JPH0372083A - Method and device for continuously forming large-area functional deposited film by microwave plasma cvd method - Google Patents
Method and device for continuously forming large-area functional deposited film by microwave plasma cvd methodInfo
- Publication number
- JPH0372083A JPH0372083A JP20785289A JP20785289A JPH0372083A JP H0372083 A JPH0372083 A JP H0372083A JP 20785289 A JP20785289 A JP 20785289A JP 20785289 A JP20785289 A JP 20785289A JP H0372083 A JPH0372083 A JP H0372083A
- Authority
- JP
- Japan
- Prior art keywords
- film
- deposited film
- forming
- microwave
- plasma
- 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
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Abstract
Description
【発明の詳細な説明】
〔発明の属する技術分野〕
本発明は、大面積に亘って均一なマイクロ波プラズマを
生起させ得る新規なマイクロ波エネルギー供給装置を用
い、これにより引き起されるプラズマ反応により、原料
ガスを分解、励起させることによって大面積の機能性堆
積膜を連続的に形成する方法及び装置に閏する。Detailed Description of the Invention [Technical field to which the invention pertains] The present invention uses a novel microwave energy supply device capable of generating uniform microwave plasma over a large area, and the plasma reaction caused thereby. The present invention describes a method and apparatus for continuously forming a large-area functional deposited film by decomposing and exciting a source gas.
更に詳しくは、前記原料ガスの利用効率を飛躍的に高め
、且つ高速で均一性の良い機能性堆積膜を大面積に亘っ
て連続的に形成することが出来る方法及び装置であって
、具体的には光起電力素子等の大面積薄膜半導体デバイ
スの量産化を低コストで実現させ得るものである。More specifically, it is a method and apparatus capable of dramatically increasing the utilization efficiency of the raw material gas and continuously forming a highly uniform functional deposited film over a large area at high speed. Accordingly, large-area thin film semiconductor devices such as photovoltaic elements can be mass-produced at low cost.
電力需要は、世界的に増大の一途をたどっており、そう
した需要を賄う電力生産を如何にして行うかが世界的課
題として検討されている。電力生産は、現在、水力発電
、火力発電、そして原子力発電により行われている。こ
れらの発電方式の中で水力発電は、降雨を利用するもの
であるところ、定常的に所定量の電力生産を行うことが
できない。The demand for electricity continues to increase worldwide, and how to produce electricity to meet such demand is being considered as a global issue. Electricity production is currently performed by hydroelectric power, thermal power generation, and nuclear power generation. Among these power generation methods, hydroelectric power generation uses rainfall, but cannot consistently produce a predetermined amount of electricity.
火力発電は、石油、石炭等のいわゆる化石燃料を利用す
るものであって、電力需要の大半はこの発電方式により
賄われているが、化石燃料が有限であること、そして発
電の際に不可避的に排出される二酸化炭素が将来的に地
球の温暖化を招くという本質的IL’fffを抱えてい
ることから他の発電方式への転換の必要性が論議されて
いる。Thermal power generation uses so-called fossil fuels such as oil and coal, and most of the electricity demand is met by this power generation method, but fossil fuels are finite and there are unavoidable problems when generating electricity. The necessity of switching to other power generation methods is being debated because the carbon dioxide emitted by the power generation system has an inherent IL'fff that will cause global warming in the future.
こうしたことから原子力発電がいきおい注目されるとこ
ろとなり、原子力発電による電力生産の比率は増大する
傾向にある。ところが原子力発電については、放射能汚
染という全ゆる生物の存亡にかかわる重大な問題の発生
の危険性があることから、安全性の確保が必須であり、
この点の検討が世界的規模でなされている。For these reasons, nuclear power generation is attracting a lot of attention, and the proportion of electricity produced by nuclear power generation is on the rise. However, with nuclear power generation, there is a risk of radioactive contamination, a serious problem affecting the survival of all living things, so it is essential to ensure safety.
This point is being considered on a global scale.
以上のような背景から最近”太陽光発電”がいきおい注
目されてきており、これについて既に多数の提案がなさ
れている。しかしながら提案されているいずれの太陽光
発電方式も電力需要を賄うという観点での電力生産を可
能にするものでは到底ない、ところで従来提案されてい
る太陽光発電方式は以下の2つの方式に大別できる。Against the above background, "solar power generation" has recently been attracting a lot of attention, and many proposals have already been made regarding this. However, none of the solar power generation methods that have been proposed are capable of producing electricity from the perspective of meeting electricity demand.By the way, the solar power generation methods that have been proposed so far can be broadly divided into the following two methods. can.
方式へ二太陽光を集光して水を加熱、沸騰させて蒸気を
発生させ(光熱変換)、ボイ
ラーで発電する(熱M、変換)。The method focuses two sunlight to heat water, boil it and generate steam (photothermal conversion), which generates electricity in a boiler (heat M, conversion).
方式B:太陽電池による光N、変換作用で発電する。Method B: Generates electricity by converting light N from solar cells.
方式Aの太陽光発電方式は、2段階のエネルギー変換の
末に発電する方式のものであって、システムの変換効率
は低く、小プラント実験は開始されてはいるが実用化に
は至っていない。The solar power generation method of method A is a method that generates electricity after two steps of energy conversion, and the conversion efficiency of the system is low, and although small plant experiments have been started, it has not been put into practical use.
一方、方式Bの太陽光発電方式については、既に数多く
の提案がなされており、その中のいくつかは腕時計や卓
上計算機等の民生用の電源用として実用化されているが
、電力用を目的とした発電設備は小規模のもので実験が
行われているが現在のところ研究段階の域を脱していな
い。On the other hand, many proposals have already been made regarding the solar power generation method of Method B, and some of them have been put into practical use as power sources for consumer products such as wristwatches and desk calculators; Although experiments are being conducted on small-scale power generation facilities, it is currently still in the research stage.
この理由は、大規模な電力を定常的に生産するための克
服ずべき課題がいくつかあり、特に発電能力が太陽電池
の面積に比例するため大規模な電力生産を可能にする大
面積の太陽電池を工業的規模で生産できるか否かが最大
の課題である。ところで太陽電池については、その重要
な構成部材たる半導体層は、いわゆるpn接合、pir
l接合等の半導体接合が形成されている。これらの半導
体接合は、導電型の異なる半導体層を積層したり、−導
電型の半導体層中に異なる導電型のドーパントをイオン
打込み法等によって打込んだり、熱拡散によって拡散さ
せたりすることにより形成される。そして、前記半導体
層を構成する材料については、多くの提案があるが、そ
れら提案は単結晶又は多結晶シリコン(以下’x−3i
“と略称する。)とアモルファスシリコン(以下“a−
3+1と略称する。)、及び化合物半導体材料に集中し
ている。The reason for this is that there are several issues that need to be overcome in order to produce large-scale electricity on a regular basis. The biggest challenge is whether batteries can be produced on an industrial scale. By the way, the semiconductor layer, which is an important component of solar cells, is a so-called pn junction, a pir junction.
A semiconductor junction such as an l junction is formed. These semiconductor junctions are formed by stacking semiconductor layers of different conductivity types, implanting dopants of different conductivity types into semiconductor layers of -conductivity type by ion implantation, or diffusing them by thermal diffusion. be done. There are many proposals regarding the material constituting the semiconductor layer, but these proposals include single crystal or polycrystalline silicon (hereinafter '
) and amorphous silicon (hereinafter referred to as “a-
It is abbreviated as 3+1. ), and compound semiconductor materials.
ところがこうしたいずれの材料を用いた場合においても
、均一性、再現性等製造上の問題、光電変換効率の問題
、製造コストの問題等から、膨大な電力需要を賄い得る
だけの大量且つ大面積の太陽電池を生産するための製造
方式や太陽電池の素子構造そのものについても未だ完成
されていない。However, when using any of these materials, there are manufacturing issues such as uniformity and reproducibility, photoelectric conversion efficiency issues, and manufacturing cost issues, which make it difficult to produce large quantities and large areas that can meet the enormous power demand. The manufacturing method for producing solar cells and the solar cell element structure itself have not yet been perfected.
特に、単結晶Siを用いた太陽電池パネルは、シリコン
・インゴットから切り出されたSiウェハーにイオン打
ち込みを行ってpn接合を形成させたものを、なるべく
隙間なく並べてそれをつなぎ合わせて作製されるが、太
陽電池素子の製造プロセスは、大面積の基板を大量に処
理するのに適した方法とは言えず、そもそも大口径の単
結晶シリコン・インゴットは極めて高価であり、また、
Siウェハーを切り出す工程においては、切り代として
利用できない部分が多く排出される。これらのことが単
結晶Si太陽電池の生産コストを高くする原因にもなっ
ている。そして、これらの問題を解消するに有効な手だ
ては今のところない。In particular, solar cell panels using single-crystal Si are manufactured by lining up Si wafers cut from silicon ingots, implanting ions into them to form p-n junctions, and connecting them together with as few gaps as possible. , the manufacturing process for solar cell elements is not suitable for processing large quantities of large-area substrates, and large-diameter single-crystal silicon ingots are extremely expensive to begin with;
In the step of cutting out a Si wafer, a large amount of portion that cannot be used as a cutting allowance is discharged. These factors are also a cause of increasing the production cost of single-crystal Si solar cells. At present, there is no effective way to solve these problems.
多結晶S1を用いた太陽電池については、その光電変換
効率は若干a−3tを用いた太陽電池を上まわるものの
、特性決定因子の一つである結晶粒径の制御技術は未完
成であり、またその素子製造プロセスは単結晶Si太陽
電池とほぼ同じであって大量生産に適した方法とは言い
難い。Although the photoelectric conversion efficiency of solar cells using polycrystalline S1 is slightly higher than that of solar cells using A-3T, the technology for controlling crystal grain size, which is one of the characteristics determining factors, is still incomplete. Furthermore, the device manufacturing process is almost the same as that for single-crystal Si solar cells, so it is difficult to say that it is a method suitable for mass production.
また、単結晶にしろ多結晶にしろx−3tは割れやすい
という結晶特有の性質のため、屋外で太陽光発電を行う
には厳重な保護材を必要とし、その結果、保護材で包ま
れた太陽電池パネル・ユニットはかなりの重量物となり
設置場所や環境に制約を受ける。In addition, due to the unique property of crystals, whether single crystal or polycrystalline, X-3T is easily broken, requiring strict protective materials for outdoor solar power generation. Solar panel units are quite heavy and are subject to restrictions on installation location and environment.
一方、a−3iを用いた大面積の太陽電池の作製におい
ては、ホスフィン(P)(3) 、ジボラン(BオH,
)等のドーパントとなる元素を含む原料ガスを主原料ガ
スであるシラン等に混合してグロー放電分解することに
より所望の導電型を有する半導体膜が得られ、所望の基
板上にこれらの半導体膜を順次積層形成することによっ
て容易に半導体接合が形成でき、前述のx−3iを用い
た場合よりかなり安価に製造できることが知られている
。On the other hand, in the production of large-area solar cells using a-3i, phosphine (P) (3), diborane (BOH,
) and other dopant elements are mixed with silane, the main raw material gas, and subjected to glow discharge decomposition, a semiconductor film having a desired conductivity type can be obtained, and these semiconductor films can be deposited on a desired substrate. It is known that a semiconductor junction can be easily formed by sequentially laminating the above-mentioned x-3i, and can be manufactured at a considerably lower cost than when using the x-3i described above.
そして、上述のグロー放電分解を行うについて、RF(
ラジオ周波数)グロー放電分解法が技術的に確立され、
広く利用されるようになってきている。しかしながらこ
の方法は、半導体膜を低い堆積速度で形成する場合に比
較的高品質のものが形成されることから、太陽電池とし
て機能させるに足る高品質の半導体膜を高速で大面積に
渡って形成することは困難であり、ましてや工業的現模
で太陽電池を作製して電力需要を賄い得るようにするこ
とは甚だ困難であった。Then, in order to perform the above-mentioned glow discharge decomposition, RF (
The glow discharge decomposition method (radio frequency) was technically established,
It is becoming widely used. However, this method produces a relatively high quality semiconductor film when it is formed at a low deposition rate, so it is possible to form a semiconductor film of high quality enough to function as a solar cell over a large area at high speed. It is difficult to do so, and it is even more difficult to manufacture solar cells in an industrial scale to meet electricity demand.
一方、高速で高品質の堆積膜を形成し得る方法として、
マイクロ波を用いたプラズマプロセスが注目されている
。マイクロ波は周波数帯が短いため従来のRFを用いた
場合よりも成膜室内での電力密度を高めることが可能で
あり、プラズマを効率良く発生させ、持続させることに
通している。On the other hand, as a method for forming high-quality deposited films at high speed,
Plasma processes using microwaves are attracting attention. Since microwaves have a short frequency band, it is possible to increase the power density within the film forming chamber compared to when conventional RF is used, allowing plasma to be generated and sustained efficiently.
例えば、米国特許第4,517,223号明細書及び同
第4,504.518号明細書には、それぞれマイクロ
波電力によりグロー放電を生起させ、低圧で基体上に堆
積膜を形成せしめる方法が開示されている。For example, U.S. Pat. No. 4,517,223 and U.S. Pat. No. 4,504,518 each disclose a method of generating a glow discharge using microwave power and forming a deposited film on a substrate at low pressure. Disclosed.
これらの公報によれば、これらの堆積膜形成方法は低圧
下で成膜を行うものであることから、大電力を投入した
場合に堆積膜の特性の低下の原因となるラジカルの再結
合が少ない、プラズマ中でのポリシラン等からなる微粉
末の発生が少ない、成膜速度の向上が図れる、といった
利点があることが理解される。しかしながら、マイクロ
波を用いたプラズマプロセスでは、マイクロ波の波長が
従来のRFに比べて180分の1程度と極めて短いため
、プラズマ密度の不均一性が生じやすいという問題を有
している。According to these publications, since these deposited film formation methods perform film formation under low pressure, there is less recombination of radicals, which causes deterioration of the properties of the deposited film when high power is applied. It is understood that there are advantages such as less generation of fine powder made of polysilane or the like in plasma and improvement in film formation rate. However, plasma processes using microwaves have a problem in that non-uniformity in plasma density tends to occur because the wavelength of microwaves is extremely short, about 1/180 of that of conventional RF.
そうした問題を回避する例として、マイクロ波電力を成
膜室内で均一化するためのマイクロ波給電手段として遅
波回路を使用する試みがあるが、該遅波回路には、マイ
クロ波発i機から遠ざかるにつれてマイクロ波給電手段
からプラズマへ供給されるマイクロ波電力が急激に減衰
するという特有の問題がある。この問題を解消するため
、被処理基体とマイクロ波給電手段との距離をマイクロ
波の進行方向において、徐々に近づけることによって基
体近傍での電力密度を一定にする方法が試みられている
。As an example of avoiding such problems, there has been an attempt to use a slow wave circuit as a microwave power supply means to equalize the microwave power within the deposition chamber, but the slow wave circuit has There is a particular problem in that the microwave power supplied to the plasma from the microwave power supply means rapidly attenuates as it moves away from the plasma. In order to solve this problem, attempts have been made to make the power density near the substrate constant by gradually increasing the distance between the substrate to be processed and the microwave power feeding means in the direction of propagation of the microwave.
例えば、米国特許第3,814,983号明細書及び同
第4.521,717号明細書には、そうした方法が開
示されている。前者においては、基体に対しである角度
にマイクロ波給電手段を傾斜させる必要性があることが
記載されているが、プラズマに対するマイクロ′ljl
電力の伝達効率は満足のゆくものではない。また、後者
にあっては基体とは平行な面内に、非平行に2つの遅波
回路となっているマイクロ波給電手段を設けることが開
示されている。即ち、マイクロ波給電手段の中心軸が、
基体に平行な面内で、且つ基体の移動方向に対して直角
な直線上で亙いに交わるように配置することが望ましい
こと、そして2つのマイクロ波給電手段間の干渉を避け
るため、マイクロ波給電手段同志を導波管の長辺の半分
の長さだけ基体の移動方向に対して横にずらして配設す
ることのそれぞれが開示されている。For example, US Pat. No. 3,814,983 and US Pat. No. 4,521,717 disclose such methods. In the former, it is stated that it is necessary to incline the microwave power supply means at a certain angle with respect to the substrate.
The power transfer efficiency is not satisfactory. Further, in the latter case, it is disclosed that microwave power feeding means, which are two slow wave circuits, are provided non-parallelly in a plane parallel to the base body. That is, the central axis of the microwave power feeding means is
It is desirable that the microwaves be arranged in a plane parallel to the substrate and on a straight line perpendicular to the direction of movement of the substrate, and to avoid interference between the two microwave power feeding means. Each of these discloses disposing the power feeding means so as to be laterally shifted from each other by half the length of the long side of the waveguide with respect to the moving direction of the base body.
また、マイクロ波給電手段の中では比較的取扱いの容易
なアンテナ方式については、例えば第17図及び第18
図に示した特公昭57−53858号公報及び特開昭6
1−283116号公報に記載されたマイクロ波プラズ
マcvoHWがある。Furthermore, among microwave feeding means, antenna systems that are relatively easy to handle are shown in Figures 17 and 18, for example.
Japanese Patent Publication No. 57-53858 and Japanese Unexamined Patent Application Publication No. 1987-6 shown in the figure
There is a microwave plasma cvoHW described in Japanese Patent No. 1-283116.
いずれの場合においてもアンテナの周囲はマイクロ波透
過性の物質で構成される筒体で囲まれており、該筒体に
よって収脱室内の気密を保ち、往−っ成膜室外部からマ
イクロ波を導入せしめ、アンテナへの膜堆積を防止する
ことでアンテナの寿命を改善して、高密度のプラズマを
広い圧力範卯lこわたって生成することができる。とこ
ろが、第18図に示した装故において、反応容器181
内には基(反ホルり’−182上に′R置された基(反
183どマイクロ波電力供給手段とが配設されている。In either case, the antenna is surrounded by a cylindrical body made of a material that is transparent to microwaves. By preventing film deposition on the antenna, the lifetime of the antenna can be improved, and high-density plasma can be generated over a wide pressure range. However, in the installation shown in FIG.
A microwave power supply means such as a group 183 placed on the 182 is disposed inside.
184は前記マイクロ波電力供給手段としての同軸線路
であり、マイクロ波電力は該同軸線路184の外部導体
の一部を切り欠いて設けられた間隙185からマイクロ
波透過性の筒体186を介して反応容器181内に投入
される。しかしながらこの装置では、大面積の基体上に
a−3i膜を均一に成膜することは明らかに困難であり
、また具体的開示もない、一方、第17図に示した装置
において、反応容器171内にはマイクロ波電力供給手
段であるロンド・アンテナ172、ガス供給口173、
真空ポンプ174に接続されたガス排気口175及び石
英筒体176上に載置された基板177とが配設されて
いる。マイクロ波発振機で発生したマイクロ波電力は導
波管178を伝送され、ロンド・アンテナ172及びマ
イクロ波透過部材179を介して石英筒体176により
卯まれた空間内に投入されてプラズマを生起しプラズマ
処理が行われる。しかしながら、マイクロ波電力はロン
ド・アンテナ上を伝播しながら順次空間中に放射される
というアンテナ固有の性質のため、該ロンド・アンテナ
の長さ方向に対してマイクロ波電力の減衰が生ずるため
、プラズマを長手方向に均一化させるここは困難である
。Reference numeral 184 denotes a coaxial line as the microwave power supply means, and the microwave power is passed through a microwave transparent cylinder 186 from a gap 185 provided by cutting out a part of the outer conductor of the coaxial line 184. It is put into the reaction container 181. However, with this apparatus, it is clearly difficult to uniformly form an a-3i film on a large-area substrate, and there is no specific disclosure.On the other hand, in the apparatus shown in FIG. Inside there is a Rondo antenna 172 which is a microwave power supply means, a gas supply port 173,
A gas exhaust port 175 connected to a vacuum pump 174 and a substrate 177 placed on a quartz cylinder 176 are provided. Microwave power generated by the microwave oscillator is transmitted through a waveguide 178 and is injected into a space surrounded by a quartz cylinder 176 via a rondo antenna 172 and a microwave transmission member 179 to generate plasma. Plasma treatment is performed. However, due to the inherent property of the antenna that the microwave power is sequentially radiated into space while propagating on the Rondo antenna, attenuation of the microwave power occurs in the length direction of the Rondo antenna, resulting in plasma This is difficult to make uniform in the longitudinal direction.
また1、別のマイクロ波給電手段として知られている空
洞共振器方式において、プラズマの均一性を保持するた
めの提案がいくつか為されている。In addition, 1. In the cavity resonator method, which is known as another microwave power feeding means, several proposals have been made for maintaining plasma uniformity.
それらの提案は例えばジャーナル・オブ・バキューム・
サイエンス・テクノロジー(Journal ofVa
euus 5cieriee Technology)
B−4(1986年1月〜2月>2’1)5)Q〜2
98貝及び同誌のB−4(1986年1月〜2月)12
6頁〜130頁に記載された報告に見られる。これらの
報告によれば、マイクロ波プラズマ・ディスク・ソース
(MPDSと略称する。)と呼ばれる円筒空洞共振器型
マイクロ波反応炉が提案されている。 Ilpちプラズ
マは円板状の形を為していて、円筒空洞共振器の一部と
して該共振2工に包含され、その直径はマイクロ波周波
数の関数となっているとしている。そしてそれらの報告
にはMPDSに共振器長可変a構をつけマイクロ波周波
数に対して同調できるようにしたことが示されている。These proposals can be found, for example, in the Journal of Vacuum
Science and Technology (Journal of Va.
euus 5cieriee Technology)
B-4 (January-February 1986 >2'1) 5) Q-2
98 shells and B-4 of the same magazine (January-February 1986) 12
See the report on pages 6-130. According to these reports, a cylindrical cavity type microwave reactor called a microwave plasma disk source (abbreviated as MPDS) has been proposed. It is said that the Ilp plasma has a disk-like shape, is included in the resonator 2 as part of a cylindrical cavity resonator, and its diameter is a function of the microwave frequency. These reports indicate that a variable cavity length structure was added to the MPDS so that it could be tuned to the microwave frequency.
2.45GHzで作動できるように設計したMPDSに
おいてはプラズマの閉じ込め直径はたかだかlo(2)
程度であり、プラズマ体積にしてもせいぜい118cm
3程度であって、大面積化とは到底言えない。また前記
報告は915MHzという低い周波数で作動するように
設計したシステムでは周波数を低くすることで約40値
のプラズマ直径、及び2000cm3のプラズマ体積が
与えられるとしている。In an MPDS designed to operate at 2.45 GHz, the plasma confinement diameter is at most lo(2).
The plasma volume is at most 118 cm.
3, which cannot be said to be a large area. The report also states that in a system designed to operate at a frequency as low as 915 MHz, lowering the frequency provides a plasma diameter of about 40 and a plasma volume of 2000 cm3.
また、前記報告は更に、より低い周波数、例えば400
MH2で作動させることにより、1mを超える直径まで
放電を拡大できるとしている。ところがこの内容を達成
する装置となると、専用の大電力用マイクロ波発振機を
開発しなければならず・それが充放しても通信障害回避
のため電波法により工業的に利用できる周波数が制限さ
れているため実施困難である。Also, the report further states that lower frequencies, e.g. 400
By operating with MH2, it is said that the discharge can be expanded to a diameter of more than 1 meter. However, in order to achieve this goal, a dedicated high-power microwave oscillator must be developed, and even if it is recharged, the frequencies that can be used industrially are restricted by the Radio Law in order to avoid communication problems. This makes it difficult to implement.
さらに別のマイクロ波給電手段として電子サイクロトロ
ン共鳴(E CR)を利用する方式が特開昭55−14
1729号公報及び特開昭57133636号公報等に
より提案されている。すなわち、本方式はプラズマ化室
となる空洞共振器の周囲に同軸状に電磁石を配設し、該
電磁石により875ガウスの磁場をマイクロ波導入窓近
傍に形威し、電子サイクロトロン共鳴(F、CR)条件
を成立させてマイクロ波のプラズマへの吸収率を高め、
高密度プラズマを発生せしめるものである。Furthermore, a method using electron cyclotron resonance (ECR) as another microwave power feeding means was disclosed in Japanese Patent Application Laid-Open No. 55-14.
This method has been proposed in Japanese Patent Application Laid-open No. 1729, Japanese Patent Application Laid-Open No. 57133636, and the like. That is, in this method, an electromagnet is placed coaxially around a cavity resonator that serves as a plasma generation chamber, and the electromagnet applies a magnetic field of 875 Gauss near the microwave introduction window to generate electron cyclotron resonance (F, CR). ) conditions to increase the absorption rate of microwaves into plasma,
This generates high-density plasma.
そして、該高密度プラズマは、前記電磁石によって形威
される発散磁界に沿って輸送され、所望の基体上に所望
の堆積膜が形威される。The high-density plasma is then transported along a diverging magnetic field formed by the electromagnet to form a desired deposited film on a desired substrate.
この方式は、前述のマイクロ波プラズマ・ディスク・ソ
ース(MPDS)方式とは空洞共振器を使用する点で類
似しているが、MPDS方式は空洞共振器の内部の一部
だけがプラズマに占有されるのに対して、上述のECR
方式は空洞共振器内部にプラズマが充満するという点及
び電子サイクロトロン共鳴現象を利用している点が異な
っている。This method is similar to the previously mentioned microwave plasma disk source (MPDS) method in that it uses a cavity resonator, but in the MPDS method, only a part of the interior of the cavity is occupied by the plasma. On the other hand, the ECR mentioned above
The method differs in that the cavity is filled with plasma and that it utilizes the electron cyclotron resonance phenomenon.
さて、学会等では、このECR方式で形威される高密度
プラズマを利用して各種の半導体薄膜を形成する例が多
数報告されている。そしてこの種のマイクロ波ECRプ
ラズマCVD装置は既に市販されるに至っている。Now, at academic conferences and the like, many examples of forming various semiconductor thin films using the high-density plasma produced by this ECR method have been reported. This type of microwave ECR plasma CVD apparatus is already commercially available.
ところが、これらのECRを用いた方法においては、プ
ラズマの制御に空洞共振器の外部から印加した発散磁界
を用いているため、電磁石が基体表面につくる磁界分布
も不均一となり、大面積の基体上に均一で均質な堆積膜
を形成するのは非常に困難である。However, in these methods using ECR, since a diverging magnetic field applied from outside the cavity resonator is used to control the plasma, the magnetic field distribution created by the electromagnet on the substrate surface is also uneven, and it is difficult to spread the magnetic field over a large area of the substrate. It is very difficult to form a uniform and homogeneous deposited film.
この困難さを一部克服して、膜厚・膜質分布を改善した
方法が特開昭63−283018号公報で開示されてい
る。即ちこれは、均一な磁界分布を生成するために前記
の空洞共振器の周囲に配置された電磁石とは別の磁界発
生手段(例えば第2の電磁石)を基体の周囲に配設し、
均一なIIl!!厚・11iSff分布を達成したもの
である。しかしながら、この第2の電磁石は既に巨大な
ものであり、そして、この巨大な磁石で装置を構成して
も今のところせいぜい15cmφ程度の膜質・膜厚の均
一性しか得られないのが実状である。A method that partially overcomes this difficulty and improves the film thickness and film quality distribution is disclosed in JP-A-63-283018. That is, this means that magnetic field generating means (e.g., a second electromagnet) other than the electromagnets arranged around the cavity resonator are arranged around the substrate in order to generate a uniform magnetic field distribution,
Uniform IIl! ! This achieves a thickness/11iSff distribution. However, this second electromagnet is already huge, and the reality is that even if a device is constructed using this huge magnet, it is only possible to obtain uniformity in film quality and thickness of about 15 cmφ at most. be.
以上説明したまうなRF或いはマイクロ波等の高周波の
給電手段の確立に加えて、複数の所望の導電型を有する
半導体膜を順次積層して半導体接合を形威し太陽電池素
子を製造するための連続成膜装置も確立しなければなら
ない。In addition to establishing a high-frequency power supply means such as RF or microwave as explained above, it is also possible to manufacture solar cell elements by sequentially laminating semiconductor films having a plurality of desired conductivity types to form semiconductor junctions. Continuous film deposition equipment must also be established.
そうした連続成膜装置の例として、複数の半導体膜を形
成するための各々独立した複数の成膜室を仕切り弁を介
して接続し、該成膜室内にはそれぞれ1&llの平行平
板形RF電極を配設し、該成膜室のそれぞれにおいて、
他の成膜室とは隔離された状態でRFグロー放電分解法
により各々の半導体膜を堆積形成する連続成膜装置が提
案されている。即ち、pin接合を有する積層型半導体
デバイスの連続成膜装置として、いわゆる3室分離型連
続戒lIl装置が提案され、前記仕切弁によりp型半導
体層、i型半導体層、n型半導体層形成用の各成膜室を
分離し、RFグロー放電分解法で各層をそれぞれ成膜す
るが、各層を積層していく過程において成膜−排気一搬
送一底膜というサイクルを繰り返すため多大の成膜時間
を要し、また基体の幅も仕切弁で制約されるため、現在
の発電方式に代替し得る大量の太陽電池素子を生産し得
る連続成膜装置では到底ない。As an example of such a continuous film-forming apparatus, a plurality of independent film-forming chambers for forming a plurality of semiconductor films are connected via a gate valve, and each film-forming chamber is equipped with 1&ll parallel plate type RF electrodes. and in each of the film forming chambers,
A continuous film forming apparatus has been proposed in which each semiconductor film is deposited by an RF glow discharge decomposition method in a state isolated from other film forming chambers. That is, a so-called three-chamber separation type continuous film forming apparatus has been proposed as a continuous film forming apparatus for stacked semiconductor devices having pin junctions, in which the gate valves are used to form a p-type semiconductor layer, an i-type semiconductor layer, and an n-type semiconductor layer. The film forming chambers are separated and each layer is formed using the RF glow discharge decomposition method. However, in the process of stacking each layer, the cycle of film formation, exhaust, transport, and bottom film is repeated, which takes a long time. Moreover, since the width of the substrate is also limited by the gate valve, it is impossible to use a continuous film-forming apparatus that can produce large quantities of solar cell elements that can replace current power generation methods.
これに対して、米国特許第4,400.4(19号明細
書に開示されているロール・ツー・ロール(Rollt
o Roll)式連読威膜装置は、前述したような成膜
時間や基体の幅の制約も少なく実用的である。In contrast, the roll-to-roll technology disclosed in U.S. Pat.
The continuous reading film apparatus of the Roll type is practical because there are fewer restrictions on the film formation time and the width of the substrate as described above.
この装置によれば、所望の幅の十分に長いフレキシブル
な帯状基体が搬送される経路に沿って複数のRFグロー
放電領域を設け、該各RFグロー放電fiIJ!Iiに
おいてa−3lを主体とする半導体装置形成し、前記帯
状基体をその長手方向にほぼ水平に連続的に搬送させる
ことによってRFグロー放を領域の数に相当する半導体
膜で構成される半導体接合を有する素子を連続形成する
ことができるとされている。尚、該明細書においては、
各半導体膜形成時に用いるドーパントガスが他のRFグ
ロー放電領域へ拡散、混入するのを防止するため、ガス
ゲートが用いられている。具体的には、ガスゲートは、
前記各RFグロー放電領域同志を、スリット状のガス隔
離通路によって相互に分離し、さらに該隔離通路に例え
ばAr、Hffi等の掃気用ガスの流れを形成させる手
段が採用されている。According to this device, a plurality of RF glow discharge regions are provided along a path along which a sufficiently long flexible strip substrate having a desired width is conveyed, and each RF glow discharge fiIJ! In step Ii, a semiconductor device mainly composed of a-3l is formed, and the strip-shaped substrate is continuously conveyed substantially horizontally in its longitudinal direction, thereby emitting RF glow. It is said that it is possible to continuously form elements having . In addition, in the specification,
A gas gate is used to prevent the dopant gas used when forming each semiconductor film from diffusing and mixing into other RF glow discharge regions. Specifically, the gas gate is
The RF glow discharge regions are separated from each other by a slit-shaped gas isolation passage, and a means is adopted for forming a flow of scavenging gas such as Ar or Hffi in the isolation passage.
しかしながら、前記各半導体層の形成はRF(ラジオ周
波数)を用いたプラズマCVD法によって行われるとこ
ろ、連続的に形成される膜の特性を維持しつつその膜堆
積速度の向上を図るにはおのずと限界がある。即ち、例
えば膜厚が高々5000Aの半導体層を形成する場合で
あっても膜堆積速度が遅いため、前記帯状基体の搬送方
向に相当長尺で大面積にわたって常時所定のプラズマを
生起し、且つ該プラズマを均一に維持する必要がある。However, since the formation of each of the semiconductor layers is performed by plasma CVD using RF (radio frequency), there is a natural limit to improving the film deposition rate while maintaining the characteristics of the continuously formed film. There is. That is, even when forming a semiconductor layer with a film thickness of at most 5000 Å, for example, the film deposition rate is slow, so a predetermined plasma is constantly generated over a fairly long and large area in the direction of conveyance of the strip-shaped substrate. It is necessary to maintain a uniform plasma.
ところが、そのようにするについては可成りの熟練を必
要とし、その為に関係する種々のプラズマ制御パラメー
ターを一般化するのは困難である。また、用いる成膜用
原料ガスの分解効率及び利用効率は高くはなく、生産コ
ストを引き上げる要因の一つともなっている。However, doing so requires considerable skill, and it is therefore difficult to generalize the various plasma control parameters involved. Furthermore, the decomposition efficiency and utilization efficiency of the film-forming raw material gas used are not high, which is one of the factors that increases production costs.
またこの他に、特開昭61−288074号公報には、
改良されたロール・ツー・ロール連続成膜法を用いた堆
積膜形成装置が開示されている。In addition to this, Japanese Patent Application Laid-open No. 61-288074 states:
A deposited film forming apparatus using an improved roll-to-roll continuous film forming method is disclosed.
この装置においては、反応容器内に設置されたフレキシ
ブルな連続帯状部材の一部に湾曲部を形成し、この巾に
前記反応容器とは異なる活性化空間にて原料ガスより生
成された活性種を前記反応容器まで輸送した後、前記反
応容器内に導入し熱エネルギーにより化学的相互作用を
せしめ、前記湾曲部を形成している帯状部材の内面に堆
積膜を形成することを特徴としている。このように湾曲
部の内面に堆積を行うことにより、装置のコンパクト化
が可能となる。さらに、あらかじめ活性化された活性種
を用いるので、従来のfil#II膜形成装置に比較し
て成膜速度を早めることができる。In this device, a curved part is formed in a part of a flexible continuous band-shaped member installed in a reaction vessel, and active species generated from a raw material gas are applied to this width in an activation space different from the reaction vessel. After being transported to the reaction vessel, it is introduced into the reaction vessel and chemical interaction is caused by thermal energy to form a deposited film on the inner surface of the band-shaped member forming the curved portion. By depositing on the inner surface of the curved portion in this manner, the device can be made more compact. Furthermore, since active species activated in advance are used, the film formation rate can be increased compared to the conventional fil#II film forming apparatus.
ところが、この装置はあくまで熱エネルギーの存在下で
の化学的相互作用による堆積膜形成反応を利用したもの
であり、熱エネルギーの供給方法、活性種と他分子との
反応の起こりやすさ、或いは活性種の失活までの寿命等
に依存して、堆積膜形成装置の反応容器と活性化空間の
距離や成膜条件が制約され、大面積化は困難である。However, this device only utilizes a deposited film formation reaction due to chemical interaction in the presence of thermal energy, and the method of supplying thermal energy, the ease with which the reaction between active species and other molecules occurs, and the Depending on the lifespan of the species until deactivation, etc., the distance between the reaction vessel and the activation space of the deposited film forming apparatus and the film forming conditions are restricted, making it difficult to increase the area.
ところで、薄膜半導体は前述した太陽電池用の用途の他
にも、液晶デイスプレィの画素を駆動するための薄膜ト
ランジスタ(T P T)や密着型イメージセンサ−用
の光電変換素子及びスイッチング素子等大面積又は長尺
であることが必要な薄膜半導体デバイス作製用にも好適
に用いられ、前記画像入出力装置用のキーコンポーネン
トとして一部実用化されているが、高品質で均一性良く
高速で大面積化できる新規な堆積膜形成法の提供によっ
て、更ニ広く一般に普及されるようになることが期待さ
れている。By the way, thin film semiconductors are used not only for the solar cells mentioned above, but also for large area or large area applications such as thin film transistors (TPT) for driving pixels of liquid crystal displays, photoelectric conversion elements and switching elements for contact image sensors, etc. It is also suitable for manufacturing thin film semiconductor devices that require long dimensions, and has been put into practical use as a key component for the above-mentioned image input/output devices. It is expected that the provision of a new method for forming a deposited film will lead to further widespread use.
本発明は、上述のごとき従来のv1i膜半導体デバイス
形成方法及び装置における諸問題を克服して、大面積に
亘って均一に、且つ高速で高品質の機能性堆積膜を形成
する新規な方法及び装置を提供することを目的とするも
のである。The present invention overcomes the problems in the conventional v1i film semiconductor device forming method and apparatus as described above, and provides a novel method and method for forming a high-quality functional deposited film uniformly over a large area and at high speed. The purpose is to provide a device.
本発明の他の目的は、帯状部材上に連続して高品質の機
能性堆積膜を形成する方法及び装置を提供することにあ
る。Another object of the present invention is to provide a method and apparatus for continuously forming a high quality functional deposited film on a strip member.
本発明の更なる目的は、堆積膜形成用の原料ガスの利用
効率を飛躍的に高めると共に、薄膜半導体デバイスの量
産化を低コストで実現し得る方法及び装置を提供するこ
とにある。A further object of the present invention is to provide a method and apparatus that can dramatically increase the utilization efficiency of raw material gas for forming deposited films and realize mass production of thin film semiconductor devices at low cost.
本発明の更に別の目的は、大面積、大容量に亘ってほぼ
均一なプラズマを生起させる方法及び装置を提供するこ
とにある。Still another object of the present invention is to provide a method and apparatus for generating substantially uniform plasma over a large area and large capacity.
本発明の更に別の目的は、大面積、大容積に亘って生起
させたマイクロ波プラズマのプラズマ電位を均一に再現
性良く、安定して制御する方法及び装置を提1共するこ
とにある。Still another object of the present invention is to provide a method and apparatus for uniformly, reproducibly, and stably controlling the plasma potential of microwave plasma generated over a large area and large volume.
本発明の更なる目的は、マイクロ波プラズマのプラズマ
電位を制御することにより、高品質で特性均一性に優れ
た機能性堆積膜を形成させるための新規な方法及び装置
を提供することにある。A further object of the present invention is to provide a novel method and apparatus for forming a functional deposited film of high quality and excellent uniformity of properties by controlling the plasma potential of microwave plasma.
本発明の更に別の目的は、比較的幅広で長尺の基板上に
連続して安定性良く、高効率で高い光電変換効率の光起
電力素子を形成するための新規な方法及び装置を提供す
るものである。Still another object of the present invention is to provide a novel method and apparatus for continuously forming a photovoltaic device with good stability, high efficiency, and high photoelectric conversion efficiency on a relatively wide and long substrate. It is something to do.
本発明者らは、従来の半導体堆積膜形Ifi装置におけ
る上述の諸問題を解決し、前記本発明の目的を遠戚すべ
く鋭意研究を進めたところ、成膜室の側壁を連続的に移
動する帯状部材で構成し、前記18室内にマイクロ波ア
ンテナ手段をマイクロ波透過性部材で包含させて突入さ
せ、前記成膜室内に成膜用原料ガスを導入し、ガス拡散
が容易に起こる適宜の圧力に保ち、前記マイクロ波アン
テナ手段にマイクロ波電源よりマイクロ波を供給し、更
に、前記帯状部材とは分離して配設したバイアス印加手
段にバイアス電圧を印加せしめたところ、前記成膜室内
において前記マイクロ波アンテナの長手方向に均一なマ
イクロ波プラズマを生起でき、且つそのプラズマ電位を
制御し得るという知見を得た。The inventors of the present invention solved the above-mentioned problems in the conventional semiconductor deposited film type Ifi apparatus, and conducted intensive research to achieve the object of the present invention. A microwave antenna means is enclosed in a microwave-transparent member and inserted into the 18 chamber, and a raw material gas for film formation is introduced into the film formation chamber, and an appropriate method is used to easily cause gas diffusion. When the pressure was maintained, microwaves were supplied from the microwave power source to the microwave antenna means, and a bias voltage was applied to the bias application means arranged separately from the band-shaped member. It has been found that uniform microwave plasma can be generated in the longitudinal direction of the microwave antenna, and that the plasma potential can be controlled.
本発明は、上述の知見に基づき更に検討を重ねた結果完
成に至ったものであり、下達するところを骨子とするマ
イクロ波プラズマCVD法により大面積の機能性堆積膜
を連続的に形成する方法及び装置を包含する。The present invention was completed as a result of further studies based on the above-mentioned findings, and is a method for continuously forming a large-area functional deposited film using a microwave plasma CVD method that mainly focuses on and equipment.
本発明の方法は、以下のとおりのものである。The method of the present invention is as follows.
即ち、長手方向に帯状部材を連続的に移動せしめながら
、その中途で前記移動する帯状部材を側壁にした実質的
に真空に保持し得る柱状の成膜空間を形成し、該成膜空
間内にガス供給手段を介して成膜用原料ガスを導入し、
同時にマイクロ波アンテナを介してマイクロ波の進行方
向に垂直な全方向にマイクロ波を放射させて前記成膜空
間内にマイクロ波電力を投入して前記成膜空間内にマイ
クロ波プラズマを生起せしめ、前記マイクロ波プラズマ
のプラズマ電位を制御しながら、該マイクロ波プラズマ
に曝される前記側壁を構成し連続的に移動する前記帯状
部材の表面上に堆積膜を形成せしめることを特徴とする
マイクロ波プラズマCVD法による大面積の機能性堆積
膜を連続的に形成する方法である。That is, while continuously moving the strip member in the longitudinal direction, a columnar film forming space that can be maintained in a substantially vacuum state is formed with the moving strip member as a side wall in the middle of the movement. Introducing raw material gas for film formation via a gas supply means,
Simultaneously, radiating microwaves in all directions perpendicular to the direction of propagation of the microwaves via a microwave antenna and injecting microwave power into the film-forming space to generate microwave plasma within the film-forming space; A microwave plasma characterized in that, while controlling the plasma potential of the microwave plasma, a deposited film is formed on the surface of the continuously moving band-shaped member that constitutes the side wall exposed to the microwave plasma. This is a method of continuously forming a large-area functional deposited film using the CVD method.
本発明の方法においては、前記移動する帯状部材の中途
において、湾曲開始端形成手段と湾曲終了端形成手段と
を用いて、前記湾曲開始端形成手段と前記湾曲終了端形
成手段との間に前記帯状部材の長手方向に間隙を残して
該帯状部材を湾曲させて前記成膜空間の側壁を成すよう
にされる。In the method of the present invention, a curved start end forming means and a curved end forming means are used in the middle of the moving band-shaped member, and the curved end forming means is provided between the curved start end forming means and the curved end forming means. The strip member is curved leaving a gap in the longitudinal direction of the strip member to form a side wall of the film forming space.
また、本発明の方法において、前記帯状部材の素材とし
ては、その線膨張係数が形成される堆積膜の線膨張係数
よりも大きいものを用い、該帯状部材を室温以上の所望
の成膜温度に保ちながら連続的に湾曲させて形成される
凹状の湾曲面上に堆積膜を形成せしめ、該堆積膜の形成
された帯状部材を成膜空間の外部において室温まで冷却
させるにつき、該帯状部材を平面状に展開して冷却させ
るようにするか又は凸状に巻取って冷却させるようにす
る。Further, in the method of the present invention, the material of the strip-shaped member is a material whose linear expansion coefficient is larger than that of the deposited film to be formed, and the strip-shaped member is heated to a desired film-forming temperature higher than room temperature. A deposited film is formed on the concave curved surface that is formed by continuously curving the deposited film while maintaining the temperature, and when the belt-shaped member on which the deposited film is formed is cooled to room temperature outside the film-forming space, the belt-shaped member is flattened. It can be rolled out into a shape and cooled, or rolled up into a convex shape and cooled.
そして、前記帯状部材を側壁として形成される柱状の成
膜空間の対向する両端面のいずれか一方より、前記成膜
空間内に前記マイクロ波アンテナ手段を突入させ、前記
成膜空間内にマイクロ波電力を投入させる。Then, the microwave antenna means is inserted into the film-forming space from either of the opposing end surfaces of the columnar film-forming space formed with the band-shaped member as a side wall, and the microwave antenna is transmitted into the film-forming space. Turn on the power.
また、前記マイクロ波アンテナ手段と前記成膜空間との
間に設けられたマイクロ波透過性部材を介して、該マイ
クロ波アンテナ手段より前記成膜空間内にマイクロ波電
力を投入させるようにし、更に、前記マイクロ波透過性
部材により前記マイクロ波アンテナ手段を前記成膜室内
に生起するプラズマから分離させる。Further, microwave power is introduced into the film forming space from the microwave antenna means via a microwave transparent member provided between the microwave antenna means and the film forming space, and , the microwave antenna means is separated from the plasma generated in the film forming chamber by the microwave transparent member.
本発明の方法においては、前記プラズマ電位は前記帯状
部材から分離されたバイアス印加手段を介して制御する
ようにする。In the method of the present invention, the plasma potential is controlled via bias application means separated from the strip member.
そして、前記バイアス印加手段は、少なくともその一部
分が前記マイクロ波プラズマに接するように配設し、前
記バイアス印加手段にバイアス電圧を印加させるように
するが、前記バイアス印加手段の前記マイクロ波プラズ
マに接する少なくとも一部分には導電処理を施すように
する。The bias applying means is disposed so that at least a portion thereof is in contact with the microwave plasma, and a bias voltage is applied to the bias applying means, but the bias applying means is arranged such that at least a portion thereof is in contact with the microwave plasma. At least a portion is subjected to conductive treatment.
更に、前記バイアス電圧としては直流、脈流及び/又は
交流が好適に用いられる。Further, as the bias voltage, direct current, pulsating current and/or alternating current are suitably used.
本発明の方法においては、前記バイアス印加手段は前記
ガス供給手段を兼ねるようにしても良いし、前記ガス供
給手段から分離して配設するようにしても良い。In the method of the present invention, the bias applying means may also serve as the gas supply means, or may be arranged separately from the gas supply means.
そして、前記バイアス印加手段は、単数又は複数のバイ
アス棒で構成させるようにする。The bias applying means may include one or more bias rods.
本発明の方法においては、前記プラズマ電位は前記帯状
部材に印加するバイアス電圧によって制御するようにし
ても良く、前記ガス供給手段は接地電位とし、少なくと
もその一部分が前記マイクロ波プラズマに接するように
配設するようにする。In the method of the present invention, the plasma potential may be controlled by a bias voltage applied to the band-shaped member, and the gas supply means is set to a ground potential, and at least a portion thereof is arranged to be in contact with the microwave plasma. be set up.
そして、前記ガス供給手段の前記マイクロ波プラズマに
接する少なくとも一部分には導電処理を施すようにする
。At least a portion of the gas supply means that is in contact with the microwave plasma is subjected to conductive treatment.
本発明の方法においては、プラズマの複素誘電率に応じ
てマイクロ波透過性部材の外径を予め調整・選択するよ
うにする。In the method of the present invention, the outer diameter of the microwave transparent member is adjusted and selected in advance according to the complex dielectric constant of the plasma.
また、前記帯状部材の前記マイクロ波プラズマに曝され
る側の面には少なくとも導電処理を施すようにする。Further, at least a surface of the band-shaped member on the side exposed to the microwave plasma is subjected to conductive treatment.
更には、本発明の装置は、以下の内容のものである。Furthermore, the apparatus of the present invention has the following contents.
即ち、連続的に移動する帯状部材上にマイクロ波プラズ
マCVD法により機能性堆積膜を連続的に形成する装置
であって、前記帯状部材をその長手方向に連続的に移動
させながら、その中途で湾曲させるための湾曲部形成手
段を介して、前記帯状部材を側壁にして形成されるその
内部を実質的に真空に保持し得る柱状の成膜室を有し、
前記成膜室内にマイクロ波プラズマを生起させるための
マイクロ波電力を供給するようにしたマイクロ波同軸線
路と、該同軸線路から供給されるマイクロ波電力を透過
せしめ、且つ前記マイクロ波プラズマから該マイクロ波
同軸線路の中心導体を分離するための中心導体分離手段
と、前記成膜室を排気する手段と、前記成膜室内に成膜
用原料ガスを導入するためのガス供給手段と、前記マイ
クロ波プラズマのプラズマ電位を制tTjするためのバ
イアス。That is, it is an apparatus that continuously forms a functional deposited film on a continuously moving strip-shaped member by microwave plasma CVD method, and while continuously moving the strip-shaped member in the longitudinal direction, A columnar film forming chamber is formed using the strip member as a side wall and can maintain a substantially vacuum inside thereof through a curved portion forming means for curving,
A microwave coaxial line for supplying microwave power for generating microwave plasma in the film forming chamber; a center conductor separating means for separating the center conductor of the wave coaxial line; a means for evacuating the film forming chamber; a gas supply means for introducing a raw material gas for film forming into the film forming chamber; Bias for controlling the plasma potential tTj of the plasma.
印加手段と、前記帯状部材を加熱及び/又は冷却するた
めの塩度ItI11御手段とを備えていて、前記連続的
に移動しながら前記成膜室の側壁を形成する帯状部材の
前記マイクロ波プラズマに曝される側の表面上に連続的
に堆積膜を形成するようにしたことを特徴とする大面積
堆積膜を連続的に形成する装置である。and a salinity ItI control means for heating and/or cooling the strip member, and the microwave plasma of the strip member forming the side wall of the film forming chamber while continuously moving. This is an apparatus for continuously forming a large area deposited film, characterized in that the deposited film is continuously formed on the surface exposed to the air.
本発明の装置において、前記湾曲部形成手段は湾曲開始
端形成ローラー、湾曲終了端形成ローラー及び対向する
湾曲部端面支持リングとからなり、前記湾曲開始端形成
ローラーと前記湾曲終了端形成ローラーとは、前記帯状
部材の長手方向に間隙を残して平行に配設される。In the apparatus of the present invention, the curved portion forming means includes a curved start end forming roller, a curved end end forming roller, and an opposing curved portion end surface support ring, and the curved start end forming roller and the curved end forming roller are , are arranged parallel to each other with a gap left in the longitudinal direction of the strip member.
本発明の装置において、前記バイアス印加手段を前記帯
状部材から分離して配設する。In the device of the present invention, the bias applying means is arranged separately from the strip member.
そして、前記バイアス印加手段は、少なくともその1部
分が前記マイクロ波プラズマに接するように配設し、前
記バイアス印加手段にバイアス電圧を印加させるように
するが、前記バイアス印加手段の前記マイクロ波プラズ
マに接する少なくとも一部分には導電処理が施される。The bias applying means is disposed such that at least a portion thereof is in contact with the microwave plasma, and a bias voltage is applied to the bias applying means. At least a portion of the contacting portion is subjected to conductive treatment.
更に、前記バイアス電圧としては、直流、脈流及び/又
は交流が好適に用いられる。Further, as the bias voltage, direct current, pulsating current and/or alternating current are suitably used.
本発明の装置において、前記バイアス印加手段は前記ガ
ス供給手段を兼ねても良いし、前記ガス供給手段から分
離して配設されても良い。In the apparatus of the present invention, the bias application means may also serve as the gas supply means, or may be arranged separately from the gas supply means.
前記バイアス印加手段は単数又は複数のバイアス棒で構
成される。The bias applying means is composed of one or more bias rods.
本発明の装置において、前記バイアス印加手段は前記帯
状部材を兼ねて配設する場合には、前記ガス供給手段を
接地し、少なくともその一部分が前記マイクロ波プラズ
マに接するように配設する。In the apparatus of the present invention, when the bias applying means is disposed also as the strip member, the gas supply means is grounded and at least a portion thereof is disposed so as to be in contact with the microwave plasma.
そして、前記ガス供給手段の前記マイクロ波プラズマに
接する少なくとも一部分には導電処理を施す。At least a portion of the gas supply means that is in contact with the microwave plasma is subjected to conductive treatment.
本発明の装置において、前記マイクロ波同軸線路の中心
導体は、前記柱状の成膜室の対向する両端面のいずれか
一方より該成膜室内部に突入され、且つ、該柱状の成膜
室の中心軸近傍に前記帯状部材の幅方向とほぼ平行に配
設される。In the apparatus of the present invention, the center conductor of the microwave coaxial line is inserted into the film forming chamber from either one of the opposing end surfaces of the columnar film forming chamber, and It is arranged near the central axis and substantially parallel to the width direction of the band-shaped member.
本発明の装置において、マイクロ波13i1J性部材で
構成される中心導体分離手段は、回転対称形であり、そ
の形状としては、円筒状、円錐台状、又は円錐状のいず
れであっても良い。In the apparatus of the present invention, the central conductor separating means constituted by the microwave 13i1J member is rotationally symmetrical, and its shape may be cylindrical, truncated conical, or conical.
さらに本発明の装置においては、前記マイクロ波同軸線
路上に少なくとも2つの同調手段が配設され、そのうち
1つが前記成膜室内部に突入された前記中心導体の挿入
長調節機構となるようにされる。Furthermore, in the apparatus of the present invention, at least two tuning means are disposed on the microwave coaxial line, one of which serves as an insertion length adjustment mechanism for the center conductor inserted into the film forming chamber. Ru.
また、前記帯状部材の前記マイクロ波プラズマに曝され
る側の面には少なくとも導電性処理が施される。Further, at least a surface of the band-shaped member on the side exposed to the microwave plasma is subjected to conductive treatment.
本発明の装置を用いて、帯状部材上に高品質の機能性堆
積膜を均一に形成するための、マイクロ波プラズマの生
起条件等について検討するため、種々実験を行ったので
、以下に詳述する。Various experiments were conducted using the apparatus of the present invention to investigate the conditions for generating microwave plasma in order to uniformly form a high-quality functional deposited film on a strip-shaped member. do.
大致髭上
本実験例においては、成膜室を円柱状の成膜室の内径を
変化させたときのプラズマの安定性、膜厚分布及び膜質
の分布々について検討した。In this experimental example, the plasma stability, film thickness distribution, and film quality distribution were investigated when the inner diameter of the cylindrical film forming chamber was changed.
具体的には、後述する装置例1の装置を用い、成膜室の
内径のみを変化させて5種類の試料を第1表の成膜条件
に従って作製した。なお、帯状部材は静止させた状態で
本検討を行った。Specifically, using the apparatus of Apparatus Example 1 to be described later, five types of samples were prepared according to the film forming conditions shown in Table 1 by changing only the inner diameter of the film forming chamber. Note that this study was conducted with the strip member stationary.
第2表に成膜室の内径を種々変化させた場合におけるプ
ラズマの状態等についての評価結果を示す。Table 2 shows the evaluation results regarding the plasma state etc. when the inner diameter of the film forming chamber was variously changed.
第2表に示した成膜室の内径が180關φ、120 s
sφの場合において、マイクロ波電力を25 (l O
Wとした以外は第1表に示したのと同様の条件でプラズ
マを生起させたところ、成膜室の内径が120 mmφ
の場合は放電が安定化したが、成膜室の内径がl 80
關φの場合は放電が生起したものの不安定で、実用に
値するものではなかった。The inner diameter of the film forming chamber shown in Table 2 is 180mmφ, 120s
In the case of sφ, the microwave power is 25 (l O
When plasma was generated under the same conditions as shown in Table 1 except that W was used, the inner diameter of the film forming chamber was 120 mmφ.
In the case of , the discharge was stabilized, but the inner diameter of the deposition chamber was
In the case of 關φ, although discharge occurred, it was unstable and not worthy of practical use.
次に、試料2−1乃至2−4について、以下に述べる評
価法により特性評価を行った。Next, the characteristics of samples 2-1 to 2-4 were evaluated using the evaluation method described below.
形成された堆積膜の膜厚はユニオン技研社製のMCPD
−2O0型分光反射率測定機を用いて測定した分光反射
率曲線の多重干渉フリンジのピーク位置から算出した。The thickness of the deposited film formed is MCPD manufactured by Union Giken Co., Ltd.
It was calculated from the peak position of the multiple interference fringe of the spectral reflectance curve measured using a -2O0 type spectral reflectance meter.
夫々の試料における膜厚の測定箇所は基板の幅方向(X
)及び長手方向(y)に79って50mごととした0次
に、このa−8i;H膜上にCrl膜を約70蒸着着し
、オーミソクTIL極を形成した。そして、暗中で該オ
ーミソク電極と帯状部材として用いた5US430BA
(0,2mm厚)薄板との間に電圧を印加して流れる電
流値から暗導電率(σ、)を求め、また、前述と同様に
電圧を印加しながら、前記C「電極側からHe−N5レ
ーザー光を照射して流れる電流値から光導電率(σ、)
を求め、それぞれの特性分布の評価を行った。なお、H
e−Neレーザー光のa−3i:)l膜中への照射強度
は、Cr電極の吸収を考慮してフォトン数で4X10”
個/−・secとした。The film thickness measurement points for each sample were in the width direction of the substrate (X
) and in the longitudinal direction (y) at intervals of 79 m and 50 m, a Crl film was deposited on this a-8i; Then, in the dark, the Ohmisoku electrode and 5US430BA used as a strip member were used.
(0.2 mm thick) The dark conductivity (σ, ) was determined from the current value flowing by applying a voltage between the thin plate, and while applying the voltage in the same manner as described above, the He- Photoconductivity (σ,) is determined from the current value flowing when irradiated with N5 laser light.
were calculated, and the characteristic distribution of each was evaluated. In addition, H
The irradiation intensity of the e-Ne laser beam into the a-3i:)l film is 4X10" in terms of the number of photons, taking into account the absorption of the Cr electrode.
pieces/-・sec.
第10図(alに試料2−1乃至2−3のX方向の膜厚
分布、第1O図山)にy方向の膜厚分布、第11図+8
+にσ1.σ、のX方向の分布、第11図+8+にσ4
.σ、のy方向の分布の夫々の測定結果を示した。ここ
で、X=Oは帯状部材の幅方向の中心、y=oは帯状部
材を長手方向に展開した時の中心を表している。Figure 10 (al shows the film thickness distribution in the X direction of samples 2-1 to 2-3, the mountain in Figure 1O shows the film thickness distribution in the y direction, Figure 11 +8
+σ1. Distribution of σ in the X direction, Fig. 11 σ4 at +8+
.. The measurement results of the distribution of σ in the y direction are shown. Here, X=O represents the center in the width direction of the band-like member, and y=o represents the center when the band-like member is expanded in the longitudinal direction.
これらの測定結果より、前記帯状部材の幅方向について
は膜厚、膜質ともに均一性が良いが、堆積される膜厚は
成膜室の内圧が大きくなるにつれ減少し、前記帯状部材
の長手方向については膜厚の均一性は保たれているもの
の、試料2−1では明らかに特性の悪化が認められる。From these measurement results, the uniformity of both the film thickness and film quality is good in the width direction of the band-shaped member, but the deposited film thickness decreases as the internal pressure of the film-forming chamber increases, and the uniformity of the film in the longitudinal direction of the band-shaped member is good. Although the uniformity of the film thickness was maintained in Sample 2-1, the characteristics clearly deteriorated.
即ち、前記成膜室の内径が大きくなるにつれて、形成さ
れるa−3i:H膜の特性が悪化する傾向がある。That is, as the inner diameter of the film forming chamber increases, the characteristics of the a-3i:H film that is formed tend to deteriorate.
なお、試料2−4は帯状部材が同軸に非常に接近してい
るが故、プラズマ密度が他の試料の場合に比較して相当
に高くなるため、基板温度は350℃以上にもなり、こ
のため成膜後に膜の剥離が生じ、評価に耐えないもので
あった。In addition, in sample 2-4, since the strip members are coaxially very close to each other, the plasma density is considerably higher than in the case of other samples, and the substrate temperature is over 350°C. Therefore, peeling of the film occurred after film formation, and the film could not withstand evaluation.
叉狸班主
本実験例においては、第1図に示す本発明の装置(後述
する装置例1参照)と第9図に示す従来のRFグロー放
電分解装置とを用いて、第3表に示す条件で堆積膜を形
成し、堆積膜形成の前後における基体の歪み量を各々測
定することによって、堆積膜中の圧縮応力の変化を検討
した。ここで、前記帯状部材となっているステンレス鋼
のヤング率は2.04 X 10’ [kf/llj
” ] 、線膨張係数は11.9 X 10” [”C
−’]であった。In this experimental example, the apparatus of the present invention shown in Fig. 1 (see apparatus example 1 described later) and the conventional RF glow discharge decomposition apparatus shown in Fig. 9 were used under the conditions shown in Table 3. We investigated changes in compressive stress in the deposited film by forming a deposited film and measuring the amount of strain on the substrate before and after the deposited film was formed. Here, the Young's modulus of the stainless steel forming the band member is 2.04 x 10' [kf/llj
” ], linear expansion coefficient is 11.9 x 10” [”C
-'].
その結果、いずれの装置を用いた場合においても、堆積
膜の’JJJ Mは認められなかったが、実際に堆積膜
中に蓄積された圧縮応力の測定結果は、第9図の従来装
置を用いた場合には、32kg/m”であり、これに比
較して第1図の本発明の装置を用いた場合には、9ky
/me”となっており、l/3.5程度に応力緩和が威
されていることが判った。As a result, 'JJJ M' was not observed in the deposited film using either device, but the measurement results of the compressive stress actually accumulated in the deposited film were as follows using the conventional device shown in Figure 9. In contrast, when using the apparatus of the present invention shown in FIG.
/me'', and it was found that the stress relaxation was effective at about 1/3.5.
大襲班1
本実験例においては、前記成膜空間の内外に圧力差をつ
ける方法について、第1図に示す装置を用い、前記第3
表の作製条件において、スリットの開口部の幅を種々変
化させた以外は同様の作製条件にてa−3t:H膜を堆
積する実験を行った。Large attack team 1 In this experimental example, a method of creating a pressure difference between the inside and outside of the film forming space was performed using the apparatus shown in FIG.
An experiment was conducted to deposit an a-3t:H film under the same manufacturing conditions as shown in the table except that the width of the slit opening was varied.
実験の結果及び評価等を第4表に示す。Table 4 shows the experimental results and evaluation.
尚、表中の実効コンダクタンスCat [1/sec]
は、流量をEsccm]から[Torr −1/se
eコに換算して成膜空間内部と外部の差圧ΔP [To
rr]で割って求めた。In addition, the effective conductance Cat [1/sec] in the table
is the flow rate from [Esccm] to [Torr −1/se
The differential pressure ΔP between the inside and outside of the film-forming space in terms of e
It was calculated by dividing by [rr].
第4表の結果より、プラズマの漏洩を防止する上では成
膜空間の内外の圧力差を9mTorrより大きくするこ
とが好ましいことが判った。From the results in Table 4, it was found that in order to prevent plasma leakage, it is preferable to make the pressure difference between the inside and outside of the film forming space larger than 9 mTorr.
大慧斑玉
本実験例においては、前記成膜空間外部の圧力を低く保
持することにより、異常放電を抑制する方法について第
1図に示す装置を用い、さらに、真空排気口に第6図に
示すようなスロ7)ルバルブを介在させ、油拡散ポンプ
を接続して実効的な排気速度が変化できるようにして第
3表の作製条件において、成膜室外部の圧力を種々変化
させた以外は同様の作製条件にて放電実験を行った。そ
れらの結果を第5表に示す。In this experimental example, the apparatus shown in Fig. 1 was used to learn how to suppress abnormal discharge by keeping the pressure outside the film forming space low, and the apparatus shown in Fig. 6 was installed at the vacuum exhaust port. The process was the same except that the pressure outside the film forming chamber was varied under the production conditions shown in Table 3 by interposing a throttle valve and connecting an oil diffusion pump so that the effective pumping speed could be varied. A discharge experiment was conducted under the following manufacturing conditions. The results are shown in Table 5.
これらの結果より、tcJI!空間外の隔離容器の圧力
が高くなり、成膜空間内部の圧力とほぼ等しくなると異
常放電、或いは放電集中が発生し密着力の悪い膜が堆積
した。従って、異常放電による膜質低下を防止する上で
前記成膜空間外部の圧力を5 m Torr以下に保持
することが好ましいことが判った。From these results, tcJI! When the pressure in the isolation container outside the space became high and almost equal to the pressure inside the film forming space, abnormal discharge or discharge concentration occurred and a film with poor adhesion was deposited. Therefore, it has been found that in order to prevent film quality deterioration due to abnormal discharge, it is preferable to maintain the pressure outside the film forming space at 5 m Torr or less.
尖狡班工
本実験例においては、後述する装置例1 (第1図)で
示す装置にて、第19図(A)に示した構成のバイアス
印加手段を具備させ、ニッケル製のガス導入管を兼ねる
バイアス印加管1903への直流バイアス印加電圧を変
化させたときのマイクロ波プラズマの制御性、プラズマ
電位及び膜質への影響等について検討を行った。In this experimental example, the apparatus shown in Device Example 1 (Fig. 1), which will be described later, was equipped with a bias applying means having the configuration shown in Fig. 19 (A), and a nickel gas introduction tube was used. We investigated the controllability of microwave plasma, the influence on plasma potential, film quality, etc. when changing the DC bias voltage applied to the bias application tube 1903, which also serves as a bias application tube 1903.
バイアス印加電圧を、−300Vから+300VまでI
OVきざみで変化させた以外は、第1表に示したのと同
様のマイクロ波プラズマ放電条件にてプラズマを生起さ
せた。なお、成膜室内径は801mφとした。なお、帯
状部材の表面温度は250℃とし、搬送速度は48cs
/sin、とした。Bias applied voltage from -300V to +300V
Plasma was generated under the same microwave plasma discharge conditions as shown in Table 1, except that the conditions were changed in OV steps. Note that the inner diameter of the film forming chamber was 801 mφ. The surface temperature of the strip member was 250°C, and the conveyance speed was 48 cs.
/sin.
また、各バイアス電圧を印加してからは10分間放電を
維持させるようにした。Furthermore, after each bias voltage was applied, discharge was maintained for 10 minutes.
第20図にX軸にバイアス印加電圧、Y軸にバイアス電
流値をとり、バイアス印加時におけるバイアス印加管と
帯状部材との間の電流−電圧特性を求めた結果を示す。FIG. 20 shows the results of determining the current-voltage characteristics between the bias application tube and the strip member during bias application, with the bias applied voltage plotted on the X-axis and the bias current value plotted on the Y-axis.
同時に、直径0.3 vs、長さ3m(ft出部分)の
タングステン線を用いたシングルプローブを用いた探針
法により、バイアス印加時のプラズマ電位V、を測定し
、バイアス印加させない時のプラズマ電位v0に対する
変化率ΔVb(=Vb/V6)を求めた結果を第21図
に示す、なお、前記シングルプローブは前記帯状部材の
湾曲部分のほぼ中央、且つ内表面よりほぼ5cmの所に
配設した。At the same time, the plasma potential V when bias was applied was measured by a probe method using a single probe using a tungsten wire with a diameter of 0.3 vs. and a length of 3 m (ft part). The results of determining the rate of change ΔVb (=Vb/V6) with respect to the potential v0 are shown in FIG. 21. The single probe was placed approximately at the center of the curved portion of the band-shaped member and approximately 5 cm from the inner surface. did.
これらの結果において、放電用の原料ガスの種類や流量
によって変化はあるものの、概ねバイアス電圧を一19
0v以下、又は+190V以上とした場合には、成膜室
内でスパーク等の異常放電が発生し、安定した放電状態
の維持は困難であっ?◆
しかしながら、マイクロ波プラズマの放電条件が一定の
時にはバイアス電圧の増加にともない電流−電圧特性は
ほぼ増加傾向の直線関係を示し、プラズマ電位もバイア
ス電圧の増加とともに、増加傾向を示すことが判った。Although these results vary depending on the type and flow rate of the raw material gas for discharge, in general, when the bias voltage is set to 19
If the voltage is below 0V or above +190V, abnormal discharge such as sparks will occur in the film forming chamber, making it difficult to maintain a stable discharge state. ◆ However, it was found that when the microwave plasma discharge conditions are constant, the current-voltage characteristics show a linear relationship with an almost increasing tendency as the bias voltage increases, and the plasma potential also shows an increasing tendency as the bias voltage increases. .
即ち、バイアス電圧を変化させることでプラズマ電位を
容易に、安定して、再現性良く制御することができた。That is, by changing the bias voltage, the plasma potential could be controlled easily, stably, and with good reproducibility.
引き続き、帯状部材としての5US430BA薄板上に
堆積形成された膜について5關×5關の試料片を切り出
し、その表面状態を超高分解能、低加速FB−3EM
(日立製作所S−900型)にて観察したところ、バイ
アス電圧が一300v乃至+IOVの範囲では数百人〜
数千人程度の表面荒れが目立ったが、+10V乃至+1
70Vの範囲ではほぼバイアス電圧の増加に伴って膜表
面が平滑化していく傾向が認められた。そして、+17
0Vを超えた範囲では膜表面が再び荒れ始め、特に+1
90vを超えて異常放電の多発した試料表面にはピンホ
ールの発生も認められた。Subsequently, a 5 x 5 sample piece was cut out for the film deposited on the 5US430BA thin plate as a strip member, and its surface condition was examined using ultra-high resolution, low acceleration FB-3EM.
(Hitachi S-900 model) When the bias voltage ranged from 1300V to +IOV, several hundred people ~
Surface roughness was noticeable for several thousand people, but +10V to +1
In the range of 70 V, it was observed that the film surface tended to become smoother as the bias voltage increased. And +17
In the range exceeding 0V, the membrane surface begins to become rough again, especially at +1
Pinholes were also observed on the surface of the sample where abnormal discharges occurred frequently at voltages exceeding 90V.
また、マイクロ波電力が一定の条件下ではS r H4
等の!離断面積の大きい原料ガスの流量比が増加するの
に伴い、電流−電圧特性の傾きは大きくなり、一方、H
!等の電離断面積の小さい原料ガスの流量比が増加する
のに伴い、電流−電圧特性の傾きは小さくなることが判
った。Moreover, under the condition that the microwave power is constant, S r H4
etc.! As the flow rate ratio of the raw material gas with a large separation cross-sectional area increases, the slope of the current-voltage characteristics increases, while H
! It was found that as the flow rate ratio of the raw material gas with a small ionization cross section increases, the slope of the current-voltage characteristic becomes smaller.
比較大鼓斑上
実験例5において、ガス導入管を兼ねるバイアス印加前
1903をニッケル製のものからアルミニウム製のもの
に変えた以外は同様の条件で電流−電圧特性を測定した
。ところが、バイアス印加電圧をOvから+55V程度
まで上昇させていった所、バイアス印加前1903は変
形を始め、ついには溶断してしまうという現象が認めら
れた。The current-voltage characteristics were measured under the same conditions as in Comparative Experimental Example 5, except that the pre-bias application 1903, which also served as the gas introduction tube, was changed from nickel to aluminum. However, when the bias applied voltage was increased from Ov to approximately +55V, a phenomenon was observed in which the pre-bias application 1903 began to deform and eventually fused.
更に、バイアス印加前1903を銅製、真ちゅう製のも
のに変えて同様の測定を行ったところ、やはり前述と同
様の現象が認められた。これらに対し、バイアス印加前
1903をステンレス・スチール製、チタン製、バナジ
ウム製、ニオブ製、タンタル製、モリブデン製、タング
ステン製等の高融点金属製、及びアルミナ・セラミック
ス管の表面にニッケル溶射を800ttm行ったものに
変えて同様の測定を行ったところ、ステンレス・スチー
ル製のものを用いた場合にはバイアス印加電圧が+11
5vを超えるあたりで変形が認められ、やはりついには
溶断してしまった以外は、他の材質のものを用いた場合
にはほぼ実験例5で得られたのと同様の測定結果が得ら
れ、特に変形等の現象も認められなかった。Furthermore, when the same measurement was performed by changing the pre-bias application 1903 to one made of copper or brass, the same phenomenon as described above was also observed. Before bias application, 1903 was sprayed with 800 ttm of nickel on the surface of high melting point metals such as stainless steel, titanium, vanadium, niobium, tantalum, molybdenum, and tungsten, and alumina ceramic tubes. When we performed similar measurements using the one made of stainless steel, we found that the applied bias voltage was +11
When using other materials, almost the same measurement results as those obtained in Experimental Example 5 were obtained, except that deformation was observed when the voltage exceeded 5V, and it finally fused. In particular, no phenomena such as deformation were observed.
迄較大翌拠1
実験例5において、帯状部材としての5US430BA
il1反をPET (ポリエチレンテレフタレート)製
シート(厚さ0.8關)に変えた以外は同様の条件で電
流−電圧特性を測定した。ところが、バイアス印加電圧
を正又は負のいずれの側に印加しても流れる電流値は、
実験例5で得られたのとほぼ同等の値を示したものの、
Fti、膜室内での異常放電の開始電圧が一95V又は
95V程度であった。目視によりその状態を観察した所
、スパークは前記バイアス印加管と帯状部材の支持・搬
送用ローラーとの間で生しており、このスパークば用い
た帯状部材が絶縁性故チャージアンプ現象を示し、rI
i、膜室内にてバイアス印加前以外では唯一導電性部材
にて構成されている前記支持・搬送用ローラーに過剰の
電流が流れているためであることが判った。Comparison basis 1 In Experimental Example 5, 5US430BA as a strip member
The current-voltage characteristics were measured under the same conditions except that the il1 sheet was replaced with a PET (polyethylene terephthalate) sheet (thickness: 0.8 mm). However, the current value that flows regardless of whether the bias voltage is applied to the positive or negative side is
Although it showed almost the same value as that obtained in Experimental Example 5,
Fti, the starting voltage of abnormal discharge in the membrane chamber was 195V or about 95V. When the state was visually observed, sparks were generated between the bias application tube and the rollers for supporting and conveying the strip member, and the strip member used exhibited a charge amplification phenomenon due to its insulating properties. rI
i. It was found that this was because an excessive current was flowing through the supporting/conveying roller, which was the only part of the membrane chamber other than before the bias was applied, which was made of a conductive member.
また、堆積形成された膜の表面状態を実験例6で行った
のと同様の方法にて観察、評価したところ、膜表面はバ
イアス印加電圧の違いによらず数百人〜数千人程度の表
面荒れが生じたままであった。In addition, when the surface condition of the deposited film was observed and evaluated using the same method as in Experimental Example 6, it was found that the surface condition of the film was approximately several hundred to several thousand, regardless of the difference in the applied bias voltage. The surface remained rough.
北本04動生1
実験例5において、成膜室内に配設されるガス導入管を
兼ねるバイアス印加前1903の位置を、成膜室のほぼ
中心軸上部(第4図、Oの位置〉から、第4図中帯状部
材の湾曲面に沿って45゛90°、135°方向にずら
せた以外は、同様の条件で1i流−電圧特性を測定した
。なお、中心軸上OH’方向へは100nの場合も同様
に測定を行った。Kitamoto 04 Motion 1 In Experimental Example 5, the position of the pre-bias application 1903, which also serves as a gas introduction pipe arranged in the film forming chamber, was changed from approximately above the central axis of the film forming chamber (position O in Fig. 4). The 1i current-voltage characteristics were measured under the same conditions except that the strip member was shifted in the 45°, 90°, and 135° directions along the curved surface of the strip member in Figure 4. Measurements were also made in the same way.
その結果、45°、90°、135°方向へずらせた場
合には実験例5と全く同様の結果が得られた。一方OH
’方向へ100 am、120璽mずらせた場合におい
ては、そもそも成膜室内への原料ガスの供給が十分に行
われないために、プラズマが安定して生起しないのと相
まって、バイアス電圧を印加してもバイアス電流はほと
んど流れず、プラズマ電位の制御は実施困難であること
が判った。As a result, results exactly the same as in Experimental Example 5 were obtained when shifting in directions of 45°, 90°, and 135°. On the other hand, OH
If the film is shifted by 100 am or 120 m in the direction of However, almost no bias current flows, making it difficult to control the plasma potential.
失慧班i
本実験例においては、実験例5で用いた構成の装置を用
い、第8表に示す種々の波形及び周波数条件のバイアス
電圧をバイアス印加管1903に印加させたときのマイ
クロ波プラズマの制御性、プラズマ電位及び膜質への影
響等について検討を行った。なお、マイクロ波プラズマ
放電条件等は実験例5と同様とした。In this experimental example, we used the apparatus with the configuration used in Experimental Example 5 to generate microwave plasma when bias voltages with various waveforms and frequency conditions shown in Table 8 were applied to the bias application tube 1903. We investigated the controllability of plasma potential, the effects on plasma potential, and film quality. Note that the microwave plasma discharge conditions and the like were the same as in Experimental Example 5.
バイアス電圧はファンクシラン・ジェネレータ(ヒユー
レット・パラカード社製HP8116A)で発生させた
種々の波形出力を精密電力増幅器(エヌエフ回路ブロッ
ク社製4500シリーズ及び特注品)にて増幅させたも
の、又は自作の整流回路装置にて出力させたものを同軸
ケーブルを介して、バイアス印加管1903に印加させ
た。Bias voltages can be obtained by amplifying various waveform outputs generated by a funxilane generator (HP8116A manufactured by Hewlett-Paracard) using a precision power amplifier (4500 series manufactured by NF Circuit Block Company and a custom-made product), or by using a homemade one. The output from the rectifier circuit device was applied to a bias application tube 1903 via a coaxial cable.
放電の状況、プラズマ電位の変化率、膜表面観察等によ
り、プラズマ電位の制御性について評価を行った結果を
第8表中に示す。これらの結果より、比較的広い周波数
範囲においてバイアス電圧を印加することによる効果が
認められることが判った。Table 8 shows the results of evaluating the controllability of the plasma potential based on discharge conditions, rate of change in plasma potential, observation of the film surface, etc. From these results, it was found that the effect of applying a bias voltage was observed in a relatively wide frequency range.
更に、バイアス電圧の周波数を固定して最大振幅電圧を
種々変化させた場合には、はぼ実験例5と同様の傾向、
即ち、直流電圧を変化させたときと同様の傾向が認めら
れ、特に、最大振幅電圧の増加によりスパーク等の異常
放電の発生頻度が増加した。Furthermore, when the frequency of the bias voltage was fixed and the maximum amplitude voltage was varied, the same tendency as in Experimental Example 5 was observed.
That is, the same tendency as when changing the DC voltage was observed, and in particular, as the maximum amplitude voltage increased, the frequency of occurrence of abnormal discharges such as sparks increased.
これらの結果より、バイアス印加管に直流電圧以外の種
々のバイアス電圧を印加させた場合においても、該バイ
アス電圧を変化させることでプラズマ電位を容易に、安
定して、再現性良く制御できることが判った。These results show that even when various bias voltages other than DC voltage are applied to the bias tube, the plasma potential can be controlled easily, stably, and with good reproducibility by changing the bias voltage. Ta.
太慧史ユ
本実験例においては、バイアス印加手段を第19図(B
)に示した構成に変えた以外は実験例5と同様の条件で
電流−電圧特性を測定した。In this experimental example, the bias application means is shown in Fig. 19 (B
) The current-voltage characteristics were measured under the same conditions as in Experimental Example 5 except that the configuration was changed to that shown in ().
その結果、実験例5とほぼ同様の結果が得られ、ガス導
入管1905とバイアス棒19o4とが独立に配設され
ていてもバイアス電圧を変化させることでプラズマ電位
を容易に、安定して、再現性良く制御できることが判っ
た。As a result, almost the same results as in Experimental Example 5 were obtained, and even though the gas introduction tube 1905 and the bias rod 19o4 were arranged independently, the plasma potential could be easily and stably changed by changing the bias voltage. It was found that it could be controlled with good reproducibility.
大豊班主
本実験例においては、バイアス印加手段を第19図(C
)に示した構成に変えた以外は実験例5と同様の条件で
電流−電圧特性を測定した。In this experimental example, the bias application means is shown in Figure 19 (C
) The current-voltage characteristics were measured under the same conditions as in Experimental Example 5 except that the configuration was changed to that shown in ().
その結果、スパーク等の異常放電の開始電圧がやや変化
し、その時には特に成膜室内の支持・搬送用リングと帯
状部材との接触部分での異常放電の発生が認められた以
外は、はぼ実験例5と同様の結果が得られた。ただし、
膜表面が平滑化するバイアス電圧は、実験例5の場合と
全く逆の極性、即ち、−10V乃至−170Vの範囲で
あった。As a result, the starting voltage of abnormal discharges such as sparks changed slightly, and at that time, there were no abnormal discharges except for the occurrence of abnormal discharges, especially at the contact area between the support/transport ring and the strip member in the deposition chamber. The same results as in Experimental Example 5 were obtained. however,
The bias voltage at which the film surface was smoothed had a polarity completely opposite to that in Experimental Example 5, that is, in the range of -10V to -170V.
勿論、この電圧範囲内においてはプラズマは安定してい
た。Of course, the plasma was stable within this voltage range.
従って、帯状部材にバイアス電圧を印加し、成膜室内に
ガス導入管を兼ねるアース棒1905を配設することで
プラズマ電位を容易に、安定して、再現性良く制御でき
ることが判っな。Therefore, it has been found that the plasma potential can be easily, stably, and reproducibly controlled by applying a bias voltage to the band-shaped member and arranging the ground rod 1905, which also serves as a gas introduction pipe, in the film forming chamber.
失慧班ユ
本実験例においては、バイアス印加手段を第19図(D
)に示した構成に変え、バイアス棒1904には実験例
7と同様の条件で直流バイアス電圧を印加し、これとは
独立にバイアス棒1906にはバイアス棒1904に印
加した直流電圧の1/4の電圧を印加したときのマイク
ロ波プラズマの制御性、プラズマ電位及びtiltへの
影響等について検討を行った。なお、マイクロ波プラズ
マ放電条件等は実験例5と同様とした。In this experimental example, the bias application means is shown in Fig. 19 (D
), a DC bias voltage was applied to the bias rod 1904 under the same conditions as in Experimental Example 7, and independently of this, 1/4 of the DC voltage applied to the bias rod 1904 was applied to the bias rod 1906. We investigated the controllability of microwave plasma, the influence on plasma potential and tilt, etc. when applying a voltage of . Note that the microwave plasma discharge conditions and the like were the same as in Experimental Example 5.
その結果、スパーク等の異常放電の発生頻度が減少し、
プラズマの安定性が向上した以外はほぼ実験例5と同様
の結果が得られた。As a result, the frequency of abnormal discharges such as sparks is reduced,
Almost the same results as in Experimental Example 5 were obtained, except that the stability of the plasma was improved.
従って、成膜室内に複数のバイアス棒を配設し、夫々独
立にバイアス電圧を印加させることで、プラズマ電位を
容易に、安定して、再現性よく制御できることが判った
。Therefore, it has been found that the plasma potential can be easily, stably, and reproducibly controlled by disposing a plurality of bias rods in the film forming chamber and applying bias voltages to each rod independently.
去起LLL土
本実験例においては、実験例9にてバイアス棒1904
に印加するバイアス電圧を直流電圧に変えて、実験例6
で実施したのと同様の種々の波后及び周波数のバイアス
電圧を印加させたときのマイクロ波プラズマの制御性、
プラズマ電位及び膜質への影響等について検討を行った
。なお、マイクロ波プラズマ放電条件等は実験例5と同
様とした。In the example of the Tsuchimoto experiment, the bias rod 1904 was used in experiment example 9.
Experimental Example 6 was carried out by changing the bias voltage applied to DC voltage to
Controllability of microwave plasma when applying bias voltages of various waves and frequencies similar to that carried out in
We investigated the effects on plasma potential and film quality. Note that the microwave plasma discharge conditions and the like were the same as in Experimental Example 5.
その結果、スパーク等の異常放電の発生頻度が減少し、
また、異常放電の開始電圧もやや低下し、プラズマの安
定性が向上した以外はほぼ実験例5と同様の結果が得ら
れた。As a result, the frequency of abnormal discharges such as sparks is reduced,
In addition, almost the same results as in Experimental Example 5 were obtained, except that the starting voltage of abnormal discharge was slightly lowered and the stability of the plasma was improved.
従って、成膜室内に複数のバイアス棒を配設し、夫々独
立にバイアス電圧を印加させることで、プラズマ電位を
容易に、安定して再現性よく制御できることが判った。Therefore, it has been found that the plasma potential can be easily, stably, and reproducibly controlled by disposing a plurality of bias rods in the film forming chamber and applying bias voltages to each rod independently.
去じ事U二し−L1
実験例7及び8において、実験例6で実施したのと同様
のバイアス電圧を印加させた実験を行ったところ、はぼ
実験例7及び8で得られたのと同様の効果が認められた
。In Experimental Examples 7 and 8, we conducted an experiment in which the same bias voltage as that in Experimental Example 6 was applied. Similar effects were observed.
去慧殖果史旦叉
本発明の方法及び装置において、マイクロ波プラズマの
安定性、均−性等は、例えばマイクロ波アプリケーター
の種類及び形状、成膜時の成膜室内の圧力、マイクロ波
電力、マイクロ波プラズマの閉じ込めの程度、放電空間
の体積及び形状等種々のパラメーターが複雑にからみ合
って維持されているので、単一のパラメーターのみで最
適条件を求めるのは困難であるが、本実験結果より、お
およそ次のような傾向及び条件範囲が判った。In the method and apparatus of the present invention, the stability, uniformity, etc. of the microwave plasma are determined by, for example, the type and shape of the microwave applicator, the pressure inside the film forming chamber during film formation, and the microwave power. Since various parameters such as the degree of confinement of the microwave plasma, the volume and shape of the discharge space, etc. are intricately intertwined and maintained, it is difficult to determine the optimal conditions using only a single parameter. The results revealed roughly the following trends and condition ranges.
本発明の方法において、前記成膜空間の内径は、好まし
くは60關φ乃至120關φとされるのが望ましい、ま
た、所望の成膜温度に加熱し、且つ柱状に湾曲させた帯
状部材の凹状の湾曲面上に堆積膜を形成し、これを平面
状に展開して冷却させることによって堆積膜中に蓄積さ
れる応力を緩和させることができる。In the method of the present invention, the inner diameter of the film forming space is preferably 60 mm to 120 mm. The stress accumulated in the deposited film can be alleviated by forming the deposited film on a concave curved surface, expanding it into a flat shape, and cooling it.
また、スリットの開口幅を変化させて成膜空間の内外の
圧力差を9 m Torr以上にすることにより、前記
成膜空間からのプラズマの漏洩が防止できる。更に、前
記成膜空間外部の圧力を6mTorr以下にすることで
、異常放電による堆積膜の膜質の低下も防止できること
が判った。Further, by changing the opening width of the slit to make the pressure difference between the inside and outside of the film forming space 9 m Torr or more, leakage of plasma from the film forming space can be prevented. Furthermore, it has been found that by setting the pressure outside the film-forming space to 6 mTorr or less, deterioration in the quality of the deposited film due to abnormal discharge can be prevented.
更に、本発明の方法及び装置において、マイクロ波プラ
ズマのプラズマ電位を制御するには、プラズマの閉じ込
められた成膜室内にバイアス電圧印加手段を設け、該バ
イアス印加手段に種々の直流電圧、又は脈流、交流電圧
にて種々の波形、周波数、及び最大振幅電圧のバイアス
電圧を印加させることが望ましいことが判った。また、
前記バイアス電圧印加手段はガス導入管を兼ねても良く
、あるいはガス導入管とは別に設けられたバイアス棒で
も良いことが判った。そして、前記帯状部材にバイアス
電圧を印加させてもほぼ同様にプラズマ電位の制御がで
きることが判った。前記バイアス電圧が直流電圧である
場合には、膜特性の改善を図る目安としてその電圧を好
ましくは+IOV乃至+200vとするのが望ましいこ
とが判った。Furthermore, in the method and apparatus of the present invention, in order to control the plasma potential of the microwave plasma, a bias voltage applying means is provided in the film formation chamber in which the plasma is confined, and various DC voltages or pulses are applied to the bias applying means. It has been found that it is desirable to apply bias voltages of various waveforms, frequencies, and maximum amplitude voltages at current and alternating current voltages. Also,
It has been found that the bias voltage applying means may also serve as the gas introduction tube, or may be a bias rod provided separately from the gas introduction tube. It has also been found that the plasma potential can be controlled in substantially the same way even if a bias voltage is applied to the band-shaped member. When the bias voltage is a DC voltage, it has been found that it is desirable to set the voltage to +IOV to +200V as a guideline for improving membrane characteristics.
以下、前述の〔実験〕により判明した事実をもとに本発
明の方法及び装置について更に詳しく説明する。Hereinafter, the method and apparatus of the present invention will be explained in more detail based on the facts found through the above-mentioned [experiments].
本発明の方法が従来の堆積膜形成方法から客観的に区別
される点は、成膜空間を柱状とし、その側壁が連続的に
移動しつつも、構造材としての機能を果たし、且つ、堆
積膜形成用の支持体をも兼ねるようにした点である。The method of the present invention is objectively different from conventional deposited film forming methods. The point is that it also serves as a support for film formation.
ここで、構造材としての機能とは、特に、成膜用の雰囲
気空間すなわち成膜空間と成膜用には関与しない雰囲気
空間とを物理的、化学的に隔離する機能であって、具体
的には、例えば、ガス&l威及びその状態の異なる雰囲
気を形成したり、ガスの流れる方向を制限したり、更に
は、圧力差の異なる雰囲気を形成したりする機能を意味
するものである。Here, the function as a structural material is specifically the function of physically and chemically separating the atmosphere space for film formation, that is, the film formation space, and the atmosphere space that is not involved in film formation. This means, for example, the function of forming atmospheres with different gases and their states, restricting the direction of gas flow, and furthermore, forming atmospheres with different pressure differences.
即ち、前記帯状部材を湾曲させて柱状の戒膜空間の側壁
を形成し、対向する両端面のいずれか一方の面より、堆
積膜形成用の原料ガス及びマイクロ波電力を前記成膜空
間内に供給し、前記側壁の一部に残された間隙より排気
させることによって、プラズマを前記成膜空間内に閉じ
込め、前記側壁をtR或する帯状部材上に機能性堆積膜
を形成せしめるものであり、前記帯状部材そのものが成
膜空間を成膜用には関与しない外部雰囲気空間から隔離
するための構造材としての重要な機能を果たしていると
ともに、堆積膜形成用の支持体として用いることもでき
る。That is, the band-like member is curved to form the side wall of the columnar film-forming space, and the raw material gas and microwave power for forming the deposited film are introduced into the film-forming space from either one of the opposing end faces. By supplying and exhausting through a gap left in a part of the side wall, plasma is confined in the film forming space and a functional deposited film is formed on a band-shaped member with the side wall at tR, The band-like member itself plays an important function as a structural member for isolating the film-forming space from an external atmospheric space that is not involved in film-forming, and can also be used as a support for forming a deposited film.
従って、前記帯状部材を側壁として構威される成膜空間
の外部の雰囲気は、前記成膜空間内とは、ガス組成及び
その状態、圧力等について全く異なる状態となっている
。Therefore, the atmosphere outside the film-forming space, which has the band-shaped member as a side wall, is completely different from the atmosphere inside the film-forming space in terms of gas composition, its state, pressure, etc.
一方、従来の堆積膜形成方法においては堆積膜形成用の
支持体は、堆積膜を形成するための成膜空間内に配設さ
れ、専ら、該成膜空間にて生成する例えば堆積膜形成用
の前駆体を堆積させる部材としてのみ機能するものであ
り、本発明の方法におけるように前記成膜空間を構成す
る構造材として機能させるものではない。On the other hand, in the conventional method for forming a deposited film, a support for forming a deposited film is disposed in a film forming space for forming a deposited film, and is used exclusively for forming a deposited film, for example, formed in the film forming space. It functions only as a member for depositing the precursor, and does not function as a structural material constituting the film forming space as in the method of the present invention.
また、従来法であるRFプラズマCVD法、スパッタリ
ング法等においては、前記堆積膜形成用の支持体は放電
の生起・維持のための電極を兼ねることはあるがプラズ
マの閉し込めは不十分であり、成膜用には関与しない外
部雰囲気空間との隔離は不十分であって、構造材として
機能しているとは言い難い。In addition, in conventional methods such as RF plasma CVD and sputtering, the support for forming the deposited film may also serve as an electrode for generating and maintaining discharge, but plasma confinement is insufficient. However, the isolation from the external atmospheric space that is not involved in film formation is insufficient, and it is difficult to say that it functions as a structural material.
要するに、本発明の方法は、機能性堆積膜形成用の支持
体として機能し得る帯状部材を前記成膜空間の側壁とし
て用い、前記構造材としての機能を発揮せしめると共に
、前記帯状部材上への機能性堆積膜の連続形成をも可能
にするものである。In short, the method of the present invention uses a band-like member that can function as a support for forming a functional deposited film as a side wall of the film-forming space, and allows the band-like member to function as the structural material, and also allows the band-like member to function as a support for forming a functional deposited film. It also enables continuous formation of functional deposited films.
本発明者らの行った実験を介しての検討結果からするに
、プラズマCVD装置として現在市販されている装置は
、RF或いはマイクロ波を使用するいずれのものであっ
ても、そのtcll室内で成膜用原料ガスが基体上に堆
積して実際に実用に供し得る堆積膜になる割合は、せい
ぜい15%程度であって、堆積膜としての回収率は実際
にはかなり低い。Based on the results of experiments conducted by the present inventors, it has been found that currently available plasma CVD equipment, whether using RF or microwave, can be formed within the TCLL chamber. The rate at which the film raw material gas is deposited on the substrate and becomes a deposited film that can actually be put to practical use is about 15% at most, and the recovery rate as a deposited film is actually quite low.
本発明者らはこの点が成膜空間の形状、構造に大きく依
存しているとの前提に立って検討を重ねたところ、成膜
空間の周囲壁を基体で構威し、該周囲壁の内面上に堆積
膜を形成させることで、前記回収率は大巾に向上するこ
とが判った。即ち、帯状部材を基体とし、これを連続的
に移動させながら、該帯状部材で成膜室の側壁を形成さ
せる。The present inventors conducted repeated studies based on the premise that this point largely depends on the shape and structure of the film-forming space, and found that the surrounding wall of the film-forming space is composed of a base body, and the surrounding wall of the film-forming space is It has been found that the recovery rate can be greatly improved by forming a deposited film on the inner surface. That is, the band-shaped member is used as a base, and the side wall of the film-forming chamber is formed by the band-shaped member while being continuously moved.
そして、該側壁の一部には前記成膜室内を排気する為に
間隙を設けるようにする。前記成膜室の形状は、好まし
くは柱状、より好ましくは円柱状である。そして、堆積
膜としての回収率を向上させるには、該成膜空間を形成
する壁面の総面積に対して前記帯状部材で構成される側
壁部分の面積の割合を大きくすることが好ましい。即ち
、前記帯状部材で形成される前記円柱状の成膜空間の具
体的な形状としては、対向する両端面の内径寸法に対す
る、側壁の長さ(帯状部材の幅寸法)の比を可能な限り
大きくさせることが望ましい、こうすることにより、前
記側壁の内壁面上に所望の機能性堆積膜を高い回収率で
形成させることができる。Then, a gap is provided in a part of the side wall for evacuating the inside of the film forming chamber. The shape of the film forming chamber is preferably columnar, more preferably cylindrical. In order to improve the recovery rate of the deposited film, it is preferable to increase the ratio of the area of the side wall portion constituted by the band-shaped member to the total area of the wall surface forming the film forming space. That is, the specific shape of the cylindrical film-forming space formed by the band-shaped member is such that the ratio of the length of the side wall (width dimension of the band-shaped member) to the inner diameter dimension of both opposing end surfaces is set as much as possible. It is desirable to increase the size. By doing so, it is possible to form a desired functional deposited film on the inner wall surface of the side wall with a high recovery rate.
本発明の方法において、基体上に形成された堆積膜が大
気中に取出された際、成膜時との温度差や湿度等の影響
で堆積膜が基体から剥離するのを回避するには、前記帯
状部材をほぼ柱状に湾曲させて予め機械的圧縮応力を加
えておき、該柱状に湾曲した帯状部材の凹状湾曲面上に
所望の成膜温度で堆積膜を形成した後、該帯状部材を平
面状或いは堆積膜の形成された側が凸面状になるように
展開して予め加えた機械的圧縮応力を機械的引張応力に
変換しながら室温まで徐冷し、その際前記帯状部材と前
記堆積膜との膨張係数の差で生ずる熱的圧縮応力を前記
機械的引張応力で緩和させる方法が好ましく用いられる
。In the method of the present invention, in order to prevent the deposited film formed on the substrate from peeling off from the substrate due to the influence of temperature difference from the time of film formation, humidity, etc. when the deposited film is taken out into the atmosphere, The strip member is curved into a substantially columnar shape and subjected to mechanical compressive stress in advance, and a deposited film is formed on the concave curved surface of the strip member curved into a columnar shape at a desired film forming temperature. The belt-shaped member and the deposited film are expanded so that the side on which the deposited film is formed is planar or convex, and slowly cooled to room temperature while converting the pre-applied mechanical compressive stress into mechanical tensile stress. Preferably, a method is used in which the thermal compressive stress caused by the difference in the expansion coefficient between the two is alleviated by the mechanical tensile stress.
前記帯状部材の材質として、その線膨張係数が前記堆積
膜の線膨張係数よりも大きいものを用いることにより、
上述のような応力緩和の方法が可能となる。By using a material for the band-shaped member whose coefficient of linear expansion is larger than that of the deposited film,
The method of stress relaxation as described above becomes possible.
従来、堆積膜の剥離を回避するためには、基体と堆積膜
との密着力の強化という観点で対策が施されてきたが、
この種の対策は基体の強度がある程度以上強いものに限
定されており、ポリイミドやPET (ポリエチレンテ
レフタレート)のような比較的軟らかい素材を利用した
基体に対しては、前述のような対策だけでは前記基体に
しわがよってしまう数十分な対策とは言い難い。従って
、密着力の強化に加えて、応力緩和も重要な対策となり
得る。Conventionally, in order to avoid peeling of the deposited film, measures have been taken from the perspective of strengthening the adhesion between the substrate and the deposited film.
This type of countermeasure is limited to cases where the strength of the base is above a certain level, and for bases made of relatively soft materials such as polyimide or PET (polyethylene terephthalate), the above-mentioned countermeasures alone will not work. This cannot be said to be a sufficient measure against wrinkles on the substrate. Therefore, in addition to strengthening adhesion, stress relaxation can also be an important measure.
特に、複数の堆積膜を積層して作製する太陽電池素子の
ような場合においては、堆積膜を積層することよって圧
縮応力が増幅されることもあり得るため、前述の本発明
の方法は重要である。In particular, in cases such as solar cell devices that are manufactured by laminating multiple deposited films, the method of the present invention described above is important because the compressive stress may be amplified by stacking the deposited films. be.
本発明の方法において、効率良くプラズマを生滅・維持
するには、マイクロ波のインピーダンスをプラズマの複
素誘電率に応じて、成膜空間内部のプラズマを含めた同
軸線路の等価的な外部導体の内径が成膜空間外部の同軸
線路の外部導体の内径と等しくなるように、マイクロ波
透過性部材の外径を予め調整・選択する。In the method of the present invention, in order to efficiently generate and maintain plasma, the impedance of the microwave must be adjusted according to the complex dielectric constant of the plasma, and the inner diameter of the equivalent outer conductor of the coaxial line including the plasma inside the deposition space. The outer diameter of the microwave transparent member is adjusted and selected in advance so that it is equal to the inner diameter of the outer conductor of the coaxial line outside the film forming space.
ここで、等価的という表現を用いたのは、実際に放電実
験を行った結果、原料ガスの種類及び流量、成膜室の圧
力、マイクロ波電力等の条件でプラズマを包含する外側
導体の内径は変化し、それがプラズマの誘電率の実数部
だけではなく虚数部、すなわち吸収率も影響し、位相反
転を生じるため理論的には外径の値を予想しがたいこと
が判明したためである。従って、プラズマで形威される
外側導体の内径は、後述のように実験で確かめることが
確実である。The expression "equivalent" used here is based on the results of actual discharge experiments, which show that the inner diameter of the outer conductor containing the plasma varies depending on conditions such as the type and flow rate of source gas, the pressure in the deposition chamber, and the microwave power. This is because it has been found that it is difficult to predict the value of the outer diameter theoretically because it affects not only the real part of the permittivity of the plasma but also the imaginary part, that is, the absorption rate, causing a phase inversion. . Therefore, it is certain that the inner diameter of the outer conductor formed by the plasma can be verified experimentally as described below.
従来、インピーダンスの不整合、すなわち強い反射面の
あるマイクロ波装置では、該反射面で生ずる反射波と同
等の強度を有し、且つ該反射波とは位相の反転した他の
反射波をチューナーで生ぜしめ、これらの2つの反・耐
波を干渉によって打ち消し合わせてインピーダンスを整
合させるという手法をとっているが、このように見かけ
上屋耐波をうち消し合わせて整合させた場合でも、前記
反射面と前記チューナーとの間には大きな定在波が生し
ており、大きなジュール熱損失を発生することがしばし
ばであった。Conventionally, in microwave devices with impedance mismatching, that is, with a strong reflective surface, the tuner is used to detect other reflected waves that have the same intensity as the reflected wave generated on the reflective surface and have an inverted phase with the reflected wave. Therefore, a method is used to match the impedance by canceling out these two anti-wave resistances by interference, but even when matching is achieved by canceling out the apparent wave resistance of the building in this way, the above-mentioned reflection surface and A large standing wave is generated between the tuner and the tuner, which often causes large Joule heat loss.
従って、このジュール熱損失をなくすには、前記反射面
と前記チューナーとの距離をできる限り接近させ、好ま
しくは一致させれば良い。即ち、本発明のマイクロ波ア
ンテナ手段においては、放電開始前の状態にては成膜室
内部と成膜室外部とはいずれも誘電率がlで同軸線路の
外部導体の内径が内部の方が大きくなっているため、成
膜室の境界面でインピーダンスの整合をとることは困難
であるが、放電開始後の状態では成膜室内部は誘電率が
lより小さいプラズマが充満して等価的な内径が小さく
なり、マイクロ波透過性部材の外径を適宜選択すれば成
膜室内外における同軸線路の外部導体の内径が一致して
整合可能な状況が生まれてくる。かくして放ti後の状
態でインピーダンスを整合させることが可能となる。Therefore, in order to eliminate this Joule heat loss, the distance between the reflective surface and the tuner should be made as close as possible, preferably coincident. That is, in the microwave antenna means of the present invention, before discharge starts, both the inside of the film forming chamber and the outside of the film forming chamber have a dielectric constant of 1, and the inner diameter of the outer conductor of the coaxial line is larger than that of the inner diameter of the outer conductor of the coaxial line. Because of the large size, it is difficult to match the impedance at the interface of the deposition chamber, but after the start of discharge, the interior of the deposition chamber is filled with plasma whose dielectric constant is smaller than l, and an equivalent If the inner diameter becomes smaller and the outer diameter of the microwave transparent member is appropriately selected, a situation will be created in which the inner diameters of the outer conductor of the coaxial line inside and outside the film forming chamber can be matched and matched. In this way, it is possible to match the impedance in the state after release.
本発明の方法においては、前記帯状部材で底膜空間を形
威し、該成膜空間内でのみ堆積膜を形成せしめるように
、前記成膜空間外におけるガス組成及びその状態は前記
成膜空間内とは異なるように条件設定する0例えば、前
記成膜空間外のガス組成については、堆積膜形成には直
接関与しないようなガス雰囲気としても良いし、前記底
膜空間から排出される原料ガスを含んだ雰囲気であって
も良い。また、前記成膜空間内にはプラズマが閉し込め
られているのは勿論であるが、前記成膜空間外には前記
プラズマ及びマイクロ波が漏洩しないようにすること及
び異常放電を抑制することが、プラズマの安定性、再現
性の向上や不要な箇所への膜堆積を防ぐ上でも有効であ
る。In the method of the present invention, the gas composition and its state outside the film-forming space are controlled so that the bottom film space is defined by the band-shaped member and the deposited film is formed only within the film-forming space. For example, the gas composition outside the film-forming space may be set to be a gas atmosphere that does not directly participate in the formation of the deposited film, or the gas composition outside the film-forming space may be set to be different from that inside the film-forming space. The atmosphere may include. Although plasma is of course confined within the film forming space, it is also necessary to prevent the plasma and microwaves from leaking outside the film forming space and to suppress abnormal discharge. However, it is also effective in improving plasma stability and reproducibility and preventing film deposition in unnecessary locations.
また、第1図の装置ではTEMモードでマイクロ波電力
を投入しているため、前記開口部の幅が狭いうちはマイ
クロ波の漏洩は該モードのため自動的に抑制されるが、
前記開口部の幅がマイクロ波の1/2波長程度になる場
合、マイクロ波の漏洩防止手段を設ける必要がある。即
ち、帯状部材の長手方向に形成された間隙部分に第6図
に示すような孔径がマイクロ波の波長の1/2o程度の
導電性のパンチング・ボード等を配設すれば良い。In addition, in the apparatus shown in FIG. 1, microwave power is input in the TEM mode, so as long as the width of the opening is narrow, microwave leakage is automatically suppressed due to this mode.
When the width of the opening is approximately 1/2 wavelength of the microwave, it is necessary to provide means for preventing microwave leakage. That is, a conductive punching board or the like having a hole diameter of about 1/2 of the wavelength of the microwave as shown in FIG. 6 may be disposed in the gap formed in the longitudinal direction of the strip member.
本発明の方法において、成膜空間外部の圧力を6mTo
rr以下に保持するのと同様の効果をもたらす代替手段
として、電離断面積の小さいガス(HeまたはH2等)
を前記成膜空間外部に流すことにより前記異常放電を抑
制しても良い、勿論、成膜空間外部の圧力を6mTor
r以下に保持しながら、同時に前記電離断面積の小さい
ガスを流してもよい。In the method of the present invention, the pressure outside the film forming space is set to 6 mTo.
As an alternative to maintaining the same effect as maintaining below rr, a gas with a small ionization cross section (such as He or H2)
The abnormal discharge may be suppressed by flowing outside the film-forming space.Of course, the pressure outside the film-forming space is set to 6 mTor.
The gas having a small ionization cross section may be flowed at the same time while maintaining the temperature at or below r.
即ち、本発明の方法において、プラズマを成膜空間内に
閉じ込め、成膜空間外部で異常放電を抑制することによ
り、堆積膜形成用原料ガスの回収率を向上せしめ、且つ
、成膜速度を飛躍的に高めることができ太陽電池の工業
的規模での生産を可能にすることができる。That is, in the method of the present invention, by confining plasma within the film-forming space and suppressing abnormal discharge outside the film-forming space, the recovery rate of the raw material gas for forming the deposited film can be improved, and the film-forming speed can be dramatically increased. This can enable the production of solar cells on an industrial scale.
本発明の方法において、大面積に渡って膜厚及び膜質が
均一な堆積膜を形成するには、前記成膜空間の側壁を構
成する帯状部材に平行になるように該マイクロ波アンテ
ナ手段を成膜空間に貫入させ、同軸線路或いはりジター
ノ・コイル等のマイクロ波の進行方向に垂直な全方向に
マイクロ波を放射するマイクロ波アンテナ手段を介して
マイクロ波電力を前記成膜空間内に投入してプラズマを
生起させることによって為される。また、長時間に亘っ
てプラズマ密度が一定の放電を持続するには、前記マイ
クロ波透過性部材で前記マイクロ波アンテナ手段を包囲
してプラズマから完全に隔離すれば良い。In the method of the present invention, in order to form a deposited film with uniform film thickness and film quality over a large area, the microwave antenna means is arranged so as to be parallel to the strip member forming the side wall of the film forming space. Microwave power is injected into the film forming space through a microwave antenna means that penetrates into the film space and radiates microwaves in all directions perpendicular to the direction of propagation of the microwaves, such as a coaxial line or a Gitano coil. This is done by generating plasma. Further, in order to sustain a discharge with a constant plasma density for a long time, it is sufficient to surround the microwave antenna means with the microwave transparent member and completely isolate it from the plasma.
本発明の方法において、前記マイクロ波アンテナ手段は
前記帯状部材に平行になるように配設し、該帯状部材と
前記マイクロ波アンテナ手段との距離は比較的短かく、
且つアンテナの長手方向においてもその距離は等しく保
たれることが望ましい。In the method of the present invention, the microwave antenna means is arranged parallel to the strip member, and the distance between the strip member and the microwave antenna means is relatively short;
It is also desirable that the distances be kept equal in the longitudinal direction of the antenna.
こうすることにより、前記側壁をtS或する帯状部材の
幅方向に対して、マイクロ波電力がほぼ均一に投入され
るアンテナ手段が配設されることで、プラズマの密度分
布が均一化される。By doing this, the antenna means to which the microwave power is applied almost uniformly in the width direction of the band-shaped member with the side wall tS is provided, so that the plasma density distribution is made uniform.
特に、前述のマイクロ波透過性部材で中心導体がプラズ
マから隔離された同軸線路の場合、該同軸線路を介して
成膜空間内部に投入するマイクロ波電力を増やしてゆく
と、成膜空間の内部に導入されて前記マイクロ波電力で
プラズマ化されるガスの種類及びそのガス流量に依存し
てプラズマへの吸収されるマイクロ?JjLt力が飽和
してしまう闇値が存在する。従って、成膜空間内部に投
入するマイクロ波電力が大電力であるほど前記の吸収電
力の飽和する領域が広がるため吸収電力が飽和した前記
闇値と同じ電力がアンテナの長手方向の各部から成膜空
間内部に投入されることとなり、プラズマ密度を均一化
、すなわち大面積に渡って膜厚及び膜質を均一化するこ
とになる。In particular, in the case of a coaxial line in which the center conductor is isolated from the plasma by the microwave-transparent member mentioned above, as the microwave power input into the deposition space via the coaxial line is increased, the inside of the deposition space Microwave absorption into the plasma depends on the type of gas introduced into the plasma and turned into plasma by the microwave power, and the gas flow rate. There is a dark value at which JjLt power becomes saturated. Therefore, the larger the microwave power input into the film forming space, the wider the region where the absorbed power is saturated, so that the same power as the dark value where the absorbed power is saturated is deposited from each part in the longitudinal direction of the antenna. The plasma is injected into the space, and the plasma density is made uniform, that is, the film thickness and quality are made uniform over a large area.
しかしながら、このような大電力のマイクロ波電力を成
膜空間内部に投入すると形成される堆積膜の電気特性が
劣化したり、前記マイクロ波透過性部材の内部で発熱し
たり、前記マイクロ波透過性部材がプラズマに晒される
ことによって生じる昇温で破損する場合があり、前述の
成膜空間内部に投入可能なマイクロ波電力が制約される
ことがある。However, when such a large amount of microwave power is input into the film-forming space, the electrical properties of the deposited film to be formed may deteriorate, heat may be generated inside the microwave-transparent member, or the microwave-transparent member may deteriorate. The member may be damaged due to temperature rise caused by exposure to plasma, and the microwave power that can be input into the film forming space may be restricted.
このような場合には、前記成膜空間に投入されるマイク
ロ波電力が制約されるため、前述の吸収電力の飽和は起
こらずプラズマ密度の均一化は起こらない、すなわち、
前記成膜空間の内部に配設されたマイクロ波アンテナ手
段から成膜空間内部に投入されるマイクロ波電力がマイ
クロ波の進行方向に沿って漸減するため、プラズマ密度
が空間的に不均一な分布をもってしまう。In such a case, the microwave power input into the film forming space is restricted, so the saturation of the absorbed power does not occur and the plasma density does not become uniform, that is,
The microwave power input into the film forming space from the microwave antenna means disposed inside the film forming space gradually decreases along the direction of propagation of the microwaves, resulting in a spatially non-uniform distribution of plasma density. I end up having it.
これを回避して大面積に渡って膜厚及び膜質が均一な堆
積膜を形成するには、マイクロ波の進行方向に沿って、
成膜空間内部に投入されるマイクロ波電力がマイクロ波
の進行方向に沿って漸減するのを補償するように内径が
漸増する円錐台状又は円錐状の形状のマイクロ波i!3
!4性部材を配設して前述した前記帯状基体と前記マイ
クロ波アンテナ手段との距離をマイクロ波の進行方向に
沿って狭くしてゆけば良い。In order to avoid this and form a deposited film with uniform thickness and quality over a large area, along the direction of microwave propagation,
The microwave i! is shaped like a truncated cone or a cone whose inner diameter gradually increases to compensate for the gradual decrease in the microwave power input into the film forming space along the direction of propagation of the microwave. 3
! The distance between the above-described band-shaped base and the microwave antenna means may be narrowed along the direction of propagation of the microwave by arranging the 4-wire member.
以上説明した通り、本発明の方法は投入するマイクロ波
電力の大きさに依らず、大面積に渡って膜厚及び膜質が
均一な堆積膜の形成を可能にするものである。As explained above, the method of the present invention makes it possible to form a deposited film with uniform thickness and quality over a large area, regardless of the magnitude of the microwave power input.
本発明の方法において、前記成膜空間の内壁面は、所望
の電流密度のバイアス電流が流れるのに必要な導電性を
有することが望ましい、そのためにはまず、前記帯状部
材は導電性の材料で構成されることが好ましいが、少な
くとも前記成膜空間に向いている側の面に導電処理が施
されていることが必要である。In the method of the present invention, it is desirable that the inner wall surface of the film-forming space has conductivity necessary for a bias current of a desired current density to flow. For this purpose, first, the strip member is made of a conductive material. However, it is necessary that at least the surface facing the film forming space is subjected to conductive treatment.
本発明の方法において、前記マイクロ波プラズマのプラ
ズマ電位を制御するには、バイアス印加手段を前記成膜
空間内に生起するプラズマに少なくともその一部分が接
するように配設するのが望ましい、前記バイアス印加手
段は成膜空間内に堆積膜形成用原料ガスを導入するため
のガス供給手段を兼ねても良く、又、前記ガス供給手段
とは別に設けられた単数本又は複数本のバイアス棒であ
っても良い。In the method of the present invention, in order to control the plasma potential of the microwave plasma, it is preferable that the bias applying means be disposed so that at least a part thereof is in contact with the plasma generated in the film forming space. The means may also serve as a gas supply means for introducing a raw material gas for forming a deposited film into the film forming space, and may also be one or more bias rods provided separately from the gas supply means. Also good.
前者の場合においては、バイアス電圧がガス供給手段を
介して原料ガスボンベ、流量制御系、配管等のいわゆる
ガス供給系に印加されて感電、制御系の破損等の事故が
発生しないように、該ガス供給系とバイアス電圧の印加
される前記ガス供給とはその中途において絶縁分離され
ていることが望ましい。そして、その絶縁分離される位
置は前記成膜空間に近接していることが好ましい。In the former case, the gas is It is desirable that the supply system and the gas supply to which the bias voltage is applied be insulated and separated in the middle. It is preferable that the insulation-isolated position be close to the film-forming space.
前記ガス供給手段を兼ねるバイアス印加手段が前記マイ
クロ波プラズマに接する少なくとも1部には、前記バイ
アス電圧が印加されるように導電処理が施されているこ
とが望ましいが、プラズマ加熱等により変形、破損、溶
断等が発生しないようにその材質は配慮される必要があ
る。具体的には高融点金属又は高融点セラミックスの上
に高融点金属をコーティング処理して構成するようにす
ることが望ましい。It is desirable that at least a portion of the bias application means that also serves as the gas supply means, which comes into contact with the microwave plasma, be subjected to conductive treatment so that the bias voltage can be applied, but it may be deformed or damaged by plasma heating or the like. , the material must be carefully selected to prevent melting, etc. Specifically, it is desirable to construct the structure by coating a high melting point metal on a high melting point metal or a high melting point ceramic.
また、前記ガス供給手段を兼ねるバイアス印加手段が前
記成膜空間内に配設される位置は、前記マイクロ波プラ
ズマがほぼ均一な導体として作用しているが故、前記マ
イクロ波プラズマに接して配設されている限り特に限定
されないが、異常放電の発生等を抑える上で前記帯状部
材の内表面からは好ましくはlQmm以上、より好まし
くは20關以上離して配設するのが望ましい。Further, the bias applying means that also serves as the gas supply means is arranged in the film forming space so that it is in contact with the microwave plasma, since the microwave plasma acts as a substantially uniform conductor. Although there is no particular limitation as long as it is provided, in order to suppress the occurrence of abnormal discharge, etc., it is preferable to arrange it at a distance of at least 1Q mm, more preferably at least 20 mm, from the inner surface of the band-shaped member.
一方、後者の場合においては、前記バイアス棒をtS威
する材質及びその配設される位置等については前述のバ
イアス印加手段がガス供給手段を兼ねる場合と同様に配
慮される。ただし、前記ガス供給手段は誘電体で構成さ
せることが、異常放電の発生の抑制や、均一なプラズマ
電位を前記成膜空間内で形成させる上で好ましいが、バ
イアス印加電圧が比較的低い場合等においては、特にそ
の材質については制限されることはない。On the other hand, in the latter case, the material for applying the bias rod and the position thereof are considered in the same manner as in the case where the bias applying means also serves as the gas supply means. However, it is preferable that the gas supply means be made of a dielectric material in order to suppress the occurrence of abnormal discharge and to form a uniform plasma potential in the film forming space, but when the applied bias voltage is relatively low, etc. There are no particular restrictions on the material.
本発明の方法において、前記バイアス棒又はガス供給手
段を兼ねるバイアス印加手段が単数本配設される場合に
は、バイアス電圧として直流、脈流及び交流電圧を単独
又は夫々を重畳させて印加させることが望ましく、前記
バイアス棒が複数本配設される場合には、夫々に同電圧
又は異なる電圧の直流電圧を印加させても良く、又、直
流、脈流及び交流電圧のそれぞれを単独又は重畳させて
印加させても良い、複数種のバイアス電圧を印加させる
ことにより、プラズマ電位の制御範囲が広がるばかりで
なく、プラズマの安定性、再現性及び膜特性の向上、欠
陥の発生の抑制等が図られる。In the method of the present invention, when a single bias rod or bias applying means that also serves as the gas supply means is provided, direct current, pulsating current, and alternating current voltage may be applied singly or in a superimposed manner as the bias voltage. is desirable, and when a plurality of bias rods are provided, the same or different DC voltages may be applied to each of them, or each of DC, pulsating current, and AC voltage may be applied singly or in a superimposed manner. By applying multiple types of bias voltages, which may be applied at different times, it is possible to not only widen the control range of the plasma potential, but also to improve plasma stability, reproducibility, and film properties, and to suppress the occurrence of defects. It will be done.
前記交2i!電圧としては、好ましくは正弦波、方形波
、三角波、パルス波、及びこれらを重畳させた波形等を
挙げることができる。又、脈流電圧としては、好ましく
は前記交流電圧を半波整流又は全波整流した波形、及び
ランプ波等を挙げることができる。更に、前記バイアス
電圧の直流電圧又は最大振幅電圧は、形成される堆積膜
の膜特性及び欠陥の発生率等との兼ね合いにて適宜設定
されるが、プラズマの生起開始時から堆積膜の形成開始
及び終了時までの間において一定に保たれていても良い
が、形成される堆積膜の特性制御や欠陥発生の抑制を図
る上で連続的又は適宜の周期で変化させることが好まし
い、特に、スパーク等の異常放電が発生した場合には、
バイアス電圧の急激な変動が起こるので、電気的にこれ
を検知し、直ちにバイアス電圧を低下させるか、又は−
時中断させて、再び所定のバイアス電圧に復帰させるこ
とが、堆積膜の欠陥発生等を抑制する上で好ましい。勿
論、これらの工程は手動にて行っても良いが、自動制御
回路をバイアス印加手段の制御回路中に設けることが堆
積膜の歩留り向上の上で好ましい。Said intersection 2i! Preferable examples of the voltage include a sine wave, a square wave, a triangular wave, a pulse wave, and a waveform obtained by superimposing these waves. In addition, examples of the pulsating voltage include a waveform obtained by preferably half-wave rectification or full-wave rectification of the AC voltage, a ramp wave, and the like. Furthermore, the direct current voltage or maximum amplitude voltage of the bias voltage is appropriately set in consideration of the film characteristics of the deposited film to be formed, the rate of occurrence of defects, etc. Although the spark may be kept constant until the end of the process, it is preferable to change it continuously or at appropriate intervals in order to control the characteristics of the deposited film formed and to suppress the occurrence of defects.In particular, the spark If an abnormal discharge such as
Since a sudden change in bias voltage occurs, it is necessary to detect this electrically and reduce the bias voltage immediately, or -
It is preferable to interrupt the process and then return to the predetermined bias voltage again in order to suppress the occurrence of defects in the deposited film. Of course, these steps may be performed manually, but it is preferable to provide an automatic control circuit in the control circuit of the bias application means in order to improve the yield of the deposited film.
本発明の方法において、前記バイアス印加手段は前記帯
状部材を兼ねても良い、この場合には、前記成膜空間内
に接地電極を設けるようにする。In the method of the present invention, the bias applying means may also serve as the strip member. In this case, a ground electrode is provided in the film forming space.
そして、前記接地電極は前記ガス供給手段を兼ねても良
い。The ground electrode may also serve as the gas supply means.
本発明の方法において、前記帯状部材は導電性材料、又
は、絶縁性材料の表面に導電性処理を施したもので構成
するようにするが、少なくとも堆積膜形成時に前記帯状
部材が加熱保持される温度において、十分な電流密度が
確保される導電率を有する材料にて構成されることが必
要である。具体的にはいわゆる金属、半導体等を挙げる
ことができる。また、前記帯状部材上には素子分離の工
程を容易にさせる等の目的で一部絶縁性部材で構成され
る領域を設けておいても良い、一方、前記絶縁性部材で
構成される領域の面積が大きい場合には、その領域にお
いてはプラズマ電位を制御された堆積膜の形成は行われ
ないが、微小面積である場合には導電性部材上に形成さ
れる膜とほぼ同じ特性を有する膜が形成される。In the method of the present invention, the strip member is made of a conductive material or an insulating material whose surface is subjected to conductive treatment, and the strip member is heated and maintained at least during the formation of the deposited film. It is necessary to be constructed of a material having a conductivity that ensures sufficient current density at the temperature. Specifically, so-called metals, semiconductors, etc. can be mentioned. Further, a region partially made of an insulating material may be provided on the band-shaped member for the purpose of facilitating the element isolation process. If the area is large, a deposited film with controlled plasma potential will not be formed in that area, but if the area is small, a film with almost the same characteristics as a film formed on a conductive member will be formed. is formed.
本発明の方法によれば、前記成膜空間の側壁を構成する
こうした帯状部材の幅方向に対して均一にマイクロ波エ
ネルギーを放射又は伝達せしめるマイクロ波アプリケー
ター手段を具備させ、マイクロ波プラズマの生起・維持
条件及びバイアス印加手段を調整、最適化することによ
って、大面積にわたって高品質の機能性堆積膜を連続し
て、均−性及び再現性良く形成することができる。According to the method of the present invention, a microwave applicator means is provided for uniformly radiating or transmitting microwave energy in the width direction of such a band-shaped member constituting the side wall of the film forming space, thereby generating and generating microwave plasma. By adjusting and optimizing the maintenance conditions and bias application means, it is possible to continuously form a high quality functional deposited film over a large area with good uniformity and reproducibility.
更に、本発明の方法によれば、プラズマ電位を適宜制御
することによって、所望の特性を有し、欠陥の少ない高
品質の機能性堆積膜を連続して効率良く高い歩留りで形
成することができる。Further, according to the method of the present invention, by appropriately controlling the plasma potential, a high-quality functional deposited film having desired characteristics and few defects can be continuously formed efficiently and at a high yield. .
本発明の方法において、前記柱状の成膜空間内において
プラズマを均一に安定して生起・維持させるためには、
前記成膜空間の形状及び容積、前記t2成膜室内に導入
する原料ガスのJ[及び流量、前記成膜空間内の圧力、
前記成膜空間内に投入されるマイクロ波電力量、及びマ
イクロ波の整合等について各々最適な条件があるものの
、これらのパラメーターは相互に有機的に結びついてお
り、−概に定義されるものではなく、適宜好ましい条件
を設定するのが望ましい。In the method of the present invention, in order to uniformly and stably generate and maintain plasma in the columnar film forming space,
The shape and volume of the film forming space, the flow rate of the raw material gas introduced into the t2 film forming chamber, the pressure in the film forming space,
Although there are optimal conditions for the amount of microwave power input into the film forming space, microwave matching, etc., these parameters are organically linked to each other and cannot be generally defined. It is desirable to set favorable conditions as appropriate.
以下、本発明の装置について更に詳しく説明する。Hereinafter, the apparatus of the present invention will be explained in more detail.
本発明の装置において、前記帯状部材を構造材として機
能させるにあたり、前記成膜室の外部は大気であっても
良いが、前記成膜室内への大気の流入によって、形成さ
れる機能性堆積膜の特性に影響を及ぼす場合には適宜の
大気流入防止手段を設ければ良い、具体的にはOリング
、ガスケット、ヘリコツレックス、磁性流体等を用いた
機械的封止構造とするか、又は、形成される堆積膜の特
性に影響が少ないかあるいは効果的な希釈ガス雰囲気、
又は適宜の真空雰囲気を形成するための隔離容器を周囲
に配設することが望ましい、前記機械的封止構造とする
場合には、前記帯状部材が連続的に移動しながら封止状
態を維持できるように特別配慮される必要がある0本発
明の装置と他の複数の堆積膜形成装置を連結させて、前
記帯状部材上に連続して堆積膜を積層させる場合には、
ガスゲート手段等を用いて各装置を連結させるのが望ま
しい、また、本発明の装置のみを複数連結させる場合に
は、各装置において成膜室は独立した成膜雰囲気となっ
ているため、前記隔離容器は単一でも良いし、各々の装
置に設けても良い。In the apparatus of the present invention, when the strip member functions as a structural material, the outside of the film forming chamber may be in the atmosphere, but the functional deposited film is formed by the inflow of air into the film forming chamber. If the characteristics of the product are affected, an appropriate means for preventing atmospheric inflow may be provided, specifically, a mechanical sealing structure using O-rings, gaskets, helicotrex, magnetic fluid, etc., or , a diluent gas atmosphere that has little or no effect on the properties of the deposited film that is formed;
Alternatively, in the case of the mechanical sealing structure, in which it is preferable to arrange an isolation container around the device to create an appropriate vacuum atmosphere, the band member can maintain a sealed state while continuously moving. Special consideration must be given to the following: 0 When the apparatus of the present invention and a plurality of other deposited film forming apparatuses are connected to successively stack deposited films on the strip-shaped member,
It is desirable to connect each device using a gas gate means or the like. Also, when multiple devices of the present invention are connected, each device has an independent film forming atmosphere in the film forming chamber. The container may be a single container or may be provided in each device.
本発明の装置において、前記成膜室の外部の圧力は減圧
状態でも加圧状態でも良いが、前記成膜室内との圧力差
によって前記帯状部材が大きく変形するような場合には
適宜の補助構造材を配設すれば良い。In the apparatus of the present invention, the pressure outside the film forming chamber may be in a reduced pressure state or a pressurized state, but if the band member is significantly deformed due to a pressure difference within the film forming chamber, an appropriate auxiliary structure may be used. All you have to do is arrange the materials.
該補助構造材としては、前記成膜室の側壁とほぼ同一の
形状を、適宜の強度を有する金属、セラごツクス又は強
化樹脂等で構成される線材、薄板等で形成したものであ
ることが望ましい、また、該補助構造材の前記マイクロ
波プラズマに曝されない側の面に接触・支持する前記帯
状部材の接触部は、実質的に該補助構造材の影となる故
、堆積膜の形成はほとんど為されない。従って、前記補
助構造材の前記帯状部材上への投影面積は可能な限り小
さくなるように設計されるのが望ましい。The auxiliary structural material may be formed of a wire rod, thin plate, etc. made of metal, ceramics, reinforced resin, etc., and having approximately the same shape as the side wall of the film forming chamber, and having an appropriate strength. Desirably, the contact portion of the strip member that contacts and supports the surface of the auxiliary structural material that is not exposed to the microwave plasma is substantially in the shadow of the auxiliary structural material, so that the formation of a deposited film is prevented. Almost never done. Therefore, it is desirable that the projected area of the auxiliary structural material onto the strip member be designed to be as small as possible.
また、該補助構造材を前記帯状部材に密着させ、且つ前
記帯状部材の搬送速度に同期させて回転又は移動させる
ことにより、前記補助構造材上に施されたメツシュ・パ
ターン等を前記帯状部材上に形成させることもできる。Further, by bringing the auxiliary structural material into close contact with the belt-like member and rotating or moving it in synchronization with the conveyance speed of the belt-like member, the mesh pattern etc. applied on the auxiliary structural member can be transferred onto the belt-like member. It can also be formed.
まず本発明の装置に使用される帯状部材の材質について
は、該帯状部材を連続的に湾曲形威しうる柔軟性を有す
るものを用い、湾曲開始端、湾曲終了端及び中途の湾曲
部分においては滑らかな形状を形成させることが望まし
い。また該帯状部材が連続的に搬送される際に、たわみ
やねじれが起こりにくい程度の強度を有するものである
ことが好ましい。First, regarding the material of the band-shaped member used in the device of the present invention, a material that has flexibility that allows the band-shaped member to be continuously curved is used, and at the curved start end, curved end, and intermediate curved part, It is desirable to form a smooth shape. Further, it is preferable that the belt-shaped member has a strength that is difficult to bend or twist when it is continuously conveyed.
具体的には、ステンレススチール、アル〔ニウム及びそ
の合金、鉄及びその合金、銅及びその合金等の金属の薄
板及びその複合体、及びそれらの表面に異種材質の金属
薄膜をスパッタ法、蒸着法、鍍金法等により表面コーテ
ィング処理を行ったもの、又、ポリイミド、ポリアミド
、ポリエチレンテレフタレート、エポキシ等の耐熱性樹
脂性シート又はこれらとガラスファイバー、カーボンフ
ァイバー、ホウ素ファイバー、金属繊維等との複合体の
表面に金属単体又は合金、及び透明導電性酸化物(TC
O)等を鍍金、蒸着、スバソタ、塗布等の方法で導電性
処理を行ったものが挙げられる。また、前述の構成の帯
状部材の導電性処理面上にS i OH,5j3Na
、Aj!!os 、A14N。Specifically, thin plates and composites of metals such as stainless steel, aluminum and its alloys, iron and its alloys, copper and its alloys, and metal thin films of different materials on their surfaces are sputtered or vapor-deposited. , those whose surface has been coated by plating method, etc., and heat-resistant resin sheets such as polyimide, polyamide, polyethylene terephthalate, epoxy, etc., or composites of these with glass fibers, carbon fibers, boron fibers, metal fibers, etc. Metals or alloys and transparent conductive oxides (TC) on the surface.
Examples include those obtained by conducting conductive treatment using methods such as plating, vapor deposition, coating, and the like. In addition, SiOH, 5j3Na was applied on the conductive treated surface of the strip member having the above-mentioned structure.
,Aj! ! os, A14N.
及び前述の耐熱性樹脂等の絶縁性薄膜を一部形成させた
ものを用いることもできる。Alternatively, a material partially formed with an insulating thin film such as the above-mentioned heat-resistant resin can also be used.
また、前記帯状部材の厚さとしては、前記搬送手段によ
る搬送時に形成される湾曲形状が維持される強度を発揮
する範囲内であれば、コスト、収納スペース等を考慮し
て可能な限り薄い方が望ましい。Further, the thickness of the band-shaped member is determined to be as thin as possible in consideration of cost, storage space, etc., as long as it is within a range that exhibits strength that maintains the curved shape formed during transportation by the transportation means. is desirable.
一方、前述の堆積膜の回収率を上げるには、第3図にお
いて308で示される湾曲部端面支持リングを帯状部材
の周縁部に各々1個ずつ配置し、周縁部にのみ接触して
該帯状部材を搬送するため、対向する一対の該湾曲部端
面支持リング間で該帯状部材がたるまないよう、該帯状
部材自身に強度が必要とされるため該帯状部材はある程
度厚い方が良い、また、前述の堆積膜の応力緩和につい
ても前記帯状部材は厚い方が良い、従って該帯状部材の
厚さはこれらの点に鑑みて適宜流められるが、該帯状部
材の材質の種類とその曲げの曲率により多少異なる0例
えば、帯状部材がステンレスの場合、その厚みは0.0
3〜0.3 w程度である。同様にアルミニウム又は銅
の場合0.05〜0.5 wn程度、更に合成樹脂の場
合0.1〜3fi程度である。On the other hand, in order to increase the recovery rate of the deposited film mentioned above, one curved end support ring, indicated by 308 in FIG. In order to convey the member, the band-like member itself needs to have strength so that it does not sag between the pair of opposing end support rings of the curved portion, so it is better for the band-like member to be somewhat thick. Regarding stress relaxation of the deposited film mentioned above, the thicker the band member is, the better.Therefore, the thickness of the band member is adjusted appropriately in consideration of these points, but the type of material of the band member and the curvature of its bending For example, if the strip member is made of stainless steel, its thickness is 0.0
It is about 3 to 0.3 w. Similarly, in the case of aluminum or copper, it is about 0.05 to 0.5 wn, and in the case of synthetic resin, it is about 0.1 to 3 fi.
前記帯状部材を太陽電池用の基板として用いる場合には
、該帯状部材が金属等の電気導電性である場合には直接
電流取り出し用の電極としても良いし、合成樹脂等の電
気絶縁性である場合には堆積膜の形成される側の表面に
A1.、Ag、Pt。When the band-shaped member is used as a substrate for a solar cell, it may be used as an electrode for direct current extraction if it is made of electrically conductive material such as metal, or it may be made of electrically insulating material such as synthetic resin. In this case, A1. , Ag, Pt.
Au、Ni、Ti、Mo、W、Fe、V、Cr。Au, Ni, Ti, Mo, W, Fe, V, Cr.
Cu、 ステンレス、真ちゅう、ニクロム、SnO,。Cu, stainless steel, brass, nichrome, SnO,.
Inn0+ 、ZnO,SnO2−1ntO3(ITO
)等のいわゆる金属単体又は合金、及び透明導電性酸化
物(TCO)を鍍金、蒸着、スバンタ等の方法であらか
じめ表面処理を行って電流取り出し用の電極を形成して
おくことが望ましい、また、素子分離の工程を容易にさ
せる目的で、一部絶縁膜を形成させておいても良い。Inn0+, ZnO, SnO2-1ntO3 (ITO
), etc., and transparent conductive oxides (TCO) are preferably surface-treated in advance by plating, vapor deposition, svanta, etc. to form electrodes for current extraction. In order to facilitate the element isolation process, an insulating film may be partially formed.
勿論、前記帯状部材が金属等の電気導電性のものであっ
ても、長波長光の基板表面上での反射率を向上させたり
、基板材質と堆積膜との間での構成元素の相互拡散を防
止したり短絡防止用の干渉層とする等の目的で異種の金
属層等を前記基板上の堆積膜が形成される側に設けても
良い、又、前記帯状部材が比較的透明であって、該帯状
部材の側から光入射を行う層構成の太陽電池とする場合
には前記透明導電性酸化物や金属薄膜等の導電性F!膜
をあらかじめ堆積形成しておくことが望ましい。Of course, even if the strip member is made of an electrically conductive material such as metal, it can improve the reflectance of long wavelength light on the substrate surface, or improve the mutual diffusion of constituent elements between the substrate material and the deposited film. A different metal layer or the like may be provided on the side on which the deposited film is formed on the substrate for the purpose of preventing this or forming an interference layer to prevent short circuits. In the case of a solar cell having a layered structure in which light enters from the side of the strip member, conductive F! of the transparent conductive oxide, metal thin film, etc. is used. It is desirable to deposit the film in advance.
また、前記帯状部材の表面性としてはいわゆる平滑面で
あっても、微小の凹凸面であっても良い。Further, the surface properties of the band-shaped member may be a so-called smooth surface or a minutely uneven surface.
微小の凹凸面とする場合にはその凹凸形状は球状、円錐
状、角錐状等であって、且つその最大高さ(Rmax)
は好ましくは500人乃至5000人とすることにより
、該表面での光反射が乱反射となり、該表面での反射光
の光路長の増大をもたらす。In the case of a minutely uneven surface, the shape of the unevenness is spherical, conical, pyramidal, etc., and the maximum height (Rmax)
is preferably 500 to 5,000 people, whereby light reflection on the surface becomes diffused reflection, resulting in an increase in the optical path length of the reflected light on the surface.
本発明の装置において、前記成膜室内で堆積される膜の
膜厚を制御するためには、前記側壁の一部分を覆い隠す
ような基板カバーを挿入させるのが好ましい。In the apparatus of the present invention, in order to control the thickness of the film deposited within the film forming chamber, it is preferable to insert a substrate cover that partially covers the side wall.
本発明の装置に使用される中心導体としては、その材質
がオーム撰の小さい金属部材で構成されるのが望ましい
。具体的には、銀、銅、アル逅ニウム製等で構成される
か或いはこれらの金属が他の材質で構成される中心導体
上に鍍金されたものかのいずれかであれば良い。本装置
においては銀鍍金されたステンレス管を使用した。The center conductor used in the device of the present invention is preferably made of a metal member with a small ohmic resistance. Specifically, the conductor may be made of silver, copper, aluminum, etc., or may be plated on a center conductor made of other materials. In this device, a silver-plated stainless steel tube was used.
また、成膜室内に突入された中心導体は、その周囲をマ
イクロ波透過性部材でプラズマから分離することで、中
心導体上に堆積膜が形成されそれがマイクロ波の吸収体
となってマイクロ波電力の投入効率が低下するのを回避
している。In addition, the center conductor that has been thrust into the film forming chamber is separated from the plasma by a microwave-transparent member around it, and a deposited film is formed on the center conductor, which acts as a microwave absorber and generates microwaves. This avoids a decrease in power input efficiency.
前記成膜室において、前記中心導体が突入された面に対
向する壁面はマイクロ波反射部材で構成されており、一
方前記中心導体が突入された面は、マイクロ波を透過し
同時に成膜室内部と外部の気密を保持する部材及びマイ
クロ波、反射部材とで構成され、前記成膜室の側壁が導
電性の帯状部材でtIlI威されているため、前記帯状
部材の幅を適宜選択すれば共振器構造となる。In the film forming chamber, the wall surface opposite to the surface into which the center conductor is inserted is made of a microwave reflecting member, while the surface into which the center conductor is inserted transmits microwaves and simultaneously reflects the inside of the film forming chamber. The side wall of the film forming chamber is covered with a conductive strip member, so if the width of the strip member is appropriately selected, resonance can be achieved. It becomes a vessel structure.
よく知られているように、w@路のインピーダンスが急
変する境界面及び短絡面では電磁波は強く反射される。As is well known, electromagnetic waves are strongly reflected at interfaces and short-circuit surfaces where the impedance of the w@ path suddenly changes.
ここでは、前述の成膜室の対向する両端面はそれぞれ前
述の境界面との短絡面に相当するためマイクロ波を強く
反射し、2つの強い反射面を適当に配置した空洞に電磁
波を投入するとQ値の高い共振器構造を構成することが
できる。Here, the opposite end surfaces of the film forming chamber described above each correspond to short-circuit surfaces with the aforementioned boundary surfaces, so they strongly reflect microwaves, and when electromagnetic waves are injected into a cavity in which two strong reflecting surfaces are appropriately arranged, A resonator structure with a high Q value can be constructed.
本発明の装置では、成膜室の対向する両端面を可動とし
て共振器構造を構成しても良いが操作性の点でより優れ
る、前記中心導体挿入長調節機構により半同軸共振器構
造を形成したり、或いはマイクロ波透過性の高誘電率部
材を成膜室の所望の場所に挿入することによって等価的
に共振器長を可変にする即ちインピーダンスを調整した
りしても良い。In the apparatus of the present invention, a resonator structure may be constructed by making both opposing end surfaces of the film forming chamber movable, but a semi-coaxial resonator structure is formed by the central conductor insertion length adjustment mechanism, which is superior in terms of operability. Alternatively, the resonator length may be equivalently made variable, that is, the impedance may be adjusted by inserting a microwave-transparent high dielectric constant member into a desired location in the film forming chamber.
上述の如く放電前に予め共振器構造となるように調節す
れば、共振器構造の電力蓄積効果によって放電開始が容
易であり、また放電後に前述の中心導体挿入長調節機構
でインピーダンスを整合させれば、広い成膜圧力範囲で
長時間に亘って定常的に一定の放電状態を持続すること
ができる。If the resonator structure is adjusted in advance before discharge as described above, discharge can be easily started due to the power storage effect of the resonator structure, and the impedance can be matched by the above-mentioned center conductor insertion length adjustment mechanism after discharge. For example, a constant discharge state can be maintained over a long period of time over a wide film-forming pressure range.
本発明の装置に使用されるマイクロ波透過性部材として
は例えば第1図において103で示される誘電体管が挙
げられる。The microwave transparent member used in the apparatus of the present invention includes, for example, a dielectric tube designated by 103 in FIG.
該誘電体管の材質としては、使用するマイクロ波帯域に
おいて誘電損失tan δ (タンデルタ)の小さいも
のであれば良いが、同時に熱伝導率が高く熱衝撃にも強
ければ前記誘電体管に付着した膜が変質してマイクロ波
電力の反射・吸収が増大することを抑止し、前記誘電体
管の熱破損も防止できるためなおさら良い。このような
条件に最適な材質としてはべりリア、アルごす・セラミ
ックス、窒化ホウ素、石英等が好適であり、特にアルミ
ナ・セラもンクスが最も好適である。The material of the dielectric tube may be any material as long as it has a small dielectric loss tan δ (tan delta) in the microwave band to be used. This is even better because it prevents the film from changing in quality and increasing the reflection and absorption of microwave power, and also prevents thermal damage to the dielectric tube. Suitable materials for such conditions include Berria, Algos ceramics, boron nitride, and quartz, with alumina ceramics being the most suitable.
マイクロ波グロー放電を生起させ、しかも安定に定常的
に放電させるためには、この誘電体管にマイクロ波を透
過させ気密を保持し得る機能が求められる。この機能を
果たすような前記誘電体管の形状としては、次の2例の
いずれかの方法が最適である。すなわち、開放円筒管の
両端に穴あきフランジを1つずつ溶着する開放端円筒管
か、或いは一方が閉端となった円筒管の開放端側に穴あ
きフランジを溶着する閉端円筒管かのいずれかである。In order to generate a microwave glow discharge and to discharge it stably and constantly, the dielectric tube is required to have the function of transmitting microwaves and maintaining airtightness. As for the shape of the dielectric tube that fulfills this function, either of the following two methods is optimal. That is, an open-end cylindrical tube in which one perforated flange is welded to each end of an open cylindrical tube, or a closed-end cylindrical tube in which a perforated flange is welded to the open end of a cylindrical tube with one end closed. Either.
そしてこのフランジ部が○リングを介して成膜室の対向
する端面の一方の壁に密着して気密が保持できるよう配
置すれば良い、保守・点検の点から言えば、後者の閉端
円筒管の方が更に好都合である。Then, the flange part should be placed in close contact with one wall of the opposite end face of the film forming chamber via the ○ ring to maintain airtightness.From the point of view of maintenance and inspection, the latter closed-end cylindrical tube is even more convenient.
本発明の装置に使用される前記のマイクロ波透過性の高
誘電率部材は、アルミナ・セラミックス、ベリリア、窒
化ホウ素等の材質で構成され、前述の中心導体挿入長調
節機構により構成される半同軸共振器構造の内部或いは
端部に配設することによって、共振器長を等傷内に変化
させる効果が得られることが、本発明者らの検討で確認
された。The microwave-transparent high dielectric constant member used in the device of the present invention is made of a material such as alumina ceramics, beryllia, or boron nitride, and is a semi-coaxial member configured by the center conductor insertion length adjustment mechanism described above. The inventors of the present invention have confirmed through studies that by disposing the resonator inside or at the end of the resonator structure, the effect of changing the resonator length within a uniform range can be obtained.
本発明者らが更に検討を行った結果、前記マイクロ波透
過性の高誘電率部材の最適な寸法が、前記中心導体の挿
入長と相関があることが判明した。As a result of further investigation by the present inventors, it was found that the optimum dimensions of the microwave-transparent high dielectric constant member have a correlation with the insertion length of the center conductor.
従って、該中心導体の挿入長を固定した状態でHP87
57Aスカラ・ネソトワーク・アナライザー(ヒエーレ
ソト・パンカード社製〉を使用して、共振周波数が2.
45GHzになるように前記マイクロ波透過性の高誘電
率部材の形状を決めれば良い。Therefore, with the insertion length of the center conductor fixed, HP87
Using the 57A Scalar Nesotowork Analyzer (manufactured by Hiereosoto Pancard), the resonant frequency was determined to be 2.
The shape of the microwave-transparent high dielectric constant member may be determined so that the frequency is 45 GHz.
本発明の装置に使用される帯状部材を支持・搬送する手
段については、前記帯状部材(基体〉が前記成膜室の側
壁を形成しているため、搬送中の前記帯状部材にねじれ
、たわみ、蛇行等を生ずると放電が不安定となり同一の
品質の膜を再現良く大量に作製することは困難になる。Regarding the means for supporting and transporting the belt-shaped member used in the apparatus of the present invention, since the belt-shaped member (substrate) forms the side wall of the film forming chamber, the belt-shaped member is twisted, bent, or bent during transport. If meandering or the like occurs, the discharge becomes unstable and it becomes difficult to produce a large quantity of films of the same quality with good reproducibility.
また、前記帯状部材を支持搬送する手段の表面に汚れや
ゴ壽が付着していると、それらが形成された堆積膜の欠
陥の原因となることがしばしば起こり、問題となってい
た。つまり、前記帯状部材を支持・搬送する手段には前
記成膜室の変形を防止することと帯状部材の堆積膜が形
成される面(これを「成膜面」と略称する)に帯状部材
を支持・搬送する手段が接触することを極力控えること
の2点が重要であることが判明した。Furthermore, if dirt or grime adheres to the surface of the means for supporting and conveying the belt-like member, this often causes defects in the deposited film, which has been a problem. In other words, the means for supporting and transporting the strip-shaped member includes preventing deformation of the film-forming chamber and placing the strip-shaped member on the surface on which the deposited film of the strip-shaped member is formed (hereinafter referred to as the "film-forming surface"). It has been found that two important points are to avoid contact between supporting and transporting means as much as possible.
すなわち、前記第−点の成膜室の変形防止には前記帯状
部材を支持・搬送する手段に公知のクラウン機構を組込
んでねじれ・蛇行を防止し、公知の張力調整機構でたわ
みを防ぐことができる。That is, in order to prevent deformation of the film forming chamber at the second point, a known crown mechanism is incorporated into the means for supporting and conveying the strip member to prevent twisting and meandering, and a known tension adjustment mechanism is used to prevent deflection. I can do it.
また、前記第二点の前記成膜面に帯状部材を支持・搬送
する手段が接触することを極力控えるには、帯状部材の
a膜面側の支持は帯状部材の周縁部のみで行い、帯状部
材の成膜面の裏面の支持は帯状部材全幅に渡って支持搬
送すれば良い。In addition, in order to prevent the means for supporting and transporting the strip member from coming into contact with the film forming surface at the second point as much as possible, support on the a-film side of the strip member is performed only at the peripheral edge of the strip member, and the strip member is The back side of the film-forming surface of the member may be supported and conveyed over the entire width of the band-shaped member.
換言すれば、前記帯状部材の湾曲部形成手段が成膜室の
内部に設置されるものは帯状部材の周縁部のみを接触・
支持する湾曲部端面支持リングであり、成膜室外部に設
置されるものは大略帯状部材の幅全体に渡って接触・支
持するローラーである。前記湾曲部端面支持リングで前
記帯状部材の内側を支持し、搬送するには、第1図にお
いて113で示される多数の湾曲部支持内側リングで支
持しても良いし、第3図において308で示される円柱
状の成膜室の対向する両端面とほぼ同じ大きさの一対の
湾曲部支持内側リングで支持しても良い。In other words, in the case where the curved portion forming means of the band-shaped member is installed inside the film-forming chamber, only the peripheral edge of the band-shaped member is contacted or
The supporting ring for supporting the curved part end face, which is installed outside the film forming chamber, is a roller that contacts and supports the belt-shaped member over the entire width thereof. In order to support and transport the inner side of the band-shaped member with the curved part end support ring, it may be supported by a number of curved part support inner rings shown at 113 in FIG. 1, or by 308 in FIG. It may be supported by a pair of curved portion support inner rings having substantially the same size as the opposing end surfaces of the cylindrical film forming chamber shown.
ここで、湾曲した帯状部材を側壁とした柱状の成膜室と
前述の帯状部材の長手方向に設けられた間隙とを形成す
るには、連続的に搬送される帯状部材を1対の開口部支
持内側ローラーと開口部支持外側ローラーとから構成さ
れる湾曲開始端形成ローラーでゆるやかにその搬送方向
を変え、前記湾曲部端面支持リングで前記帯状部材を成
膜室の側壁を為すように湾曲させ、前述とは別の1対の
開口部支持内側ローラーと開口部支持外側ローラーとか
ら構成される湾曲終了端形成ローラーでゆるやかにその
搬送方向を変えることによって為される。Here, in order to form a columnar film forming chamber with a curved strip member as a side wall and a gap provided in the longitudinal direction of the strip member described above, the strip member that is continuously conveyed is connected to a pair of openings. The conveyance direction is gently changed by a bending start end forming roller consisting of a support inner roller and an opening support outer roller, and the belt-like member is curved to form a side wall of the film forming chamber by the curved part end support ring. This is done by gently changing the conveyance direction of the curved end forming roller, which is composed of a pair of opening support inner roller and opening support outer roller, which are different from those mentioned above.
ここで、前記開口部支持外側ローラーの直径が大きすぎ
ると中心導体から帯状部材までの距離が方向によって異
なるためプラズマ密度の不均一な部分を多く生じ型車し
くない、一方前述の開口部支持外側ローラーの直径が小
さすぎると、曲げ応力により前記帯状部材に歪みを残し
たり、膜の剥離を起こす、そこで、厚さ0.15mの金
属帯状部材では直径60關φ〜100mφのローラー、
厚さ0.05關では直径25wφ程度のローラーを使用
することが望ましい、さらに、メンテナンス後の真空引
きを速やかに終了するため、前記湾曲開始端形成ローラ
ーと前記湾曲終了端形成ローラーとの間隔を可変できる
ような装置構成としても良い。Here, if the diameter of the aperture support outer roller is too large, the distance from the center conductor to the strip member varies depending on the direction, resulting in many areas with uneven plasma density, which is undesirable. If the diameter of the roller is too small, the bending stress will leave distortions in the strip member or cause the film to peel off. Therefore, for a metal strip member with a thickness of 0.15 m, a roller with a diameter of 60 mφ to 100 mφ,
For a thickness of 0.05 mm, it is desirable to use a roller with a diameter of about 25 wφ.Furthermore, in order to quickly finish vacuuming after maintenance, the distance between the curved start end forming roller and the curved end forming roller is adjusted. The device may have a variable configuration.
なお、湾曲部端面支持リングにて前記帯状部材を支持・
搬送する方法としては単なる滑り摩擦のみによっても良
いし、あるいは前記帯状部材にスプロケット六等の加工
を施し、同時に、湾曲部端面支持リングがスプロケット
でも良い。Note that the band-shaped member is supported by the curved part end face support ring.
The conveying method may be simple sliding friction alone, or the strip member may be processed into a sprocket 6 or the like, and at the same time, the curved portion end support ring may be a sprocket.
また、本発明の装置においても、前記帯状部材の表面温
度は堆積膜の膜質を左右する重要なパラメーターである
が、該帯状部材の表面温度の制御方法である第2図に示
すようなランプ輻射加熱により該帯状部材を前記成膜面
の裏面から加熱することができる。しかしながら該帯状
部材の搬送速度が遅い、即ち前記成膜室内に該帯状部材
が滞留する時間が長い場合及びマイクロ波の投入電力が
大きい場合は前記帯状部材は著しく昇温してしまい、ラ
ンプ輻射加熱のみでは温度調整できなくなる場合がある
。このような場合には、第3図において308で示され
る湾曲部支持内側リングの他に、湾曲部支持外側ローラ
ー(不図示)を設け、前記帯状部材の成膜面の裏面の全
幅に渡って該湾曲部支持外側ローラーを圧接させ、該湾
曲部支持外側ローラー内部に熱交換媒体を組込むことに
より、加熱・冷却とも可能となり、温度調整できるよう
になる。Furthermore, in the apparatus of the present invention, the surface temperature of the strip member is an important parameter that influences the film quality of the deposited film, and lamp radiation as shown in FIG. By heating, the belt-shaped member can be heated from the back side of the film-forming surface. However, if the conveyance speed of the belt-shaped member is slow, that is, the time the belt-shaped member stays in the film forming chamber is long, or if the input power of the microwave is large, the temperature of the belt-shaped member increases significantly, and lamp radiation heats the belt-shaped member. You may not be able to adjust the temperature if you do so only. In such a case, in addition to the curved part supporting inner ring shown at 308 in FIG. By bringing the curved portion supporting outer roller into pressure contact and incorporating a heat exchange medium inside the curved portion supporting outer roller, both heating and cooling become possible and temperature adjustment becomes possible.
本発明者らは、下達する(i)乃至(iii )の問題
の生起を未然に防ぐ機能を成膜用原料ガスを導入する手
段及び前記成膜室を排気する手段に盛り込んで検討を行
った。The present inventors have investigated incorporating a function to prevent the occurrence of problems (i) to (iii) below into the means for introducing the film-forming raw material gas and the means for evacuating the film-forming chamber. .
(1)膜のIRI離で成膜面に欠陥が発生する;(ii
)原料ガスを導入する手段にほとんどの膜が堆積する;
そして、
(iii )原料ガスの空間分布が不均一であること。(1) Defects occur on the film formation surface due to IRI separation of the film; (ii
) most of the film is deposited on the means of introducing the source gas;
and (iii) the spatial distribution of the source gas is non-uniform.
その結果下達するところが判明した。As a result, it became clear that there was a decline.
即ち、上記(i)の問題については、第5図に示すよう
なロードロック機構を設け、堆積作業中に著しく堆積膜
が剥離するようになった場合、そこで堆積作業を中止し
、成膜室内部の固定部材、例えば原料ガス導入管や誘電
体管等を交換することで膜の剥離を抑制できる。That is, regarding the problem (i) above, a load lock mechanism as shown in Figure 5 is installed, and if the deposited film begins to peel off significantly during the deposition process, the deposition process is stopped and the film forming chamber is closed. Peeling of the film can be suppressed by replacing the internal fixing members, such as the raw material gas introduction pipe and the dielectric pipe.
(it)については、原料ガスを導入する手段が高温に
なると原料ガスが熱分解されて原料ガスを導入する手段
に付着してしまうのでこれを防ぐため金属製、特にニッ
ケルやステンレス等の材料が好適である。Regarding (it), if the means for introducing the raw material gas becomes high temperature, the raw material gas will be thermally decomposed and will stick to the means for introducing the raw material gas, so to prevent this, it should be made of metal, especially nickel or stainless steel. suitable.
一方、(iii )については、原料ガス導入管を兼ね
るバイアス印加前106の表面に設けられた複数の小孔
を、第4図に示したようにスリット状開口部110とは
反対方向を向け、公知のように小孔の開けられた間隔を
上流側はど長く、下流側はど短くすれば良い。On the other hand, regarding (iii), the plurality of small holes provided on the surface of the bias application front 106 which also serves as the raw material gas introduction pipe are oriented in the opposite direction to the slit-shaped opening 110 as shown in FIG. As is well known, the distance between the small holes may be made longer on the upstream side and shorter on the downstream side.
本発明の装置において、プラズマ電位を制御するために
設けられるバイアス印加手段は前記成膜室内に生起する
プラズマに少なくともその一部分が接するように配設さ
れる。以下、図面を用いてその配置等についての典型例
を具体的に説明するが、本発明のViaにおけるバイア
ス印加手段はこれらに限定されるわけではない。In the apparatus of the present invention, the bias applying means provided for controlling the plasma potential is arranged so that at least a portion thereof is in contact with the plasma generated in the film forming chamber. Typical examples of the arrangement and the like will be specifically explained below with reference to the drawings, but the bias applying means in the via of the present invention is not limited to these.
第19図(A)乃至第19図(D)に、第1図に示した
本発明の装置の、第4図に示した断面模式図中のHH’
方向での側断面模式図を示した。19(A) to 19(D) show HH' in the cross-sectional schematic diagram shown in FIG. 4 of the apparatus of the present invention shown in FIG.
A schematic side cross-sectional view in the direction is shown.
これらの図面においては主要構成部材のみを示しである
。In these drawings, only the main constituent members are shown.
第19図(A)に示す例は、バイアス印加手段がガス供
給手段を兼ねる場合の典型例であり、帯状部材1901
は接地され、支持・搬送用ローラー1902によって湾
曲形状が保たれながら搬送されている。1903はガス
導入管を兼ねるバイアス印加管であり、ガス供給管19
10と絶縁性継手l9(19にて接続されている。そし
て、ガス導入管を兼ねるバイアス印加前1903にはバ
イアス印加用電源1907にて発生させたバイアス電圧
が印加される。該バイアス印加用電源1907としては
、市販されている直流安定化電源、交流電源、高周波電
源等の他、種々の波形及び周波数を有するバイアス電圧
を印加させるために、例えばファンクション・ジェネレ
ーターにて発生させた波形出力を精密電力増幅器にて増
幅させる電源システムを自作して用いることができる。The example shown in FIG. 19(A) is a typical example where the bias application means also serves as a gas supply means, and the belt-like member 1901
is grounded and is being conveyed while maintaining its curved shape by support/conveyance rollers 1902. 1903 is a bias application tube that also serves as a gas introduction tube, and the gas supply tube 19
10 and an insulating joint 19 (19). A bias voltage generated by a bias application power supply 1907 is applied to a bias application front 1903 which also serves as a gas introduction pipe. In addition to commercially available DC stabilized power supplies, AC power supplies, high-frequency power supplies, etc., the 1907 can also be used to precisely convert the waveform output generated by a function generator in order to apply bias voltages with various waveforms and frequencies. You can make your own power supply system that amplifies it with a power amplifier.
バイアス印加電圧及びバイアス電流値は記録計等にて絶
えずモニターすることが好ましく、プラズマの安定性・
再現性の向上や異常放電の発生を抑制するための制御回
路にそのデータを取り込むようにすることが望ましい。It is preferable to constantly monitor the bias applied voltage and bias current value using a recorder, etc., to ensure plasma stability and
It is desirable to incorporate this data into a control circuit for improving reproducibility and suppressing the occurrence of abnormal discharge.
バイアス印加前1903が前記成膜室内に配設される位
置は、前記マイクロ波プラズマに該バイアス印加前19
03が接して配設される限り特に限定されることはない
が、異常放電の発生等を抑える上で、前記帯状部材19
01の内表面から好ましくは10四以上、より好ましく
は20f1以上離して配設されるのが望ましい。The position where the pre-bias application 1903 is disposed in the film forming chamber is such that the pre-bias application 1903 is placed in the microwave plasma.
Although there is no particular limitation as long as the strip members 19 are arranged in contact with each other, in order to suppress the occurrence of abnormal discharge etc.
It is desirable that the distance from the inner surface of 01 is preferably 104 or more, more preferably 20f1 or more.
バイアス印加管1903はガス導入管を兼ねるのでその
周方向、特に長手方向には均一に原料ガスが放出される
ような孔又はスリフトが開けられているのが望ましい。Since the bias application tube 1903 also serves as a gas introduction tube, it is desirable that holes or thrusts are formed in the circumferential direction, particularly in the longitudinal direction, so that the raw material gas can be discharged uniformly.
また、その管径及び管長については、所望の電流密度が
確保されるように設計されるが、その表面積は前記電流
密度が確保される限り小さくさせることが好ましい。そ
れにより、表面に堆積膜が形成されることによる原料ガ
スの利用効率の低下及び堆積した膜の剥がれ、飛散によ
る帯状部材上に形成される堆積膜の欠陥発生率の増大を
抑制することができる。また、本構成とすることにより
原料ガスの分解効率のより一層の向上も図れる。Further, the diameter and length of the tube are designed to ensure a desired current density, but the surface area is preferably made as small as possible as long as the current density is ensured. Thereby, it is possible to suppress a decrease in the utilization efficiency of the raw material gas due to the formation of a deposited film on the surface, and an increase in the defect occurrence rate of the deposited film formed on the strip member due to peeling of the deposited film and scattering. . Moreover, by adopting this configuration, it is possible to further improve the decomposition efficiency of the raw material gas.
第19図(B)及び第19図CD>に示す例は、ガス供
給手段とバイアス印加手段とを各々独立に設ける場合の
典型例であり、第19図(B)にはバイアス棒1904
が1本、第19図(D)にはバイアス棒1904及び第
2バイアス棒1906が設けられている例を示したが、
所望により更に別のバイアス棒を追加配設しても良い。The example shown in FIG. 19 (B) and FIG. 19 CD> is a typical example in which the gas supply means and the bias application means are provided independently.
Although one bias rod 1904 and a second bias rod 1906 are provided in FIG. 19(D),
If desired, another bias rod may be additionally provided.
1907.1908は各々バイアス印加用電源であり、
その仕様は全く同じであっても良いし、各々独立のバイ
アス電圧が印加できるように異なった仕様のものであっ
ても良い、原料ガスはガス導入管1905を介して前記
成膜室内に導入される。バイアス棒1904及び第2バ
イアス棒は各々耐熱性金属、例えばステンレススチール
、ニッケル、チタン、バナジウム、ニオブ、タンタル、
モリブデン、タングステン等で構成される棒状又は管状
のものを用いることが好ましい。管状構造とすることに
よって、その中に冷却媒体を流してバイアス棒の異常発
熱・等を抑えることができる。1907 and 1908 are power supplies for bias application, respectively;
The specifications may be exactly the same, or they may be of different specifications so that independent bias voltages can be applied to each.The raw material gas is introduced into the film forming chamber through the gas introduction pipe 1905. Ru. The bias rod 1904 and the second bias rod are each made of a heat-resistant metal such as stainless steel, nickel, titanium, vanadium, niobium, tantalum,
It is preferable to use a rod-like or tubular material made of molybdenum, tungsten, or the like. By having a tubular structure, it is possible to flow a cooling medium therein to suppress abnormal heat generation of the bias rod.
また、これらの配設される位置は前記バイアス印加管1
103の場合とほぼ同様である。Moreover, the positions where these are arranged are the same as those of the bias application tube 1.
This is almost the same as the case of 103.
ガス導入管1905は異常放電の発生の抑制や、均一な
プラズマ電位を形成させる上で誘電体で構成させること
が好ましいが、導電性であって接地されていても支障な
く用いることもできる。The gas introduction pipe 1905 is preferably made of a dielectric material in order to suppress the occurrence of abnormal discharge and form a uniform plasma potential, but it can also be used without any problem even if it is conductive and grounded.
第19図(C)に示す例は、帯状部材にバイアス電圧を
印加させる場合の典型例であり、帯状部材】901にバ
イアス印加用電源1907が接続されている。そして、
ガス導入管1905は導電性部材で構成され、且つ接地
されている。なお、ガス導入管1905を誘電体で構成
し、これとは別に接地電極を設けても良い。前記ガス導
入管1905の配設される位置はプラズマに接している
限り、特に制限はない。The example shown in FIG. 19(C) is a typical example in which a bias voltage is applied to a band-shaped member, and a bias-applying power source 1907 is connected to the band-shaped member 901. and,
The gas introduction pipe 1905 is made of a conductive member and is grounded. Note that the gas introduction pipe 1905 may be made of a dielectric material, and a ground electrode may be provided separately from this. The position where the gas introduction pipe 1905 is disposed is not particularly limited as long as it is in contact with the plasma.
本発明の装置によれば、バイアス印加手段に適宜のバイ
アス電圧を単独又は重畳させて印加させることにより、
所望のプラズマ電位を制御することができる。そして、
そのことにより、高品質で、欠陥の少ない機能性堆積膜
を連続して効率良く、高い歩留りで再現性良く形成する
ことができる。According to the device of the present invention, by applying appropriate bias voltages to the bias applying means alone or in combination,
A desired plasma potential can be controlled. and,
As a result, a high-quality functional deposited film with few defects can be continuously and efficiently formed with high yield and good reproducibility.
本発明の方法及び装置において連続形成される機能性堆
積膜としては、非晶質、結晶質を問わず、3i、Qe、
C等いわゆる■族生導体薄膜、5iGe、SiC,5i
Sn等いわゆる■族合金半導体′iR’iIf!、Ga
As、GaP、GaSb。The functional deposited films that are continuously formed in the method and apparatus of the present invention include 3i, Qe,
So-called group III raw conductor thin films such as C, 5iGe, SiC, 5i
So-called ■ group alloy semiconductors such as Sn'iR'iIf! , Ga
As, GaP, GaSb.
InP、InAs等いわゆるm−v族化合物半導体薄膜
、及びZn5e、ZnS、ZnTe+Cd5CdSe、
CdTe等いわゆるII−VI族化合物半導体薄膜等が
挙げられる。So-called m-v group compound semiconductor thin films such as InP and InAs, and Zn5e, ZnS, ZnTe+Cd5CdSe,
Examples include so-called II-VI group compound semiconductor thin films such as CdTe.
本発明の方法及び装置において用いられる前記機能性堆
積膜形成用原料ガスとしては、上述した各種半導体薄膜
の+**元素の水素化物、ハロゲン化物、有機金属化合
物等で前記成膜室内へ好ましくは気体状態で導入できる
ものが選ばれ使用される。The raw material gas for forming the functional deposited film used in the method and apparatus of the present invention is preferably a hydride, a halide, an organometallic compound, etc. of the +** element of the various semiconductor thin films described above. Those that can be introduced in a gaseous state are selected and used.
勿論、これらの原料化合物は1種のみならず、2種以上
混合して使用することもできる。又、これらの原料化合
物はTTe、Ns、Ar、Kr。Of course, these raw material compounds can be used not only alone, but also in combination of two or more. Further, these raw material compounds are TTe, Ns, Ar, and Kr.
Xe、Rn等の希ガス、及びH! 、HF、HCl等の
希釈ガスと混合して導入されても良い。Noble gases such as Xe and Rn, and H! , HF, HCl, or the like.
また、連続形成される前記半導体薄膜は価電子制御及び
禁制帯幅制御を行うことができる。具体的には価電子制
御剤又は禁制帯幅制御剤となる元素を含む原料化合物を
単独で、又は前記堆積膜形成用原料ガス又は前記希釈ガ
スに混合して前記成膜室内へ導入してやれば良い。Further, the continuously formed semiconductor thin film can perform valence electron control and forbidden band width control. Specifically, a raw material compound containing an element serving as a valence electron control agent or a forbidden band width control agent may be introduced into the film forming chamber alone or mixed with the deposited film forming raw material gas or the diluent gas. .
以下、図面を用いて本発明の具体的装置例を挙げて説明
するが、本発明はこれらの装置例によって何ら限定され
るものではない。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, specific examples of devices of the present invention will be described with reference to the drawings, but the present invention is not limited to these device examples.
装置燃上
第1図は本発明の特徴である、移動する帯状部材をその
側壁にして構成される成膜室及びその周辺機構の典型的
な例を模式的に示す透視図である。FIG. 1 is a perspective view schematically showing a typical example of a film-forming chamber and its peripheral mechanism, which is constructed by using a moving band-shaped member as a side wall, which is a feature of the present invention.
第1図において、101は帯状部材、102はマイクロ
波を投入するための同軸線路の中心導体、103はマイ
クロ波透過性部材である誘電体管、104は成膜室、1
05は小孔、106は原料ガス導入管を兼ねるバイアス
印加管、107は真空排気口、108は帯状部材支持外
側ローラー1(19は帯状部材支持内側ローラー、11
0は成膜室のスリント状開口部、111は開口部支持外
側ローラー、112は開口部支持内側ローラー113は
湾曲部支持内側リング、114は絶縁性継手、115は
ガス供給管、116はバイアス印加用電源、117は導
線である。In FIG. 1, 101 is a band-shaped member, 102 is a center conductor of a coaxial line for inputting microwaves, 103 is a dielectric tube that is a microwave-transparent member, 104 is a film forming chamber, 1
05 is a small hole, 106 is a bias application tube that also serves as a raw material gas introduction tube, 107 is a vacuum exhaust port, 108 is a strip member supporting outer roller 1 (19 is a strip member supporting inner roller, 11
0 is a slint-like opening of the film forming chamber, 111 is an outer roller supporting the opening, 112 is an inner roller supporting the opening 113 is an inner ring supporting the curved part, 114 is an insulating joint, 115 is a gas supply pipe, and 116 is a bias application 117 is a conductive wire.
尚、第1図中の2つの矢印はそれぞれ原料ガスの流れを
示す。Note that the two arrows in FIG. 1 each indicate the flow of the raw material gas.
第1図において、帯状部材101で構成される成膜室1
04は円柱状であり、該成膜室の回転軸上に同軸線路の
中心導体102を配設し、成膜室104の内部でこの中
心導体102と同軸状にマイクロ波透過性部材である誘
電体管103を配設する。この成膜室104は、開口部
支持外側ローラー111と開口部支持内側ローラー11
2とで帯状部材101を挟み込みながらその搬送方向を
変え、外側に凸状になるように湾曲させた帯状部材の周
縁部に対向させて複数個配設した湾曲部支持内側リング
113を介して帯状部材101を支持・搬送して円柱の
側壁を構成させ、再び開口部支持外側ローラー111と
開口部支持内側ローラー112とで帯状部材101を挟
み込みながらその搬送方向を変えることにより、円柱状
に形成することかできる。また、前述のように、帯状部
材101の搬送中のねじれ・たるみ等を防止するため、
帯状部材101の湾曲部以外の部分にも、帯状部材支持
外側ローラー108と帯状部材支持内側ローラー1(1
9とで帯状部材101を挟み込みながら支持・搬送する
ようにする。In FIG. 1, a film forming chamber 1 composed of a strip member 101 is shown.
Reference numeral 04 has a cylindrical shape, and a central conductor 102 of a coaxial line is disposed on the rotation axis of the film forming chamber, and a dielectric conductor which is a microwave transparent member is coaxially connected to the central conductor 102 inside the film forming chamber 104. A body tube 103 is arranged. This film forming chamber 104 includes an opening support outer roller 111 and an opening support inner roller 11.
2, the belt-shaped member 101 is sandwiched between the belt-shaped member 101 and the belt-shaped member 101, and the direction of conveyance is changed. The member 101 is supported and conveyed to form a columnar side wall, and the belt-shaped member 101 is again sandwiched between the opening support outer roller 111 and the opening support inner roller 112 while changing its conveyance direction, thereby forming a columnar shape. I can do it. In addition, as described above, in order to prevent twisting, sagging, etc. of the belt-shaped member 101 during transportation,
The belt-like member supporting outer roller 108 and the belt-like member supporting inner roller 1 (1
The belt-shaped member 101 is supported and conveyed while being sandwiched between the belt-shaped member 9 and the belt-shaped member 9.
第1図において、帯状部材101で構成されるスリット
状の開口部110は、開口支持外側ローラー111、開
口部支持内側ローラー112で帯状部材101を支持す
ることにより前記開口部の形状を維持させる。開口部支
持内側ローラー112は帯状部材101の周縁部のみと
接触し、別に設けた駆動機構(不図示)にて成膜室外部
より前記帯状部材101を駆動させる。前記駆動機構に
張力調整機構を設けることによってたるみのない搬送を
行うことができる。In FIG. 1, a slit-shaped opening 110 formed of a strip member 101 maintains the shape of the opening by supporting the strip member 101 with an opening support outer roller 111 and an opening support inner roller 112. The opening support inner roller 112 contacts only the peripheral edge of the strip member 101, and drives the strip member 101 from outside the film forming chamber by a separately provided drive mechanism (not shown). By providing the drive mechanism with a tension adjustment mechanism, it is possible to carry out the conveyance without slack.
第1図において、原料ガス導入管を兼ねるバイアス印加
管106は、成膜室104の内部に導入され、その配置
は第4図に示すように、誘電体管103に対して成膜室
104のスリット状開口部+10の反対側に配設され、
原料ガス導入管を兼ねるバイアス印加管106上に設け
られた多数の小孔105が帯状部材101に向かう方向
に配設する。In FIG. 1, a bias application tube 106 that also serves as a raw material gas introduction tube is introduced into the film forming chamber 104, and its arrangement is as shown in FIG. Arranged on the opposite side of the slit-shaped opening +10,
A large number of small holes 105 are provided on a bias application tube 106 that also serves as a source gas introduction tube, and are arranged in a direction toward the strip member 101 .
原料ガス導入管を兼ねるバイアス印加管106には導線
117を介して、バイアス印加用電源+16にて発生さ
せたバイアス電圧が印加される。A bias voltage generated by a bias application power supply +16 is applied to the bias application tube 106, which also serves as a raw material gas introduction pipe, via a conductive wire 117.
又、ガス導入管を兼ねるバイアス印加管106は絶縁性
継手114を介してガス供給管115とは絶縁分離され
ている。Further, the bias application tube 106 which also serves as a gas introduction tube is insulated and separated from the gas supply tube 115 via an insulating joint 114.
帯状部材101は接地されるが、前記柱状の成膜室の側
壁部分のほぼ全面にわたり均一に接地されることが好ま
しく、開口部支持外側ローラー111、開口部支持内側
ローラー112、湾曲部支持内側リング113、及び前
記帯状部材101の側壁に接触する電気ブラシ(不図示
)等を介して接地されるのが望ましい。The strip member 101 is grounded, but is preferably grounded uniformly over almost the entire side wall portion of the columnar film forming chamber, and includes an opening support outer roller 111, an opening support inner roller 112, and a curved portion support inner ring. 113, and an electric brush (not shown) that contacts the side wall of the strip member 101.
第1図で示した成膜室104の内部にマイクロ波電力を
導入する機構については第3図を用いて説明する。A mechanism for introducing microwave power into the film forming chamber 104 shown in FIG. 1 will be explained using FIG. 3.
第3図では、マイクロ波アンテナ手段の1例として同軸
線路について説明するが、リジターノ・コイル等のアン
テナ手段であっても良い。In FIG. 3, a coaxial line will be described as an example of the microwave antenna means, but antenna means such as a Risitano coil may also be used.
第3図において、301は方形導波管、302は同軸プ
ランジャー(可動P端)、303,304は1i磁シ一
ルド部材、305は同軸プランジャー固定部材、306
は円形チジーク・フランジ、307はマイクロ波透過性
の高誘電率部材、308は湾曲部支持内側リング、3(
19はローラーまたはベアリング、310は中心導体冷
却気体導入口、311は小孔、312はストッパー31
3は導波管同軸変換器である。In FIG. 3, 301 is a rectangular waveguide, 302 is a coaxial plunger (movable P end), 303 and 304 are 1i magnetic shield members, 305 is a coaxial plunger fixing member, and 306
307 is a microwave transparent high dielectric constant member, 308 is a curved part support inner ring, 3 (
19 is a roller or bearing, 310 is a center conductor cooling gas inlet, 311 is a small hole, 312 is a stopper 31
3 is a waveguide coaxial converter.
第3図に示したとおり、中心導体102は中空構造であ
って、その一端が成膜室104の内部に突入され、導波
管同軸変換器313を経て同軸線路の外部に出て、他端
が中心導体冷却気体導入口310となっている。中心導
体102は、ばね材でできた電磁シールド部材303,
304及び不図示の中心導体固定部材で電気的接触が良
く保たれている。中心導体固定部材は、例えば同軸プラ
ンジャー固定部材305と同一の構造で取付位置が中心
導体の軸の回りに90°回転した配置のものであっても
良い、第3図では、この固定部材は単なるボルトで代用
している。この中心導体102のうち、電磁シールド部
材304が接触している近傍の部分を動かすことによっ
て、中心導体102の成膜室104内部への挿入長を同
軸線路の外部から調節することができる。As shown in FIG. 3, the center conductor 102 has a hollow structure, one end of which is inserted into the film forming chamber 104, exits to the outside of the coaxial line via a waveguide coaxial converter 313, and the other end of the center conductor 102 is hollow. serves as a center conductor cooling gas inlet 310. The center conductor 102 includes an electromagnetic shielding member 303 made of spring material,
304 and a central conductor fixing member (not shown), electrical contact is well maintained. For example, the center conductor fixing member may have the same structure as the coaxial plunger fixing member 305, but the mounting position may be rotated by 90 degrees around the axis of the center conductor. In FIG. 3, this fixing member is A simple bolt is used instead. By moving a portion of the center conductor 102 in the vicinity of which the electromagnetic shielding member 304 is in contact, the insertion length of the center conductor 102 into the film forming chamber 104 can be adjusted from outside the coaxial line.
第3図において、同軸プランジャー302は、図からも
明らかなように前記同軸線路の外部から操作できる構造
になっている。この同軸プランジャー302には、ばね
材により電気的接触を良好にする電磁シールド部材30
3が締結又はスポッH8接等で固定されている。この同
軸プランジャー302の中心には、中心導体102が貫
通できる孔がおいており、同軸プランジャー302が中
心導体102に沿って滑らかにスライドできるよう、ば
ね材で構成される別の電磁シールド部材303が接触部
に設けられている。In FIG. 3, the coaxial plunger 302 has a structure that can be operated from outside the coaxial line, as is clear from the figure. This coaxial plunger 302 includes an electromagnetic shielding member 30 that uses a spring material to make good electrical contact.
3 is fixed by fastening or spot H8 contact. A hole through which the center conductor 102 can pass is provided in the center of the coaxial plunger 302, and another electromagnetic shielding member made of a spring material is provided so that the coaxial plunger 302 can slide smoothly along the center conductor 102. 303 is provided at the contact portion.
さらに、中心導体102には途中で段差部を設けておき
、例えばストッパー312等を設けて、マイクロ波透過
性の誘電体管103と中心導体102の終端が接触して
前記誘電体管103を破損しないように工夫した方が実
用上便利である。Further, the center conductor 102 is provided with a stepped portion in the middle, for example, a stopper 312 or the like is provided, so that the microwave-transparent dielectric tube 103 and the end of the center conductor 102 come into contact and break the dielectric tube 103. It is more convenient in practice to take measures to prevent this from happening.
同様のストノバーを同軸プランジャー302の他端に設
け、同軸プランジャー302の終端面が導波管同軸変換
部313まではみ出さないようにする。この部分がはみ
出すと、同軸プランジャー302と外側導体との接触を
良好にしている電磁シールド部材303に異常放電が生
じやすく、場合によっては焼損して実用上支障をきたす
ことになる。A similar stop bar is provided at the other end of the coaxial plunger 302 to prevent the end surface of the coaxial plunger 302 from protruding to the waveguide coaxial conversion section 313. If this part protrudes, abnormal discharge is likely to occur in the electromagnetic shielding member 303 that maintains good contact between the coaxial plunger 302 and the outer conductor, and in some cases, it may burn out, causing a practical problem.
第3図において、導波管同軸変換器313は、方形導波
管301の内部に102を中心導体とする同軸線路を貫
入させることによって形成される。In FIG. 3, a waveguide coaxial converter 313 is formed by penetrating a coaxial line having a center conductor 102 into a rectangular waveguide 301.
第3図において、方形導波管301は、不図示の工ヴイ
ック商会(株)製の2.45GHzのマイクロ波発振機
と締結されている。In FIG. 3, the rectangular waveguide 301 is connected to a 2.45 GHz microwave oscillator manufactured by Kouwick Shokai Co., Ltd. (not shown).
第3図において、マイクロ波透過性の高誘電率部材30
7の形状は、大略円錐台で、円錐面上に冷却気体を排出
する孔が複数個設けられている。In FIG. 3, a microwave transparent high dielectric constant member 30
The shape of 7 is approximately a truncated cone, and a plurality of holes for discharging cooling gas are provided on the conical surface.
従って、中心導体冷却気体は、中心導体冷却気体導入口
310から中空構造の中心導体102の中心を流れ、中
心導体102の終端開口を経由してマイクロ波透過性誘
電体管103の内面に沿って、マイクロ波透過性の高誘
電率部材307の円錐面上に設けられた排出口を通って
、方形導波管301の側壁に設けられた複数の小孔31
1より排出される。Therefore, the center conductor cooling gas flows through the center of the hollow center conductor 102 from the center conductor cooling gas inlet 310, passes through the end opening of the center conductor 102, and flows along the inner surface of the microwave transparent dielectric tube 103. , a plurality of small holes 31 provided in the side wall of the rectangular waveguide 301 pass through an outlet provided on the conical surface of the microwave-transparent high dielectric constant member 307.
It is discharged from 1.
第3図において、帯状部材101は、その周縁部のみが
一対の湾曲部支持内側リング308で支持・搬送され、
円柱状空間を形成している。湾曲部支持内側リング30
8は、その周囲に配置されたローラー(又はベアリング
)3(19によって回転自在に支持されており、いずれ
も接地されている。該湾曲部支持内側リングは、第1図
に示したような複数の小さなリングを対向させて帯状基
体101の周縁部に配設したものであっても良い。In FIG. 3, only the peripheral edge of the band member 101 is supported and conveyed by a pair of curved part supporting inner rings 308,
It forms a cylindrical space. Curved part support inner ring 30
8 is rotatably supported by rollers (or bearings) 3 (19) arranged around it, both of which are grounded. Alternatively, small rings may be disposed on the peripheral edge of the strip-shaped base 101 so as to face each other.
第3図において、中心導体102は、誘電体管103に
よってJf[室104内に生成されるプラズマから隔離
されている#該誘電体管103は、一端が半球状で閉管
となっており他端には真空フランジを有し、その間が円
筒になっていて、該真空フランジで真空封止が可能な構
造となっている。In FIG. 3, the center conductor 102 is isolated from the plasma generated in the Jf chamber 104 by a dielectric tube 103. The dielectric tube 103 has a hemispherical shape at one end and is a closed tube, and the other end. has a vacuum flange, and the space between them is cylindrical, and the structure is such that vacuum sealing is possible with the vacuum flange.
第3図において、円形チョーク・フランジ306は、前
記誘電体管103の真空フランジと密着するように締結
され、該円形チョーク・フランジ306と誘電体管10
3の真空封止のための金属面との電気的接触が良くない
場合でもマイクロ波の漏洩が無い構造となっている。In FIG. 3, a circular choke flange 306 is tightly fastened to the vacuum flange of the dielectric tube 103, and the circular choke flange 306 and the dielectric tube 10
The structure is such that there is no leakage of microwaves even if the electrical contact with the metal surface for vacuum sealing in step 3 is poor.
本発明の装置は、上述のようなマイクロ波プラズマCV
D装置としての主要機構の他に、ロードロック機構を補
助機構として具備している。The apparatus of the present invention is a microwave plasma CV as described above.
In addition to the main mechanism as the D device, a load lock mechanism is provided as an auxiliary mechanism.
即ち、第5図のロードロック機構を設けたことで欠陥の
減少のみならず、保守性能も飛躍的に向上した。以下に
ロードロック機構の詳細について説明する。That is, by providing the load lock mechanism shown in FIG. 5, not only the number of defects was reduced, but also maintenance performance was dramatically improved. The details of the load lock mechanism will be explained below.
第5図において、501は交換用ロードロック室、50
2はゲートバルブ、503は交換扉、504は真空排気
口、■は堆積膜形成時の誘電体管と原料ガス導入管の所
定の位置であり、■はこれらの交換のために所定の位置
から引き抜かれた場合の位置を表す。In FIG. 5, 501 is a replacement load lock chamber;
2 is a gate valve, 503 is a replacement door, 504 is a vacuum exhaust port, ■ is a predetermined position of a dielectric tube and a raw material gas introduction tube during deposition film formation, and ■ is a predetermined position for replacing these. Represents the position when pulled out.
第5図において、中心導体102、誘電体窓103及び
原料ガス導入管を兼ねるバイアス印加管106をユニッ
トにして交換できるようになっており、これらは■、■
いずれの位置でも各々固定できるよう不図示の固定部材
かの、■各々の位置に予め準備されている。また、位置
■から位置■まで前記ユ;、ントを移動するための不図
示のアームも交換用ロードロック室501内に備えられ
ている。真空排気口504には、不図示の真空ポンプが
接続され、交換用ロードロンク室501の内部を真空引
きできるようになっている。さらに、中心導体102及
び原料ガス導入管を兼ねるバイアス印加管106は、ど
ちらもゲートバルブ502付近で着脱できるような構造
にしておく。In FIG. 5, the center conductor 102, dielectric window 103, and bias application tube 106, which also serves as a raw material gas introduction tube, can be replaced as a unit.
Fixing members (not shown) are prepared in advance at each position so that they can be fixed at any position. Further, an arm (not shown) for moving the unit from position (2) to position (2) is also provided in the replacement load lock chamber 501. A vacuum pump (not shown) is connected to the vacuum exhaust port 504, so that the inside of the replacement loadronk chamber 501 can be evacuated. Further, the center conductor 102 and the bias application tube 106 which also serves as a raw material gas introduction tube are both structured so that they can be attached and detached near the gate valve 502.
第5図に示すロードロック機構は、第1図に示した成膜
室104に対してゲートバルブ502を介して隣接する
ように配置されている。The load lock mechanism shown in FIG. 5 is arranged adjacent to the film forming chamber 104 shown in FIG. 1 via a gate valve 502.
以上説明してきた本発明のマイクロ波プラズマCVD装
置を作動させるに当たっては、先ず、初期放電が生起し
易くさせることと、所望の堆積膜の形成を実施する放電
の状態に合わせて1′li、膜室104に突入されてい
ない部分の同軸線路と成膜室104内部に突入されてい
る部分の同軸線路とがインピーダンスの整合がとれるよ
うに誘電体管103の外径を予め調整・選択すること、
という2つの設定を行っておく、勿論、この設定を行わ
なくても本装置の作動には支障が無い状態もあり得るが
、本装置の機能を最大限に発揮されるようにする為には
、前記の設定が重要である。In operating the microwave plasma CVD apparatus of the present invention as described above, first, it is necessary to make the initial discharge easy to occur, and to adjust the 1'li and film thickness according to the discharge conditions to form the desired deposited film. Adjusting and selecting the outer diameter of the dielectric tube 103 in advance so that impedance matching can be achieved between the coaxial line in the portion that has not entered the chamber 104 and the coaxial line in the portion that has entered the interior of the film forming chamber 104;
Of course, there may be situations where there is no problem with the operation of this device even if you do not perform these settings, but in order to make the most of the functions of this device, , the above settings are important.
まず、前記の第一の設定である初期放電が生起し易くさ
せるには、前記成膜室内の圧力を上昇させたり、投入す
るマイクロ波電力を増大させたり、テスラー・コイル等
で火花放電を起こさせたりと様々な方法が公知となって
いる0本発明の装置では成膜室104が前述の半同軸共
振器を構成するようにすることで、前述の従来の初期放
電を生起し易くさせる方法に比較して、広い成膜圧力範
囲で長時間に亘って定常的に一定の放電を持続できると
いうことが判明した。ここで、半同軸共振器を構成させ
るには、誘電体管103が所定の位置に取付けられた状
態で半同軸共振器となるように、HP8757Aスカラ
・ネソトワーク・アナライザー(ヒユーレット・パラカ
ード社製)を使って共振状態を確認しながら、予め中心
導体102の成膜室104内部への挿入長を調節すれば
良い。First, in order to make it easier for the initial discharge to occur, which is the first setting, it is necessary to increase the pressure inside the deposition chamber, increase the input microwave power, or cause a spark discharge using a Tesler coil, etc. In the apparatus of the present invention, the film forming chamber 104 constitutes the above-mentioned semi-coaxial resonator, thereby making it easier to generate the initial discharge as described above. It has been found that a constant discharge can be sustained over a long period of time over a wide range of film-forming pressures. Here, to configure a semi-coaxial resonator, use an HP8757A Scalar Nesotowork Analyzer (manufactured by Hewlett-Paracard) to form a semi-coaxial resonator with the dielectric tube 103 attached at a predetermined position. The insertion length of the center conductor 102 into the film forming chamber 104 may be adjusted in advance while confirming the resonance state using the .
次に、前記第2の設定である誘電体管103の外径の調
整・選択は、成膜室104に突入されていない部分の同
軸線路と成膜室104内部に突入されている部分の同軸
線路とがインピーダンスの整合をとるように行えば良い
、すなわち、放電が生起した成膜室104内部には、プ
ラズマ密度に応じて等傷内な同軸線路が形成されている
。プラズマ密度すなわちプラズマの複素誘電率は、主と
してガス混合比、ガス圧或いは導入するマイクロ波電力
誘電体管の寸法等によって変化する。これら4つの変数
は相互に関連しているため、前述の成膜室に突入された
同軸線路と突入されない同軸線路とが整合状態となる誘
電体管103の最適径は理論的には予想は困難である。Next, the adjustment and selection of the outer diameter of the dielectric tube 103, which is the second setting, is carried out between the coaxial line of the part that has not entered the film forming chamber 104 and the coaxial line of the part that has entered the inside of the film forming chamber 104. This can be done so that impedance matching can be achieved between the coaxial line and the line; that is, a coaxial line with uniform scratches is formed in accordance with the plasma density inside the film forming chamber 104 where the discharge has occurred. The plasma density, that is, the complex dielectric constant of the plasma, changes mainly depending on the gas mixture ratio, gas pressure, or the dimensions of the microwave power dielectric tube introduced. Since these four variables are interrelated, it is difficult to theoretically predict the optimal diameter of the dielectric tube 103 that will bring the coaxial line that has entered the film forming chamber into a matching state with the coaxial line that has not entered the film forming chamber. It is.
従って、この誘電体管103の外径の選択と放電後の中
心導体102の成膜室104内部への挿入長との調節と
で実験的に整合状態を確認すれば良い。Therefore, it is sufficient to experimentally confirm the matching state by selecting the outer diameter of the dielectric tube 103 and adjusting the insertion length of the central conductor 102 into the film forming chamber 104 after discharge.
その具体例として後述する成膜例8の第8表に示す条件
の場合には、次のようになる。即ち、内径が40■φの
成膜室においては、中心導体が6關φ、外部導体が20
nφの同軸線路であって誘電体管の外径を約1.8nφ
とし、中心導体の挿入長は452市とするのが好ましい
、また、内径105關φの成膜室においては、中心導体
が15−φ、外部導体が30闘φの同軸線路であって、
誘電体管の外径は約23tmφとし、中心導体の挿入長
は455nとするのが好ましい。As a specific example, in the case of the conditions shown in Table 8 of Film Formation Example 8, which will be described later, the conditions are as follows. That is, in a film forming chamber with an inner diameter of 40 mm, the center conductor is 6 mm in diameter and the outer conductor is 20 mm in diameter.
It is a coaxial line of nφ, and the outer diameter of the dielectric tube is approximately 1.8nφ.
It is preferable that the insertion length of the center conductor is 452 mm.In addition, in a film forming chamber with an inner diameter of 105 mm, the center conductor is a coaxial line of 15 mm and the outer conductor is a coaxial line of 30 mm.
Preferably, the outer diameter of the dielectric tube is approximately 23 tmφ, and the insertion length of the center conductor is 455 nm.
以上説明した本発明のマイクロ波プラズマCVD装置を
作動させると、次のようになる。When the microwave plasma CVD apparatus of the present invention described above is operated, the following occurs.
第1図の成膜室104は、不図示の真空ポンプによりス
リット状開口部110及び真空排気口107を介して真
空引きされる。成膜室内部の圧力が1 x 10−”T
orrに達した後、不図示のマスフロー・コントローラ
ーで流量を制御された成膜用原料ガスを、原料ガス導入
管を兼ねるバイアス印加管106を介して小孔105よ
り噴出させて成膜室104内に導入する。この状態で成
膜室内部の圧力が所定の圧力に達した後、不図示の2.
45GH2のマイクロ波発振機(例えば、工ヴイック商
会(株)製)にて発生させたマイクロ波電力を、第3図
に示す方形導波管301、導波管同軸変換器313、中
心導体102及びマイクロ波透過性の誘電体管103を
介して、成膜室内部に投入する。マイクロ波電力を有効
に利用するには、公知の通り、マイクロ波のインピーダ
ンスの整合をとることが好ましい。本発明の装置におい
て、第3図に示す中心導体102の挿入長調節機構と同
軸プランジャー302がマイクロ波のインピーダンス整
合m構として組込んである。これらのマイクロ波のイン
ピーダンス整合機構のうち、前者の中心導体挿入長1!
!ff機構の方が整合範囲が広いため、はじめに同軸或
いは導波管内部の反射電力を監視する反射電力計で反射
電力が極力小さくなるよう、挿入長調節機構で調整し、
引き続いて同軸プランジャー302で微調整してインピ
ーダンスを整合させるのが好ましい。その結果、成膜室
104内部にプラズマが生起されるので、直ちにバイア
ス印加用電源116よりバイアス電圧を導線117を介
して原料ガス導入管を兼ねるバイアス印加管106に印
加する。このようにして、プラズマ電位の制御されたプ
ラズマの作用で帯状部材101上に所望の高品質の機能
性堆積膜が形成される。The film forming chamber 104 in FIG. 1 is evacuated via a slit opening 110 and a vacuum exhaust port 107 by a vacuum pump (not shown). The pressure inside the deposition chamber is 1 x 10-”T
orr, the film-forming raw material gas whose flow rate is controlled by a mass flow controller (not shown) is ejected from the small hole 105 through the bias application tube 106 which also serves as a raw material gas introduction pipe to enter the film-forming chamber 104. to be introduced. In this state, after the pressure inside the film forming chamber reaches a predetermined pressure, 2.
Microwave power generated by a 45GH2 microwave oscillator (for example, manufactured by Kouwick Shokai Co., Ltd.) is transmitted through a rectangular waveguide 301, a waveguide coaxial converter 313, a center conductor 102, and a waveguide coaxial converter 313 as shown in FIG. It is introduced into the film forming chamber through a dielectric tube 103 that is transparent to microwaves. As is well known, in order to effectively utilize microwave power, it is preferable to match the impedance of the microwaves. In the apparatus of the present invention, a mechanism for adjusting the insertion length of the center conductor 102 and a coaxial plunger 302 shown in FIG. 3 are incorporated as a microwave impedance matching m structure. Among these microwave impedance matching mechanisms, the center conductor insertion length of the former is 1!
! Since the ff mechanism has a wider matching range, first adjust the insertion length adjustment mechanism using a reflected power meter that monitors the reflected power inside the coaxial or waveguide so that the reflected power is as small as possible.
Preferably, the impedances are then matched by fine adjustment using the coaxial plunger 302. As a result, plasma is generated inside the film forming chamber 104, so that a bias voltage is immediately applied from the bias application power source 116 via the conductive wire 117 to the bias application tube 106 which also serves as a raw material gas introduction tube. In this way, a desired high-quality functional deposited film is formed on the strip member 101 by the action of plasma with a controlled plasma potential.
次に、補助機構である第5図に示すロードロック41!
!横の作動手順を説明する。まず、中心導体102及び
原料ガス導入管を兼ねるバイアス印加管106をゲート
バルブ502付近で取り外し、交換すべきマイクロ波透
過性誘電体管103及び原料ガス導入管を兼ねるバイア
ス印加管106とを図中のの位置から■の位置まで引き
抜き、ゲートバルブ502を閉じる0次に、ロードロン
ク室501をN8又はAr等の不活性ガスを用いて大気
圧に戻して変換器503を開き、誘電体管103及び原
料ガス導入管を兼ねるRイアス印加管106とを交換す
る。その後、変換器503を再び閉して排気口504よ
り不図示の排気ポンプを介して排気を行って前記ロード
ロソク室501と前記成膜室との圧力が等しくなったと
ころでゲートバルブ502を開き、誘電体管103及び
原料ガス導入管を兼ねるバイアス印加管106とを■の
位置に戻し、中心導体102及び原料ガス導入管を兼ね
るバイアス印加管106とをゲートバルブ502付近で
再び接続する。そして堆積膜の形成を再開することがで
きる。Next, the load lock 41 shown in FIG. 5, which is an auxiliary mechanism!
! Explain the horizontal operating procedure. First, remove the center conductor 102 and the bias application tube 106 that also serves as a source gas introduction tube near the gate valve 502, and remove the microwave transparent dielectric tube 103 and the bias application tube 106 that also serves as a source gas introduction tube to be replaced as shown in the figure. Then, the loadronic chamber 501 is returned to atmospheric pressure using an inert gas such as N8 or Ar, the converter 503 is opened, and the dielectric tube 103 and The Rias application tube 106, which also serves as a raw material gas introduction tube, is replaced. Thereafter, the converter 503 is closed again, and exhaust is performed from the exhaust port 504 via an exhaust pump (not shown). When the pressures in the load candle chamber 501 and the film forming chamber become equal, the gate valve 502 is opened and the dielectric The body tube 103 and the bias application tube 106 which also serves as a source gas introduction tube are returned to the position (3), and the center conductor 102 and the bias application tube 106 which also serves as a source gas introduction tube are connected again near the gate valve 502. Formation of the deposited film can then be resumed.
以上のように、ロードロック機構は装置の稼動率を高め
るのに重要な役割を持っているが、これとは別に第1図
の排気口107の位置にコンダクタンス調整機構を具備
すれば更に装置の稼動率は上がり、設備の償却が早まる
ことになる。As mentioned above, the load lock mechanism plays an important role in increasing the operating rate of the device, but if a conductance adjustment mechanism is installed at the exhaust port 107 in Fig. 1, the device will be further improved. Utilization rates will increase and equipment will be depreciated faster.
コンダクタンス調整機構は第6図に示すように回転可能
なコンダクタンス調整板601或いはメソシェ構造をも
つマイクロ波反射板602を設ける構造のものを利用し
、初期の真空引きの時には回転して全開とし、所定の圧
力に達した後に所望のコンダクタンスとなるよう回転位
置を決めて原料ガスを流せば良い。As shown in FIG. 6, the conductance adjustment mechanism uses a structure in which a rotatable conductance adjustment plate 601 or a microwave reflection plate 602 with a mesochet structure is provided, and at the time of initial evacuation, it is rotated to fully open and set to a predetermined value. After reaching the pressure, the rotational position is determined so that the desired conductance is achieved, and the raw material gas is allowed to flow.
また、他のコングクタンス調整機構としては、第6図で
示される対向するローラー111及び112の位置を左
右にずらし、結果的にスリット状開口部110の面積を
変えてコンダクタンスを制御しても良い。Further, as another conductance adjustment mechanism, the conductance may be controlled by shifting the positions of the opposing rollers 111 and 112 shown in FIG. 6 to the left and right, thereby changing the area of the slit-shaped opening 110. .
なお、本装置例では第19図(A)に示した構成のバイ
アス印加手段を具備しているが、もちろん第19図(B
)乃至第19図(D)に示した構成のいずれのバイアス
印加手段を具備しても良い。Note that although this example device is equipped with a bias applying means having the configuration shown in FIG.
) to FIG. 19(D) may be provided.
責塁班1
本装置例は、第1図に示した成膜室を3室連結し、連続
的に移動する帯状部材上にn型半導体層、型半導体層、
p型半導体層を連続的に順次積層堆積してpin型光起
電力素子を作製するのに好適なマイクロ波プラズマCV
D装置であり、第2図に模式的断面概略図を示す。Responsible team 1 In this example, three film forming chambers shown in FIG. 1 are connected, and an n-type semiconductor layer, a type semiconductor layer,
Microwave plasma CV suitable for manufacturing a pin-type photovoltaic device by successively stacking p-type semiconductor layers one after another
D device, and a schematic cross-sectional view is shown in FIG.
第2図において、201は帯状部材、202は帯状部材
搬入室、203〜205は隔離容器、206はガス隔離
通路、207は帯状部材搬出室、208は帯状部材繰り
出しローラー、2(19は帯状部材回収(Sき上げ)ロ
ーラー、210は掃気ガス導入口、211〜213は成
膜室、214〜216はマイクロ波同軸線路導入部、2
17〜225は排気口、226は帯状部材の温度制御機
構、227〜229は原料ガス導入管を兼ねるバイアス
印加管である。In FIG. 2, 201 is a strip-shaped member, 202 is a strip-shaped member loading chamber, 203 to 205 are isolation containers, 206 is a gas isolation passage, 207 is a strip-shaped member delivery chamber, 208 is a strip-shaped member delivery roller, 2 (19 is a strip-shaped member 210 is a scavenging gas inlet, 211 to 213 are film forming chambers, 214 to 216 are microwave coaxial line introduction parts, 2
17 to 225 are exhaust ports, 226 is a temperature control mechanism for the strip member, and 227 to 229 are bias application tubes that also serve as raw material gas introduction tubes.
第4図において、隔離容器203〜205には、不図示
のゲートバルブを介して装置例1で説明したロードロッ
ク機構が隣接して設置しても良い。In FIG. 4, the load lock mechanism described in device example 1 may be installed adjacent to isolation containers 203 to 205 via gate valves (not shown).
また、帯状部材搬入室202及び帯状部材搬出室207
にも同様のロードロック機構を設置しても良い。In addition, a belt-shaped member carrying-in chamber 202 and a belt-shaped member carrying-out chamber 207
A similar load-lock mechanism may also be installed.
第2図において帯状部材搬入室202に隣接して加熱室
を設置したり、帯状部材搬出室207の手前に冷却室を
設置したり、成膜室内部のプラズマからの熱の流入・流
出に応じて適宜冷却室や加熱室を本発明の装置に組込ん
でも良い。In FIG. 2, a heating chamber is installed adjacent to the strip material carrying-in chamber 202, a cooling chamber is installed in front of the strip-shaped material carrying chamber 207, and a cooling chamber is installed in front of the strip material carrying-in chamber 207, depending on the inflow and outflow of heat from the plasma inside the film forming chamber. A cooling chamber or a heating chamber may be incorporated into the apparatus of the present invention as appropriate.
第2図において、成膜室211〜213の内径は所望の
堆積膜の膜厚が異なっても帯状部材201の搬送速度が
一定になるよう調整されている。In FIG. 2, the inner diameters of the film forming chambers 211 to 213 are adjusted so that the transport speed of the strip member 201 remains constant even if the desired thickness of the deposited film varies.
第2図において、ガス隔離通路206は、全ての隣接す
る隔離容器の間に設置され、その内部には掃気ガス導入
口210を介して掃気ガスが導入されるようになってい
る。In FIG. 2, a gas isolation passage 206 is installed between all adjacent isolation vessels, into which scavenging gas is introduced via a scavenging gas inlet 210.
前記ガス隔離通路217は、隣り合う隔離容器間で相互
に使用している堆積膜形成用原料ガスが拡散しない機能
が求められる。その基本概念は米国特許第4.438,
723号に開示される手段を採用することができるが、
本発明においては、更にその能力が改善されなければな
らない、その根拠は、本発明の成膜室の少なくとも1つ
においては104〜10−3Torr程度の圧力下で堆
積膜が形成されることが望ましく、前記米国特許第4.
438,723号で開示された威服圧力よりも本発明に
おける成膜圧力が低く、前記原料ガスが容易に拡散しや
すいためである。具体的には最大106倍程度の圧力差
に耐え得ることが必要であり、排気ポンプとしては排気
能力の大きい油拡散ポンプ、ターボ分子ポンプ、メカニ
カルブースターポンプ等或いはこれらの組合わせが好適
に用いられる。The gas isolation passage 217 is required to have a function of preventing the deposited film forming raw material gas used between adjacent isolation containers from diffusing. The basic concept is U.S. Patent No. 4.438,
Although the means disclosed in No. 723 can be adopted,
In the present invention, the ability must be further improved, and the reason for this is that it is desirable that the deposited film be formed under a pressure of about 104 to 10-3 Torr in at least one of the film forming chambers of the present invention. , said U.S. Pat. No. 4.
This is because the film forming pressure in the present invention is lower than that disclosed in No. 438,723, and the source gas can easily diffuse. Specifically, it is necessary to be able to withstand a pressure difference of up to 106 times, and as an exhaust pump, an oil diffusion pump, a turbo molecular pump, a mechanical booster pump, etc. with a large exhaust capacity, or a combination thereof is preferably used. .
前記ガス隔Nil路217はコンダクタンスを小さくし
て隔離機能を高めるため、その断面形状は帯状部材の断
面とほぼ同程度の大きさとし、ガス隔#浦路217の全
長を変えることによって隔離能力を変えることができる
。更に、隔離能力を高めるためには掃気ガスを併用する
ことが好ましく、そのようなガスとしてはAr、Ne、
Kr、Xe等の希ガスのようにターボ分子で排気し
やすいガスや、H2ガスのように油拡散ポンプで排気し
やすいガス等が好適である。前記ガス隔離通路内へ導入
される最適な前記掃気ガスの流量は、前記ガス隔離通路
の形状、及び掃気ガスと堆積膜形成用原料ガスとの相互
拡散係数でほぼ決定されるが、実際には質量分析計等を
用いて相互に拡散してくるガス量を測定し最適条件を決
定するのが望ましい。In order to reduce the conductance and improve the isolation function, the gas separation passage 217 has a cross-sectional shape that is approximately the same size as the cross section of the strip member, and the isolation capacity can be changed by changing the total length of the gas separation passage 217. be able to. Furthermore, in order to increase the isolation ability, it is preferable to use scavenging gas together, and such gases include Ar, Ne,
Gases that can be easily exhausted using turbo molecules, such as rare gases such as Kr and Xe, and gases that can be easily exhausted using an oil diffusion pump, such as H2 gas, are suitable. The optimum flow rate of the scavenging gas introduced into the gas isolation passage is approximately determined by the shape of the gas isolation passage and the mutual diffusion coefficient between the scavenging gas and the raw material gas for forming the deposited film, but in reality, It is desirable to determine the optimal conditions by measuring the amount of mutually diffusing gas using a mass spectrometer or the like.
このgHの作動に先立って、前処理の終わった帯状部材
101を繰出しローラー208にセントし、繰出しロー
ラー208と巻き上げローラー2(19とを帯状部材1
01で連結するため、各成膜室202〜206の所定の
径路を通し、その後各威膜室の蓋を閉じて気密状態にし
てからl×10−’Torr程度まで真空引きして準備
完了となる。このとき使用する真空ポンプはロータリー
ポンプ、メカニカルブースターポンプ、油拡散ポンプの
組合わせである。Prior to the operation of this gH, the pretreated strip member 101 is placed on the feeding roller 208, and the feeding roller 208 and winding roller 2 (19) are placed on the strip material 101.
01, pass through the predetermined path of each film forming chamber 202 to 206, then close the lid of each film chamber to make it airtight, and then evacuate to about 1 x 10-'Torr to complete preparations. Become. The vacuum pump used at this time is a combination of a rotary pump, a mechanical booster pump, and an oil diffusion pump.
この装置を作動させると、次のようになる。帯状部材1
01は一定の搬送速度で帯状部材搬入室201から予備
加熱室202まで送られ、ここで所定の温度まで加熱さ
れ、続いて、203,204゜205の各隔離容器で1
1[膜が3層積層形威され、冷却室206で所定の温度
まで冷却され、最後に巻き上げローラー2(19で巻き
上げられる。その後帯状部材搬出室207から3層の堆
積膜が積層形成された帯状部材のロールが取り出される
ようになっている。When this device is activated, the following occurs. Band member 1
01 is conveyed at a constant conveyance speed from the belt-shaped member carrying-in chamber 201 to the preheating chamber 202, where it is heated to a predetermined temperature, and then 1
1. The film is formed into a three-layer stack, cooled to a predetermined temperature in a cooling chamber 206, and finally rolled up by a winding roller 2 (19). After that, three layers of deposited film are formed in a stack from a strip-shaped member carrying-out chamber 207. A roll of strip material is adapted to be removed.
なお、本装置例においては隔離容器203〜205中に
は第19図(A)に示した構成のバイアス印加手段を具
備した例を示したが、各々の隔離容器中には第19図(
A)乃至第19図(D)に示した構成のいずれのバイア
ス印加手段を具備しても良い。In this device example, the isolation containers 203 to 205 are equipped with bias applying means shown in FIG.
Any of the bias applying means having the configurations shown in A) to FIG. 19(D) may be provided.
帯状部材の巻き上げ、脱着について以下に詳述する。Winding up and detachment of the strip member will be described in detail below.
まず、帯状部材の巻き上げ機構について説明する0本発
明の装置における巻き上げ機構に関して、iv)巻上げ
時に堆積した膜を保護すること、■)膜の剥離を起こさ
ないローラー形状とすること、が機能として盛り込まれ
ていることが望ましい。First, we will explain the winding mechanism of the belt-shaped member. Regarding the winding mechanism of the device of the present invention, the functions include iv) protecting the film deposited during winding, and ■) creating a roller shape that does not cause peeling of the film. It is desirable that the
即ち、帯状部材が巻き上げローラー2(19に巻き取ら
れる際、帯状部材と一緒にポリイミド系のグラルウール
(いわゆる合紙)をはさみ込んで巻き上げれるのが望ま
しい。That is, when the strip-shaped member is wound up by the winding roller 2 (19), it is desirable that polyimide grar wool (so-called interleaf paper) be sandwiched together with the strip-shaped member.
前記合紙の材質としては150℃程度の耐熱性と柔軟性
とを有しているのが好ましく、また、膜の剥離を起こさ
ないためには、ローラー外径は好ましくは100闘φ以
上、より好ましくは3001−φであることが望ましい
。The material of the interleaving paper preferably has heat resistance of about 150°C and flexibility, and in order to prevent the film from peeling off, the outer diameter of the roller is preferably 100 mm or more, or more. Preferably, it is 3001-φ.
次に、帯状部材の脱着(取出し及び装着)機構について
説明する。Next, a mechanism for attaching and detaching (taking out and attaching) the strip member will be explained.
第7図及び第8図(1)〜(v)は、前記帯状部材処理
室の概略及び帯状部材等の成膜時の作動を説明するため
の模式図を示した。FIG. 7 and FIG. 8 (1) to (v) are schematic diagrams for explaining the outline of the band-shaped member processing chamber and the operation during film formation of the band-shaped member and the like.
第7図及び第8図において、701は帯状部材の送り出
し側に設けられた帯状部材処理室、801は帯状部材の
巻き取り側に設けられた帯状部材処理室であり、その内
部にはパイトン製ローラー707.807、切断刃70
8,808、溶接治具7(19,8(19が収納されて
いる。In FIGS. 7 and 8, 701 is a strip processing chamber provided on the delivery side of the strip member, and 801 is a strip processing chamber provided on the winding side of the strip member. Roller 707.807, cutting blade 70
8,808, welding jig 7 (19,8 (19) is stored.
即ち、第7図(1)は、通常成膜時の状態であり、帯状
部材702が図中矢印方向に移動していて、ローラー7
07、切断刃708、及び溶接治具7(19は帯状部材
702に接触していない。That is, FIG. 7(1) shows a state during normal film formation, in which the strip member 702 is moving in the direction of the arrow in the figure, and the roller 7
07, the cutting blade 708, and the welding jig 7 (19 are not in contact with the strip member 702.
710は帯状部材収納容器(不図示)との接続管、71
1は成膜室(不図示)との接続管である。710 is a connecting pipe with a strip member storage container (not shown); 71
1 is a connecting pipe with a film forming chamber (not shown).
第7図(その1)(ii)は、1巻の帯状部材への成膜
工程が終了した後、新しい帯状部材と交換するための第
1工程を示している。まず、帯状部材702を停止させ
、ローラー707を図中点線で示した位置から矢印方向
へ移動させ帯状部材702及び帯状部材処理室701の
壁と密着させる。この状態で帯状部材収納容器と成膜室
とは気密分離される0次に、切断刃70Bを図中矢印方
向に動作させ帯状部材702を切断する。この切断刃7
08は機械的、電気的、熱的に帯状部材702を切断で
きるもののうちのいずれかにより構成される。FIG. 7 (Part 1) (ii) shows the first step for replacing the belt-shaped member with a new one after the film-forming process for one roll of the belt-shaped member is completed. First, the strip member 702 is stopped, and the roller 707 is moved in the direction of the arrow from the position indicated by the dotted line in the figure to bring it into close contact with the strip member 702 and the wall of the strip member processing chamber 701. In this state, the strip member storage container and the film forming chamber are hermetically separated. Next, the cutting blade 70B is moved in the direction of the arrow in the figure to cut the strip member 702. This cutting blade 7
08 is made of any one of those capable of cutting the strip member 702 mechanically, electrically, or thermally.
第7図(その1)(iii)では、切断分離された帯状
部材703が帯状部材収納容器側へ巻き取られる様子を
示している。FIG. 7 (Part 1) (iii) shows how the cut and separated strip member 703 is wound up toward the strip member storage container.
上述した切断及び巻き取り工程は帯状部材収納容器内は
真空状態又は大気圧リーク状態のいずれかで行われても
良い。The above-described cutting and winding steps may be performed in either a vacuum state or an atmospheric pressure leak state inside the band-shaped member storage container.
第7図(その2) (iv)では、新しい帯状部材7
04が送り込まれ、帯状部材702と接続される工程を
示している。帯状部材704と702とはその端部が接
せられ溶接治具7(19にて溶接接続される。In FIG. 7 (Part 2) (iv), a new strip member 7
04 is fed in and connected to the strip member 702. The end portions of the band members 704 and 702 are brought into contact and welded together using a welding jig 7 (19).
第7図(その2)(v)では、帯状部材収納容器(不図
示)内を真空排気し、十分成膜室との圧力差が少なくな
った後、ローラー707を帯状部材702及び帯状部材
処理室701の壁から離し、帯状部材702,704を
巻き取っている状態を示している。In FIG. 7 (part 2) (v), the inside of the strip member storage container (not shown) is evacuated, and after the pressure difference with the film forming chamber is sufficiently reduced, the roller 707 is moved to the strip member 702 and the strip member processing chamber. The state in which the band-shaped members 702 and 704 are rolled up away from the wall of the chamber 701 is shown.
次に、帯状部材の巻き取り側での動作を説明する。Next, the operation on the winding side of the strip member will be explained.
第8図(その1)(i)は、通常酸膜時の状態であるが
、各治具は第7図(その1)(i)で説明したのとほぼ
対称に配置されている。FIG. 8 (Part 1) (i) shows the state during normal acid film, and the jigs are arranged almost symmetrically to that described in FIG. 7 (Part 1) (i).
第8図(その1)(ii)は、IIの帯状部材への成膜
工程が終了した後、これを取り出し、次の成膜工程処理
された帯状部材を巻き取るための空ボビンと交換するた
めの工程を示している。Figure 8 (Part 1) (ii) shows that after the film forming process on the band member II is completed, it is taken out and replaced with an empty bobbin for winding up the band member that has been subjected to the next film forming process. It shows the process for
まず、帯状部材802を停止させ、ローラー807を図
中点線で示した位置から矢印方向へ移動させ、帯状部材
802及び帯状部材処理室801の壁と密着させる。こ
の状態で帯状部材収納容器と成膜室とは気密分離される
0次に、切断刃808を図中矢印方向に動作させ、帯状
部材802を切断する。この切断刃808は機械的、電
気的、熱的に帯状部材802を切断できるもののうちの
いずれかにより構成される。First, the strip member 802 is stopped, and the roller 807 is moved in the direction of the arrow from the position indicated by the dotted line in the figure to bring it into close contact with the strip member 802 and the wall of the strip member processing chamber 801. In this state, the strip member storage container and the film forming chamber are hermetically separated. Next, the cutting blade 808 is moved in the direction of the arrow in the figure to cut the strip member 802. The cutting blade 808 is made of one that can cut the strip member 802 mechanically, electrically, or thermally.
第8図(その1)(iii)では、切断分離された成膜
工程終了後の帯状部材805が帯状部材収納容器側へ巻
き取られる様子を示している。FIG. 8 (Part 1) (iii) shows how the cut and separated strip member 805 after the film forming process is wound up toward the strip member storage container.
上述した切断及び巻き取り工程は帯状部材収納容器内は
真空状態又は大気圧リーク状態のいずれかで行われても
良い。The above-described cutting and winding steps may be performed in either a vacuum state or an atmospheric pressure leak state inside the band-shaped member storage container.
第8図(その2) (iv)では、新しい巻き取りボ
ビンに取り付けられている予備巻き取り用帯状部材80
6が送り込まれ、帯状部材802と接続される工程を示
している。予備巻き取り用帯状部材806と帯状部材8
02とはその端部が接せられ、溶接治具8(19にて溶
接接続される。FIG. 8 (Part 2) (iv) shows a preliminary winding strip member 80 attached to a new winding bobbin.
6 is fed in and connected to the strip member 802. Preliminary winding strip member 806 and strip member 8
02 is brought into contact with its end, and is welded and connected with the welding jig 8 (19).
第8図(その2)(v)では、帯状部材収納容器(不図
示)内を真空排気し、十分成膜室との圧力差が少なくな
った後、ローラー807を帯状部材802及び帯状処理
室801の壁から離し、帯状部材802.806を巻き
取っている状態を示している。In FIG. 8 (Part 2) (v), after the inside of the strip member storage container (not shown) is evacuated and the pressure difference with the film forming chamber is sufficiently reduced, the roller 807 is moved between the strip member 802 and the strip processing chamber. The state in which the strip members 802 and 806 are rolled up away from the wall of 801 is shown.
第7図及び第8図に示すごとく、成膜室内の真空状態を
保持したまま、帯状部材の交換作業が容易に行えるため
、作業効率の向上が図れ、また、成膜室内が大気圧に曝
されることがないため成膜室内壁への吸着水の発生を無
くすことができ、安定して高品質の半導体デバイスを形
成できる。As shown in Figures 7 and 8, the strip member can be easily replaced while maintaining the vacuum state inside the deposition chamber, which improves work efficiency and also allows the deposition chamber to be exposed to atmospheric pressure. Therefore, the generation of adsorbed water on the inner wall of the film forming chamber can be eliminated, and high quality semiconductor devices can be stably formed.
本発明において、成膜室内の清掃は真空状態保持のまま
必要に応じドライエツチングにより実施することができ
る。In the present invention, the inside of the film forming chamber can be cleaned by dry etching as needed while maintaining the vacuum state.
本発明の方法及び装置によって好適に製造される半導体
デバイスの一例として太陽電池が挙げられる。その層構
成として、典型的な例を模式的に示す図を第13図乃至
第16図に示す。A solar cell is an example of a semiconductor device suitably manufactured by the method and apparatus of the present invention. Figures 13 to 16 schematically show typical examples of the layer structure.
第13図に示す例は、支持体1301上に下部電極13
02、n型半導体層1303、l型半導体層1304、
p型半導体11305、透明電極1306及び集電電極
1307をこの順に堆積形成した光起電力素子1300
である。なお、本光起電力素子では透明電極1306の
側より光の入射が行われることを前提としている。In the example shown in FIG. 13, a lower electrode 13 is placed on a support 1301.
02, n-type semiconductor layer 1303, l-type semiconductor layer 1304,
A photovoltaic element 1300 in which a p-type semiconductor 11305, a transparent electrode 1306, and a current collecting electrode 1307 are deposited in this order.
It is. Note that this photovoltaic element is based on the premise that light is incident from the transparent electrode 1306 side.
第14図に示す例は、透光性の支持体140I上に透明
電極1406、p型半導体層1405、l型半導体層1
404、n型半導体層1403及び下部電極1402を
この順に堆積形成した光起電力素子1400である。本
光起電力素子では透光性の支持体1401の側より光の
入射が行われることを前提としている。In the example shown in FIG. 14, a transparent electrode 1406, a p-type semiconductor layer 1405, an l-type semiconductor layer 1 are placed on a transparent support 140I.
404, a photovoltaic element 1400 in which an n-type semiconductor layer 1403 and a lower electrode 1402 are deposited in this order. This photovoltaic element is based on the premise that light is incident from the transparent support 1401 side.
第15図に示す例は、バンドギャップ及び/又は層厚の
異なる2種の半導体層をi層として用いたpin接合型
光起電力素子1511.1512を2素子積層して構成
されたいわゆるタンデム型光起電力素子1513である
。1501は支持体であり、下部電極1502、n型半
導体層1503.1型半導体層1504、p型半導体J
i1505、n型半導体層1508、i型半導体層15
(19、p型半導体層1510.透明電極1506及び
集電電極1507がこの順に積層形成され、本光起電力
素子では透明電極1506の側より光の入射が行われる
ことを前提としている。The example shown in FIG. 15 is a so-called tandem type, which is constructed by laminating two pin junction type photovoltaic elements 1511 and 1512 using two types of semiconductor layers with different band gaps and/or layer thicknesses as the i-layer. This is a photovoltaic element 1513. 1501 is a support body, which includes a lower electrode 1502, an n-type semiconductor layer 1503, a 1-type semiconductor layer 1504, and a p-type semiconductor J.
i1505, n-type semiconductor layer 1508, i-type semiconductor layer 15
(19. A p-type semiconductor layer 1510. A transparent electrode 1506 and a current collecting electrode 1507 are laminated in this order, and it is assumed that light is incident from the transparent electrode 1506 side in this photovoltaic element.
第1R1ffに示す例は、バンドギャップ及び/又は層
厚の異なる3種の半導体層をiNとして用いたpin接
合型光起電力素子1620,1621゜1623を3素
子積層して構成された、いわゆるトリプル型光起電力素
子1624である。1601は支持体であり、下部電極
1602、n型半導体JiF1603、i型半導体層1
6o4、p型半導体層1605、n型半導体Nl 61
4、i型半導体層1615、p型半導体層1616、n
型半導体層1617、i型半導体層1618、p型半導
体層1619、透明型11606及び集電電極1607
がこの順に積層形成され、本光起電力素子では透明電極
1606の側より光の入射が行われることを前提として
いる。The example shown in the 1st R1ff is a so-called triple stacked pin junction photovoltaic device 1620, 1621°1623 using three types of semiconductor layers with different band gaps and/or layer thicknesses as iN. It is a type photovoltaic element 1624. 1601 is a support body, which includes a lower electrode 1602, an n-type semiconductor JiF 1603, and an i-type semiconductor layer 1.
6o4, p-type semiconductor layer 1605, n-type semiconductor Nl 61
4, i-type semiconductor layer 1615, p-type semiconductor layer 1616, n
type semiconductor layer 1617, i-type semiconductor layer 1618, p-type semiconductor layer 1619, transparent mold 11606, and current collecting electrode 1607
are laminated in this order, and this photovoltaic element is based on the premise that light is incident from the transparent electrode 1606 side.
なお、いずれの光起電力素子においてもn型半導体層と
p型半導体層とは目的に応して各層の積層順を入れ変え
て使用することもできる。Note that in any photovoltaic element, the n-type semiconductor layer and the p-type semiconductor layer can be used by changing the stacking order of each layer depending on the purpose.
以下・これらの光起電力素子の構成について説明する。The configurations of these photovoltaic elements will be explained below.
支捧生
本発明において用いられる支持体13o1乃至1601
は、フレキシブルであって湾曲形状を形成し得る材質の
ものが好適に用いられ、導電性のものを採用する。さら
には、それらは透光性のものであっても、また非透光性
のものであってもよいが、支持体1301乃至16o1
の側より光入射が行われる場合には、もちろん透光性で
あることが必要である。Supports 13o1 to 1601 used in the present invention
A material that is flexible and capable of forming a curved shape is suitably used, and is electrically conductive. Further, although they may be transparent or non-transparent, the supports 1301 to 16o1
When light is incident from the side, it is of course necessary to be transparent.
具体的には、本発明において用いられる前記帯状部材を
挙げることができ、該基板を用いることにより、作製さ
れる太陽電池の軽量化、強度向上、運搬スペースの低減
等が図れる。Specifically, the above-mentioned band-shaped member used in the present invention can be mentioned, and by using the substrate, it is possible to reduce the weight, improve the strength, and reduce the transportation space of the manufactured solar cell.
互盪
本発明の光起電力素子においては、当該素子の構成形態
により適宜のtpiが選択使用される。それらの電極と
しては、下部電極、上部電極(透明電極)、集電電極を
挙げることができる。(ただし、ここでいう上部電極と
は光の入射側に設けられたものを示し、下部電極とは半
導体層を挟んで上部電極に対向して設けられたものを示
すこととする。)
これらの電極について以下に詳しく説明する。In the photovoltaic device of the present invention, an appropriate tpi is selected and used depending on the configuration of the device. Examples of these electrodes include a lower electrode, an upper electrode (transparent electrode), and a current collecting electrode. (However, the upper electrode here refers to the one provided on the light incident side, and the lower electrode refers to the one provided opposite the upper electrode with the semiconductor layer in between.) The electrodes will be explained in detail below.
ユニと工星隻檀
本発明において用いられる下部電極1302乃至160
2としては、上述した支持体1301乃至1601の材
料が透光性であるか否かによって、光起電力発生用の光
を照射する面が異なる故(たとえば支持体1301が金
属等の非透光性の材料である場合には、第13図で示し
たごとく透明電極1306側から光起電力発生用の光を
照射する。)、その設置される場所が異なる。Lower electrodes 1302 to 160 used in the present invention
2, because the surface to which light for photovoltaic generation is irradiated differs depending on whether the material of the supports 1301 to 1601 described above is translucent or not (for example, if the support 1301 is made of metal or other non-transparent material) (If the transparent material is made of a transparent material, the light for generating photovoltaic force is irradiated from the transparent electrode 1306 side as shown in FIG. 13), but the location where it is installed differs.
具体的には、第13図のような層構成の場合には支持体
1301とn型半導体層1303との間に下部電極13
02が設けられる。しかし、支持体1301が導電性で
ある場合には、該支持体が下部電極を兼ねることができ
る。ただし、支持体1301が導電性であってもシート
抵抗値が高い場合には、電流取り出し用の低抵抗の電極
として、あるいは支持体面での反射率を高め入射光の有
効利用を図る目的で電極1302を設置してもよい。Specifically, in the case of a layer structure as shown in FIG.
02 is provided. However, when the support 1301 is conductive, the support can also serve as the lower electrode. However, even if the support 1301 is conductive, if the sheet resistance value is high, the electrode may be used as a low-resistance electrode for current extraction or for the purpose of increasing the reflectance on the support surface and making effective use of incident light. 1302 may be installed.
第15図、第16図のような場合も同じである。The same applies to the cases shown in FIGS. 15 and 16.
第14図の場合には透光性の支持体14o1が用いられ
ており、支持体1401の側から光が入射されるので、
電流取り出し及び当該電極での光反射用の目的で、下部
@pi1402が半導体層を挟んで支持体1401と対
向して設けられている。In the case of FIG. 14, a transparent support 14o1 is used, and light enters from the support 1401 side, so
For the purpose of extracting current and reflecting light at the electrode, a lower @pi 1402 is provided facing the support 1401 with the semiconductor layer in between.
また、支持体1401として電気絶縁性のものを用いる
場合には電流取り出し用の電極として、支持体1401
とn型半導体層14o3との間に下部電極1402が設
けられる。In addition, when an electrically insulating material is used as the support 1401, the support 1401 can be used as an electrode for taking out current.
A lower electrode 1402 is provided between the n-type semiconductor layer 14o3 and the n-type semiconductor layer 14o3.
電極材料としては、Ag、Au、Pt、Ni。The electrode materials include Ag, Au, Pt, and Ni.
Cr、Cu、ACTi、Zn、Mo、W等の金属又はこ
れらの合金が挙げられ、これ等の金属の薄膜を真空蒸着
、電子ビーム蒸着、スパッタリング等で形成する。また
、形成された金属薄膜は光起電力素子の出力に対して抵
抗成分とならぬように配慮されねばならず、シート抵抗
値として好ましくは50Ω以下、より好ましくはlOΩ
以下であることが望ましい。Examples include metals such as Cr, Cu, ACTi, Zn, Mo, and W, or alloys thereof, and thin films of these metals are formed by vacuum evaporation, electron beam evaporation, sputtering, or the like. In addition, care must be taken so that the formed metal thin film does not become a resistance component with respect to the output of the photovoltaic element, and the sheet resistance value is preferably 50Ω or less, more preferably 1OΩ.
The following is desirable.
下部電極1302乃至1602とn型半導体層1303
乃至1603との間に、図中には示されていないが、導
電性酸化亜鉛等の拡散防止層を設けても良い、該拡散防
止層の効果としては電極1302乃至1602を構成す
る金属元素がn型半導体層中へ拡散するのを防止するの
みならず、若干の抵抗値をもたせることで半導体層を挟
んで設けられた下部電極1302乃至1602と透明電
$li!306乃至1606との間にピンホール等の欠
陥で発生するシタートを防止すること、及び薄膜による
多重干渉を発生させ入射された光を光起電力素子内に閉
し込める等の効果を挙げることができる。Lower electrodes 1302 to 1602 and n-type semiconductor layer 1303
Although not shown in the figure, a diffusion prevention layer such as conductive zinc oxide may be provided between the electrodes 1302 to 1603. In addition to preventing diffusion into the n-type semiconductor layer, by providing a slight resistance value, the lower electrodes 1302 to 1602 provided across the semiconductor layer and the transparent electrode $li! 306 to 1606 due to defects such as pinholes, and the thin film generates multiple interference to confine incident light within the photovoltaic element. can.
(11)上。 (゛)
本発明において用いられる透明電極1306乃至160
6としては太陽や白色蛍光灯等からめ光を半導体層内に
効率良く吸収させるために光の透過率が85%以上であ
ることが望ましく、さらに、電気的には光起電力素子の
出力に対して抵抗成分とならぬようにシート抵抗値は1
00Ω以下であることが望ましい、このような特性を備
えた材料として3nOH、In103 、ZnO,Cd
O。(11) Above. (゛) Transparent electrodes 1306 to 160 used in the present invention
As for 6, it is desirable that the light transmittance is 85% or more in order to efficiently absorb light from the sun, white fluorescent lamp, etc. into the semiconductor layer, and furthermore, electrically, it is desirable that The sheet resistance value is set to 1 so that it does not become a resistance component.
00Ω or less, materials with such characteristics include 3nOH, In103, ZnO, and Cd.
O.
CdzSnOa 、 I To (In*03 +
5110g )などの金属酸化物や、Au、AI、Cu
等の金属を極めて薄く半透明状に成膜した金属薄膜等が
挙げられる。i3明電極は第13図、第15図及び第1
6図においてはp型半導体F11305,1505゜1
605層の上に積層され、第14図においては基板14
01の上に積層されるものであるため、互いの密着性の
良いものを選ぶことが必要である。CdzSnOa, I To (In*03 +
5110g), and metal oxides such as Au, AI, Cu
Examples include metal thin films made of extremely thin, translucent metals such as metals. The i3 bright electrode is shown in Figures 13, 15, and 1.
In Figure 6, the p-type semiconductor F11305, 1505°1
605 layers, and in FIG.
Since it is to be laminated on top of 01, it is necessary to select materials that have good adhesion to each other.
これらの作製方法としては、抵抗加熱蒸着法、電子ビー
ム加熱蒸着法、スパンタリング法、スプレー法等を用い
ることができ所望に応じて適宜選択される。As a method for producing these, a resistance heating evaporation method, an electron beam heating evaporation method, a sputtering method, a spray method, etc. can be used, and the method is appropriately selected depending on the desire.
〕」ユ」v44損
本発明において用いられる集電電極1307乃至160
7は、透明電極1306乃至1606の表面抵抗値を低
減させる目的で透明電極1306乃至1606上に設け
られる。電極材料としてはAg、Cr、Ni、A1.A
g、Au、Ti。] "U" v44 loss Current collecting electrodes 1307 to 160 used in the present invention
7 is provided on the transparent electrodes 1306 to 1606 for the purpose of reducing the surface resistance value of the transparent electrodes 1306 to 1606. The electrode materials include Ag, Cr, Ni, A1. A
g, Au, Ti.
PL、Cu、Mo、W等の金属またはこれらの合金の薄
膜が挙げられる。これらの薄膜は積層させて用いること
ができる。また、半導体層への光入射光量が十分に確保
されるよう、その形状及び面積が適宜設計される。Examples include thin films of metals such as PL, Cu, Mo, and W, or alloys thereof. These thin films can be used in a stacked manner. Further, the shape and area of the semiconductor layer are appropriately designed so that a sufficient amount of light incident on the semiconductor layer is ensured.
たとえば、その形状は光起電力素子の受光面に対して一
様に広がり、且つ受光面積に対してその面積は好ましく
は15%以下、より好ましくは10%以下であることが
望ましい。For example, it is desirable that the shape spreads uniformly over the light-receiving surface of the photovoltaic element, and that its area is preferably 15% or less, more preferably 10% or less of the light-receiving area.
また、シート抵抗値としては、好ましくは50Ω以下、
より好ましくは10Ω以下であることが望ましい。In addition, the sheet resistance value is preferably 50Ω or less,
More preferably, it is 10Ω or less.
ユ10革斃医亘
本光起電力素子において好適に用いられるi型半導体層
を構成する半導体材料としては、a−Si :I(、a
−3i :F、 a−3i:H:F。As the semiconductor material constituting the i-type semiconductor layer suitably used in the photovoltaic device, a-Si:I(, a
-3i:F, a-3i:H:F.
a−3iC:H,a−3iC:F、 a−3iC:H
:F、 a−3iGe:H,a−3iGe:F。a-3iC:H, a-3iC:F, a-3iC:H
:F, a-3iGe:H, a-3iGe:F.
a−5+Ge:H:F、 poly−5r:H。a-5+Ge:H:F, poly-5r:H.
poly−3i:F、poly−3t:H:F等いわゆ
る■族及び■族合金系半導体材料の他、■■族及びm−
v族のいわゆる化合物半導体材料等が挙げられる。In addition to the so-called ■group and ■group alloy semiconductor materials such as poly-3i:F, poly-3t:H:F, ■■group and m-
Examples include so-called compound semiconductor materials of the V group.
導 びn 体
本光起電力素子において好適に用いられるp型又はn型
半導体層を#I戒する半導体材料としては前述したi型
半導体層を構成する半導体材料に価電子制御剤をドーピ
ングすることによって得られる。An example of a semiconductor material for controlling the p-type or n-type semiconductor layer suitably used in the photovoltaic element is doping the semiconductor material constituting the above-mentioned i-type semiconductor layer with a valence electron control agent. obtained by.
以下、本発明のマイクロ波プラズマCVD装置を用いて
の具体的成膜例を示すが、本発明はこれらの成膜例によ
って何ら限定されるものではない。Hereinafter, specific examples of film formation using the microwave plasma CVD apparatus of the present invention will be shown, but the present invention is not limited to these film formation examples in any way.
衣笠五よ
装置例2で示した連続式マイクロ波プラズマCVD装置
(第2図)を用い、アモルファスシリコン膜の連続堆積
を行った。Using the continuous microwave plasma CVD apparatus (FIG. 2) shown in Goyo Kinugasa Apparatus Example 2, amorphous silicon films were continuously deposited.
まず、帯状部材送り出し機構を有する帯状部材搬入室2
02に、十分に脱脂、洗浄を行った5US430BA製
帯状部材(幅46備×長さ100mx厚さ0.2 m+
+ )の巻きつけられた帯状部材繰り出しローラー20
8をセントし、該帯状部材201をガス隔離通路206
及び各隔離容器203乃至205中の開口部支持外側ロ
ーラー1.1L開ロ部支持内側ローラー112、及び湾
曲部支持内側リング113を介して、帯状部材回収ロー
ラー2(19の配設された帯状部材搬出室207まで通
し、たるみのない程度に張力調整を行った。帯状部材の
湾曲形状等の条件を第6表に示す。First, a belt-shaped member loading chamber 2 having a belt-shaped member delivery mechanism
02, a 5US430BA strip member (width 46mm x length 100m x thickness 0.2m+) was thoroughly degreased and washed.
+) Wrapped belt-shaped member feeding roller 20
8, and the strip member 201 is connected to the gas isolation passage 206.
And the opening support outer roller 1.1L in each of the isolation containers 203 to 205. The strip was passed through to the unloading chamber 207, and the tension was adjusted to such an extent that there was no slack.Table 6 shows the conditions such as the curved shape of the strip member.
そこで、帯状部材搬入室201、帯状部材搬出室207
、及び隔離容器203〜205を不図示のロータリーポ
ンプで荒引きし、次いで不図示のメカニカルブースター
ポンプを起動させlo−3T orr付近まで真空引き
した後、更に隔離容器204内に設置された温度制御機
構226のみを動作させ、基板表面温度を250℃に保
持しつつ、不図示の油拡散ポンプ(バリアン製HS−3
2)にて5 X I O−”Torr以下まで真空引き
した。Therefore, the belt-shaped member carrying-in chamber 201 and the belt-shaped member carrying-out chamber 207
, and the isolation containers 203 to 205 are roughly pumped with a rotary pump (not shown), and then a mechanical booster pump (not shown) is started to evacuate to around lo-3 Torr, and then a temperature control device installed inside the isolation container 204 is applied. While operating only the mechanism 226 and maintaining the substrate surface temperature at 250°C, an oil diffusion pump (not shown) (Varian HS-3) was operated.
2), the vacuum was evacuated to 5 X I O-'' Torr or less.
十分に脱ガスが行われた時点で、ガス導入管を兼ねるバ
イアス印加管106より、5iHn140sccm、
5jFn 2sccm、 Hl 80sccsを導入
し、前記油拡散ポンプに取り付けられたスロフトルバル
ブの開度を調整して成膜室212内の圧力を24mTo
rrに保持した。このとき、隔離容器204内の圧力は
13mTorrであった。圧力が安定したところで、不
図示のマイクロ波″gl源より、実効パワーで1.4
k Wのマイクロ波を中心導体102より放射させた。When sufficient degassing has been performed, 5iHn 140 sccm,
5jFn 2sccm and Hl 80sccs were introduced, and the pressure inside the film forming chamber 212 was adjusted to 24mTo by adjusting the opening degree of the throttle valve attached to the oil diffusion pump.
It was held at rr. At this time, the pressure inside isolation container 204 was 13 mTorr. When the pressure stabilized, a microwave with an effective power of 1.4
Microwaves of kW were radiated from the central conductor 102.
直ちに、導入された原料ガスはプラズマ化し、成膜室2
12内にプラズマ領域を形成した。Immediately, the introduced raw material gas turns into plasma and enters the film forming chamber 2.
A plasma region was formed within 12.
そこで、バイアス印加用型1iut6より+70Vの直
流電圧を導線117を介してガス導入管を兼ねるバイア
ス印加管106に印加させたところ、6.7Aのバイア
ス電流が流れ、目視によるとプラズマの輝度が若干増し
た。Therefore, when a DC voltage of +70V was applied from the bias application type 1iut6 to the bias application tube 106, which also serves as a gas introduction pipe, through the conductor 117, a bias current of 6.7A flowed, and the brightness of the plasma was slightly reduced by visual observation. Increased.
そこで開口部支持外側ローラー111、開口部支持内側
ローラー112、及び湾曲部支持内側リング113 (
いずれも駆動機構は不図示)を起動し、前記帯状部材の
搬送速度が43cm/s+inとなるように制御した。Therefore, the opening support outer roller 111, the opening support inner roller 112, and the curved part support inner ring 113 (
In both cases, a drive mechanism (not shown) was started, and the conveyance speed of the strip member was controlled to be 43 cm/s+in.
tS送を開始してもプラズマは安定しており、バイアス
電圧、電流ともに変化はなかった。Even after starting tS feeding, the plasma remained stable, and there was no change in either the bias voltage or current.
尚、ガス隔離通路206には掃気ガス導入口210より
掃気ガスとしてH!ガスを50sccm流した。*送を
開始してから30分間、連続して堆積膜の形成を行った
。なお、長尺の帯状部材を用いているため、本成膜例の
終了後、引き続き他の堆積膜の形成を実施し、すべての
堆積終了後、前記帯状部材を冷却して取り出し、本成膜
例において形成された帯状部材上の堆積膜膜厚分布を幅
方向及沙蚕平方向について測定したところ5%以内に納
まっており、堆積速度は平均115人/secであった
。また、その一部を切り出し、FT−IR(パーキン・
エルマー社製1720X)を用い反射法により赤外吸収
スペクトルを測定したところ、2000ロー1及び63
0cm弓に吸収が認められa−3i:H:F膜に特有の
吸収パターンであった。更に、RHEED (JEM−
1003X。Note that H! gas is supplied to the gas isolation passage 206 from the scavenging gas inlet 210 as scavenging gas. Gas was flowed at 50 sccm. *The deposited film was formed continuously for 30 minutes after the start of feeding. Note that since a long strip-shaped member is used, after the completion of this film-forming example, another deposited film is formed, and after all the depositions are completed, the strip-shaped member is cooled and taken out, and then the main film-forming process is carried out. When the thickness distribution of the deposited film on the strip-shaped member formed in the example was measured in the width direction and the sand direction, it was within 5%, and the average deposition rate was 115 people/sec. In addition, a part of it was cut out and FT-IR (Parkin
When the infrared absorption spectrum was measured by the reflection method using Elmer's 1720X), 2000 Rho 1 and 63
Absorption was observed at the 0 cm arch, which was an absorption pattern specific to the a-3i:H:F film. Furthermore, RHEED (JEM-
1003X.
日本電子型)により膜の結晶性を評価したところ、ハロ
ーで、非晶質であることが判った。また、金属中水素分
析計(EMGA−1100、堀場製作所製)を用いて膜
中水素量を定量したところ21±2ato■ic%であ
った。When the crystallinity of the film was evaluated by JEOL Ltd., it was found to be amorphous with a halo. Further, the amount of hydrogen in the film was quantified using a hydrogen in metal analyzer (EMGA-1100, manufactured by Horiba, Ltd.) and found to be 21±2 atomic%.
更に、帯状部材上に堆積形成されたアモルファスシリコ
ン膜を約5−の領域にわたって機械的に8Mさせてその
体積を測定し、ひき続き、ESR装置(JES−RE2
X、日本電子型)にてスピン密度を測定したところ、3
.5 X I O”5pins /c1であり、欠陥の
少ない膜であることが判った。Furthermore, the amorphous silicon film deposited on the strip member was mechanically moved to 8M over an area of approximately 5 mm to measure its volume, and then an ESR device (JES-RE2
When the spin density was measured with X, JEOL type), it was 3
.. 5 X IO"5 pins/c1, and it was found that the film had few defects.
また、前記帯状部材の他の部分よりl as X l
csの試料片を任意に5ケ所切り出し、反応性スパッタ
リング装置(自社内製品)にセットしてアモルファスシ
リコン膜の堆積された面上にtsoo人のITO(rn
tos +5nOt )膜を堆積した。Moreover, l as X l from other parts of the band-shaped member
A sample piece of CS was arbitrarily cut out at 5 locations, set in a reactive sputtering device (in-house product), and a layer of ITO (rn
tos +5nOt) film was deposited.
そして、この試料片をCPM (Constant P
hoto−current Method)装置(自社
内製装置)にセットし、ITO膜側から光入射を行って
アーバンク裾(Urbach Ta1l)の傾きを測定
したところ、50±1+meVで、欠陥の少ない膜であ
ることが判った。Then, this sample piece was subjected to CPM (Constant P
When the inclination of the urban hem (Urbach Ta1l) was measured by setting it in a photo-current method (in-house manufactured device) and injecting light from the ITO film side, it was 50 ± 1 + meV, indicating that it was a film with few defects. It turns out.
衣股撚主
成膜例1において実施した堆積膜形成工程にひき続き、
用いた原料ガスの導入を止め、隔離容器204の内圧を
5 X 10−’Torr以下まで真空引きした後、ガ
ス導入管を兼ねるバイアス印加管106より、SiH4
22sccs、G e H,18sccs+sS i
Fal、5sccm、 Hz 50scc剛を導入し、
成膜室212の内圧を21 mTorrに保持し、マイ
クロ波電力を0.75 k Wとした以外は同様の堆積
膜形m条件でアモルファスシリコンゲルマニウム膜の連
続堆積を行った。Continuing from the deposited film formation step carried out in Kinomata twist main film formation example 1,
After stopping the introduction of the used raw material gas and evacuating the internal pressure of the isolation container 204 to 5×10-' Torr or less, SiH4
22sccs, G e H, 18sccs+sS i
Introduced Fal, 5sccm, Hz 50scc,
Continuous deposition of amorphous silicon germanium films was performed under the same deposition film conditions except that the internal pressure of the film forming chamber 212 was maintained at 21 mTorr and the microwave power was 0.75 kW.
なお、バイアス印加用電源116より+40Vの直流電
圧を導&11117を介してガス導入管を兼ねるバイア
ス印加管106に印加させたところ、6.2Aのバイア
ス電流が流れ、目視によるとプラズマの輝度が若干増し
た。In addition, when a DC voltage of +40V was applied from the bias application power supply 116 to the bias application tube 106 which also serves as a gas introduction tube through the conductor &11117, a bias current of 6.2A flowed, and the brightness of the plasma was slightly decreased by visual observation. Increased.
本成膜例及び他の酸膜例終了後、帯状部材を冷却して取
り出し、本成膜例において形成された堆積膜の膜厚分布
を幅方向及び長手方向について測定したところ5%以内
に納まっており、堆積速度は平均34人/secであっ
た・
また、その一部を切り出し、FT−IR(パーキン・エ
ルマー社製1720X)を用い反射法により赤外吸収ス
ペクトルを測定したところ、2000cm−’、188
0cm−’及び630cm−’に吸収が認められa−3
iGe:H:F膜に特有の吸収パターンであった。更に
、RHEED (JEM−100SX、日本電子型)に
より膜の結晶性を評価したところ、ハローで、非晶質で
あることが判った。また、金属中水素分析計(EMGA
−1100、堀場製作所製〉を用いて膜中水素量を定量
したところ15±2atomic%であった。After this film formation example and other acid film examples were completed, the strip member was cooled and taken out, and the film thickness distribution of the deposited film formed in this film formation example was measured in the width direction and longitudinal direction, and it was within 5%. The deposition rate was 34 persons/sec on average. In addition, when we cut out a part of it and measured its infrared absorption spectrum by reflection method using FT-IR (Perkin Elmer 1720X), we found that it was 2000 cm- ', 188
Absorption was observed at 0 cm-' and 630 cm-' a-3
The absorption pattern was unique to the iGe:H:F film. Furthermore, when the crystallinity of the film was evaluated by RHEED (JEM-100SX, JEOL Ltd.), it was found that it was halo and amorphous. In addition, the hydrogen in metal analyzer (EMGA)
-1100, manufactured by Horiba, Ltd.), and the amount of hydrogen in the film was determined to be 15±2 atomic%.
更に、帯状部材上に堆積形成されたアモルファスシリコ
ンゲルマニウム膜を約5cdの領域にわたって機械的に
剥離させてその体積を測定し、ひき続き、ESR装置(
JES−RE2X、日本電子型)にてスピン密度を測定
したところ4.8X10”5pins 7cm3であり
、欠陥の少ない膜であることが判った。Furthermore, the amorphous silicon germanium film deposited on the strip member was mechanically peeled off over an area of about 5 cd to measure its volume, and then the ESR device (
When the spin density was measured using a JES-RE2X (JEOL model), it was found to be 4.8 x 10''5 pins 7 cm3, indicating that the film had few defects.
また、前記帯状部材の他の部分より1(JIXICll
の試料片を任意に5ケ所切り出し、反応性スパッタリン
グ装置(自社内製品)にセントしてアモルファスシリコ
ンゲルマニウム膜の堆積された面上に1500人のIT
O(rnx03 +5nOt)膜を堆積した。そして、
この試料片をCPM(ConstantPhotocu
rrent Method)装置(自社内製装置)にセ
ットし、ITO膜側から光入射を行ってアーバンク裾(
Urbach Ta1l)の傾きを測定したところ55
±1meVで、欠陥の少ない膜であることが判った。Also, 1 (JIXICll
Five sample pieces were arbitrarily cut out, placed in a reactive sputtering device (in-house product), and 1,500 IT professionals
An O(rnx03 +5nOt) film was deposited. and,
This sample piece was processed using CPM (Constant Photo Shoot).
rrrent Method) device (in-house manufactured device), and incident light from the ITO film side to create an urban hem (
When the slope of Urbach Ta1l) was measured, it was 55
It was found that the film had a value of ±1 meV with few defects.
處挟班主
酸膜例1において実施した堆積膜形成工程にひき続き、
用いた原料ガスの導入を止め、隔離容器204の内圧を
5 X 10−”Torr以下まで真空引きした後、ガ
ス導入管を兼ねるバイアス印加管106より、5iH4
58sccm、CHa 9 sccm、5iFa 2
sccmSHg 180sccmを導入し、成膜室2
12の内圧を25 m Torrに保持した以外は同様
の堆積膜形成条件でアモルファスシリコンカーバイド膜
の連続堆積を行った。Continuing from the deposited film forming step carried out in Sandwich Team Main Acid Film Example 1,
After stopping the introduction of the used raw material gas and evacuating the internal pressure of the isolation container 204 to 5×10-” Torr or less, 5iH4
58sccm, CHa 9 sccm, 5iFa 2
sccmSHg 180sccm was introduced into the film forming chamber 2.
Continuous deposition of amorphous silicon carbide films was performed under the same deposition film forming conditions except that the internal pressure of No. 12 was maintained at 25 m Torr.
なお、バイアス印加用電源116より+60Vの直流電
圧を導線117を介してガス導入管を兼ねるバイアス印
加管106に印加させたところ、6.3へのバイアス電
流が流れ、目視によるとプラズマの輝度が若干増した。Note that when a DC voltage of +60V was applied from the bias application power supply 116 to the bias application tube 106 which also serves as a gas introduction tube through the conductor 117, a bias current to 6.3 flows, and as visually observed, the brightness of the plasma increased. It increased slightly.
本成膜例及び他の酸膜例終了後、帯状部材を冷却して取
り出し、本成膜例において形成された堆積膜の膜厚分布
を幅方向及び長手方向について測定したところ5%以内
に納まっており、堆積速度は平均54人7secであっ
た。After this film formation example and other acid film examples were completed, the strip member was cooled and taken out, and the film thickness distribution of the deposited film formed in this film formation example was measured in the width direction and longitudinal direction, and it was within 5%. The average deposition speed was 7 seconds for 54 people.
また、その一部を切り出し、FT−IR(パーキン・エ
ルマー社製1720X)を用い、反射法により赤外吸収
スペクトルを測定したところ、2080cm−’、12
50cm−’、960cm−’、 777113− ’
及び660c*−’に吸収が認められa−3iC:)(
:F膜に特有の吸収パターンであった。更に、1?HE
ED (JEM−100SX、日本電子型)により膜の
結晶性を評価したところ、ハローで、非晶質であること
が判った。また、金属中水素分析計(EMGA−110
0、堀場製作所製)を用いて膜中水素量を定量したとこ
ろ14±2atosic%であった。In addition, when a part of it was cut out and the infrared absorption spectrum was measured by the reflection method using FT-IR (1720X manufactured by Perkin Elmer), the results were 2080 cm-', 12
50cm-', 960cm-', 777113-'
Absorption was observed at 660c*-' and a-3iC:)(
:The absorption pattern was unique to F film. Furthermore, 1? H.E.
When the crystallinity of the film was evaluated by ED (JEM-100SX, JEOL Ltd.), it was found to be halo and amorphous. We also have a metal hydrogen analyzer (EMGA-110
The amount of hydrogen in the film was quantified using a method (manufactured by Horiba, Ltd.) and found to be 14±2 atomic%.
更に、帯状部材上に堆積形成されたアモルファスシリコ
ンカーバイド膜を約5−の領域にわたって機械的に剥離
させてその体積を測定し、ひき続き、ESR装置(JE
S−RE2X、日本電子型)にてスピン密度を測定した
ところ8.5X101Sspins 7cm3であり、
欠陥の少ない膜であることが判った。Furthermore, the amorphous silicon carbide film deposited on the strip member was mechanically peeled off over an area of about 5 mm to measure its volume, and then an ESR device (JE
When the spin density was measured with S-RE2X (JEOL), it was 8.5X101Sspins 7cm3,
It was found that the film had few defects.
また、前記帯状部材の他の部分よりlc*X1cs+の
試料片を任意に5ケ所切り出し、反応性スパンタリング
装置(自社内製品)にセントしてアモルファスシリコン
カーバイド膜の堆積された面上に1500λのITO(
In2O2+Snow)IIIを堆積した。そして、こ
の試料片をCPM(ConstantPhotocur
rent Method)装置(自社内製装置)にセッ
トし、ITO膜側から光入射を行ってアーバンク裾(U
rbach Ta11)の傾きを測定したところ57±
1meVで、欠陥の少ない膜であることが判った。In addition, five sample pieces of lc*X1cs+ were arbitrarily cut out from other parts of the band-shaped member, placed in a reactive sputtering device (in-house product), and placed on the surface on which the amorphous silicon carbide film was deposited. ITO(
In2O2+Snow) III was deposited. Then, this sample piece was processed using CPM (Constant Photocurrence)
Rent Method) equipment (in-house manufactured equipment), and light is incident from the ITO film side to create an urban hem (U).
When the slope of rbach Ta11) was measured, it was 57±
At 1 meV, it was found that the film had few defects.
虞撲斑土
成膜例1において実施した堆積膜形成工程にひき続き、
用いた原料ガスの導入を止め、隔離容器204の内圧を
5 X 10−’Torr以下まで真空引きした後、ガ
ス導入管を兼ねるバイアス印加管より、5iHa 6
0sccm、 B F3(30001)lull H!
希釈) 14sccms S i F、 3sccm
s Hz 180secm+を導入し、成膜室212
の内圧を33mTorrに保持し、マイクロ波電力を1
.7 k Wにした以外は同様の堆積膜形成条件でp型
の微結晶シリコン膜の連続堆積を行った。Continuing from the deposited film formation step carried out in Example 1 of the Floating Mottled Film Formation Example,
After stopping the introduction of the raw material gas used and evacuating the internal pressure of the isolation container 204 to 5 X 10-' Torr or less, 5iHa 6
0sccm, B F3 (30001)lull H!
Dilution) 14sccms S i F, 3sccm
s Hz 180sec+ was introduced into the film forming chamber 212.
The internal pressure of the was maintained at 33 mTorr, and the microwave power was set to 1
.. P-type microcrystalline silicon films were continuously deposited under the same deposition film formation conditions except that the power was 7 kW.
なお、バイアス印加用型′a116より+70Vの直流
電圧を導線117を介してガス導入管を兼ねるバイアス
印加管106に印加させたところ、6.6へのバイアス
電流が流れ、目視によるとプラズマの輝度が若干増した
。When a DC voltage of +70V was applied from the bias application type 'a116 to the bias application tube 106, which also serves as a gas introduction tube, through the conductor 117, a bias current of 6.6 flows, and the brightness of the plasma was visually observed. has increased slightly.
本成膜例及び他の成膜例終了後、基板を冷却して取り出
し、本成膜例において形成された堆積膜のIIII厚分
布を幅方向及び長手方向について測定したところ、5%
以内に納まっており、堆積速度は平均46人/secで
あった。After the completion of this film formation example and other film formation examples, the substrate was cooled and taken out, and the III thickness distribution of the deposited film formed in this film formation example was measured in the width direction and longitudinal direction, and it was found that it was 5%
The average deposition rate was 46 persons/sec.
また、その一部を切り出し、FT−IR(パーキン・エ
ルマー社製1720X)を用い反射法により赤外吸収ス
ペクトルを測定したところ、2100cm−’及び63
0値−1に吸収が認められμC−3i:H:F膜に特有
の吸収パターンであった。更に、RHEED (JEM
−1003X。In addition, when a part of it was cut out and the infrared absorption spectrum was measured by the reflection method using FT-IR (1720X manufactured by Perkin Elmer), the infrared absorption spectrum was found to be 2100 cm-' and 63 cm-'.
Absorption was observed at the 0 value -1, which was an absorption pattern unique to the μC-3i:H:F film. Furthermore, RHEED (JEM
-1003X.
日本電子型)により膜の結晶性を評価したところ、リン
グ状で、無配向の多結晶質であることが判った。また、
金属中水素分析計(EMGA−1100、堀場製作所製
)を用いて膜中水素量を定量したところ4±1 ato
+*ic%であった。When the crystallinity of the film was evaluated by JEOL Ltd., it was found to be ring-shaped and non-oriented polycrystalline. Also,
When the amount of hydrogen in the film was determined using a metal hydrogen analyzer (EMGA-1100, manufactured by Horiba, Ltd.), it was 4 ± 1 ato.
+*ic%.
更に、帯状部材上に堆積形成された膜について、5 f
lX 5 tmの試料片を任意に5ケ所切り出し、その
表面状態を超高分解能、低加速FB−3EM(日立製作
所S−900型〉にて観察したところ、膜表面は平滑で
あり、異常突起の発生はほとんど認められなかった。Furthermore, for the film deposited on the strip member, 5 f
A sample piece of lX 5 tm was arbitrarily cut out at five locations, and its surface condition was observed using an ultra-high resolution, low acceleration FB-3EM (Hitachi S-900 model). The film surface was smooth and there were no abnormal protrusions. Almost no occurrence was observed.
虞僕斑Σ
成膜例1において実施した堆積膜形成工程にひき続き、
用いた原料ガスの導入を止め、隔離容器204の内圧を
5 X 10−”Torr以下まで真空引きした後、ガ
ス導入管を兼ねるバイアス印加管106より、5iH4
88sccm、 P Hz(1%H2希釈) 11S
CC11% 5iF45secs、 Hz 25sec
sを導入し、成膜室212の内圧を38mTorrに保
持し、マイクロ波電力を1.05kWとした以外は同様
の堆積膜形成条件でn型のアモルファスシリコン膜の連
続堆積を行った。Continuing from the deposited film formation step carried out in Film Formation Example 1,
After stopping the introduction of the used raw material gas and evacuating the internal pressure of the isolation container 204 to 5×10-” Torr or less, 5iH4
88sccm, P Hz (1% H2 dilution) 11S
CC11% 5iF45secs, Hz 25sec
An n-type amorphous silicon film was continuously deposited under the same deposition film forming conditions except that the internal pressure of the film forming chamber 212 was maintained at 38 mTorr, and the microwave power was set at 1.05 kW.
なお、バイアス印加用電源116より+65Vの直流電
圧を導線117を介してガス導入管を兼ねるバイアス印
加管106に印加させたところ、6.4Aのバイアス電
流が流れ、目視によるとプラズマの輝度が若干増した。Note that when a DC voltage of +65V was applied from the bias application power supply 116 to the bias application tube 106 that also serves as a gas introduction tube through the conductor 117, a bias current of 6.4A flowed, and as visually observed, the brightness of the plasma slightly increased. Increased.
本成膜例及び他の成膜例終了後、帯状部材を冷却して取
り出し、本成膜例において形成された堆積膜の膜厚分布
を幅方向及び長手方向について測定したところ5%以内
に納まっており、堆積速度は平均70人/secであっ
た。After this film formation example and other film formation examples were completed, the strip member was cooled and taken out, and the film thickness distribution of the deposited film formed in this film formation example was measured in the width direction and longitudinal direction, and it was within 5%. The average deposition rate was 70 persons/sec.
また、その一部を切り出し、FT−IR(パーキン・エ
ルマー社製1720X)を用い反射法により赤外吸収ス
ペクトルを測定したところ、2000cm−’及び63
0(J−’に吸収が認められ、a−3i:H:F膜に特
有の吸収パターンであった。更に、RHEED (JE
M−1003X、日本電子製)により膜の結晶性を評価
したところ、ハローで、非晶質であることが判った。ま
た、金属中水素分析計(EMGA−1100、堀場製作
所製)を用いて膜中水素量を定量したところ22±2a
tomic%であった。In addition, when a part of it was cut out and the infrared absorption spectrum was measured by the reflection method using FT-IR (1720X manufactured by Perkin Elmer), the infrared absorption spectrum was found to be 2000 cm-' and 63 cm-'.
Absorption was observed at 0(J-', which was an absorption pattern specific to a-3i:H:F film. Furthermore, RHEED (JE
When the crystallinity of the film was evaluated using M-1003X (manufactured by JEOL Ltd.), it was found to be halo and amorphous. In addition, the amount of hydrogen in the film was determined using a metal hydrogen analyzer (EMGA-1100, manufactured by Horiba, Ltd.) and was found to be 22±2a.
tomic%.
更に、帯状部材上に堆積形成された膜について、5 i
@X 5關の試料片を任意に5ケ所切り出し、その表面
状態を超高分解能、低加速FE−3EM(日立製作所S
−900型)にて観察したところ、膜表面は平滑であり
、異常突起の発生はほとんど認められなかった。Furthermore, for the film deposited on the strip member, 5 i
@
-900 model), the film surface was smooth and almost no abnormal protrusions were observed.
成膜例6
成膜例1において、5US430BA製帯状基板のかわ
りに、堆積膜の形成される側の面にAl膜を2μm蒸着
した(うち、その一部には中70μm、長さ1(Inの
くし型ギヤ・7プを幅及び長手方向に20cmごとに形
成した。)PET (ポリエチレンテレフタレート)装
帯状基板(幅46C1lX長さlQQmX厚さ0.8
mm )を用い、基板表面温度を210℃とした以外は
、全く同様の操作にてアモルファスシリコン膜の連続堆
積を行った。Film Formation Example 6 In Film Formation Example 1, instead of the 5US430BA band-shaped substrate, an Al film of 2 μm thick was deposited on the side on which the deposited film was formed (part of it had an Al film of 70 μm in diameter and a length of 1 (In PET (polyethylene terephthalate) band-shaped substrate (width 46C1l x length lQQm x thickness 0.8
An amorphous silicon film was continuously deposited using exactly the same procedure except that the substrate surface temperature was 210°C.
なお、バイアス印加用電源116より+70Vの直流電
圧を導線117を介してガス導入管を兼ねるバイアス印
加管106に印加させたところ、6.6へのバイアス電
流が流れ、目視によるとプラズマの輝度が若干増した。Note that when a DC voltage of +70V was applied from the bias application power supply 116 to the bias application tube 106 which also serves as a gas introduction tube through the conductor 117, a bias current of 6.6 flows, and as visually observed, the brightness of the plasma increased. It increased slightly.
基板を冷却後取り出し、まず、膜厚分布を幅方向及び長
手方向について測定したところ5%以内に納まっており
、堆積速度は平均112 A/seeであった。また、
その一部を切り出し、FT−IR(パーキン・エルマー
社製1720X)を用い、リフアレンスミ3過法により
赤外吸収スペクトルを測定したところ、2000c11
−’及び630cm−’に吸収が認められ、a−3i:
H:F膜に特有の吸収パターンであった。また、200
0cm−’付近の5i−Hに帰属される吸収から膜中水
素量を定量したところ、22±2atosic%であっ
た。After the substrate was cooled, it was taken out, and the film thickness distribution was measured in both the width direction and the length direction, and it was found to be within 5%, and the average deposition rate was 112 A/see. Also,
A part of it was cut out and its infrared absorption spectrum was measured using FT-IR (Perkin Elmer 1720X) using the reference Mimic 3-pass method.
Absorption was observed at -' and 630 cm-', a-3i:
The absorption pattern was unique to the H:F film. Also, 200
When the amount of hydrogen in the film was determined from the absorption attributed to 5i-H near 0 cm-', it was found to be 22±2 atomic%.
更に、RHEED (JEM−100sX、日本電子製
)により、膜の結晶性を評価したところ、ハローで、非
晶質であることが判った。Furthermore, when the crystallinity of the film was evaluated by RHEED (JEM-100sX, manufactured by JEOL Ltd.), it was found that it was amorphous with a halo.
また、あらかじめ形成しであるギャソブ電極のうち20
f1所をランダムに切り出し、それぞれについ%AM−
1光、 (100mW/cj)照射下での光電流値、及
び暗中での暗電流値をI(P4140Bを用いて測定し
、明春電率σP(S/ell) 、及び暗導電率σd
(S / cs )を求めたところ、それぞれ(4,0
±0.5) X 10−’S/cm及び(2,0±0.
5)×10°IIS/(2)の範囲内に納まっていた。In addition, 20 of the pre-formed gasob electrodes
Randomly cut out f1 locations and calculate %AM- for each
The photocurrent value under 1 light (100 mW/cj) irradiation and the dark current value in the dark were measured using I (P4140B), and the Meishun electrical conductivity σP (S/ell) and the dark conductivity σd
(S/cs) was found to be (4,0
±0.5) x 10-'S/cm and (2,0±0.
5)×10°IIS/(2).
また、この試料片をCPM (Constant Ph
oto−current Method)装置(自社内
製装置)にセットし、ITO膜側から光入射を行ってア
ーバック据(Urbach Ta11)の傾きを測定し
たところ51±1meVで、欠陥の少ない膜であること
が判った。In addition, this sample piece was subjected to CPM (Constant Ph
The inclination of Urbach Ta11 was measured by setting it in an in-house Oto-Current Method device (in-house manufactured device) and injecting light from the ITO film side, and it was 51 ± 1 meV, indicating that it was a film with few defects. It turns out.
農脛與ユニ上上
成膜例1〜5の成膜条件において、バイアス印加電圧を
第9表に示す条件に変えた以外は同様の操作及びプラズ
マ生起条件等にて、各堆積膜の形成を行った。Each deposited film was formed under the same operations and plasma generation conditions as in Examples 1 to 5 of film formation on agricultural products, except that the applied bias voltage was changed to the conditions shown in Table 9. went.
形成された堆積膜の評価を、威膜例1〜5と同様の方法
にて行った結果を総合して、第9表中に示したが、いず
れの場合においても異常放電は発生せずプラズマは安定
しており、良好な特性の膜が得られた。The results of evaluation of the formed deposited film using the same method as in Film Examples 1 to 5 are summarized in Table 9. In all cases, no abnormal discharge occurred and no plasma was detected. was stable and a film with good properties was obtained.
城逮115ヒニ16
威膜例1〜5の成膜条件において、第2のバイアス棒に
印加するバイアス印加電圧を第10表に示す条件に変え
た以外は同様の操作及びプラズマ生起条件等にて、各堆
積膜の形成を行った。なお、バイアス印加方法は第19
図(D)に示した方法にて、第1のバイアス棒にはいず
れの場合も+30vを印加した。Johan 115 Hini 16 Films were formed using the same operations and plasma generation conditions as in Film Examples 1 to 5, except that the bias voltage applied to the second bias rod was changed to the conditions shown in Table 10. , each deposited film was formed. The bias application method is the 19th
In each case, +30 V was applied to the first bias rod using the method shown in Figure (D).
形成された堆積膜の評価を、成膜例1〜5と同様の方法
にて行った結果を総合して、第1O表中に示したが、い
ずれの場合においても異常放電は発生せずプラズマは安
定しており、良好な特性の膜が得られた。The results of evaluating the formed deposited film using the same method as in Film Forming Examples 1 to 5 are summarized in Table 1. In all cases, no abnormal discharge occurred and no plasma was detected. was stable and a film with good properties was obtained.
底投班土1
本成膜例では、第2図に示した装置で帯状部材を50c
m/PAinの搬送速度で搬送しながら第12図のN構
成をもつショットキー・ダイオードを作製した。第12
図において、I201はステンレス製帯状部材、120
2はCr蒸着層(0,1μm厚)、1203はn型a−
3i:H膜(0,2,c+m厚、以下n”−3i層と略
記)、1204はノンドープのa−3i:H膜(0,4
μm厚、以下1−3i層と略記)、1205は金蒸着1
(100人厚)、1206.1207は電気的接続端子
である。1. In this film-forming example, a strip of 50cm
A Schottky diode having the N configuration shown in FIG. 12 was fabricated while being transported at a transport speed of m/PAin. 12th
In the figure, I201 is a stainless steel strip member, 120
2 is a Cr vapor deposited layer (0.1 μm thick), 1203 is an n-type a-
3i:H film (0,2,c+m thickness, hereinafter abbreviated as n''-3i layer), 1204 is a non-doped a-3i:H film (0,4
μm thick, hereinafter abbreviated as 1-3i layer), 1205 is gold vapor deposition 1
(100 people thick), 1206 and 1207 are electrical connection terminals.
以下に、その作製手順について説明する。The manufacturing procedure will be explained below.
まず、成膜例1と同様の洗浄処理を行った帯状部材12
01上に膜厚1000人のCr層1202を連続真空薄
着装置を用いて形成した0次に、該帯状部材1201を
第2図に示す本発明のマイクロ波プラズマCVD装置に
前記Cr層1202が蒸着された側が図中下側になるよ
うセットし、第10表に示す成膜条件にて成膜例1と同
様の操作にてn’−3iN1203を形成した。First, the band-shaped member 12 was subjected to the same cleaning treatment as in Film Formation Example 1.
A Cr layer 1202 with a thickness of 1,000 thick was formed on the strip member 1201 using a continuous vacuum thin deposition apparatus.Then, the Cr layer 1202 was deposited on the strip member 1201 using a microwave plasma CVD apparatus of the present invention as shown in FIG. n'-3iN1203 was formed in the same manner as in Film Forming Example 1 under the film forming conditions shown in Table 10.
20分間連続成膜後、n”−3i層12o3の形成を終
え、マイクロ波電力、S + H4、Hを希釈PH,+
の導入を停止し、隔離容器203内をIX 10−’T
orrまで真空引きした。After continuous film formation for 20 minutes, the formation of the n''-3i layer 12o3 was completed, and the microwave power, S + H4, H was diluted with PH, +
10-'T in the isolation container 203.
Vacuumed to orr.
次に、帯状部材回収ローラー208に巻き取られた帯状
部材201を図中右側から左側方向へ逆転搬送しつつ、
第10表に示す成膜条件にて既述した手順に従って1−
3i層1204の連続形成を20分間に渡って行った。Next, while the strip member 201 wound around the strip member collection roller 208 is conveyed in reverse from the right side to the left side in the figure,
1- according to the procedure described above under the film-forming conditions shown in Table 10.
Continuous formation of the 3i layer 1204 was performed for 20 minutes.
なお、この時の搬送速度は50cm/sinとした。Note that the conveyance speed at this time was 50 cm/sin.
1−3i層1204の形成完了後、既述した手順に従っ
て帯状基体201を帯状部材搬出室202から取出した
。After the formation of the 1-3i layer 1204 was completed, the strip-shaped substrate 201 was taken out from the strip-shaped member carrying-out chamber 202 according to the procedure described above.
このときn” −3i層と1−3i層の合計膜厚の平均
は約0.6μmで、面内の均一性は±4%と良好なもの
であった。At this time, the average total thickness of the n''-3i layer and the 1-3i layer was about 0.6 μm, and the in-plane uniformity was as good as ±4%.
さらに、該帯状部材201の中から任意に20箇所から
試料片を切り出し各々を真空蒸着装置にセットし、1−
3i層1204上に直径5關φ、+11i厚100人の
金蒸着膜1205を形成した。Furthermore, sample pieces are arbitrarily cut out from 20 locations in the strip member 201, and each sample piece is set in a vacuum evaporation apparatus.
On the 3i layer 1204, a gold evaporated film 1205 of 100 layers with a diameter of 5 mm and a thickness of +11i was formed.
この金蒸着膜及びCr蒸着膜に電気的接続端子1206
.1207をそれぞれ圧接してショットキー・ダイオー
ドの特性を調べたところ、ダイオード因子n=1.I2
±0.05の良好なダイオード特性を示すことが判明し
た。また、面内の特性の均一性も良好なものであった。Electrical connection terminals 1206 are connected to the gold vapor deposited film and the Cr vapor deposited film.
.. 1207 was pressed into contact with each other and the characteristics of the Schottky diode were investigated, and the diode factor n=1. I2
It was found that good diode characteristics of ±0.05 were exhibited. Further, the uniformity of in-plane properties was also good.
底撲斑土1
第2図に示した本発明の連続式マイクロ波プラズマCV
D装置を用いて第13図に示す層構成のpin型a−S
+太!池を連続的に製造した。Continuous microwave plasma CV of the present invention shown in Fig. 2
A pin type a-S with the layer structure shown in FIG.
+ Thick! The ponds were produced continuously.
第13図において、1301はステンレス(SUS43
0BA)装帯状部材、1302はアルミニウム及びC「
の2層でできた下部電極、1303はn型a−3i層(
n−3i)、1304は1型a−3i層(i−3i)
、1305はp型マイクロクリスタルSt層(以後p型
μx−3illと略記)、1306は透明電極、130
7はアルミニウム集IIi電極である。In Fig. 13, 1301 is stainless steel (SUS43
0BA) Band-like member, 1302 is made of aluminum and C"
The lower electrode is made up of two layers, 1303 is an n-type a-3i layer (
n-3i), 1304 is type 1 a-3i layer (i-3i)
, 1305 is a p-type microcrystal St layer (hereinafter abbreviated as p-type μx-3ill), 1306 is a transparent electrode, 130
7 is an aluminum collection IIi electrode.
まず、ステンレス(SUS430BA)装帯状部材を十
分に洗浄、脱脂を行ったのち、不図示の連続式真空蒸着
装置を用いAI及びCrを連続蒸着し、下部電極130
2を形成した。下部電極1302まで形成された該帯状
部材201を第2図に示す装置に下部電極1302の形
成された側の面が図中下側を向くようにセットし、第1
1表に示す成膜条件にて既述の手順に従って、nSt、
、1−3iSp型px−3tの順に堆積膜を連続して積
層形成した。First, after thoroughly cleaning and degreasing a stainless steel (SUS430BA) band-like member, AI and Cr are continuously deposited using a continuous vacuum deposition device (not shown), and the lower electrode 130 is
2 was formed. The strip member 201, which has been formed up to the lower electrode 1302, is set in the apparatus shown in FIG. 2 so that the surface on which the lower electrode 1302 is formed faces downward in the figure.
nSt,
, 1-3iSp type px-3t were successively stacked in this order.
更に、p型μx−3L膜上に透明電極であるインジウム
錫酸化膜1306(ITO)を蒸着し、集電電極である
All極1307を蒸着し、表面保護層として樹脂を塗
布して第13図のNfjl成の太陽電池を製造した。完
成した太陽電池をAMl、 5 (100mW/−)
のソーラーシミュレータ−で測定した結果、光電変換効
率は平均8.4%以上で良好な特性であった。Furthermore, an indium tin oxide film 1306 (ITO) as a transparent electrode is deposited on the p-type μx-3L film, an All electrode 1307 as a current collecting electrode is deposited, and a resin is applied as a surface protective layer. A solar cell of Nfjl composition was manufactured. The completed solar cell is AMl, 5 (100mW/-)
As a result of measurement using a solar simulator, the photoelectric conversion efficiency was 8.4% or more on average, indicating good characteristics.
更に、シッート等による欠陥発生率をバイアス電圧を印
加させずに形成した太陽電池モジュールの場合と比較し
たところ、20%以上向上していた。Furthermore, when the defect occurrence rate due to sheets etc. was compared with that of a solar cell module formed without applying a bias voltage, it was found to be improved by more than 20%.
域仕ill生
第2図の本発明の連続式マイクロ波CVD装置を用いて
、第13図に示す層構成のpin型a−3i/a−3i
C太11iSii池を連続的に製造した。Using the continuous microwave CVD apparatus of the present invention shown in Fig. 2, pin type a-3i/a-3i with the layer structure shown in Fig.
C. 11iSii ponds were produced continuously.
但し、第13図において、l304を1−3+C層、1
305をp型μx−3+(:膜と変更した。However, in Fig. 13, l304 is 1-3+C layer, 1
305 was changed to p-type μx-3+ (: membrane).
それ以外は成膜例18と全く同様であり、第12表に示
す成膜条件にて既述の手順に従って、n−3+% 1−
3iCSp−μx−3iCの順に堆積膜を形成した。Other than that, the process was completely the same as that of film formation example 18, and n-3+% 1-
Deposited films were formed in the order of 3iCSp-μx-3iC.
また、1−3iC層形威時の原料ガス利用効率は50%
であり、成膜例18で用いたのと同様のソーラーシミュ
レーターで測定評価した結果、光電変換効率は平均6.
3%以上であった。In addition, the raw material gas utilization efficiency when using a 1-3iC layered structure is 50%.
As a result of measurement and evaluation using a solar simulator similar to that used in Film Formation Example 18, the average photoelectric conversion efficiency was 6.
It was 3% or more.
また、AMl、5 (100mW/aj)光の500時
間連続照射後の光電変換効率の初期値に対する変化率を
測定したところ9%以内に納まった。Further, when the rate of change in photoelectric conversion efficiency with respect to the initial value was measured after 500 hours of continuous irradiation with AMl,5 (100 mW/aj) light, it was within 9%.
嚢脛史主l
第2図に示した連続式マイクロ波CVD装置戒膜室20
5と帯状部材搬出室207の間に、新たに3つの成膜室
を連結したflI戒にした装置(不図示)を用いて第1
5図に示す層t#戒のタンデム型太陽電池を連続的に製
造した。Continuous microwave CVD device membrane chamber 20 shown in Figure 2
5 and the belt-shaped member carrying-out chamber 207, using a device (not shown) newly connected with three film-forming chambers.
A tandem solar cell with a layer of t# as shown in FIG. 5 was manufactured continuously.
第15図において、1501はステンレス製帯状部材、
1502はAA’引出し電極とAg反射層の2Nで構成
される下部電極、1503は第1のn型a−3i層、1
504は第1のi型アモルファスシリコンゲルマニウム
(i −a−31Ge)JfW、1505は第1のp型
px−3i層、1508は第2のn型a−3+層、15
(19は第2の1−aSiji、1510は第2のp型
px−3i層、1506は透明導電膜、1507はパタ
ーニングされたAl集電電極である。In FIG. 15, 1501 is a stainless steel strip member;
1502 is a lower electrode composed of 2N of an AA' extraction electrode and an Ag reflective layer, 1503 is a first n-type a-3i layer, 1
504 is the first i-type amorphous silicon germanium (i-a-31Ge) JfW, 1505 is the first p-type px-3i layer, 1508 is the second n-type a-3+ layer, 15
(19 is the second 1-aSiji, 1510 is the second p-type px-3i layer, 1506 is a transparent conductive film, and 1507 is a patterned Al current collecting electrode.
本装置は、第13表に示される成膜条件、及び、装置例
8で説明したのと同様の手順で太陽電池を連続的に製造
した。そして、成膜例18で用いたのと同様のソーラー
シミュレーターで測定した結果、光電変換効率は平均6
.6%以上であった。This apparatus continuously manufactured solar cells under the film-forming conditions shown in Table 13 and the same procedure as described in Apparatus Example 8. As a result of measurement using a solar simulator similar to that used in Film Formation Example 18, the photoelectric conversion efficiency was 6 on average.
.. It was more than 6%.
また、AM 1.5 (100mW/cd)光の500
時間連続照射後の光電変換効率の初期値に対する変化率
を測定したところ9%以内に納まった。In addition, 500 mW/cd of AM 1.5 (100 mW/cd) light
When the rate of change in photoelectric conversion efficiency with respect to the initial value after continuous irradiation was measured, it was within 9%.
更に、ショート等による欠陥発生率をバイアス電圧を印
加させずに形成した太陽電池モジュールの場合と比較し
たところ、20%以上向上していた。これらのモジュー
ルを接続して3kWの電力iJL給システムを作製する
ことができた。Furthermore, when compared with the case of a solar cell module formed without applying a bias voltage, the defect occurrence rate due to short circuits and the like was improved by more than 20%. By connecting these modules, we were able to create a 3kW power iJL supply system.
(以下余白)
第
表
第
表
第
3
表
第
表
第
表
第
10
表
第
1
表
〔発明の効果の概要〕
本発明の方法によれば、成膜空間の側壁を構成する帯状
部材を連続的に移動せしめると共に、前記成膜空間の側
壁を構威す゛る帯状部材の幅方向に平行になるようにマ
イクロ波アンテナ手段を該成膜空間に突入させ、該マイ
クロ波アンテナ手段からマイクロ波の進行方向に垂直な
全方向にマイクロ波電力を放射させてプラズマを発生さ
せることによって、大面積の機能性堆積膜を連続して、
均一性良く形成することができる。(The following are blank spaces) Table 3 Table 3 Table 10 Table 1 [Summary of the effects of the invention] According to the method of the present invention, the strip-shaped member constituting the side wall of the film-forming space is continuously formed. At the same time, microwave antenna means is thrust into the film-forming space so as to be parallel to the width direction of the band-shaped member that constitutes the side wall of the film-forming space, and a microwave antenna is directed from the microwave antenna means in the direction of propagation of the microwave. By emitting microwave power in all vertical directions to generate plasma, a large area of functional deposited films can be continuously deposited.
It can be formed with good uniformity.
また、本発明の方法によれば、プラズマ電位を適宜制御
することによって、所望の特性を有し、欠陥の少ない高
品質の機能性堆積膜を連続して効率良く高い歩留りで形
成することができる。Furthermore, according to the method of the present invention, by appropriately controlling the plasma potential, a high-quality functional deposited film having desired characteristics and few defects can be continuously formed efficiently and at a high yield. .
本発明の方法及び装置により、プラズマを前記成膜空間
内に閉じ込め、プラズマ電位を制御することにより、プ
ラズマの安定性、再現性が向上すると共に堆積膜形成用
原料ガスの利用効率を飛躍的に高めることができる。更
に、前記帯状部材を連続して搬送させることによって、
湾曲の長さ、及び搬送速度を種々変化させることによっ
て任意の膜厚の堆積膜を大面積に渡り均一性よく、連続
して堆積形成できる。By confining the plasma within the film forming space and controlling the plasma potential, the method and apparatus of the present invention improve the stability and reproducibility of the plasma, and dramatically improve the utilization efficiency of the raw material gas for forming the deposited film. can be increased. Furthermore, by continuously conveying the belt-shaped member,
By varying the length of the curve and the conveyance speed, a deposited film of any thickness can be continuously deposited over a large area with good uniformity.
本発明の方法及び装置によれば、比較的幅広で、且つ長
尺の帯状部材の表面上に連続して均一性良く機能性堆積
膜を形成できる。従って、特に大面積太陽電池の量産機
として好適に用いることができる。According to the method and apparatus of the present invention, it is possible to form a functional deposited film continuously and with good uniformity on the surface of a relatively wide and long strip member. Therefore, it can be particularly suitably used as a mass production machine for large-area solar cells.
また、放電を止めることなく、連続して堆積膜が形成で
きるため、積層型デバイス等を作製するときには良好な
界面特性が得られる。Further, since a deposited film can be continuously formed without stopping the discharge, good interface characteristics can be obtained when manufacturing a stacked device or the like.
また、低圧下での堆積膜形成が可能となり、ポリシラン
粉の発生を抑えられ、また、活性種のポリマリゼーシ3
ン等を抑えられるので欠陥の減少及び、膜特性の向上、
膜特性の安定性の向上等が図れる。In addition, it is possible to form a deposited film under low pressure, suppressing the generation of polysilane powder, and reducing the amount of polymerization of active species.
This reduces defects and improves film properties.
The stability of film properties can be improved.
従って、稼動率、歩留りの向上が図れ、安価で高効率の
太陽電池を!産化することが可能となる。Therefore, you can improve the operating rate and yield, and create inexpensive and highly efficient solar cells! It becomes possible to commercialize it.
更に、本発明の方法及び装置によって作製された太陽電
池は光電変換効率が高く、且つ、長期に渡って特性劣化
の少ないものとなる。Furthermore, the solar cell produced by the method and apparatus of the present invention has high photoelectric conversion efficiency and exhibits little property deterioration over a long period of time.
【図面の簡単な説明】
第1図は本発明の装置のうち成膜室及びその周辺機構の
透視説明図、
第2図は、太陽電池のpin各層を形成する装置配列を
示す模式図、
第3図は、マイクロ波同軸線路の詳細説明図、第4図は
、第3図のA−A ’断面図、第5図は、誘電体管及び
原料ガス導入管の交換機構説明図、
第6図は、成膜室排気口動作説明図、
第7図、第8図は、帯状基体脱着機構説明模式第9図は
、従来のRFプラズマCVD装置の模式図、
第10図、第11図は、威膜結果評価例のデータ、
第12〜16図は、積層膜構成図、
第17図、第18図は、従来のマイクロ波アンテナ方式
の説明図、
第19図は、バイアス印加手段の典型的配置を示す図で
ある。
第20図は、本発明の実験例において得られたバイアス
電圧印加時の電流−電圧特性図である。
第21図は、本発明の実験例において得られたバイアス
電圧印加時のプラズマ電位の変化率を示した図である。
第1図乃至第19図の夫々について、
101.1901・・・帯状部材、102・・・中心導
体、103・・・誘電体管、104・・・成膜室、10
61903・・・原料ガス導入管を兼ねるバイアス印加
管、110・・・スリット状開口部、113・・・湾曲
部支持内側リング、114.19(19・・・絶縁性継
手、115.1910・・・ガス供給管、116,19
07゜1908・・・バイアス印加用電源、117・・
・i線、201・・・帯状部材、203〜205・・・
隔離容器、206・・・ガス隔離通路、210・・・掃
気ガス導入口、211〜213・・・成膜室、214〜
216・・・マイクロ波同軸vA路導入部、217〜2
25・・・排気口、301・・・方形導波管、302・
・・同軸プランジャ、307・・・マイクロ波透過性の
高誘電率部材、313・・・導波管同軸変換器、501
・・・交換用ロードロック室、502・・・ゲートバル
ブ、601・・・コンダクタンス調整板、602・・・
メツシュ構造をもつマイクロ波反射板、701・・・帯
状基体の送り出し側に設けられた帯状基体処理室、80
1・・・帯状基体の巻き取り側に設けられた帯状基体処
理室、708.808・・・切断刃、7(19,8(1
9・・・溶接治具、902・・・カソード電極、903
・・・基体、904・・・基体ホルダー、905・・・
ヒーターを内蔵した支持台、1301,1401.15
01゜1601・・・支持体、1302,1402.1
502゜1602・・・下部電極、1303,1403
゜1503.1508.1603,1614.1617
・−・n型半導体層、1304,1404,15041
5(19.1604,1615.1618・・・i型半
導体層、1305,1405,1505゜1510.1
605,1616.1619・・・p型半導体層、13
06,1406,1506゜1606・・・透明電極、
1307.1507゜1607・・・集電電極、171
・・・反応容器、172・・・ロンド・アンテナ、17
9・・・マイクロ波透過部材、181・・・反応容器、
184・・・同軸線路、185・・・外部導体に設けら
れた間隙、186・・・筒体、1904. I 90
6・/<イ7ス棒、1905・・・ガス導入管。[BRIEF DESCRIPTION OF THE DRAWINGS] Fig. 1 is a transparent explanatory view of the film forming chamber and its peripheral mechanism in the apparatus of the present invention; Fig. 2 is a schematic diagram showing the arrangement of the apparatus for forming each pin layer of a solar cell; 3 is a detailed explanatory diagram of the microwave coaxial line, FIG. 4 is a sectional view taken along line A-A' in FIG. The figure is an explanatory diagram of the operation of the exhaust port of the film-forming chamber. Figures 7 and 8 are a schematic diagram of the strip-shaped substrate attachment and detachment mechanism. Figure 9 is a schematic diagram of a conventional RF plasma CVD apparatus. Figures 10 and 11 are , data of membrane result evaluation examples, Figures 12 to 16 are laminated film configuration diagrams, Figures 17 and 18 are explanatory diagrams of conventional microwave antenna systems, and Figure 19 is a typical bias application means. FIG. FIG. 20 is a current-voltage characteristic diagram when a bias voltage is applied, obtained in an experimental example of the present invention. FIG. 21 is a diagram showing the rate of change in plasma potential during application of a bias voltage obtained in an experimental example of the present invention. Regarding each of FIG. 1 to FIG. 19, 101.1901... Band-shaped member, 102... Center conductor, 103... Dielectric tube, 104... Film forming chamber, 10
61903... Bias application tube that also serves as source gas introduction tube, 110... Slit-shaped opening, 113... Curved part support inner ring, 114.19 (19... Insulating joint, 115.1910...・Gas supply pipe, 116, 19
07゜1908...Bias application power supply, 117...
・i-line, 201... band-shaped member, 203-205...
Isolation container, 206... Gas isolation passage, 210... Scavenging gas inlet, 211-213... Film forming chamber, 214-
216...Microwave coaxial vA path introduction part, 217-2
25...Exhaust port, 301...Rectangular waveguide, 302...
... Coaxial plunger, 307 ... Microwave transparent high dielectric constant member, 313 ... Waveguide coaxial converter, 501
... Replacement load lock chamber, 502... Gate valve, 601... Conductance adjustment plate, 602...
Microwave reflecting plate with mesh structure, 701... Strip-shaped substrate processing chamber provided on the delivery side of the strip-shaped substrate, 80
1... Strip-shaped substrate processing chamber provided on the winding side of the strip-shaped substrate, 708.808... Cutting blade, 7 (19, 8 (1)
9... Welding jig, 902... Cathode electrode, 903
...Base body, 904...Base body holder, 905...
Support stand with built-in heater, 1301, 1401.15
01゜1601...Support, 1302, 1402.1
502゜1602...lower electrode, 1303, 1403
゜1503.1508.1603,1614.1617
---n-type semiconductor layer, 1304, 1404, 15041
5 (19.1604, 1615.1618...i-type semiconductor layer, 1305, 1405, 1505° 1510.1
605,1616.1619...p-type semiconductor layer, 13
06,1406,1506°1606...transparent electrode,
1307.1507゜1607...Collecting electrode, 171
... Reaction vessel, 172 ... Rondo antenna, 17
9... Microwave transmission member, 181... Reaction container,
184... Coaxial line, 185... Gap provided in outer conductor, 186... Cylindrical body, 1904. I90
6./<I7S rod, 1905...Gas introduction pipe.
Claims (36)
、その中途で前記移動する帯状部材を側壁にした実質的
に真空に保持し得る柱状の成膜空間を形成し、 該成膜空間内にガス供給手段を介して成膜用原料ガスを
導入し、同時にマイクロ波アンテナを介してマイクロ波
の進行方向に垂直な全方向にマイクロ波を放射させて前
記成膜空間内にマイクロ波電力を投入して前記成膜空間
内にマイクロ波プラズマを生起せしめ、 前記マイクロ波プラズマのプラズマ電位を制御しながら
、 該マイクロ波プラズマに曝される前記側壁を構成し連続
的に移動する前記帯状部材の表面上に堆積膜を形成せし
めることを特徴とするマイクロ波プラズマCVD法によ
る大面積の機能性堆積膜を連続的に形成する方法。(1) While continuously moving a strip member in the longitudinal direction, a columnar film forming space that can be maintained in a substantially vacuum state is formed with the moving strip member as a side wall midway through the movement, and within the film forming space. A source gas for film formation is introduced into the film formation space through a gas supply means, and at the same time, microwaves are radiated in all directions perpendicular to the direction of propagation of the microwaves through a microwave antenna to supply microwave power into the film formation space. of the band-shaped member that constitutes the side wall exposed to the microwave plasma and moves continuously while controlling the plasma potential of the microwave plasma. A method for continuously forming a large-area functional deposited film using a microwave plasma CVD method, which is characterized by forming a deposited film on a surface.
端形成手段と湾曲終了端形成手段とを用いて、該湾曲開
始端形成手段と該湾曲終了端形成手段との間に前記帯状
部材の長手方向に間隙を残して該帯状部材を湾曲させて
前記成膜空間の側壁を形成する請求項1に記載の大面積
の機能性堆積膜を連続的に形成する方法。(2) In the middle of the moving band-like member, a curved start end forming means and a curved end forming means are used to create a space between the curved start end forming means and the curved end forming means, so that the longitudinal direction of the band-like member is 2. The method for continuously forming a large area functional deposited film according to claim 1, wherein the side wall of the film forming space is formed by curving the strip member leaving a gap in the direction.
前記堆積膜の線膨張係数よりも大きいものを用い、該帯
状部材を室温以上の所望の成膜温度に保ちながら連続的
に湾曲させて形成される凹状の湾曲面上に堆積膜を形成
せしめ、該堆積膜の形成された帯状部材を前記成膜空間
の外部において室温まで冷却させるにつき、該帯状部材
を平面状に展開して冷却させるようにするか、又は凸状
に巻取って冷却させるようにする請求項2に記載の大面
積の機能性堆積膜を連続的に形成する方法。(3) As the material for the band-shaped member, a material whose linear expansion coefficient is larger than that of the deposited film is used, and the band-shaped member is continuously curved while maintaining the desired film-forming temperature above room temperature. A deposited film is formed on the concave curved surface formed by the deposited film, and the belt-shaped member on which the deposited film is formed is cooled to room temperature outside the film-forming space, and the belt-shaped member is expanded into a flat shape and cooled. 3. The method for continuously forming a large-area functional deposited film according to claim 2, wherein the functional deposited film is formed in a convex shape and cooled.
成膜空間の対向する両端面のいずれか一方より、前記成
膜空間内に前記マイクロ波アンテナ手段を前記帯状部材
と平行になるように突入させて前記成膜空間内にマイク
ロ波電力を投入させる請求項1に記載の大面積の機能性
堆積膜を連続的に形成する方法。(4) The microwave antenna means is inserted into the film forming space from either one of the opposing end surfaces of the columnar film forming space formed with the band member as a side wall so as to be parallel to the band member. 2. The method for continuously forming a large-area functional deposited film according to claim 1, further comprising the step of injecting microwave power into the film forming space.
間に設けられたマイクロ波透過性部材を介して、該マイ
クロ波アンテナ手段より前記成膜空間内にマイクロ波電
力を投入させる請求項4に記載の大面積の機能性堆積膜
を連続的に形成する方法。(5) Microwave power is introduced into the film forming space from the microwave antenna means through a microwave transparent member provided between the microwave antenna means and the film forming space. A method for continuously forming a large-area functional deposited film as described in .
ロ波アンテナ手段を前記成膜空間内に生起するプラズマ
から分離させる請求項5に記載の大面積の機能性堆積膜
を連続的に形成する方法。(6) Continuously forming a large area functional deposited film according to claim 5, wherein the microwave antenna means is separated from the plasma generated in the film forming space via the microwave transparent member. Method.
たバイアス印加手段を介して制御するようにする請求項
1に記載の大面積の機能性堆積膜を連続的に形成する方
法。(7) The method for continuously forming a large-area functional deposited film according to claim 1, wherein the plasma potential is controlled via bias applying means separated from the strip member.
前記マイクロ波プラズマに接するように配設し、前記バ
イアス印加手段にバイアス電圧を印加させる請求項7に
記載の大面積の機能性堆積膜を連続的に形成する方法。(8) The large area functional deposited film according to claim 7, wherein the bias applying means is disposed so that at least a portion thereof is in contact with the microwave plasma, and a bias voltage is applied to the bias applying means. How to form.
に接する少なくとも一部分には導電処理を施すようにす
る請求項8に記載の大面積の機能性堆積膜を連続的に形
成する方法。(9) The method for continuously forming a large-area functional deposited film according to claim 8, wherein at least a portion of the bias applying means that is in contact with the microwave plasma is subjected to a conductive treatment.
である請求項8に記載の大面積の機能性堆積膜を連続的
に形成する方法。(10) The method for continuously forming a large-area functional deposited film according to claim 8, wherein the bias voltage is a direct current, a pulsating current, and/or an alternating current.
ねるようにする請求項8に記載の大面積の機能性堆積膜
を連続的に形成する方法。(11) The method for continuously forming a large-area functional deposited film according to claim 8, wherein the bias applying means also serves as the gas supplying means.
分離して配設するようにする請求項8に記載の大面積の
機能性堆積膜を連続的に形成する方法。(12) The method for continuously forming a large-area functional deposited film according to claim 8, wherein the bias application means is arranged separately from the gas supply means.
アス棒で構成させるようにする請求項12に記載の大面
積の機能性堆積膜を連続的に形成する方法。(13) The method for continuously forming a large-area functional deposited film according to claim 12, wherein the bias applying means comprises one or more bias rods.
イアス電圧によって制御するようにする請求項1に記載
の大面積の機能性堆積膜を連続的に形成する方法。(14) The method for continuously forming a large area functional deposited film according to claim 1, wherein the plasma potential is controlled by a bias voltage applied to the strip member.
その一部分が前記マイクロ波プラズマに接するように配
設するようにする請求項14に記載の大面積の機能性堆
積膜を連続的に形成する方法。(15) The method for continuously forming a large-area functional deposited film according to claim 14, wherein the gas supply means is set to a ground potential and is disposed so that at least a portion thereof is in contact with the microwave plasma. .
接する少なくとも一部分には導電処理を施すようにする
請求項14に記載の大面積の機能性堆積膜を連続的に形
成する方法。(16) The method for continuously forming a large-area functional deposited film according to claim 14, wherein at least a portion of the gas supply means that is in contact with the microwave plasma is subjected to a conductive treatment.
性部材の外径を予め調整・選択する請求項1に記載の大
面積の機能性堆積膜を連続的に形成する方法。(17) The method for continuously forming a large area functional deposited film according to claim 1, wherein the outer diameter of the microwave transparent member is adjusted and selected in advance according to the complex dielectric constant of the plasma.
れる側の面には少なくとも導電処理を施すようにする請
求項1に記載の大面積の機能性堆積膜を連続的に形成す
る方法。(18) The method of continuously forming a large-area functional deposited film according to claim 1, wherein at least a conductive treatment is performed on the side of the band-shaped member exposed to the microwave plasma.
ズマCVD法により機能性堆積膜を連続的に形成する装
置であって、 前記帯状部材をその長手方向に連続的に移動させながら
、その中途で湾曲させるための湾曲部形成手段を介して
、前記帯状部材を側壁にして形成され、その内部を実質
的に真空に保持し得る柱状の成膜室を有し、 前記成膜室内にマイクロ波プラズマを生起させるための
マイクロ波電力を供給するようにしたマイクロ波同軸線
路と、 該マイクロ波同軸線路から供給されるマイクロ波電力を
透過せしめ、且つ前記マイクロ波プラズマから該マイク
ロ波同軸線路の中心導体を分離するための中心導体分離
手段と、 前記成膜室を排気する手段と、 前記成膜室内に成膜用原料ガスを導入するためのガス供
給手段と、 前記マイクロ波プラズマのプラズマ電位を制御するため
のバイアス印加手段と、 前記帯状部材を加熱及び/又は冷却するための温度制御
手段とを備えていて、 前記連続的に移動しながら前記成膜室の側壁を形成する
帯状部材の前記マイクロ波プラズマに曝される側の表面
上に、連続的に堆積膜を形成するようにしたことを特徴
とする大面積の機能性堆積膜を連続的に形成する装置。(19) An apparatus for continuously forming a functional deposited film by a microwave plasma CVD method on a continuously moving strip-shaped member, wherein the strip-shaped member is continuously moved in its longitudinal direction, and A columnar film forming chamber is formed using the band-shaped member as a side wall and can maintain a substantially vacuum inside the film forming chamber through a curved part forming means for curving the film at A microwave coaxial line configured to supply microwave power for generating plasma; and a microwave coaxial line configured to transmit the microwave power supplied from the microwave coaxial line, and to transmit the microwave power from the microwave plasma to the center of the microwave coaxial line. a center conductor separating means for separating the conductors; a means for evacuating the film forming chamber; a gas supply means for introducing a film forming raw material gas into the film forming chamber; and a plasma potential of the microwave plasma. a bias applying means for controlling the temperature control means for heating and/or cooling the strip-shaped member, and a temperature control means for heating and/or cooling the strip-shaped member, the strip-shaped member forming the side wall of the film-forming chamber while continuously moving. 1. An apparatus for continuously forming a large-area functional deposited film, characterized in that the deposited film is continuously formed on a surface exposed to microwave plasma.
、湾曲終了端形成ローラー及び対向する湾曲部端面支持
リングとからなり、前記湾曲開始端形成ローラーと前記
湾曲終了端形成ローラーとを、前記帯状部材の長手方向
に間隙を残して平行に配設する請求項19に記載の大面
積の機能性堆積膜を連続的に形成する装置。(20) The curved portion forming means includes a curved start end forming roller, a curved end end forming roller, and an opposing curved portion end surface support ring, and the curved end forming roller and the curved end forming roller are connected to each other in the strip shape. 20. The apparatus for continuously forming a large-area functional deposited film according to claim 19, wherein the members are disposed in parallel with a gap left in the longitudinal direction of the members.
して配設する請求項19に記載の大面積の機能性堆積膜
を連続的に形成する装置。(21) The apparatus for continuously forming a large-area functional deposited film according to claim 19, wherein the bias applying means is arranged separately from the strip member.
が前記マイクロ波プラズマに接するように配設し、前記
バイアス印加手段にバイアス電圧を印加させる請求項2
1に記載の大面積の機能性堆積膜を連続的に形成する装
置。(22) The bias applying means is arranged such that at least a portion thereof is in contact with the microwave plasma, and a bias voltage is applied to the bias applying means.
An apparatus for continuously forming a large-area functional deposited film according to item 1.
マに接する少なくとも一部分には導電処理が施される請
求項22に記載の大面積の機能性堆積膜を連続的に形成
する装置。(23) The apparatus for continuously forming a large-area functional deposited film according to claim 22, wherein at least a portion of the bias applying means that is in contact with the microwave plasma is subjected to conductive treatment.
である請求項22に記載の大面積の機能性堆積膜を連続
的に形成する装置。(24) The apparatus for continuously forming a large-area functional deposited film according to claim 22, wherein the bias voltage is a direct current, a pulsating current, and/or an alternating current.
ねる請求項22に記載の大面積の機能性堆積膜を連続的
に形成する装置。(25) The apparatus for continuously forming a large-area functional deposited film according to claim 22, wherein the bias application means also serves as the gas supply means.
分離して配設される請求項22に記載の大面積の機能性
堆積膜を連続的に形成する装置。(26) The apparatus for continuously forming a large-area functional deposited film according to claim 22, wherein the bias application means is arranged separately from the gas supply means.
ス棒で構成される請求項26に記載の大面積の機能性堆
積膜を連続的に形成する装置。(27) The apparatus for continuously forming a large-area functional deposited film according to claim 26, wherein the bias applying means comprises one or more bias rods.
配設される請求項19に記載の大面積の機能性堆積膜を
連続的に形成する装置。(28) The apparatus for continuously forming a large-area functional deposited film according to claim 19, wherein the bias applying means also serves as the strip member.
部分が前記マイクロ波プラズマに接するように配設する
請求項28に記載の大面積の機能性堆積膜を連続的に形
成する装置。(29) The apparatus for continuously forming a large-area functional deposited film according to claim 28, wherein the gas supply means is grounded and arranged so that at least a portion thereof is in contact with the microwave plasma.
接する少なくとも一部分には導電処理が施される請求項
29に記載の大面積の機能性堆積膜を連続的に形成する
装置。(30) The apparatus for continuously forming a large-area functional deposited film according to claim 29, wherein at least a portion of the gas supply means in contact with the microwave plasma is subjected to conductive treatment.
状の成膜室の対向する両端面のいずれか一方より該成膜
室内部に突入され、且つ該柱状の成膜室の中心軸近傍に
前記帯状部材の幅方向とほぼ平行に配設される請求項1
9に記載の大面積の機能性堆積膜を連続的に形成する装
置。(31) The center conductor of the microwave coaxial line is inserted into the film forming chamber from either one of the opposing end surfaces of the columnar film forming chamber, and is located near the central axis of the columnar film forming chamber. Claim 1: The strip member is arranged substantially parallel to the width direction of the strip member.
9. An apparatus for continuously forming a large-area functional deposited film according to 9.
項19に記載の大面積の機能性堆積膜を連続的に形成す
る装置。(32) The apparatus for continuously forming a large-area functional deposited film according to claim 19, wherein the center conductor separating means is rotationally symmetrical.
円錐状の形状である請求項32に記載の大面積の機能性
堆積膜を連続的に形成する装置。(33) The apparatus for continuously forming a large-area functional deposited film according to claim 32, wherein the center conductor separating means has a cylindrical shape, a truncated conical shape, or a conical shape.
同調手段が配設される請求項19に記載の大面積の機能
性堆積膜を連続的に形成する装置。(34) The apparatus for continuously forming a large-area functional deposited film according to claim 19, wherein at least two tuning means are arranged on the microwave coaxial line.
部に突入された前記中心導体の挿入長調節機構である請
求項34に記載の大面積の機能性堆積膜を連続的に形成
する装置。(35) Continuously forming a large-area functional deposited film according to claim 34, wherein one of the two tuning means is an insertion length adjusting mechanism for the center conductor inserted into the film forming chamber. Device.
れる側の面には少なくとも導電性処理が施される請求項
19に記載の大面積の機能性堆積膜を連続的に形成する
装置。(36) The apparatus for continuously forming a large-area functional deposited film according to claim 19, wherein at least a conductive treatment is performed on the side of the band-shaped member exposed to the microwave plasma.
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP20785289A JPH0372083A (en) | 1989-08-14 | 1989-08-14 | Method and device for continuously forming large-area functional deposited film by microwave plasma cvd method |
US07/543,431 US5114770A (en) | 1989-06-28 | 1990-06-26 | Method for continuously forming functional deposited films with a large area by a microwave plasma cvd method |
DE69022664T DE69022664T2 (en) | 1989-06-28 | 1990-06-27 | Method and device for the continuous production of functional vapor-deposited films of large surface area by means of microwave plasma CVD. |
EP90112245A EP0411317B1 (en) | 1989-06-28 | 1990-06-27 | Method and apparatus for continuously forming functional deposited films with a large area by microwave plasma CVD |
CN90106810A CN1032021C (en) | 1989-06-28 | 1990-06-28 | Method and apparatus for continuously forming functional deposited films with large area by microwave plasma CVD method |
US08/426,629 US5527391A (en) | 1989-06-28 | 1995-04-21 | Method and apparatus for continuously forming functional deposited films with a large area by a microwave plasma CVD method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP20785289A JPH0372083A (en) | 1989-08-14 | 1989-08-14 | Method and device for continuously forming large-area functional deposited film by microwave plasma cvd method |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0372083A true JPH0372083A (en) | 1991-03-27 |
Family
ID=16546593
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP20785289A Pending JPH0372083A (en) | 1989-06-28 | 1989-08-14 | Method and device for continuously forming large-area functional deposited film by microwave plasma cvd method |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0372083A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63226284A (en) * | 1986-10-06 | 1988-09-20 | Hitachi Ltd | Separation and purification of amylase and adsorbent and apparatus used therefor |
WO2015025783A1 (en) * | 2013-08-21 | 2015-02-26 | コニカミノルタ株式会社 | Device for producing gas barrier film and method for producing gas barrier film |
JP5678369B2 (en) * | 2012-05-25 | 2015-03-04 | 株式会社ティサポート | CO2 recycling device and CO2 recycling system |
-
1989
- 1989-08-14 JP JP20785289A patent/JPH0372083A/en active Pending
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63226284A (en) * | 1986-10-06 | 1988-09-20 | Hitachi Ltd | Separation and purification of amylase and adsorbent and apparatus used therefor |
JPH0648982B2 (en) * | 1986-10-06 | 1994-06-29 | 株式会社日立製作所 | Method for separating and purifying amylase, adsorbent used therefor, and apparatus for separating and purifying the same |
JP5678369B2 (en) * | 2012-05-25 | 2015-03-04 | 株式会社ティサポート | CO2 recycling device and CO2 recycling system |
WO2015025783A1 (en) * | 2013-08-21 | 2015-02-26 | コニカミノルタ株式会社 | Device for producing gas barrier film and method for producing gas barrier film |
JPWO2015025783A1 (en) * | 2013-08-21 | 2017-03-02 | コニカミノルタ株式会社 | Gas barrier film manufacturing apparatus and gas barrier film manufacturing method |
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