JPS62158870A - Manufacture of multi-layered structure film - Google Patents
Manufacture of multi-layered structure filmInfo
- Publication number
- JPS62158870A JPS62158870A JP60298040A JP29804085A JPS62158870A JP S62158870 A JPS62158870 A JP S62158870A JP 60298040 A JP60298040 A JP 60298040A JP 29804085 A JP29804085 A JP 29804085A JP S62158870 A JPS62158870 A JP S62158870A
- Authority
- JP
- Japan
- Prior art keywords
- raw material
- gas
- multilayer structure
- film
- material gas
- 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
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims description 85
- 238000000034 method Methods 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 239000012808 vapor phase Substances 0.000 claims description 4
- 150000001722 carbon compounds Chemical class 0.000 claims description 2
- 150000002291 germanium compounds Chemical class 0.000 claims description 2
- 150000003377 silicon compounds Chemical class 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 18
- 229910021417 amorphous silicon Inorganic materials 0.000 abstract description 5
- 229910006160 GeF4 Inorganic materials 0.000 abstract description 4
- 229910004014 SiF4 Inorganic materials 0.000 abstract description 4
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 abstract description 4
- PPMWWXLUCOODDK-UHFFFAOYSA-N tetrafluorogermane Chemical compound F[Ge](F)(F)F PPMWWXLUCOODDK-UHFFFAOYSA-N 0.000 abstract description 4
- 229910000577 Silicon-germanium Inorganic materials 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 16
- 230000000704 physical effect Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- -1 eF2C12 ゚GeCl4 Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 108091008695 photoreceptors Proteins 0.000 description 3
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/08—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic
- G03G5/082—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic and not being incorporated in a bonding material, e.g. vacuum deposited
- G03G5/08214—Silicon-based
- G03G5/08278—Depositing methods
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/20—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials
- H01L31/202—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials including only elements of Group IV of the Periodic System
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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などの用途に有用な多層構
造膜の作製法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention is applicable to functional films, particularly 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 producing a multilayer structure film useful for applications such as
半導体膜、絶縁膜、光導電膜、磁性膜、金属膜等の非晶
質、多結晶質などの多層構造の堆積膜を用いた素子は、
単層構造の堆積膜には望めない物、理的特性や用途を期
待できるため、近年盛んに研究が進められている。特に
、大面積素子という観点から、２種類以上の非晶質層を
積層させた多層構造膜が興味をもたれている。Elements using deposited films with multilayer structures such as amorphous and polycrystalline materials such as semiconductor films, insulating films, photoconductive films, magnetic films, and metal films are
In recent years, research has been actively conducted on this material, as it promises physical properties and uses that cannot be expected from single-layer deposited films. In particular, from the viewpoint of large-area devices, multilayer structure films in which two or more types of amorphous layers are laminated are of interest.
例えば、非晶質シリコン層と非晶質シリコンカーバイド
層、あるいは非晶質シリコン層と非晶質シリコンゲルマ
ニウム層を交互に積層させた多層構造膜をプラズマＣＶ
Ｄ法や光ＣＶＤ法等此等化学的気相法り作製することが
検討されており、太陽電池やその他のデバイスへの応用
が考えられている。For example, plasma CV
Chemical vapor phase methods such as the D method and photo-CVD method are being considered, and applications to solar cells and other devices are being considered.
特に、プラズマＣＶＤ法による堆積膜の形成は、その反
応機構も不明な点が少なくない等問題点もあるが、生産
性や膜の特性を考えた場合、現在最良の方法であるため
、広く太陽電池、電子写真感光体の製造等に応用されて
いる。しかしながら、堆積膜の形成パラメーターも多く
（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
ターの組み合せによるため、時にはプラズマが不安定な
状態になり、形成された堆積膜に著しい悪影響を与える
ことが少な（ない。In particular, the formation of deposited films by the plasma CVD method has some problems, such as the reaction mechanism being unclear, but it is currently the best method in terms of productivity and film characteristics, and is widely used in solar radiation. It is applied to the manufacture of batteries, electrophotographic photoreceptors, etc. However, there are many formation parameters for the deposited film (e.g., substrate temperature, flow rate and ratio of introduced gas, pressure during formation, high frequency power, electrode structure, reaction vessel structure, pumping speed, plasma generation method, etc.). Due to the combination of these parameters, the plasma sometimes becomes unstable, which rarely has a significant negative effect on the deposited film.
特に、プラズマＣＶＤ法により多層構造膜を形成する場
合、層を変えるたび毎に放電の制御やガス導入の制御を
行なう必要がある。In particular, when forming a multilayer structure film by the plasma CVD method, it is necessary to control discharge and gas introduction every time a layer is changed.
しかしながら、ガス導入量を大幅に変化させると反応空
間内の圧力が変化するため、放電の状態が不安定となり
、膜の構造や特性に悪影響を与える。従って、従来放電
をオンにしたままガス導入量の制御のみで多層膜を形成
すると、膜の特性が常に良い条件とするのが難しい。However, if the amount of gas introduced changes significantly, the pressure within the reaction space changes, which makes the discharge state unstable and adversely affects the structure and properties of the membrane. Therefore, if a multilayer film is conventionally formed only by controlling the amount of gas introduced while the discharge is turned on, it is difficult to maintain conditions in which the film properties are always good.
一方、放電の制御、即ち放電をオフさせてガスを入れ換
え、圧力が平衡になった後放電を再オンして堆積膜を形
成する方法は、時間が極めて長（かかり、生産性が悪い
。また、プラズマ放電において、通常、放電をオンさせ
た直後、放電が安定しないため、特性の悪い界面をもっ
た多層膜となる。On the other hand, the method of controlling the discharge, that is, turning off the discharge, replacing the gas, and then turning the discharge back on after the pressure has reached equilibrium to form a deposited film, is extremely time consuming and poor in productivity. In plasma discharge, the discharge is usually unstable immediately after the discharge is turned on, resulting in a multilayer film with interfaces with poor characteristics.
本発明の目的は、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単に
得られる多層構造膜の作製法を提供することにある。An object of the present invention is to provide a method for producing a multilayer structure 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. .
上記目的は、化学的気相法により堆積膜を形成するにあ
たり、多流型成分である主体の原料ガス（Ａ）と少流量
成分である客体の原料ガス（Ｂ）を反応空間に導入し、
前記客体の原料ガス（Ｂ）の導入量を周期的に制御する
ことにより多層構造の堆積膜を形成せしめることを特徴
とする本発明の多層構造膜の作製法によって達成される
。The above purpose is to introduce a main raw material gas (A), which is a multi-flow component, and an object raw material gas (B), which is a low-flow component, into a reaction space when forming a deposited film by a chemical vapor phase method.
This is achieved by the method for producing a multilayer structure film of the present invention, which is characterized in that a deposited film with a multilayer structure is formed by periodically controlling the amount of the object raw material gas (B) introduced.
上記の本発明の堆積膜形成法によれば、例えばプラズマ
ＣＶＤ法等の化学的気相法により膜特性の良い多層構造
膜が得られると同時に大面積化、膜厚均一性、膜品質の
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 present invention described above, a multilayer structure film with good film properties can be obtained by a chemical vapor phase method such as plasma CVD method, and at the same time, a large area, uniform film thickness, and uniform film quality can be obtained. We aim to simplify management and mass production by fully satisfying the customer's needs.
There is no need for large capital investment in mass production equipment, the management items for mass production are clear, the management tolerance is wide, and equipment adjustment becomes easy.
本発明の多層構造膜の作製法によれば、例えば物性の異
なる２種類の層を交互に積層させた多層膜等２種類以上
の層で構成される多層構造膜を容易且つ迅速に作製する
ことができる。また、夫々の層も、例えば１０Å〜２０
０人といった極めて薄い層として多層構造膜を作製する
ことができる。According to the method for producing a multilayer structure film of the present invention, a multilayer structure film composed of two or more types of layers, such as a multilayer film in which two types of layers with different physical properties are alternately laminated, can be easily and quickly produced. I can do it. Further, each layer also has a thickness of, for example, 10 Å to 20 Å.
A multilayer structure film can be produced as an extremely thin layer with zero layers.
前記多流型成分である主体の原料ガス（Ａ）の反応空間
への導入量ａに対する少流量成分である客体の原料ガス
（Ｂ）の反応空間への導入ｌｂは、１／２ａ以下、更に
は１／１０ ａ以下とされるのが望ましい。The introduction amount lb of the object raw material gas (B), which is a small flow rate component, into the reaction space with respect to the amount a of the main raw material gas (A), which is the multi-flow type component, introduced into the reaction space is 1/2a or less, and further is preferably 1/10 a or less.
主体の原料ガス（Ａ）は、多層構造を形成する例えば物
性の異なる２つの層にともに含まれる元素よりなるガス
で構成することができ、かつ反応性が客体の原料ガス（
Ｂ）に比べ著しく小さいため客体の原料ガスＣＢ）に比
べ、極めて多量反応空間内に導入しなくてはいけない様
なガスで構成することができる。The main raw material gas (A) can be composed of a gas consisting of an element contained in, for example, two layers with different physical properties forming a multilayer structure, and the raw material gas (A) whose reactivity is the object (
Since it is significantly smaller than B), it can be composed of a gas that must be introduced into the reaction space in an extremely large amount compared to the object raw material gas CB).
また客体の原料ガス（Ｂ）は、多層構造を形成する例え
ば物性の異なる２つの層のうち片方の層のみに含まれる
元素よりなるガスで構成することができ、かつ反応性が
主体の原料ガス（Ａ）に比べ著しく大きいため主体の原
料ガス（Ａ）より少量のガスの導入で良いガスで構成す
ることができる。In addition, the object raw material gas (B) can be composed of a gas consisting of an element contained in only one of two layers with different physical properties forming a multilayer structure, and the raw material gas (B) is mainly reactive. Since it is significantly larger than (A), it can be configured with a gas that can be introduced in a smaller amount than the main raw material gas (A).
このような２種類のガスで多層構造膜を作ろうとすると
、ＡとＢとの元素を含む膜を成膜するときには、主体の
原料ガス（Ａ）を多量に、客体の原料ガス（Ｂ）を少量
に導入してもグロー放電分解の結果はぼ均等に近い元素
比のＡとＢの元素よりなる膜が得られる。When trying to make a multilayer structure film using these two types of gases, when forming a film containing elements A and B, a large amount of the main raw material gas (A) and a large amount of the object raw material gas (B) are required. Even when introduced in a small amount, glow discharge decomposition results in a film consisting of elements A and B in a nearly equal element ratio.
次にＡのみの元素よりなる膜を成膜しようとし、客体の
原料ガス（Ｂ）の反応空間への導入を停止しても、反応
チャンバー内の圧力変化は極めて小さい。Next, even if an attempt is made to form a film made of only element A and the introduction of the object raw material gas (B) into the reaction space is stopped, the pressure change within the reaction chamber is extremely small.
具体的にＳｉ元素を中心とした多層構造膜、例えばａ−
３ｉとａ−５ｉＧｅとの多層構造膜、あるいはａ−３ｉ
とａ−５ｉＣとの多層構造膜を作る場合を考えると、主
体となる原料ガス（Ａ）としては５ｉＦａ、５ｉＣ１４
゜５ｉＦｚＣ１ｚ等のケイ素の化合物等が挙げられる。Specifically, a multilayer structure film mainly containing Si element, such as a-
Multilayer structure film of 3i and a-5iGe, or a-3i
Considering the case of making a multilayer structure film of a-5iC and a-5iC, the main source gas (A) is 5iFa, 5iC
Examples include silicon compounds such as ゜5iFzC1z.
また客体となる原料ガス（Ｂ）としては、ＧｅＦａ、Ｇ
ｅＦ２Ｃ１２゜ＧｅＣｌ４等のゲルマニウムの化合物、
ＣＦ４．Ｃ２Ｆ６．ＣＣｌ４等の炭素の化合物が挙げら
れる。In addition, as the object raw material gas (B), GeFa, G
Germanium compounds such as eF2C12゜GeCl4,
CF4. C2F6. Examples include carbon compounds such as CCl4.
例えば、５ｉ−Ｆ４とＧｅＦ ４よりａ−５ｉＧｅ膜を
作る場合、成膜した膜に求める物性量によってことなる
が、通常５ｉ−ＦａとＧｅＦ、の比は１０：１以下、望
ましくは１００：１以下になるように流す。For example, when making an a-5iGe film from 5i-F4 and GeF4, the ratio of 5i-Fa to GeF is usually 10:1 or less, preferably 100:1, although it depends on the physical properties required for the formed film. Flow as shown below.
ところで、ハロゲン化ケイ素系化合物のガスは、それ自
体ではほとんど成膜する能力がないため、水素ガスを導
入し、グロー放電で分解して生成される水素の活性種と
ハロゲン化ケイ素系化合物の活性種との反応により成膜
能力を高めなければならない。導入する水素ガス量は通
常例えばＳｉＦ、の流量に対し１７４〜１の限られた範
囲とされる。By the way, the gas of the silicon halide compound has almost no ability to form a film by itself, so hydrogen gas is introduced and decomposed by glow discharge to generate active species of hydrogen and the activity of the silicon halide compound. Film-forming ability must be increased by reaction with seeds. The amount of hydrogen gas to be introduced is usually within a limited range of 174 to 1 relative to the flow rate of SiF, for example.
第１図は本発明の多層構造の堆積膜形成法を具現するに
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 implementing the method of forming a deposited film having a multilayer structure according to the present invention.
１０１は主体となる原料ガスの導入口であり、１０２は
客体となる原料ガスの導入口である。101 is an inlet for the main raw material gas, and 102 is an inlet for the object raw material gas.
１０３は三方コニックの電磁弁で反応チャンバー１００
内につながっているガス導入管１０４あるいは排気装置
１０６につながっているガス排出管１０５に接続される
。１０７はＲＦ電源１）１につながった電極で、下の電
極１０８との間にグロー放電プラズマが起こせる構造に
なっている。103 is a three-way conic solenoid valve that connects the reaction chamber 100.
It is connected to a gas inlet pipe 104 that is connected to the interior of the exhaust system or to a gas exhaust pipe 105 that is connected to an exhaust device 106 . Reference numeral 107 is an electrode connected to the RF power source 1) 1, and has a structure in which glow discharge plasma can be generated between it and the lower electrode 108.
１０９は基板である。１）０は反応チャンバーを排気す
るための真空排気装置である。109 is a substrate. 1) 0 is a vacuum evacuation device for evacuating the reaction chamber.
以下実施例にもとづき本発明を具体的に説明する。The present invention will be specifically described below based on Examples.
〔実施例１〕
第１図に示した堆積膜形成装置を用いてａ−３ｉＧｅ：
Ｈ（Ｆ）膜とａ−３ｉ：Ｈ（Ｆ）膜の多層構造膜を有す
る読み取りセンサーを形成した。ガス導入管１０１を通
して、主体の原料ガスとして５ｉＦｎ及びＨ２ガスをチ
ャンバー１００内に導入した。また、ガス導入管１０２
を通して客体の原料ガスとしてＧｅＦ４ガスもチャンバ
ー１００内に導入した。ガス導入管１０２には、三方弁
のついた電磁弁１０３が接続されており、電気信号によ
りガス導入管１０２がガス導入管１０４に接続されるか
、あるいはガス排出管１０５に接続されるか選択的に切
り換えられるようになっている。ガス排出管１０５は、
真空排気装置１０６に接続されている。[Example 1] Using the deposited film forming apparatus shown in FIG. 1, a-3iGe:
A reading sensor having a multilayer structure of an H(F) film and an a-3i:H(F) film was formed. 5iFn and H2 gas were introduced into the chamber 100 as main source gases through the gas introduction pipe 101. In addition, the gas introduction pipe 102
GeF4 gas was also introduced into the chamber 100 as an object raw material gas through the chamber 100. A solenoid valve 103 with a three-way valve is connected to the gas introduction pipe 102, and an electric signal selects whether the gas introduction pipe 102 is connected to the gas introduction pipe 104 or the gas discharge pipe 105. It is possible to switch between them. The gas exhaust pipe 105 is
It is connected to a vacuum evacuation device 106.
このような装置構成により、つねに一定流量のＧｅＦ
ａガスが電気信号によって断続的にチャンバー内に導入
され、導入されたガスは、電極１０７と電極１０８とに
印加された１３．５６ＭＨｚの高周波電力により、グロ
ー放電分解され、発生したラジカルの化学反応により、
ａ−ＳｉＧｅ：ＩＩ（Ｆ）とａ−５ｉ：Ｈ（Ｆ）との多
層構造膜がガラス基板（コーニング７０５９）上に堆積
される。With this equipment configuration, a constant flow rate of GeF is always available.
A gas is intermittently introduced into the chamber by an electric signal, and the introduced gas is decomposed by glow discharge by the 13.56 MHz high frequency power applied to the electrodes 107 and 108, and a chemical reaction of the generated radicals occurs. According to
A multilayer film of a-SiGe:II(F) and a-5i:H(F) is deposited on a glass substrate (Corning 7059).
成膜に寄与しなかったガスは、真空排気装置１）０によ
り、チャンバー外に排気される。Gas that did not contribute to film formation is exhausted to the outside of the chamber by a vacuum exhaust device 1)0.
以下読み取りセンサー内のａ−３ｉＧｅ：Ｈ（Ｆ）膜と
、ａ−Ｓｉ ：Ｈ（Ｆ）膜との多層構造よりなる読み取
りセンサーの作製方法について記述する。ＳｉＦ４ガス
を３９．７３ｓｅｃｍ 、 Ｈｚガスを１２ｓｅｃｍを
ガス導入管１０１よりＧｅＦ ａガスを０．４ｓｅｃｍ
ガス導入管１０２よりチャンバー内に導入した。基板と
してはコーニング７０５９ガラスを用いた。ガラス基板
温度は３００℃に設定した。A method for manufacturing a read sensor having a multilayer structure of an a-3iGe:H(F) film and an a-Si:H(F) film within the read sensor will be described below. SiF4 gas for 39.73 sec, Hz gas for 12 sec, and GeFa gas for 0.4 sec from the gas introduction pipe 101.
The gas was introduced into the chamber through the gas introduction pipe 102. Corning 7059 glass was used as the substrate. The glass substrate temperature was set at 300°C.
このときチャンバー内の圧力は、３００ミリｔｏｒｒで
、ＧｅＦ ａを流すときと流さないときの差は２ミリｔ
ｏｒｒ以内であった。この状態で１３．５６Ｍ１ｆｚＯ
高周波電力を３０Ｗ印加えした。（電力密度ＩＷ／ｃｎ
ｆ）。At this time, the pressure inside the chamber was 300 millitorr, and the difference between when GeFa was flowing and when it was not flowing was 2 millitorr.
It was within orr. In this state 13.56M1fzO
A high frequency power of 30W was applied. (Power density IW/cn
f).
ＧｅＦ ４の流れをオン・オフさせても、放電状態には
、はとんど変化がみられなかった。Even when the flow of GeF 4 was turned on and off, there was almost no change in the discharge state.
この状態で７０秒ごとにＧｅＦ ａの導入管上にある三
方弁を切り換えた。約２００回の三方弁のオン・オフの
繰り返しの後、放電をとめ、ガスをとめ、基板を室温ま
で冷却し反応チャンバーよりとりだし別の真空蒸着装置
でＡＩのくし形電極（ギャップ長２００μｍ）をつけた
後、試料を真空クライオスタンド中にいれ暗導電率（σ
ｄ）、及び６００ｎｍ、０．３ｍＷ／ａｄの光照射時の
導電率σｐを測定した。In this state, the three-way valve on the GeFa inlet pipe was switched every 70 seconds. After turning the three-way valve on and off about 200 times, the discharge was stopped, the gas was stopped, the substrate was cooled to room temperature, and the substrate was taken out from the reaction chamber and a comb-shaped electrode (gap length 200 μm) of AI was formed using another vacuum evaporation device. After that, the sample was placed in a vacuum cryostand and the dark conductivity (σ
d) and conductivity σp upon irradiation with light of 600 nm and 0.3 mW/ad.
得られた値は
σｄ ＝ ２ Ｘ Ｉ Ｑ−” Ｓ／ｃｍσＩ） ＝
Ｉ Ｘ １０−６Ｓ／ｃｍと、極めてσｐ／σｄ比の良
い光センサーが得られた。The obtained value is σd = 2 X I Q-”S/cmσI) =
An optical sensor with an extremely good σp/σd ratio of I×10 −6 S/cm was obtained.
〔実施例２〕
第１図に示した装置を用い、１０００人のＩＴＯ膜を堆
積したガラス基板上にＰＩＮ構造の光ダイオードを作製
した。基板をセットした後、基板温度を２５０℃に保っ
た。まずガス導入管１０１を通して、主体の原料ガスと
して３０００ｐｐｍの８□１）、を添加したａ ５ｉＦ
４ガスを３５ｓｅｃｍ、 Ｈ２ガスを１２ｓｅｃｍチャ
ンバー１００内に導入した。[Example 2] Using the apparatus shown in FIG. 1, a PIN-structured photodiode was fabricated on a glass substrate on which 1000 ITO films were deposited. After setting the substrate, the substrate temperature was maintained at 250°C. First, through the gas introduction pipe 101, 3000 ppm of 8□1) was added as the main raw material gas.
4 gas was introduced into the chamber 100 for 35 seconds, and H2 gas was introduced for 12 seconds into the chamber 100.
またガス導入管１０２を通して客体の原料ガスとしてＣ
１Ｆ６ガス５ ｓｃｃｍもチャンバー１００内に導入し
た。ＲＦ電源より３０Ｗの高周波電力を電極１０７に印
加し、プラズマをたてた。ガス導入管１０２に接続して
いる三方弁をオンを１００秒オフを５０秒で３回くりか
えした。その結果約５０人厚のａ−ＳｉＣ層と約５０人
厚のａ−５ｉ層との多層膜のＰ型の膜が約３００人形成
された。その後Ｃ，Ｆｔ、ガスをＧｅＦ ａガスにいれ
かえた後、実施例１に記載したのと同じ条件でドーピン
グしていないａ−ＳｉＧｅ層とａ−３ｉ層との多層膜を
約８０００人形成した。その後、ＧｅＦ４のガスの流れ
をとめた後、ガス導入管１０１より３０００ｐｐｍのＰ
Ｈｓを添加したＳｉＦ４ガスを４０ｓｅｃｍ、 Ｈｚガ
スを１２ｓｅｃｍチャンバー内に導入し、３０Ｗの高周
波電力を５分間印加し、約３００人のＮ型のａ−Ｓｉ膜
をその上に成膜した。ガスを十分に排気した後、基板が
室温にもどってから、その上にφ１０ｍｍのＡ１電極を
蒸着した。In addition, C as the raw material gas of the object is passed through the gas introduction pipe 102.
5 sccm of 1F6 gas was also introduced into the chamber 100. A high frequency power of 30 W was applied to the electrode 107 from an RF power source to generate plasma. The three-way valve connected to the gas inlet pipe 102 was turned on and off for 100 seconds and then turned off for 50 seconds three times. As a result, about 300 multilayer P-type films including an a-SiC layer with a thickness of about 50 layers and an a-5i layer with a thickness of about 50 layers were formed. Thereafter, after replacing the C, Ft, and gases with GeFa gas, about 8,000 people formed a multilayer film of an undoped a-SiGe layer and an a-3i layer under the same conditions as described in Example 1. After that, after stopping the flow of GeF4 gas, 3000 ppm of P was introduced from the gas introduction pipe 101.
Hs-added SiF4 gas was introduced into the chamber for 40 seconds and Hz gas was introduced for 12 seconds into the chamber, and a high frequency power of 30 W was applied for 5 minutes to form about 300 N-type a-Si films thereon. After the gas was sufficiently exhausted and the substrate returned to room temperature, an A1 electrode with a diameter of 10 mm was deposited thereon.
その結果ガラス基板、ＩＴＯ膜、Ｐ型ａ−５ｉＣ及びａ
−３ｉの多層構造膜、ドーピングしていないａ−３ｉＧ
ｅ及びａ−Ｓｉの多層構造膜、ｎ型ａ−５ｉ膜、及びＡ
Ｉの積層体となった。ＰＸＮ構造の光ダイオードが形成
された。ＡＭ−１，１００ｍＷ／ｃｎｌの光を照射し、
太陽電池特性を測定したところ、
開放電圧 ０．９■
短絡電流 １４ｍＡ／ｃｄ
で変換効率８．８％の良好な値を得た。As a result, glass substrate, ITO film, P type a-5iC and a
-3i multilayer structure film, undoped a-3iG
e and a-Si multilayer structure film, n-type a-5i film, and A
This resulted in a laminate of I. A photodiode with a PXN structure was formed. AM-1, irradiated with light of 100 mW/cnl,
When the solar cell characteristics were measured, good values of an open circuit voltage of 0.9 mm, a short circuit current of 14 mA/cd, and a conversion efficiency of 8.8% were obtained.
〔実施例３〕
へ１基板の上に表１の手順でＡ１基板／Ｐ型ａ−Ｓｉ層
／ａ−３ｉＧｅとａ−５ｉとの多層構造ｆｌｕ／ａ−ｓ
ｉｃとａ−３ｉの多層構造膜より電子写真感光体を成膜
した。[Example 3] A multilayer structure flu/as of A1 substrate/P type a-Si layer/a-3iGe and a-5i was prepared on the first substrate according to the procedure shown in Table 1.
An electrophotographic photoreceptor was formed from a multilayer structure film of ic and a-3i.
表 １
ＳｉＦ４ガス、Ｈ２ガスは導入管１０１より、ＧｅＦａ
、 ＣｚＦｂはガス導入管１０２より導入し、三方弁で
ガスの反応チャンバーへの導入を制御した。Table 1 SiF4 gas and H2 gas are supplied from the introduction pipe 101 to GeFa
, CzFb was introduced from the gas introduction pipe 102, and the introduction of the gas into the reaction chamber was controlled by a three-way valve.
その他の成膜条件は、
内 圧 ３Ｑ Ｃ１）ｔｎ ｔｏｒｒ基板温度
２５０°に
の電子写真感光体に■のコロナ帯電を０．２秒し゛たと
ころ、受容電位３６０■を得た。Other film-forming conditions were: internal pressure: 3Q C1) tn torr, substrate temperature: 250°, and an electrophotographic photoreceptor was corona-charged for 0.2 seconds to obtain an acceptance potential of 360°.
その後７８８ｒ＋ｍ、 ２μＪの光強度の半導体レーザ
ー光で露光したところ、３５Ｖになった。Thereafter, exposure to semiconductor laser light at 788r+m and a light intensity of 2 μJ resulted in a voltage of 35V.
本発明の多層構造膜の作製法によれば、特性の著しい向
上がはかれる。また、本発明の方法は製造条件のコント
ロールの制御及びプロセスが容易であり、量産化に適し
ている。According to the method for producing a multilayer structure film of the present invention, the characteristics can be significantly improved. Further, the method of the present invention is easy to control manufacturing conditions and processes, and is suitable for mass production.
第１図は本発明の多層構造膜の作製法を実施するための
装置の１例を示す模式的説明図である。
１０１・・・主体の原料ガスの導入管、１０２・・・客
体の原料ガスの導入管、１０３・・・三方弁、１０４・
・・ガスの導入管、１０５・・・ガスの排出管、１０６
・・・排気装置、１０７，１０８・・・電極、１００・
・・反応チャンバー、１０９・・・基板、１）０・・・
真空排気装置、１）１・・・高周波電源。
代理人 弁理士 山 下 穣 平
図面の浄Ｉ（内容に変更なし）
第１図
手続補正書
昭和６１年 ２月２７日
特許庁長官 宇 賀 道 部 殿
１、事件の表示
特願昭６０−２９８０４０号
２、発明の名称
多層構造膜の作製法
３、補正をする者
事件との関係 特許出願人
名 称 （１００）キャノン株式会社４、代理人
住所 東京都港区虎ノ門五丁目１３番１号虎ノ門４０森
ビル氏名 （６５３８） 弁理士 山 下 積
乎丁；−）５、補ＴＥ（７）対え
ｊｌ’ｉ”：：・・：図面の
浄書及び委任状
一〜−一
１〜 ／′
手続補正書
昭和６１年 ３月 ４日FIG. 1 is a schematic explanatory diagram showing an example of an apparatus for carrying out the method for producing a multilayer structure film of the present invention. 101...Main material gas introduction pipe, 102...Object material gas introduction pipe, 103...Three-way valve, 104.
...Gas inlet pipe, 105...Gas discharge pipe, 106
...exhaust device, 107,108...electrode, 100.
...Reaction chamber, 109...Substrate, 1)0...
Vacuum exhaust equipment, 1) 1...High frequency power supply. Agent Patent attorney Jo Yamashita Drawing I (no change in content) Figure 1 procedural amendment February 27, 1985 Commissioner of the Patent Office Michibe Uga 1, patent application for indication of case 1988-298040 No. 2, Name of the invention Method for producing a multilayer structure film 3, Relationship with the amended case Patent applicant name (100) Canon Co., Ltd. 4, Agent address 40 Toranomon, 5-13-1 Toranomon, Minato-ku, Tokyo Mori Building Name (6538) Patent Attorney Seki Yamashita ;-) 5, Opponent to Assistant TE (7)
jl'i"::...: Engraving of drawings and power of attorney 1~-11~ /' Procedural amendment March 4, 1986
Claims (8)
多流量成分である主体の原料ガス（Ａ）と少流量成分で
ある客体の原料ガス（Ｂ）を反応空間に導入し、前記客
体の原料ガス（Ｂ）の導入量を周期的に制御することに
より多層構造の堆積膜を形成せしめることを特徴とする
多層構造膜の作製法。(1) When forming a deposited film by chemical vapor phase method,
Introducing the main raw material gas (A), which is a high flow rate component, and the object raw material gas (B), which is a low flow rate component, into the reaction space, and periodically controlling the amount of the introduced object raw material gas (B). A method for producing a multilayer structure film, characterized by forming a deposited film with a multilayer structure.
の範囲にある特許請求の範囲第（１）項記載の多層構造
膜の作製法。(2) The thickness of each layer of the multilayer structure film is 10 Å to 200 Å
A method for producing a multilayer structure film according to claim (1).
原料ガス（Ｂ）の導入量ｂを１／２ａ以下とする特許請
求の範囲第（１）項記載の多層構造膜の作製法。(3) The multilayer structure film according to claim (1), wherein the amount b of the object raw material gas (B) introduced is 1/2a or less with respect to the introduced amount a of the main raw material gas (A). Fabrication method.
いる特許請求の範囲第（１）項記載の多層構造膜の作製
法。(4) A method for producing a multilayer structure film according to claim (1), in which a silicon compound is used as the main raw material gas (A).
物を用いる特許請求の範囲第（４）項記載の多層構造膜
の作製法。(5) A method for producing a multilayer structure film according to claim (4), in which a germanium compound is used as the object raw material gas (B).
る特許請求の範囲第（４）項又は第（５）項記載の多層
構造膜の作製法。(6) A method for producing a multilayer structure film according to claim (4) or (5), using a carbon compound as the object raw material gas (B).
求の範囲第（４）項乃至第（６）項のうちの１に記載の
多層構造膜の作製法。(7) The method for producing a multilayer structure film according to any one of claims (4) to (6), wherein the main raw material gas (A) includes hydrogen gas.
求の範囲第（４）項乃至第（６）項のうちの１に記載の
多層構造膜の作製法。(8) The method for producing a multilayer structure film according to any one of claims (4) to (6), in which hydrogen gas is included in the object raw material gas (B).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60298040A JPS62158870A (en) | 1985-12-28 | 1985-12-28 | Manufacture of multi-layered structure film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60298040A JPS62158870A (en) | 1985-12-28 | 1985-12-28 | Manufacture of multi-layered structure film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62158870A true JPS62158870A (en) | 1987-07-14 |
Family
ID=17854342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60298040A Pending JPS62158870A (en) | 1985-12-28 | 1985-12-28 | Manufacture of multi-layered structure film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62158870A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02282481A (en) * | 1989-04-24 | 1990-11-20 | Matsushita Electric Ind Co Ltd | Formation of amorphous multilayered thin film |
| JPWO2004085309A1 (en) * | 2003-03-24 | 2006-06-29 | 独立行政法人科学技術振興機構 | Highly efficient synthesis method of carbon nanostructure, apparatus and carbon nanostructure |
| US7565880B2 (en) | 2002-12-18 | 2009-07-28 | Sharp Kabushiki Kaisha | Plasma CVD apparatus, and method for forming film and method for forming semiconductor device using the same |
| CN103132049A (en) * | 2011-11-25 | 2013-06-05 | 中芯国际集成电路制造(上海)有限公司 | Forming method of silicon thin film and forming device |
-
1985
- 1985-12-28 JP JP60298040A patent/JPS62158870A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02282481A (en) * | 1989-04-24 | 1990-11-20 | Matsushita Electric Ind Co Ltd | Formation of amorphous multilayered thin film |
| US7565880B2 (en) | 2002-12-18 | 2009-07-28 | Sharp Kabushiki Kaisha | Plasma CVD apparatus, and method for forming film and method for forming semiconductor device using the same |
| JPWO2004085309A1 (en) * | 2003-03-24 | 2006-06-29 | 独立行政法人科学技術振興機構 | Highly efficient synthesis method of carbon nanostructure, apparatus and carbon nanostructure |
| JP4691625B2 (en) * | 2003-03-24 | 2011-06-01 | 独立行政法人科学技術振興機構 | Method and apparatus for highly efficient synthesis of carbon nanostructures |
| US8505478B2 (en) | 2003-03-24 | 2013-08-13 | Taiyo Nippon Sanso Corporation | Apparatus for high-efficiency synthesis of carbon nanostructure |
| CN103132049A (en) * | 2011-11-25 | 2013-06-05 | 中芯国际集成电路制造(上海)有限公司 | Forming method of silicon thin film and forming device |
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