JPH0353391B2 - - Google Patents
Info
- Publication number
- JPH0353391B2 JPH0353391B2 JP59067516A JP6751684A JPH0353391B2 JP H0353391 B2 JPH0353391 B2 JP H0353391B2 JP 59067516 A JP59067516 A JP 59067516A JP 6751684 A JP6751684 A JP 6751684A JP H0353391 B2 JPH0353391 B2 JP H0353391B2
- Authority
- JP
- Japan
- Prior art keywords
- transmission window
- reaction vessel
- substrate
- shutter
- 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.)
- Expired - Lifetime
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
- H01J37/32321—Discharge generated by other radiation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/517—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using a combination of discharges covered by two or more of groups C23C16/503 - C23C16/515
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Chemical Vapour Deposition (AREA)
Description
【発明の詳細な説明】 本発明は光化学反応装置に関するものである。[Detailed description of the invention] The present invention relates to a photochemical reaction device.
最近、電子複写機の感光ドラムや太陽電池など
に使用されるアモルフアスシリコンの薄膜の形成
方法が研究されている。また、他方では各種の絶
縁膜や保護膜の形成にも蒸着方法が利用され、用
途によつては種々の蒸着方法が提案されている
が、このなかでも光化学反応を利用した光化学蒸
着方法は被膜形成速度が著しく早く、大面積部に
も均一な被膜を形成できるなどの利点を有し、最
近特に注目を集めている。 Recently, research has been conducted into methods for forming thin films of amorphous silicon used in photosensitive drums of electronic copying machines, solar cells, and the like. On the other hand, vapor deposition methods are also used to form various insulating films and protective films, and various vapor deposition methods have been proposed depending on the application. It has the advantage of being extremely fast in formation and being able to form a uniform coating even over a large area, and has recently attracted particular attention.
従来の光化学反応を利用した化学蒸着ないし堆
積方法は、紫外線をよく透過する窓を有する反応
容器内に基板を配置し、光反応用ガスを流すとと
もに、容器外から、紫外線光源で当該ガスを光化
学反応せしめ、その反応生成物を基板に蒸着又は
堆積せしめるものであつて、前記の大きな利点を
有するが、反面、反応生成物が容器の透過窓にも
蒸着又は堆積してしまい、紫外線の透過を大きく
阻害する欠点があることが分つた。 In conventional chemical vapor deposition or deposition methods that utilize photochemical reactions, a substrate is placed inside a reaction vessel that has a window that allows ultraviolet rays to pass through, and a photoreaction gas is passed through it, and the gas is photochemically exposed to an ultraviolet light source from outside the vessel. This method involves reacting and vapor-depositing or depositing the reaction product on the substrate, and has the above-mentioned great advantages, but on the other hand, the reaction product is also vapor-deposited or deposited on the transparent window of the container, which prevents the transmission of ultraviolet rays. It turns out that there are some major drawbacks.
このため従来は、透過窓に油を塗布したり、ア
ルゴンなどの不活性ガスをフローさせたりして透
過窓に蒸着又は堆積することを抑えていたが、こ
れらの対策では効果が小さく、長時間操業してい
ると紫外線の透過が次第に阻害されていた。こと
に操業途中で紫外線の透過率が許容範囲以下にな
ると、操業を中断して基板を反応容器から取り出
し、透過窓の堆積物を除去しなければならない
が、基板を反応容器から取り出すと、基板の表面
に大気中の水蒸気やCO2ガスなどが吸着されてし
まい、当該基板に対する操業を再開するとこれら
のガスが基板の特性を悪化させてしまう問題点が
ある。 For this reason, in the past, vapor deposition or deposition on the transmission window was suppressed by applying oil to the transmission window or flowing inert gas such as argon, but these measures had little effect and could last for a long time. During operation, the transmission of ultraviolet rays was gradually blocked. In particular, if the transmittance of ultraviolet light falls below the allowable range during operation, the operation must be interrupted, the substrate must be removed from the reaction vessel, and the deposits on the transmission window must be removed. There is a problem in that water vapor, CO 2 gas, etc. in the atmosphere are adsorbed on the surface of the substrate, and when the operation of the substrate is restarted, these gases deteriorate the characteristics of the substrate.
そこで本発明は、除去作業によつて基板の特性
を悪化させることなく、透過窓の堆積物を完全に
取り去ることが可能であり、長時間操業しても紫
外線の透過が阻害されることのない光化学反応装
置を提供することを目的とし、その構成は、紫外
線の透過窓を有する反応容器と、この反応容器内
に光反応性ガスを供給する第１ガス給排機構と、
反応容器外より透過窓を通して被処理物である基
板上を照射する紫外線光源とを含む光化学反応装
置であつて、該透過窓と第１ガス給排機構との間
にシヤツターを設けて反応容器内を区画可能とす
るとともに、透過窓とシヤツターとの空間にエツ
チング用ガスの第２給排機構とプラズマ放電機構
とを設け、該シヤツターを閉じることにより、基
板を反応容器から取り出すことなく、透過窓の内
表面にプラズマ粒子を投射可能としたことを特徴
とする。 Therefore, the present invention makes it possible to completely remove the deposits on the transmission window without deteriorating the properties of the substrate during the removal process, and allows the transmission of ultraviolet rays to be unobstructed even during long-term operation. The purpose of the present invention is to provide a photochemical reaction device, and its configuration includes a reaction container having an ultraviolet ray transmission window, a first gas supply/discharge mechanism that supplies a photoreactive gas into the reaction container,
A photochemical reaction device including an ultraviolet light source that irradiates a substrate, which is an object to be processed, from outside the reaction vessel through a transmission window, and a shutter is provided between the transmission window and a first gas supply/exhaust mechanism. In addition, by providing a second supply and discharge mechanism for etching gas and a plasma discharge mechanism in the space between the transmission window and the shutter, and closing the shutter, the transmission window can be separated without taking out the substrate from the reaction vessel. It is characterized by being able to project plasma particles onto the inner surface of the device.
以下に図面に示す実施例に基いて本発明を具体
的に説明する。 The present invention will be specifically described below based on embodiments shown in the drawings.
反応容器１には光反応性ガスの導入孔１１と、
減圧装置に接続される排気孔１２が設けられてこ
れらが第１ガス給排機構を構成し、内部中央には
石英ガラス製の基板支持台１３が上下動可能に配
設されている。そして、上面は石英ガラスからな
る紫外線の透過窓１４が設けられているが、その
上部に灯体２が一体に連設され、その天井部には
反射部材２１を介して紫外線光源である紫外線ラ
ンプ３が複数個並設されている。ここで紫外線ラ
ンプ３は管径が18mm、点灯開始電圧が350V、点
灯電圧が90Vで電流が5Aの交流点灯の低圧水銀
灯であるが、これに限られるものではなく、無電
極型のランプ装置やプラズマ発生装置でもよく、
要は所定量の紫外線を発生させるものであればよ
い。又、必要に応じて、灯体２内部はガスをフロ
ーさせたり、真空にすることが可能である。 The reaction vessel 1 has a photoreactive gas introduction hole 11,
An exhaust hole 12 connected to a pressure reducing device is provided, and these constitute a first gas supply/discharge mechanism, and a substrate support stand 13 made of quartz glass is disposed at the center of the interior so as to be movable up and down. The upper surface is provided with an ultraviolet light transmitting window 14 made of quartz glass, and a lamp body 2 is integrally connected to the upper part of the window 14, and an ultraviolet lamp, which is an ultraviolet light source, is connected to the ceiling through a reflective member 21. 3 are arranged in parallel. Here, the ultraviolet lamp 3 is an AC lighting low-pressure mercury lamp with a tube diameter of 18 mm, a lighting start voltage of 350 V, a lighting voltage of 90 V, and a current of 5 A, but is not limited to this, and may be an electrodeless lamp device or A plasma generator may also be used.
In short, it is sufficient as long as it generates a predetermined amount of ultraviolet light. Further, if necessary, the inside of the lamp body 2 can be made to flow with gas or be made into a vacuum.
基板支持台１３には図示略の温度調節器が取付
けられており、これに支持される基板４は外径が
160mmのアルミナ板であつて約150℃に加熱されて
いる。なお、この基板支持台１３をターンテーブ
ル状に回転可能としたり、反応容器１内を移動可
能とし、運搬機構で基板４を出し入れして多数の
基板４を効率良く処理できるようにすることがで
きる。導入孔１１からはキヤリアガスのアルゴ
ン、光増感剤の水銀ガス、分解蒸着用ガスの四水
素化珪素からなる混合ガスが反応容器１内に供給
されるが、予め混合すると反応するような光反応
性ガスを使用するときは複数本の導入孔１１を設
けて各ガスを個別に導入し、反応容器１内で混合
するようにするのが良い。そして、この導入孔１
１には温度調節器を設け、各ガスを最適温度に調
整して光化学反応を増進させるのが良い。 A temperature controller (not shown) is attached to the substrate support stand 13, and the substrate 4 supported by this has an outer diameter of
It is a 160mm alumina plate heated to approximately 150℃. Note that this substrate support stand 13 can be made rotatable like a turntable or movable within the reaction vessel 1, so that a large number of substrates 4 can be efficiently processed by loading and unloading the substrates 4 with a transport mechanism. . A mixed gas consisting of argon as a carrier gas, mercury gas as a photosensitizer, and silicon tetrahydride as a decomposition vaporization gas is supplied from the introduction hole 11 into the reaction vessel 1. When using a reactive gas, it is preferable to provide a plurality of introduction holes 11 to introduce each gas individually and mix them within the reaction vessel 1. And this introduction hole 1
1 is preferably equipped with a temperature controller to adjust each gas to an optimal temperature to promote photochemical reactions.
次に、導入孔１１より上方にはシヤツター５が
設けられており、これが開いているときは紫外線
の照射の妨げとならず、これが閉じることによつ
て反応容器１内が区画される。このシヤツター５
は、複数個のステンレス製セクターが左右に開く
引戸式の構造のものであり、中央で一部が重なり
あう２枚のセクターにそれぞれ連結されたステン
レス製ワイヤーロツド（図示略）が内部の気密性
を保持した状態で反応容器１外に導かれ、このワ
イヤーロツドの先端がエアシリンダー（図示略）
に連結されている。従つて、このエアシリンダー
を所定の信号に基ずいて駆動するとシヤツター５
は左右に開閉する。なお、容器内の気密性を保持
しながら内部に配置された被駆動部材を外部から
駆動する技術は多数開発されており、前述の構造
に限られるものではない。そして、シヤツター５
自体も左右に開く引戸式のものではなく、各セク
ターが同心円状に開くものであつてもよく、要
は、後に説明するプラズマ粒子が基板４上に投射
されないように区画するものであればよい。そし
て、このシヤツター５の上方には、塩素やフツ
素、またはこれらの化合物であるエツチング用ガ
スの注入口１５と排出口１６が設けられ、これら
が第２ガス給排機構を構成している。更に、シヤ
ツター５と透過窓１４の間であつて、第２ガス給
排機構が設けられた空間には電極６ａ，６ｂが対
向して配設され、これに高周波電源７が接続され
て両電極６ａ，６ｂ間で放電される。この放電に
よりエツチング用ガスがプラズマ状態となりプラ
ズマ粒子が周囲に投射される。又、このプラズマ
放電を生じさせる手段としては、無電極でもよ
く、要は、プラズマを発生できればよい。 Next, a shutter 5 is provided above the introduction hole 11, and when it is open, it does not interfere with the irradiation of ultraviolet rays, and when it is closed, the inside of the reaction vessel 1 is partitioned. This shutter 5
has a sliding door structure with multiple stainless steel sectors that open left and right, and stainless steel wire rods (not shown) connected to each of the two sectors that partially overlap in the center ensure airtightness inside. While being held, it is guided outside the reaction vessel 1, and the tip of this wire rod is connected to an air cylinder (not shown).
is connected to. Therefore, when this air cylinder is driven based on a predetermined signal, the shutter 5
opens and closes to the left and right. Note that many techniques have been developed for driving a driven member disposed inside the container from the outside while maintaining airtightness inside the container, and the structure is not limited to the above-described structure. And shutter 5
It does not need to be a sliding door type that opens left and right, but may be one in which each sector opens concentrically.In short, it may be partitioned so that plasma particles, which will be described later, are not projected onto the substrate 4. . An inlet 15 and an outlet 16 for an etching gas such as chlorine, fluorine, or a compound thereof are provided above the shutter 5, and these constitute a second gas supply/discharge mechanism. Further, electrodes 6a and 6b are disposed facing each other in the space between the shutter 5 and the transmission window 14 and where the second gas supply/discharge mechanism is provided, and a high frequency power source 7 is connected to the electrodes 6a and 6b. Discharge occurs between 6a and 6b. This discharge turns the etching gas into a plasma state, and plasma particles are projected to the surrounding area. Further, the means for generating this plasma discharge may be electrodeless, as long as it can generate plasma.
しかして上記装置において、まずシヤツター５
が開いた状態で反応容器１内が減圧されて紫外線
ランプ３が点灯される。もつとも、反応容器１内
を減圧せずに常圧下で光化学反応を起させてもよ
い。そして、導入孔１１より５mmHgのアルゴン、
３mmHgの四水素化珪素、３×10-3mmHgの水銀蒸
気が導入されるが、紫外線は透過窓１４を透過し
て下方の基板４に照射され、これによつて四水素
化珪素が光分解し、アモルフアスの珪素が基板４
の表面に蒸着又は堆積される。このとき、光反応
性ガスの一部分は上昇して透過窓１４の方向に進
み、ここでも光分解が起つて生成物が堆積を始め
る。従つて、紫外線の透過率が徐々に低下する
が、例えば、1nm程度まで堆積して透過率が許容
範囲内の95％程度になつた時点で、シヤツター５
が閉じられるとともに注入口１５よりエツチング
用ガスとして0.5mmHgのCF4が注入される。そし
て、電極６ａ，６ｂに0.5W／cm2のパワーが加え
られるとCF4がプラズマ状態となり、その粒子が
透過窓１４の内表面に投射される。このため堆積
物はプラズマエツチング作用により容易に除去さ
れて、約10秒後に100％近くまで回復する。なお、
このときはシヤツター５が閉じているので、基板
４上にはプラズマ粒子は投射されず、蒸着又は堆
積したアモルフアスの珪素が損傷することはな
い。次に、透過率が回復すると、放電が中止され
て、シヤツター５が開かれる。これにより基板４
上に再び蒸着又は堆積され、以上のサイクルが繰
返される。このため紫外線の透過率は常に許容範
囲内に保たれ、良好な状態で光蒸着することがで
きる。そして、プラズマ粒子を投射するときに基
板４を反応容器１外に取り出す必要がないので、
基板４の表面に大気中の水蒸気やCO2ガスなどが
吸着されず、基板１上に再び蒸着や堆積したとき
にこれらのガスが基板１の特性を悪化させること
がない。更には、基板４を反応容器１外に取り出
すためのロスタイムがないので、処理時間を短縮
できる利点を有する。 However, in the above device, first the shutter 5
With the door open, the pressure inside the reaction vessel 1 is reduced and the ultraviolet lamp 3 is turned on. However, the photochemical reaction may be caused under normal pressure without reducing the pressure inside the reaction vessel 1. Then, from the introduction hole 11, 5 mmHg of argon,
Silicon tetrahydride at 3 mmHg and mercury vapor at 3 x 10 -3 mmHg are introduced, but ultraviolet light passes through the transmission window 14 and irradiates the substrate 4 below, which causes the silicon tetrahydride to be photodecomposed. However, amorphous silicon is used as the substrate 4.
evaporated or deposited on the surface of At this time, a portion of the photoreactive gas rises and travels toward the transmission window 14, where photolysis also occurs and products begin to accumulate. Therefore, the transmittance of ultraviolet rays gradually decreases, but when the transmittance reaches about 95%, which is within the allowable range, when the ultraviolet rays have accumulated to about 1 nm, the shutter 5
is closed, and 0.5 mmHg of CF 4 is injected from the injection port 15 as an etching gas. Then, when a power of 0.5 W/cm 2 is applied to the electrodes 6a and 6b, the CF 4 becomes a plasma state, and its particles are projected onto the inner surface of the transmission window 14. Therefore, the deposits are easily removed by the plasma etching action, and recovery to nearly 100% occurs after about 10 seconds. In addition,
Since the shutter 5 is closed at this time, no plasma particles are projected onto the substrate 4, and the amorphous silicon that has been vapor-deposited or deposited will not be damaged. Next, when the transmittance is restored, the discharge is stopped and the shutter 5 is opened. As a result, the board 4
The above cycle is repeated. Therefore, the transmittance of ultraviolet rays is always kept within an allowable range, and photo-evaporation can be performed in good condition. Furthermore, since there is no need to take out the substrate 4 outside the reaction vessel 1 when projecting plasma particles,
Water vapor, CO 2 gas, etc. in the atmosphere are not adsorbed onto the surface of the substrate 4, and these gases do not deteriorate the characteristics of the substrate 1 when they are deposited or deposited on the substrate 1 again. Furthermore, since there is no loss time for taking the substrate 4 out of the reaction vessel 1, there is an advantage that the processing time can be shortened.
以上説明したように、本発明は、透過窓と光反
応性ガス給排機構との間にシヤツターを設けて反
応容器内を区画可能とするとともに、透過窓とシ
ヤツターとの空間にエツチングガス給排機構とプ
ラズマ放電機構とを設け、透過窓の内表面にプラ
ズマ粒子を投射可能としたので、透過窓の堆積物
を短時間で完全に取り去ることが可能であり、本
発明に従えば、長時間操業しても紫外線の透過が
阻害されることのない光化学反応装置を提供する
ことができる。 As explained above, the present invention provides a shutter between the transmission window and the photoreactive gas supply/discharge mechanism to partition the inside of the reaction vessel, and also provides an etching gas supply/discharge mechanism in the space between the transmission window and the shutter. Since a mechanism and a plasma discharge mechanism are provided to make it possible to project plasma particles onto the inner surface of the transmission window, it is possible to completely remove the deposits on the transmission window in a short time. It is possible to provide a photochemical reaction device in which the transmission of ultraviolet rays is not inhibited even during operation.
図面は本発明実施例の断面図である。
１……反応容器、３……紫外線ランプ、４……
基板、１４……透過窓、５……シヤツター、６
ａ，６ｂ……電極。
The drawings are cross-sectional views of embodiments of the present invention. 1... Reaction container, 3... Ultraviolet lamp, 4...
Substrate, 14... Transmission window, 5... Shutter, 6
a, 6b... Electrode.
Claims (1)
応容器内に光反応性ガスを供給する第１ガス給排
機構と、反応容器外より透過窓を通して被処理物
である基板上を照射する紫外線光源とを含む光化
学反応装置であつて、該透過窓と第１ガス給排機
構との間にシヤツターを設けて反応容器内を区画
可能とするとともに、透過窓とシヤツターとの空
間にエツチング用ガスの第２ガス給排機構とプラ
ズマ放電機構とを設け、該シヤツターを閉じるこ
とにより、基板を反応容器から取り出すことな
く、透過窓の内表面にプラズマ粒子を投射可能と
したことを特徴とする光化学反応装置。1. A reaction vessel having an ultraviolet ray transmission window, a first gas supply/exhaust mechanism that supplies a photoreactive gas into the reaction vessel, and an ultraviolet light source that irradiates the substrate, which is the object to be processed, from outside the reaction vessel through the transmission window. A photochemical reaction device comprising: a shutter is provided between the transmission window and the first gas supply/discharge mechanism to partition the inside of the reaction vessel, and an etching gas is provided in the space between the transmission window and the shutter. A photochemical reaction characterized in that a second gas supply/exhaust mechanism and a plasma discharge mechanism are provided, and by closing the shutter, plasma particles can be projected onto the inner surface of the transmission window without removing the substrate from the reaction vessel. Device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6751684A JPS60212223A (en) | 1984-04-06 | 1984-04-06 | Photochemical reaction apparatus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6751684A JPS60212223A (en) | 1984-04-06 | 1984-04-06 | Photochemical reaction apparatus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60212223A JPS60212223A (en) | 1985-10-24 |
| JPH0353391B2 true JPH0353391B2 (en) | 1991-08-14 |
Family
ID=13347224
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6751684A Granted JPS60212223A (en) | 1984-04-06 | 1984-04-06 | Photochemical reaction apparatus |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60212223A (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5644763A (en) * | 1979-09-20 | 1981-04-24 | Toshiba Corp | Cvd device under reduced pressure |
| JPS56120064A (en) * | 1980-02-26 | 1981-09-21 | Hitachi Ltd | Method for operation of scanning electron microscope and the likes |
-
1984
- 1984-04-06 JP JP6751684A patent/JPS60212223A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60212223A (en) | 1985-10-24 |
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