr by adjusting the opening/closing degree of the vacuum pulp 119.
以上のような方法で第２図に示す薄膜トランジスター（
以下ＴＰＴという）を作製した。Using the method described above, the thin film transistor shown in Figure 2 (
(hereinafter referred to as TPT) was produced.
前記ＴＦＴは、コーニング社製７０５９ガラス２３４、
非晶質シリコン層（第１層厚さ７０００人）２３３、リ
ンを高濃度にドープした非晶質シリコン層（第２層厚さ
５００人）２３２、酸化シリコン層（第３層厚さ１００
０人）２３１、Ａ文電極２２９から構成されている。Ｔ
ＰＴに必要な半導体層および絶縁層はドープ層と同様の
方法で作製された。The TFT is made of Corning 7059 glass 234,
Amorphous silicon layer (first layer thickness: 7,000 layers) 233, amorphous silicon layer doped with phosphorus at a high concentration (second layer thickness: 500 layers) 232, silicon oxide layer (third layer thickness: 100 layers)
0 person) 231, A sentence electrode 229. T
The semiconductor and insulating layers required for PT were fabricated in the same manner as the doped layers.
本実施例のＴＰＴは、１０％改善されたｏｎ。The TPT of this example was improved by 10% on.
ｏｆｆ比を示した。The off ratio is shown.
実施例２
第１図に示す堆積膜形成装置を用いて、本発明の堆積膜
形成法に従って第３図に示す太陽電池を作製した。Example 2 Using the deposited film forming apparatus shown in FIG. 1, a solar cell shown in FIG. 3 was produced according to the deposited film forming method of the present invention.
前記太陽電池は、透明電極を蒸着したコーニング７０５
９ガラス３００．Ｐ型の半導体層（第１層厚さ５００人
）３０１．ｉ型の半導体層（第２Ｍ厚さｌｐｍ）３０２
、ｎｅの半導体層（第３層厚さ５００人）３０３、Ａ文
電極から構成されている。The solar cell is made of Corning 705 with a transparent electrode deposited on it.
9 glass 300. P-type semiconductor layer (first layer thickness: 500 layers) 301. I-type semiconductor layer (2nd M thickness lpm) 302
, ne semiconductor layer (third layer thickness: 500 layers) 303, and an A-type electrode.
第１層および第３層形成時に、価電子制御剤Ｂ２Ｈ６ま
たはＰＨ３を堆積膜形成室１２０へ導入しＰ型またはｎ
型の第１層および第２層を形成した。他の条件は、第２
表に示す条件で太陽電池に必要な半導体層を形成した。At the time of forming the first layer and the third layer, a valence electron control agent B2H6 or PH3 is introduced into the deposited film forming chamber 120.
The first and second layers of the mold were formed. The other conditions are the second
A semiconductor layer necessary for a solar cell was formed under the conditions shown in the table.
こうして得られた太陽電池は、これまでの太陽電池より
１０％向上した変換効率を示した。The solar cell thus obtained showed a conversion efficiency that was 10% higher than that of conventional solar cells.
実施例３
第１図の堆積膜形成装置を利用して、本発明の堆積膜形
成法に従って第 図に示す電子写真用像形成部材を作成
した。Example 3 Using the deposited film forming apparatus shown in FIG. 1, an electrophotographic image forming member shown in FIG. 1 was produced according to the deposited film forming method of the present invention.
第４図に示す前記電子写真用像形成部材は、Ａｎ基体４
００．電荷注入阻止層（第１層、Ｂをドープした非晶質
シリコン層０．５ｇｍ）４０１、感光層（第２層非晶質
シリコン層１８ルｍ）４０２、表面保護層（第３層非晶
質炭化シリコン層０．５ＪＬｍ）４０３から構成される
装る。The electrophotographic image forming member shown in FIG.
00. Charge injection blocking layer (first layer, B-doped amorphous silicon layer 0.5 gm) 401, photosensitive layer (second layer amorphous silicon layer 18 gm) 402, surface protection layer (third layer amorphous silicon layer) A silicon carbide layer (0.5JLm) 403 of high quality silicon carbide is used.
本実施例においては、ホウ素を高濃度にドープした非晶
質シリコン層の堆積にあたって、価電子制御剤Ｂ２Ｈ６
を堆積室１２０に導入して、ホウ素を高濃度にドープし
た非晶質シリコン層を堆積した。In this example, when depositing an amorphous silicon layer doped with boron at a high concentration, a valence electron control agent B2H6 was used.
was introduced into the deposition chamber 120 to deposit an amorphous silicon layer doped with boron at a high concentration.
他の条件は第３表に示す条件で電子写真用像形成部材を
作製した。Electrophotographic image forming members were produced under other conditions shown in Table 3.
このようにして作製した電子写真用像形成部材は、５０
％以上改善された帯電能を示した。The electrophotographic imaging member thus produced had a
The charging ability was improved by more than %.
第１表
第２表
第３表
〔効果〕
以上の詳細な説明及び各実施例より１本発明の堆積膜形
成法によれば、省エネルギー化を計ると同時に膜品質の
管理が容易で大面積に亘ってドーピング効率の良い均一
物理特性の堆積膜が得られる。又、生産性、量産性に優
れ、高品質で電気的、光学的、半導体的等の物理特性に
優れた膜を簡便に得ることが出来る。Table 1 Table 2 Table 3 [Effects] Based on the above detailed explanation and each example, the deposited film forming method of the present invention saves energy, makes it easy to control the film quality, and can be applied to a large area. As a result, a deposited film with uniform physical properties and good doping efficiency can be obtained. Furthermore, it is possible to easily obtain a film with excellent productivity and mass production, and with high quality and excellent physical properties such as electrical, optical, and semiconductor properties.
第１図は本発明の実施例に用いた成膜装置の模式的概略
図である。第２図は本発明の実施例に用いた薄膜トラン
ジスターの模式的概略図である。第３図は、本発明の実
施例に用いた太陽電池の模式的概略図である。第４図は
、本発明の実施例で用いた、電子写真用像形成部材の模
式的概略図である。
１０１ Ｎ１０８−−−−−−−−−−−−−−−−ガ
スボンベ、１０１ ａ 〜１０８ ａ−−−−−−−−
−−ガスの導入管、１０１ｂ〜１０８ ｂ−−−−−−
マスフロメーター、１０１ ｃ −１０８ｃ−−−−−
−−−−−−−ガス圧力計。
ｆｏｌｄ−１０８ｄ及び
１０１ ｅ −１０８ｅ−−−−−−−−−−−−−−
−−バルブ、１０１ ｆ ＮＩ Ｏ８ｆ −−−−一−
−−−−−−−−−−圧力計、１０９ 、 ｌ ｌ Ｏ
、ｌ ｌ １−−−−−−−−ガス導入管。
ｔ ｌ ２−−−−−一−−−−−−−−−−−−−−
−−基体ホルダー。
１１３−−−−＝−−−−−−−−−−一基体加熱用ヒ
ーター、１１６−−−−−−−−−−基体温度モニター
用熱電対、１１８−−−−−−−−−−−−−−−−−
一−−−−−−−−−−−−基体。
１１９−−−−−−−−−−−−−−一−−−−−真空
排気バルブ。
１２３〜ｌ ２５−−−−−−ガス供本会パイプライン
。
２２８−−一−−−−−−−−−−−−−Ａ文電極（ソ
ース）、２２９−一−−−−−−−−−−−−−−Ａ
ｌ電極（ゲート）、２３０−−−−−−一−−−−−−
−Ａ ｕ Ｗ極（ドレイン）、２３１−−−−−−−−
−−−−−−−−−−一−−−−−−−−−絶縁層、２
３２−−−−−−−−−−−−−−−一−−−−−−−
−−−ｎ十型層、２３３−−−−−−−−−−−−−−
−−−−−−−−−−−−−− ｉ型層、２３４−−一
−−−−−−−−−−−−−−−−−−−−−ガラス基
板、３００−−−−−一−−−−−−−−透明電極をコ
ーティングしたガラス基板、
３０１−−−−−−−−−−−−−−−−一−−−−−
−−−−−−Ｐ型層、３０２−−−−−−−−−−−−
−−−−−−−−−−−−一−−−感光層、３０３−−
−一−−−−−−−−−−−−−−−−−−−−−−−
−ｎ型層、３０４−−−−−−−−−−−一−−−−−
−−−−−−−−−Ａ文電極。
４００−−−−−−−−−−−−−−一−−−−−−−
−−−−Ａ Ｍ基板、４０１−−−−−−−−−−−−
−−−−−一−−電荷注入阻止層。
４０２−−−−、−−一−−−−−−−−−−−−−−
−−−−−一感光層、４０３−−一−−−−−−−−−
−−−−−−−−−−−一表面保護層。FIG. 1 is a schematic diagram of a film forming apparatus used in an example of the present invention. FIG. 2 is a schematic diagram of a thin film transistor used in an example of the present invention. FIG. 3 is a schematic diagram of a solar cell used in an example of the present invention. FIG. 4 is a schematic diagram of an electrophotographic image forming member used in an example of the present invention. 101 N108------------ Gas cylinder, 101 a ~ 108 a------------
--Gas introduction pipe, 101b to 108b------
Mass flow meter, 101c-108c------
-----------Gas pressure gauge. fold-108d and 101e-108e---------------
--Valve, 101f NI O8f -----1-
-----------Pressure gauge, 109, l l O
, l l 1---------Gas introduction tube. t l 2-------1----------------
--Substrate holder. 113-----=-----------Heater for heating one substrate, 116--------Thermocouple for monitoring substrate temperature, 118----------- −−−−−−−−
----------Base. 119------------------------ Vacuum exhaust valve. 123~l 25------Gas Supply Main Association Pipeline. 228--1----------A sentence electrode (source), 229-1---------------------A
l electrode (gate), 230-------1------
-A u W pole (drain), 231---------
−−−−−−−−−−−−−−−−−−−1 −−−−−−−−Insulating layer, 2
32----------
---n 10-type layer, 233------------------------
−−−−−−−−−−−−−− I-type layer, 234−−−−−−−−−−−−−−−−−− Glass substrate, 300−−− −−1−−−−−−−Glass substrate coated with transparent electrode, 301−−−−−−−−−−−−−−−−−1−−−−−
--------P-type layer, 302---------
------------1----Photosensitive layer, 303--
−1−−−−−−−−−−−−−−−−−−−−−−−
-n-type layer, 304--------1------
----------A sentence electrode. 400--------------1----------
-----AM board, 401------------
----Charge injection blocking layer. 402----,--1-------------
------One photosensitive layer, 403--One---------
−−−−−−−−−−−One surface protective layer.
Claims (21)
ｃ（但し、Ａは周期律表第IV族元素、Ｘはハロゲン元素
、ａ、ｂ、ｃは０でない整数）なる構造の原料物質と該
原料物質に酸化作用をする性質を有する気体状ハロゲン
系酸化剤と、価電子制御剤となる成分を構成要素として
含む気体状物質（Ｄ）と、を反応空間内に導入して接触
させ、前記反応空間内圧と前記導入ガス滞留時間の積が
０．０１〜１００（Ｔｏｒｒ・ｓｅｃ）なる範囲におい
て励起状態の前駆体を含む複数の前駆体を生成し、これ
らの前駆体の内少なくとも１つの前駆体を堆積膜構成要
素の供給源として成膜空間内にある基体上に堆積膜を形
成することを特徴とする堆積膜形成法。(1) A_aH_bX_ that can be made into a gas for forming a deposited film
A raw material with the structure c (where A is a Group IV element of the periodic table, X is a halogen element, and a, b, and c are integers that are not 0) and a gaseous halogen system that has the property of oxidizing the raw material. An oxidizing agent and a gaseous substance (D) containing a component serving as a valence electron control agent are introduced into a reaction space and brought into contact with each other, and the product of the internal pressure of the reaction space and the residence time of the introduced gas is 0. A plurality of precursors including precursors in an excited state are generated in a range of 01 to 100 Torr/sec, and at least one of these precursors is used as a source of a deposited film component in a film forming space. A deposited film forming method characterized by forming a deposited film on a substrate.
Ｓｎのうち少なくとも１種類の元素を含む特許請求の範
囲第１項に記載の堆積膜形成法。(2) The constituent elements of the gaseous raw material are Si, Ge,
The method for forming a deposited film according to claim 1, which contains at least one element of Sn.
、Ｉのうち少なくとも１種類のハロゲン元素を含む特許
請求の範囲第１項に記載の堆積膜形成法。(3) The constituent elements of the gaseous raw material are F, Cl, and Br.
, I. The deposited film forming method according to claim 1, which contains at least one halogen element among , I.
る特許請求の範囲第１項に記載の堆積膜形成法。(4) The deposited film forming method according to claim 1, wherein the gaseous raw material is a linear silane compound.
である特許請求の範囲第１項に記載の堆積膜形成法。(5) The deposited film forming method according to claim 1, wherein the gaseous raw material is a branched chain silane compound.
シラン化合物である特許請求の範囲第１項に記載の堆積
膜形成法。(6) The deposited film forming method according to claim 1, wherein the gaseous raw material is a silane compound having a silicon ring structure.
る特許請求の範囲第１項に記載の堆積膜形成法。(7) The deposited film forming method according to claim 1, wherein the gaseous raw material is a chain germane compound.
特許請求の範囲第１項に記載の堆積膜形成法。(8) The deposited film forming method according to claim 1, wherein the gaseous raw material is a tin hydride compound.
である特許請求の範囲第１項に記載の堆積膜形成法。(9) The deposited film forming method according to claim 1, wherein the gaseous raw material is a tetrahedral compound.
を含む特許請求の範囲第１項に記載の堆積膜形成法。(10) The deposited film forming method according to claim 1, wherein the gaseous halogen-based oxidizing agent contains halogen gas.
む特許請求の範囲第１項に記載の堆積膜形成法。(11) The deposited film forming method according to claim 1, wherein the gaseous halogen-based oxidizing agent contains fluorine gas.
む特許請求の範囲第１項に記載の堆積膜形成法。(12) The deposited film forming method according to claim 1, wherein the gaseous halogen-based oxidizing agent contains chlorine gas.
成成分として含むガスである特許請求の範囲第１項に記
載の堆積膜形成法。(13) The deposited film forming method according to claim 1, wherein the gaseous halogen-based oxidizing agent is a gas containing fluorine atoms as a constituent component.
ハロゲンを含む特許請求の範囲第１項に記載の堆積膜形
成法。(14) The deposited film forming method according to claim 1, wherein the gaseous halogen-based oxidizing agent contains halogen in a nascent state.
ハロゲン系酸化剤の前記反応空間への導入方向に対して
対向する位置に配設される特許請求の範囲第１項に記載
の堆積膜形成法。(15) The deposition according to claim 1, wherein the substrate is disposed at a position opposite to the direction in which the gaseous raw material and the gaseous halogen-based oxidizing agent are introduced into the reaction space. Film formation method.
素を含有している特許請求の範囲第１項に記載の堆積膜
形成法。(16) The deposited film forming method according to claim 1, wherein the gaseous substance (D) contains an element of group 3A of the periodic table.
＿６）、フッ化ホウ素（ＢＦ＿３）である特許請求の範
囲第１項に記載の堆積膜形成法。(17) The gaseous substance (D) is diborane (B_2H
_6), the deposited film forming method according to claim 1, wherein boron fluoride (BF_3) is used.
素を含有している特許請求の範囲第１項に記載の堆積膜
形成法。(18) The deposited film forming method according to claim 1, wherein the gaseous substance (D) contains an element of group 5A of the periodic table.
３）、５フッ化リン（ＰＦ＿５）、アルシン（ＡｓＨ＿
３）である特許請求の範囲第１項に記載の堆積膜形成法
。(19) The gaseous substance (D) is phosphine (PH_
3), phosphorus pentafluoride (PF_5), arsine (AsH_
3) The deposited film forming method according to claim 1.
Ａｒ、Ｋｒ、Ｘｅ、Ｒｎの内少なくとも１種類のガスで
、希釈して、反応空間に導入する特許請求の範囲第１項
に記載の堆積膜形成法。(20) The gaseous substance (D) is H_2, He, Ne,
2. The deposited film forming method according to claim 1, wherein the gas is diluted with at least one gas among Ar, Kr, Xe, and Rn and introduced into the reaction space.
化剤は前記反応空間へ、多重管構造の輸送管から導入さ
れる特許請求の範囲第１項に記載の堆積膜形成法。(21) The deposited film forming method according to claim 1, wherein the gaseous raw material and the gaseous halogen-based oxidizing agent are introduced into the reaction space from a transport pipe having a multi-tube structure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7226986A JPS62229827A (en) | 1986-03-29 | 1986-03-29 | Formation of deposited film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7226986A JPS62229827A (en) | 1986-03-29 | 1986-03-29 | Formation of deposited film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62229827A true JPS62229827A (en) | 1987-10-08 |
Family
ID=13484395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7226986A Pending JPS62229827A (en) | 1986-03-29 | 1986-03-29 | Formation of deposited film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62229827A (en) |
-
1986
- 1986-03-29 JP JP7226986A patent/JPS62229827A/en active Pending
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