JPH10310862A - Production of deposited coating and production of photovolatic element - Google Patents
Production of deposited coating and production of photovolatic elementInfo
- Publication number
- JPH10310862A JPH10310862A JP9122184A JP12218497A JPH10310862A JP H10310862 A JPH10310862 A JP H10310862A JP 9122184 A JP9122184 A JP 9122184A JP 12218497 A JP12218497 A JP 12218497A JP H10310862 A JPH10310862 A JP H10310862A
- Authority
- JP
- Japan
- Prior art keywords
- film
- chamber
- layer
- substrate
- transparent conductive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は光電変換素子の反射
層及びその上に積層される透明導電層の製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a reflective layer of a photoelectric conversion element and a transparent conductive layer laminated thereon.
【０００２】[0002]
【従来の技術】従来より、半導体層通過した光を反射層
により反射させて再び半導体層で吸収させる構成の光電
変換素子が知られている。更に半導体層と反射層との間
に金属酸化物などからなる透明導電層を介在させること
が知られている。また、反射層及び／又は透明導電層の
表面を凹凸構造（テキスチャー構造）にすることによ
り、反射光の光路長を伸ばすことが知られている。2. Description of the Related Art Conventionally, there has been known a photoelectric conversion element having a configuration in which light that has passed through a semiconductor layer is reflected by a reflection layer and is absorbed again by the semiconductor layer. Further, it is known that a transparent conductive layer made of a metal oxide or the like is interposed between the semiconductor layer and the reflection layer. It is also known that the surface of the reflective layer and / or the transparent conductive layer is made to have an uneven structure (texture structure) to extend the optical path length of the reflected light.
【０００３】たとえば米国特許４，４１９，５３３では
反射層が光電気変換部へ拡散しないように酸化亜鉛等の
バリア層を設ける技術とが開示されている。また、米国
特許４，５３２，３７２には反射層の上に透明導電層を
形成し半導体層の欠陥による短絡を防止する技術が開示
されている。For example, US Pat. No. 4,419,533 discloses a technique in which a barrier layer such as zinc oxide is provided so that a reflection layer does not diffuse into a photoelectric conversion unit. U.S. Pat. No. 4,532,372 discloses a technique for forming a transparent conductive layer on a reflective layer to prevent a short circuit due to a defect in a semiconductor layer.
【０００４】反射層としてはアルミニウムを用いること
が知られている。特開昭６２−２１１３７７では酸素ガ
スを供給し４重極質量分析計でその量を監視しつつ酸素
ガス流量を制御しながらスパッタリングをおこないアル
ミニウム膜を作製する方法が開示されており、アルミニ
ウムの粒径が制御できると示されている。It is known that aluminum is used as a reflective layer. Japanese Patent Application Laid-Open No. 62-21377 discloses a method for producing an aluminum film by supplying oxygen gas and performing sputtering while controlling the oxygen gas flow rate while monitoring the amount by a quadrupole mass spectrometer. It is shown that the diameter can be controlled.
【０００５】特開平０２−２９７７３７では不活性ガス
を１０ｍｔｏｒｒ以上の圧力に保ち腐食や変形欠陥を防
止したアルミニウム膜をスパッタリングする方法が開示
されている。特開平０５−１７１４３４では真空容器内
に残留空気を残した状態でアルミニウム膜をスパッタリ
ングし突起のないアルミニウム膜を形成する方法が開示
されている。Japanese Patent Application Laid-Open No. 02-297737 discloses a method of sputtering an aluminum film in which an inert gas is maintained at a pressure of 10 mtorr or more to prevent corrosion and deformation defects. Japanese Patent Application Laid-Open No. 05-171434 discloses a method in which an aluminum film is sputtered with residual air left in a vacuum vessel to form an aluminum film without protrusions.
【０００６】特開平０６−１１６７２３ではアルミニウ
ムをスパッタリングして作製する工程とこのアルミニウ
ム膜を窒素と酸素の混合ガスにさらす工程を繰り返すこ
とにより平滑なアルミニウム膜を得る方法が開示されて
いる。Japanese Patent Application Laid-Open No. 06-116723 discloses a method of obtaining a smooth aluminum film by repeating a process of manufacturing by sputtering aluminum and a process of exposing the aluminum film to a mixed gas of nitrogen and oxygen.
【０００７】特開平０６−１１６７２２では長尺基板を
移動させつつ、その上に金属層と透明導電層を連続して
スパッタ法で形成することが記載されている（Roll to
Roll法）。Japanese Patent Application Laid-Open No. 06-116722 describes that a metal layer and a transparent conductive layer are continuously formed thereon by a sputtering method while a long substrate is moved (Roll to
Roll method).
【０００８】[0008]
【発明が解決しようとする課題】反射層としてアルミニ
ウムを用い、その上に透明導電層を積層した光電変換素
子には以下の問題点があることが明らかになった。It has been found that a photoelectric conversion element in which aluminum is used as a reflection layer and a transparent conductive layer is laminated thereon has the following problems.
【０００９】アルミニウムの作製温度を高くすることは
密着性を高めたり、結晶性を高め凸凹を形成することに
なるが、アルミニウムの粒界が光を吸収し反射率が低下
してしまい半導体層での電気に変換できる光の量を低下
させていることが判明した。また、Roll to Roll方式の
装置で反射層と透明導電層を連続して作製する場合に反
射率が低下することが判明した。Increasing the manufacturing temperature of aluminum increases the adhesion, increases the crystallinity, and forms irregularities. However, the grain boundaries of aluminum absorb light and reduce the reflectivity. It has been found that the amount of light that can be converted into electricity is reduced. In addition, it has been found that the reflectivity decreases when a reflective layer and a transparent conductive layer are successively formed using a roll-to-roll system.
【００１０】また、真空装置内の膜が付着する構造物や
材料であるターゲットは定期的なメンテナンスが必要で
あり装置内部を大気状態にする必要がある。大気開放後
の膜作製では光電変換素子の変換効率が安定しないこと
があった。特に、Roll to Roll法では複数の成膜室が連
結しており、該成膜室を長尺基板が搬送されながら成膜
が行われる為、成膜時間が長時間に渡る。この場合、上
述の変換効率の不安定さが顕著に現れた。例えば、成膜
前に成膜時の温度条件で１２時間にわたる予備加熱を行
った後、成膜を開始し、１０時間経過後の装置で金属層
を作製した場合、該金属層を有する光起電力素子の変換
効率は最高の効率を有するものと比べて４％ほど低い変
換効率が得られる場合があった。[0010] Further, a target which is a structure or a material to which a film adheres in a vacuum apparatus needs regular maintenance, and the inside of the apparatus needs to be in an atmospheric state. In the production of the film after opening to the atmosphere, the conversion efficiency of the photoelectric conversion element was sometimes not stable. In particular, in the roll-to-roll method, a plurality of film formation chambers are connected, and film formation is performed while a long substrate is transported in the film formation chamber, so that the film formation time is long. In this case, the above-mentioned instability of the conversion efficiency was remarkable. For example, after performing preheating for 12 hours under the temperature conditions at the time of film formation before film formation, film formation is started, and when a metal layer is manufactured by an apparatus after 10 hours, a photovoltaic device having the metal layer is formed. In some cases, the conversion efficiency of the power element is about 4% lower than that of the power element having the highest efficiency.
【００１１】また真空排気を基板の幅方向に行う場合は
変換効率が幅方向に大きな分布を持つ場合もある。この
原因は明らかではないが成膜中の残留不純物ガス等の影
響で透明導電層の伝導状態が変動し半導体接合へ影響を
及ぼしている可能性もあると考えている。When the vacuum evacuation is performed in the width direction of the substrate, the conversion efficiency may have a large distribution in the width direction. Although the cause is not clear, it is considered that the conduction state of the transparent conductive layer may fluctuate due to the influence of the residual impurity gas during the film formation, which may affect the semiconductor junction.
【００１２】以上のように従来知られた方法だけでは所
望のテクスチャー構造で、反射率が高く、安価で、信頼
性の高い反射層と透明導電層を安定して得ることは容易
ではなかった。As described above, it has not been easy to obtain a reliable reflective layer and a transparent conductive layer with a desired texture structure, high reflectivity, low cost, and high reliability by using only the conventionally known method.
【００１３】[0013]
【課題を解決するための手段】成膜室を大気開放した後
に、該成膜室を減圧し、該成膜室を所定の成膜温度以上
に加熱した後、冷却または放冷し、該成膜室を所定の成
膜温度に設定し、基板上に金属反射層を形成する工程
と、該金属反射層表面に活性酸素を接触させる工程と、
透明導電層を形成する工程とを有することを特徴とする
堆積膜製造方法、及び該方法を用いて金属層、及び透明
導電層を形成した後、半導体層を形成する光起電力素子
の製造方法とする。After the film forming chamber is opened to the atmosphere, the pressure in the film forming chamber is reduced, and the film forming chamber is heated to a predetermined film forming temperature or higher, and then cooled or cooled. Setting the film chamber to a predetermined film formation temperature, forming a metal reflective layer on the substrate, and contacting active oxygen to the metal reflective layer surface,
Forming a transparent conductive layer, and a method for manufacturing a photovoltaic element in which a metal layer and a transparent conductive layer are formed using the method, and then a semiconductor layer is formed. And
【００１４】[0014]
〔光電変換素子の製造方法〕図１は本発明による光電変
換素子の断面の一例で、基板101上に反射層102、透明導
電層103、半導体層104、透明電極108、及び集電電極109
が順に積層されている。[Method of Manufacturing Photoelectric Conversion Element] FIG. 1 is an example of a cross section of a photoelectric conversion element according to the present invention. A reflection layer 102, a transparent conductive layer 103, a semiconductor layer 104, a transparent electrode 108, and a current collecting electrode 109 are formed on a substrate 101.
Are sequentially stacked.
【００１５】図２は図1に示す光電変換素子を長尺基板
上に作製するための製造装置の一例である。この装置に
より以下の手順で成膜がなされる。FIG. 2 shows an example of a manufacturing apparatus for manufacturing the photoelectric conversion element shown in FIG. 1 on a long substrate. Film formation is performed by this apparatus in the following procedure.
【００１６】（1）ロール状基板２０２を送り出し室２
０１から巻き取り室２１０に渡し、真空ポンプ２３９、
２４０で真空排気する。(1) The roll-shaped substrate 202 is delivered to the delivery chamber 2
01 to the winding chamber 210, and the vacuum pump 239,
Evacuate at 240.
【００１７】（2）所定の圧力まで真空排気した後、ガ
ス供給管２３０、２３３、２３４からアルゴンガス等の
不活性ガスを供給し、２３１、２３２のガス供給管から
は酸素ガスを供給し不図示の排気バルブの開度を調整し
所定の圧力に調整する。各室に備えたヒータユニット２
３６、２３７、２３８、２２４、２２５の複数本の赤外
線ランプを点灯し、装置内壁や仕切り板２２７、２２
８、２２９や基板２０４を加熱する。温度は基板近傍に
温度センサーを設けておき成膜時の温度以上に制御す
る。この時各処理室に電力を供給して放電を発生させる
ことが望ましい。(2) After evacuating to a predetermined pressure, an inert gas such as an argon gas is supplied from the gas supply pipes 230, 233, and 234, and an oxygen gas is supplied from the gas supply pipes 231 and 232 to supply the inert gas. The opening degree of the illustrated exhaust valve is adjusted to a predetermined pressure. Heater unit 2 provided in each room
36, 237, 238, 224, and 225, a plurality of infrared lamps are turned on, and the inner wall of the device and the partition plates 227 and 22
8, 229 and the substrate 204 are heated. The temperature is controlled to be higher than the temperature at the time of film formation by providing a temperature sensor near the substrate. At this time, it is desirable to supply electric power to each processing chamber to generate discharge.
【００１８】また成膜時温度以上に温度が到達してから
加熱用のランプを消し加熱時間程度冷却したのち再度加
熱しても良い。この温度サイクルプロセスは装置を構成
する材料を収縮させ、その結果、ガス溜りを解消する効
果がある。この事は特に装置の構成要素が複雑な場合に
効果があり、たとえば基板を所定の位置に保つために使
用される磁石を内部に備えたマグネットローラー２３５
等を使用する場合は効果が高い。Alternatively, the heating lamp may be turned off after the temperature reaches a temperature higher than the film forming temperature, cooled for about the heating time, and then heated again. This temperature cycling process has the effect of shrinking the material making up the device and, as a result, eliminating gas pools. This is particularly effective when the components of the device are complex, for example, a magnet roller 235 with magnets used to keep the substrate in place.
The effect is high when using etc.
【００１９】（3）所定の時間加熱した後、冷却または
放冷し、所定の成膜温度にする。この後サーボモータで
巻き取りロール２１１を回転させ基板１０１、２０４を
一定速度で搬送させてから成膜を開始する。(3) After heating for a predetermined time, it is cooled or left to cool to a predetermined film forming temperature. Thereafter, the take-up roll 211 is rotated by the servomotor to transport the substrates 101 and 204 at a constant speed, and then the film formation is started.
【００２０】（4）まず反射層作製室２０５でアルミニ
ウムまたはその含有物のターゲット２１４をカソード電
極とし直流電源２１９にてスパッタリングして反射層１
０２を作製する。マグネトロンスパッタリングを用いて
もよい。(4) First, in the reflective layer production chamber 205, the reflective layer 1 is sputtered by a DC power supply 219 using aluminum or its target 214 as a cathode electrode.
02 is manufactured. Magnetron sputtering may be used.
【００２１】（5）次に反射層を作製した基板２０４を
搬送し、酸素ガスを含む雰囲気で直流電源２２０、２２
１によりグロー放電を発生させる活性酸素処理室２０
６、２０７を通過させ反射層の表面１００をイオンやラ
ジカルや励起状態等の活性酸素に接触させる。なお活性
酸素処理室と反射層の作製室の間には隙間を狭くしアル
ゴン等の不活性ガスを流すガスゲート又はピンチバルブ
２２６を設けて、活性酸素処理室の酸素ガスが反射層作
製室に混入する量を制限している。(5) Next, the substrate 204 on which the reflection layer has been formed is transported, and DC power supplies 220 and 22 are placed in an atmosphere containing oxygen gas.
1. An active oxygen processing chamber 20 for generating glow discharge
6 and 207, the surface 100 of the reflective layer is brought into contact with active oxygen such as ions, radicals, and excited states. A gas gate or pinch valve 226 for narrowing the gap and flowing an inert gas such as argon is provided between the active oxygen processing chamber and the chamber for forming the reflective layer, and oxygen gas in the active oxygen processing chamber is mixed into the reflective layer manufacturing chamber. The amount to do is limited.
【００２２】（6）次に活性酸素処理室２０６、２０７
を通過した基板２０４を透明導電層作製室２０８、２０
９に搬送し酸化亜鉛を主成分とするターゲット２１７、
２１８に直流電源２２２、２２３にてスパッタリングし
て透明導電層１０３を作製して巻き取り室に巻き取る。
この時作製温度と直流電力を適当に選ぶことにより透明
導電層１０３の表面に数１００ｎｍの大きさの凹凸を作
製することができ光の散乱の効果を利用できる。第１図
ではこの凹凸を摸式的に強調して記している。(6) Next, the active oxygen processing chambers 206 and 207
The transparent conductive layer forming chambers 208 and 20
9, a target 217 containing zinc oxide as a main component,
The transparent conductive layer 103 is formed by sputtering the DC power supply 218 with DC power supplies 222 and 223, and wound into a winding chamber.
At this time, by appropriately selecting the production temperature and the DC power, irregularities having a size of several 100 nm can be produced on the surface of the transparent conductive layer 103, and the effect of light scattering can be utilized. In FIG. 1, the irregularities are schematically emphasized.
【００２３】以上のようにして基板上に反射層と透明電
極が連続して作製できる。なお、活性酸素処理室と透明
導電層作製室は透明導電層が酸化膜である場合は厳密に
空間を分離する必要はなく、膜の回り込みを低減する程
度の簡単な仕切り程度でも良い。As described above, the reflection layer and the transparent electrode can be continuously formed on the substrate. When the transparent conductive layer is an oxide film, it is not necessary to strictly separate the space between the active oxygen treatment chamber and the transparent conductive layer forming chamber, and a simple partition may be used to reduce the wraparound of the film.
【００２４】活性酸素処理室２０６、及び２０７にはア
ルゴンが混入し、透明導電層作製室２０８、及び２０９
には酸素ガスが混入する場合があるが、堆積する材料に
よってはガスゲート、ピンチバルブ等を設けてこれらの
処理室間を分離してもよい。Argon is mixed into the active oxygen processing chambers 206 and 207, and the transparent conductive layer forming chambers 208 and 209 are mixed.
May be mixed with oxygen gas, but depending on the material to be deposited, a gas gate, a pinch valve or the like may be provided to separate these processing chambers.
【００２５】透明導電層は図２に示すように複数の作製
室で堆積することが望ましく、特に作製室２０８での作
製温度を作製室２０９での作製温度より低くして堆積し
た透明導電層を有する光起電力素子は優れた特性を有す
ることがわかった。The transparent conductive layer is preferably deposited in a plurality of manufacturing chambers as shown in FIG. 2. In particular, the transparent conductive layer deposited at a lower manufacturing temperature in the manufacturing chamber 208 than in the manufacturing chamber 209 is used. It has been found that the photovoltaic element has excellent characteristics.
【００２６】更に別の堆積装置を用いて半導体層、透明
電極を作製し、集電電極が形成される。更に保護樹脂を
設けてもよい。A semiconductor layer and a transparent electrode are formed by using another deposition apparatus, and a current collecting electrode is formed. Further, a protective resin may be provided.
【００２７】この様な手順によって作製した反射層と透
明導電層は反射率が良好であり、反射した光が半導体層
で効果的に吸収され光電気変換効率が向上する。また長
時間にわたり特性に変化がなく信頼性も良い。The reflective layer and the transparent conductive layer produced by such a procedure have good reflectivity, and the reflected light is effectively absorbed by the semiconductor layer to improve the photoelectric conversion efficiency. In addition, there is no change in characteristics for a long time, and the reliability is good.
【００２８】前述の工程（2）における事前加熱と、光
起電力素子の変換効率が関係することを本発明者は見出
した。具体的には、工程（6）で形成する透明導電層103
表面の凹凸形状が事前加熱の時間によって変化する。本
発明者の実験で、事前加熱時間を0分から720分まで変化
させ、また加熱温度を250℃から600℃まで変化させ、変
換効率との関係を調べた。その結果を表に示す。表の横
軸は事前加熱温度、縦軸は加熱時間で、250℃・事前加熱
0分の場合を1とした時の変換効率を、1.0〜1.05を△、
1.05〜1.15を○、1.15より優れたものを◎で示した。The present inventor has found that the preheating in the above step (2) is related to the conversion efficiency of the photovoltaic element. Specifically, the transparent conductive layer 103 formed in step (6)
The surface irregularities change depending on the preheating time. In the experiment of the inventor, the relationship between the preheating time was changed from 0 minutes to 720 minutes and the heating temperature was changed from 250 ° C to 600 ° C, and the conversion efficiency was examined. The results are shown in the table. The horizontal axis in the table is the preheating temperature, and the vertical axis is the heating time, 250 ° C, preheating.
The conversion efficiency when the case of 0 minutes is 1 is 1.0 to 1.05,
1.05 to 1.15 were indicated by ○, and those superior to 1.15 were indicated by ◎.
【００２９】[0029]
【表１】 [Table 1]
【００３０】事前加熱により光電変換効率は改善される
が、加熱時間が長すぎると変換効率が低下することがわ
かった。この原因は明らかではないが、加熱時間が長す
ぎると透明導電層103表面の形状が光起電力素子に適し
た形状とならない、あるいはアルミニウム膜の結晶化が
進行し、粒界が発達し、この粒界が光を吸収して反射率
が低下する、等の理由が考えられる。したがって、事前
加熱は400℃から500℃の範囲で、かつ15分から120分の
範囲で実施する事が好適である。It has been found that the photoelectric conversion efficiency is improved by preheating, but the conversion efficiency is reduced if the heating time is too long. Although the cause is not clear, if the heating time is too long, the shape of the surface of the transparent conductive layer 103 does not become a shape suitable for the photovoltaic element, or crystallization of the aluminum film proceeds, and grain boundaries develop, It is considered that the grain boundary absorbs light and the reflectance is reduced. Therefore, it is preferable that the preheating is performed in the range of 400 ° C. to 500 ° C. and in the range of 15 minutes to 120 minutes.
【００３１】なおここでは例としてRoll to Roll方式を
示したが、本発明はこの方式に限らず、長尺基板を間欠
的に搬送する方式や、枚葉式のインライン方式にも適用
できる。Although the Roll to Roll method has been described as an example here, the present invention is not limited to this method, and can be applied to a method of intermittently transporting a long substrate or a single-wafer type in-line method.
【００３２】〔光電変換素子の構成要素〕 （基板１０１）基板１０１は金属や合金あるいはその積
層品、カーボンシート、ポリイミドなどの樹脂フィルム
などが使用可能である。これらはロール状で利用できる
ため連続作製に好適である。その表面が導電性を有する
場合には光起電力素子の一方の電極も兼ねる事ができ
る。[Components of Photoelectric Conversion Element] (Substrate 101) As the substrate 101, a metal or alloy or a laminate thereof, a carbon sheet, a resin film such as polyimide, or the like can be used. Since these can be used in the form of a roll, they are suitable for continuous production. When the surface has conductivity, it can also serve as one electrode of the photovoltaic element.
【００３３】また用途によってはシリコン等の結晶基
板、ガラスやセラミックスの板を用いる事もできる。基
板の表面は研磨や洗浄をしても良いが、そのまま用いて
も良い。また表面に凹凸を有したものも使用可能であ
る。また、ＳＵＳ４３０のような磁性体を用いると磁石
を内蔵したローラで位置を正確に制御しつつ搬送するこ
とも可能である。Depending on the application, a crystal substrate of silicon or the like, or a glass or ceramic plate may be used. The surface of the substrate may be polished or cleaned, but may be used as it is. Further, those having irregularities on the surface can also be used. When a magnetic material such as SUS430 is used, it is possible to convey while controlling the position accurately with a roller having a built-in magnet.
【００３４】（反射層１０２）反射層１０２はＡｌ、Ａ
ｇ、Ｃｕ等が用いられる。Ａｌはマイグレーションの問
題が生じないためとくに好適に用いられる。その表面は
平滑であっても、凹凸を有していてもよい。スパッタリ
ング法や真空蒸着法や化学的気相成長法やイオンプレー
ティング法やイオンビーム法などで作製できる。(Reflective Layer 102) The reflective layer 102 is made of Al, A
g, Cu, etc. are used. Al is particularly preferably used because no migration problem occurs. The surface may be smooth or may have irregularities. It can be manufactured by a sputtering method, a vacuum evaporation method, a chemical vapor deposition method, an ion plating method, an ion beam method, or the like.
【００３５】図２を用いて反射層１０２の形成方法の一
例である直流マグネトロンスパッタリング法について述
べる。２０５は作製室であり、排気ポンプ２４０で真空
排気できる。この作製室に、不図示のガスボンベに接続
されたガス導入管２３０より、アルゴン等の不活性ガス
をマスフローコントローラを用いて所定流量導入させ、
排気弁の開度を調整し作製室２０５内を所定の圧力とす
る。２１４はターゲットで、その内部に不図示の磁石を
備えたカソード電極がある。カソード電極には直流電源
２１９が接続され電力を供給してスパッタリングを行
う。A DC magnetron sputtering method, which is an example of a method for forming the reflection layer 102, will be described with reference to FIG. Reference numeral 205 denotes a production chamber, which can be evacuated by an exhaust pump 240. Into this production chamber, an inert gas such as argon is introduced at a predetermined flow rate using a mass flow controller from a gas introduction pipe 230 connected to a gas cylinder (not shown),
The opening degree of the exhaust valve is adjusted to make the inside of the manufacturing chamber 205 a predetermined pressure. A target 214 has a cathode electrode provided with a magnet (not shown) therein. A DC power supply 219 is connected to the cathode electrode to supply power and perform sputtering.
【００３６】（活性酸素処理とガスゲート）作製した反
射層を接触させる活性酸素の発生方法としては、アノー
ド電極とカソード電極を用いる直流法、交流法、高周波
法やホロカソードタイプなどのイオンビーム法やマイク
ロウェーブ法が利用できる。酸素ガスを供給し放電を発
生させた空間たとえば第２図の２０６、２０７に反射層
の形成された基板２０４を通過させれば良い。(Active Oxygen Treatment and Gas Gate) As a method for generating active oxygen for bringing the produced reflective layer into contact, an ion beam method such as a direct current method using an anode electrode and a cathode electrode, an alternating current method, a high frequency method, a hollow cathode type, and the like. A microwave method can be used. The substrate 204 having the reflective layer may be passed through a space where oxygen gas is supplied to generate a discharge, for example, 206 and 207 in FIG.
【００３７】この時、活性酸素処理室から反射層の作製
室への酸素の混入は反射率を低下させる別の要因となる
ため一定量以下に制限する必要がある。この方法として
は一般的に知られているような隙間を狭くかつ長くして
コンダクタンスを小さくしたゲート２２６などが効果的
である。さらにこのゲート２２６に不活性ガス等を基板
上下面に供給することにより雰囲気ガスの分離性能を上
げることも可能である。また、ピンチバルブを用い、成
膜処理又は活性酸素処理時にロール状基板の移動を停止
し、バルブを閉じてもよい。At this time, the incorporation of oxygen from the active oxygen processing chamber into the chamber for forming the reflection layer is another factor that lowers the reflectance, so it is necessary to limit the mixing to a certain amount or less. As this method, it is effective to use a generally known gate 226 having a narrow and long gap to reduce conductance. Further, by supplying an inert gas or the like to the gate 226 to the upper and lower surfaces of the substrate, it is possible to improve the separation performance of the atmospheric gas. Alternatively, a pinch valve may be used to stop the movement of the roll-shaped substrate during the film forming process or the active oxygen process, and then close the valve.
【００３８】（透明導電層１０３）透明導電層１０３も
スパッタリング法や真空蒸着法や化学的気相成長法やイ
オンプレーティング法やイオンビーム法などで作製でき
る。反射層まで光を透過させるため透明度が高いことが
望ましい。また、半導体層の欠陥を通じて流れる電流を
抑制するため適度の抵抗を持つことが望ましい。具体的
には導電率が１０-8（１／Ωｃｍ）以上、１０-1（１／
Ωｃｍ）以下であることが望ましい。(Transparent Conductive Layer 103) The transparent conductive layer 103 can also be formed by a sputtering method, a vacuum evaporation method, a chemical vapor deposition method, an ion plating method, an ion beam method, or the like. It is desirable that the transparency be high in order to transmit light to the reflective layer. Further, it is desirable to have an appropriate resistance in order to suppress a current flowing through a defect in the semiconductor layer. Specifically, the conductivity is 10 -8 (1 / Ωcm) or more and 10 -1 (1 / Ωcm).
Ωcm) or less.
【００３９】材料としては酸化亜鉛や酸化チタンや酸化
インジウムや酸化錫またはその含有物などが利用でき
る。酸化物を利用する場合には活性酸素処理室と同じ真
空装置内で連続して作製することも可能である。また作
製条件を適当に選ぶことにより表面に数１００ｎｍの大
きさの凹凸を作製することができ光の散乱の効果を利用
できる。例えば第１の透明導電層を比較的低い成膜温度
で形成し、その上に第２の透明導電層を第１の透明導電
層成膜温度より高い温度で形成することにより、下地と
の密着性を確保しつつ好適な凹凸形状を形成することが
できる。As the material, zinc oxide, titanium oxide, indium oxide, tin oxide or a substance containing the same can be used. When an oxide is used, it can be manufactured continuously in the same vacuum apparatus as the active oxygen processing chamber. Also, by appropriately selecting the manufacturing conditions, unevenness having a size of several 100 nm can be formed on the surface, and the effect of light scattering can be utilized. For example, the first transparent conductive layer is formed at a relatively low deposition temperature, and the second transparent conductive layer is formed thereon at a temperature higher than the first transparent conductive layer deposition temperature, so that the first transparent conductive layer can be adhered to the base. It is possible to form a suitable uneven shape while ensuring the property.
【００４０】（半導体層１０４）半導体層１０４は非単
結晶半導体が好適に用いられ、その作成には高周波電力
やマイクロウェーブ電力を利用するＣＶＤ装置などが利
用できる。半導体層１０４は反射層１０２及び透明導電
層１０３の成膜装置と単一の真空室を構成するように連
結した成膜装置で形成してもよいし、別の装置で形成し
てもよい。(Semiconductor Layer 104) As the semiconductor layer 104, a non-single-crystal semiconductor is preferably used, and a CVD device using high-frequency power or microwave power can be used for the formation thereof. The semiconductor layer 104 may be formed by a film formation apparatus connected to a film formation apparatus of the reflective layer 102 and the transparent conductive layer 103 so as to form a single vacuum chamber, or may be formed by another apparatus.
【００４１】真空室内に材料ガスとして ＳｉＨ4 、Ｓ
ｉＦ4 、ＰＨ3 、Ｈ2などを供給し、電力を投入して、
これによりｎ型 ａ−Ｓｉ層１０５が透明導電層１０３
上に形成できる。さらにＳｉＨ4 、ＳｉＦ4 、Ｈ2など
を用い、これによりｉ型 ａ−Ｓｉ層１０６がｎ型 ａ−
Ｓｉ層１０５上に形成でき、今度はＳｉＨ4 、ＢＦ3、
Ｈ2などを用い、ｐ型μｃ−Ｓｉ層１０７が ｉ型ａ−Ｓ
ｉ層１０６上に形成でき、ｎｉｐの半導体接合が形成で
きる。この半導体層はアモルファスやマイクロクリスタ
ルに制限されず、ｎｉｐの構成もｐｉｎでも可能であ
り、半導体接合も複数層も受けても良い。SiH 4, S as material gases in a vacuum chamber
Supply iF4, PH3, H2, etc., turn on the power,
As a result, the n-type a-Si layer 105 becomes transparent conductive layer 103
Can be formed on. Further, SiH4, SiF4, H2, or the like is used, so that the i-type a-Si layer 106 becomes an n-type a-
Can be formed on the Si layer 105, this time SiH4, BF3,
The p-type μc-Si layer 107 is made of i-type a-S
A nip semiconductor junction can be formed on the i-layer 106. This semiconductor layer is not limited to amorphous or microcrystal, and the configuration of the nip may be a pin, and a semiconductor junction or a plurality of layers may be used.
【００４２】（透明電極１０８）透明電極１０８は半導
体層を介した基板とは反対側の電極を兼ね、低抵抗であ
ることが望ましい。酸化インジウムや酸化錫や酸化チタ
ンや酸化亜鉛やその混合物などを原材料にし、抵抗加熱
や電子ビームによる真空蒸着法やスパッタリング法、Ｃ
ＶＤ法、スプレー法、浸積法等で作製できる。良好な反
射防止効果を得るために透明電極の膜厚は、主に反射を
防止したい光の波長に比べ、反射防止膜の屈折率の４倍
分の１程度が良い。また屈折率の異なる材料を積層する
構成でも良い。(Transparent Electrode 108) The transparent electrode 108 also serves as an electrode on the side opposite to the substrate via the semiconductor layer, and preferably has a low resistance. Using indium oxide, tin oxide, titanium oxide, zinc oxide or a mixture thereof as a raw material, resistance heating, vacuum evaporation method using electron beam, sputtering method, C
It can be produced by a VD method, a spray method, an immersion method, or the like. In order to obtain a good anti-reflection effect, the thickness of the transparent electrode is preferably about one-fourth of the refractive index of the anti-reflection film as compared with the wavelength of the light whose reflection is mainly desired to be prevented. Alternatively, a structure in which materials having different refractive indexes are stacked may be used.
【００４３】（集電電極１０９）透明電極の上には電流
を効率よく集電するために、格子状の集電電極１０９を
設けてもよい。集電電極の形成方法としては、マスクパ
ターンを用いたスパッタリング、抵抗加熱、ＣＶＤ法
や、全面に金属膜を蒸着した後で不必要な部分をエッチ
ングで取り除きパターニングする方法、光ＣＶＤにより
直接グリッド電極パターンを形成する方法、グリッド電
極パターンのネガパターンのマスクを形成した後にメッ
キする方法、導電性ペーストを印刷する方法、金属線を
導電性ペーストで固着する方法などがある。(Current Collecting Electrode 109) A grid-like current collecting electrode 109 may be provided on the transparent electrode in order to efficiently collect current. As a method of forming the current collecting electrode, sputtering using a mask pattern, resistance heating, CVD method, a method of removing unnecessary portions by etching after depositing a metal film on the entire surface and patterning, a grid electrode directly by optical CVD There are a method of forming a pattern, a method of plating after forming a mask of a negative pattern of a grid electrode pattern, a method of printing a conductive paste, and a method of fixing a metal wire with a conductive paste.
【００４４】なおこの後、必要に応じて起電力を取り出
すために出力端子１１０を基板と集電電極に取り付けて
もよい。さらに必要に応じて樹脂フィルムを接着するな
どして保護樹脂１１１を設けてもよい。同時に鋼板等の
補強材を併用してもよい。After that, the output terminal 110 may be attached to the substrate and the current collecting electrode to take out the electromotive force if necessary. Further, if necessary, the protective resin 111 may be provided by bonding a resin film or the like. At the same time, a reinforcing material such as a steel plate may be used in combination.
【００４５】[0045]
（実施例１）本実施例においては、図１の断面模式図に
示す構成の光電変換素子を図２の装置で作成した。(Example 1) In this example, a photoelectric conversion element having the structure shown in the schematic sectional view of FIG. 1 was produced by the apparatus shown in FIG.
【００４６】図２の装置をメンテナンス等の為に大気開
放した後、ロール状基板２０２を基板送り出し室２０１
にセットし、反射層作製室２０５、活性酸素処理室２０
６、２０７、透明導電層作製室２０８、２０９それぞれ
に基板２０４を貫通させ、基板巻き取り室２１０のロー
ル２１１に固定する。基板２０４には幅１２０ｍｍ、厚
さ ０．１５ｍｍ、長さ１５０ｍ の表面に凹凸をダル仕
上げで残したＳＵＳ４３０を使用した。After the apparatus of FIG. 2 is opened to the atmosphere for maintenance or the like, the roll-shaped substrate 202 is transferred to the substrate delivery chamber 201.
And the reflective layer production chamber 205 and the active oxygen treatment chamber 20
6, 207 and the transparent conductive layer forming chambers 208 and 209, respectively, are passed through the substrate 204, and are fixed to the roll 211 of the substrate winding chamber 210. For the substrate 204, SUS430 having a width of 120 mm, a thickness of 0.15 mm, and a length of 150 m, which had irregularities left by dull finishing on its surface, was used.
【００４７】続いて圧力が１０-4ｔｏｒｒ以下になるま
で排気した。この後反射層作製室２０５と透明導電層作
製室２０８、２０９にガス供給管２３０、２３３、２３
４から不活性ガスとしてアルゴンガスを各々３０ｓｃｃ
ｍ供給し、活性酸素処理室２０６、２０７へは酸素ガス
をガス供給管２３１、２３２から各々１０ｓｃｃｍ供給
した。またゲート２２６へもアルゴンガスを３０ｓｃｃ
ｍ供給した。この状態で排気バルブの開度を調整して真
空室内の圧力を３ｍＴｏｒｒに保った。Subsequently, the air was evacuated until the pressure became 10 -4 torr or less. Thereafter, the gas supply pipes 230, 233, and 23 are inserted into the reflection layer production chamber 205 and the transparent conductive layer production chambers 208, 209.
4 to 30 scc each of argon gas as an inert gas
m, and oxygen gas was supplied to the active oxygen processing chambers 206 and 207 from the gas supply pipes 231 and 232, respectively, at 10 sccm. Argon gas is also supplied to the gate 226 at 30 scc.
m. In this state, the opening degree of the exhaust valve was adjusted to maintain the pressure in the vacuum chamber at 3 mTorr.
【００４８】反射層作製室２０５、活性酸素処理室２０
６、２０７、透明導電層作製室２０８、２０９それぞれ
に１００ｗの赤外線ランプ６本セットにしたヒータユニ
ット２３６、２３７、２３８、２２４、２２５をステン
レス製の反射板と共に設けておき基板の成膜面の反対の
表面に熱電対を接触させて４００℃になるよう温度を制
御して加熱した。設定温度に約１５分で到達した後２時
間この状態を保った後、反射層作製室２０５、活性酸素
処理室２０６、２０７のヒータを消し、透明導電層作製
室２０８の設定温度を１５０℃に下げ、透明導電層作製
室２０９の設定温度を２５０℃に下げた。約３０分で透
明導電層作製室の温度が設定温度まで下がった。The reflection layer forming chamber 205 and the active oxygen processing chamber 20
6, 207, and heater units 236, 237, 238, 224, and 225, each of which is a set of six 100-watt infrared lamps, are provided in each of the transparent conductive layer forming chambers 208 and 209 together with a stainless steel reflecting plate. A thermocouple was brought into contact with the opposite surface and the temperature was controlled so as to be 400 ° C. and heating was performed. After reaching the set temperature in about 15 minutes and maintaining this state for 2 hours, the heaters in the reflective layer forming chamber 205 and the active oxygen processing chambers 206 and 207 are turned off, and the set temperature in the transparent conductive layer forming chamber 208 is set to 150 ° C. The temperature of the transparent conductive layer preparation chamber 209 was lowered to 250 ° C. In about 30 minutes, the temperature of the transparent conductive layer production chamber dropped to the set temperature.
【００４９】続いてサーボモータを動作し巻き取りロー
ル２１１を回転させ毎分１７０ｍｍで基板２０４の搬送
を開始した。Subsequently, the take-up roll 211 was rotated by operating the servo motor, and the transfer of the substrate 204 was started at 170 mm / min.
【００５０】反射層作製用のターゲット２１４には純度
９９．９９重量％のアルミニウムを使用し、２５ｃｍ×
２５ｃｍの大きさで、４００Ｗの直流電力を印加した。
基板２０４がターゲット２１４上を通過する約９０秒の
間に約２００ｎｍの厚みのアルミニウム反射層１０１を
作製した。As the target 214 for forming the reflective layer, aluminum having a purity of 99.99% by weight was used.
A DC power of 400 W was applied with a size of 25 cm.
The aluminum reflective layer 101 having a thickness of about 200 nm was formed in about 90 seconds when the substrate 204 passed over the target 214.
【００５１】活性酸素処理室２０６、２０７のカソード
電極２１５、２１６には各々４０Ｗの直流電力を印加し
た。反射層を作成された基板２０４は続き搬送され活性
酸素処理室を通過する約１８０秒の間、酸素ガスを含む
プラズマに接触する。なお本実施例ではカソード電極２
１５にはアルミニウムのターゲットを使用し、カソード
２１６では酸化亜鉛のターゲットを使用した。どちらも
純度９９．９９重量％、２５ｃｍ×２５ｃｍの大きさで
あった。A DC power of 40 W was applied to the cathode electrodes 215 and 216 of the active oxygen processing chambers 206 and 207, respectively. The substrate 204 on which the reflective layer is formed is subsequently brought into contact with a plasma containing oxygen gas for about 180 seconds while passing through the active oxygen processing chamber. In this embodiment, the cathode electrode 2
An aluminum target was used for 15 and a zinc oxide target was used for the cathode 216. Both had a purity of 99.99% by weight and a size of 25 cm × 25 cm.
【００５２】透明導電層作製室２０８、２０９に基板２
０４を引き続き搬送した。純度９９．９９重量％、２５
ｃｍ×２５ｃｍの大きさの酸化亜鉛ターゲット２１７、
２１８を用いて各々２８００Ｗの直流電力を印加した。
空間を通過する約１８０秒の間に酸化亜鉛の透明導電層
１０３が約１０００ｎｍ作製できた。なおこの時透明導
電層の表面に高低差が数１００ｎｍの大きさの凹凸が発
達した。The substrate 2 was placed in the transparent conductive layer forming chambers 208 and 209.
04 was subsequently transported. Purity 99.99% by weight, 25
a zinc oxide target 217 having a size of cm × 25 cm,
218 were used to apply a DC power of 2800 W each.
A transparent conductive layer 103 of zinc oxide having a thickness of about 1000 nm was formed in about 180 seconds after passing through the space. At this time, irregularities having a height difference of several 100 nm developed on the surface of the transparent conductive layer.
【００５３】透明導電層まで作製した基板２０４は巻き
取り室２１０で巻き取った。なお透明導電層の表面を傷
つけないようにポリエステルフィルムの合紙２１３を巻
き取り時基板と基板の間にはさみ込んだ。The substrate 204 formed up to the transparent conductive layer was wound in a winding chamber 210. Note that the interleaving paper 213 made of a polyester film was sandwiched between the substrates during winding so as not to damage the surface of the transparent conductive layer.
【００５４】このような状態を約１０時間保ち、毎分１
７０ｍｍの搬送速度で約１００ｍにわたり反射層と透明
導電層を作製した。This state is maintained for about 10 hours, and 1 minute per minute.
The reflection layer and the transparent conductive layer were formed over a distance of about 100 m at a conveyance speed of 70 mm.
【００５５】この反射層と透明導電層の形成された基板
の一部を取りだし分光光度計で反射率を測定したところ
８００ｎｍの波長で、比較例１の反射率を１００％とし
て比べた時、１２０％の高い反射率であった。A part of the substrate on which the reflective layer and the transparent conductive layer were formed was taken out, and the reflectance was measured by a spectrophotometer. When the reflectance of Comparative Example 1 was set to 100% at a wavelength of 800 nm, 120 %.
【００５６】さらに反射層と透明導電層の形成された基
板を５ｃｍ×５ｃｍの大きさに切断し、市販の容量結合
型高周波ＣＶＤ装置にセットした。排気ポンプにて、反
応容器の排気管を介して、荒引き、高真空引き操作を行
った。この時、基板の表面温度は２５０℃となるよう、
温度制御機構により制御した。十分に排気が行われた時
点で、ガス導入管より、Ｓｉ2Ｈ6１ｓｃｃｍ、ＰＨ3 ／
Ｈ2(１％Ｈ2希釈)０．５ｓｃｃｍ、Ｈ2４０ｓｃｃｍを
導入し、スロットルバルブの開度を調整して、反応容器
の内圧を１ｔｏｒｒに保持し、圧力が安定したところ
で、直ちに高周波電源より３Ｗの電力を投入した。プラ
ズマは１８０秒間持続させた。これにより、ｎ型 ａ−
Ｓｉ層１０５が透明層１０３上に形成された。再び排気
をした後に、今度はガス導入管よりＳｉ2Ｈ6４０ｓｃｃ
ｍ、Ｈ2４０ｓｃｃｍを導入し、スロットルバルブの開
度を調整して、反応容器の内圧を１ｔｏｒｒに保持し、
圧力が安定したところで、直ちに高周波電源より２Ｗの
電力を投入し、プラズマは600秒間持続させた。これに
よりｉ型a-Ｓｉ層１０６がｎ型 ａ−Ｓｉ層１０５上に
形成された。再び排気をした後に、今度はガス導入管よ
りＳｉＨ4 ／Ｈ2（１０％Ｈ2希釈）０．５ｓｃｃｍ、
ＢＦ3／Ｈ2（１％Ｈ2希釈）１ｓｃｃｍ、Ｈ2５０ｓｃｃ
ｍを導入し、スロットルバルブの開度を調整して、反応
容器の内圧を１ｔｏｒｒに保持し、圧力が安定したとこ
ろで、直ちに高周波電源より２００Ｗの電力を投入し
た。プラズマは120秒間持続させた。これによりｐ型μ
ｃ−Ｓｉ層１０７がｉ型 ａ−Ｓｉ層１０６上に形成さ
れた。Further, the substrate on which the reflective layer and the transparent conductive layer were formed was cut into a size of 5 cm × 5 cm, and set in a commercially available capacitively coupled high-frequency CVD apparatus. Rough evacuation and high vacuum evacuation operations were performed by an evacuation pump through the evacuation pipe of the reaction vessel. At this time, the surface temperature of the substrate becomes 250 ° C.
Controlled by a temperature control mechanism. When the gas was sufficiently exhausted, 1 sccm of Si 2 H 6 and PH 3 /
0.5 sccm of H2 (1% H2 dilution) and 40 sccm of H2 were introduced, the opening degree of the throttle valve was adjusted, the internal pressure of the reaction vessel was maintained at 1 torr. I put it in. The plasma was maintained for 180 seconds. Thereby, the n-type a-
An Si layer 105 was formed on the transparent layer 103. After exhausting again, this time, 40 scc of Si 2 H 6 was
m, 40 sccm of H 2 were introduced, the opening of the throttle valve was adjusted, and the internal pressure of the reaction vessel was maintained at 1 torr.
Immediately after the pressure was stabilized, 2 W of power was supplied from the high frequency power supply, and the plasma was maintained for 600 seconds. Thus, an i-type a-Si layer 106 was formed on the n-type a-Si layer 105. After evacuating again, this time, 0.5 sccm of SiH 4 / H 2 (10% H 2 dilution) was introduced from the gas inlet tube.
BF 3 / H 2 (1% H 2 dilution) 1 sccm, H 2 50 scc
m, the opening of the throttle valve was adjusted, the internal pressure of the reaction vessel was maintained at 1 torr, and when the pressure was stabilized, 200 W of electric power was immediately supplied from the high frequency power supply. The plasma was maintained for 120 seconds. This gives the p-type μ
The c-Si layer 107 was formed on the i-type a-Si layer 106.
【００５７】次に試料を高周波ＣＶＤ装置より取り出
し、ＤＣマグネトロンスパッタ装置のアノードの表面に
取り付け、ステンレススティールのマスクで試料の周囲
を遮蔽して、中央部４．５ｃｍ×４．５ｃｍの領域に１
０重量％の酸化錫と９０重量％の酸化インジウムからな
るターゲットを用いてスパッタリングした。堆積条件は
基板温度２００℃、不活性ガスとしてアルゴンの流量５
０ｓｃｃｍ 、酸素ガス０．５ｓｃｃｍ、堆積室内の圧
力３ｍＴｏｒｒ、ターゲットの単位面積当たりの投入電
力量 ０．２Ｗ／ｃｍ2にて約１００秒で厚さが６０ｎｍ
となるように堆積した。膜の厚みは前もって同じ条件で
堆積時間との関係を検量して堆積することにより所定の
厚みとした。Next, the sample was taken out of the high-frequency CVD apparatus, attached to the surface of the anode of the DC magnetron sputtering apparatus, and the periphery of the sample was shielded with a stainless steel mask.
Sputtering was performed using a target composed of 0% by weight of tin oxide and 90% by weight of indium oxide. The deposition conditions were a substrate temperature of 200 ° C. and a flow rate of argon as an inert gas of 5
0 sccm, oxygen gas 0.5 sccm, pressure in the deposition chamber 3 mTorr, input electric power per unit area of target 0.2 W / cm 2, thickness is 60 nm in about 100 seconds.
It deposited so that it might become. The thickness of the film was adjusted to a predetermined thickness by previously calibrating the relationship with the deposition time under the same conditions.
【００５８】以上のようにして作製した試料に銀ペース
トをスクリーン印刷して集電電極１０９を面積の２％の
領域に形成し出力端子１１０を付け、保護樹脂１１１を
接着した。ＡＭ１.５（１００ｍＷ／ｃｍ2）の光照射下
にて特性評価を行ったところ、光電変換効率で比較例１
の変換効率を１００％として比べた時、１２０％の優れ
た変換効率が得られた。A silver paste was screen-printed on the sample prepared as described above to form a collecting electrode 109 in a region of 2% of the area, an output terminal 110 was attached, and a protective resin 111 was adhered. The characteristics were evaluated under irradiation of light of AM 1.5 (100 mW / cm 2).
When the conversion efficiency was compared with 100%, an excellent conversion efficiency of 120% was obtained.
【００５９】さらにこのサンプルを温度８５℃、湿度８
５％の環境試験箱による１０００時間の環境試験を行っ
た。変換効率の変化は０．０２％低下しただけで全く問
題なかった。Further, this sample was subjected to a temperature of 85 ° C. and a humidity of 8
An environmental test was conducted for 1000 hours using a 5% environmental test box. The change in conversion efficiency was only 0.02%, and was no problem at all.
【００６０】（実施例２）真空排気およびガス供給後、
ヒータユニット２３６、２３７、２３８、２２４、２２
５を５００℃になるよう温度を制御して２時間加熱した
以外は実施例１と同じ条件で作製した。Example 2 After evacuation and gas supply,
Heater units 236, 237, 238, 224, 22
5 was manufactured under the same conditions as in Example 1 except that the temperature was controlled to 500 ° C. and heated for 2 hours.
【００６１】途中反射層と透明導電層の形成された基板
を分光光度計で反射率を測定したところ８００ｎｍの波
長で比較例１の反射率を１００％として比べた時、１２
０％の高い反射率であった。また完成後ＡＭ１.５（１
００ｍＷ／ｃｍ2）の光照射下にて特性評価を行ったと
ころ、光電変換効率で比較例１の変換効率を１００％と
して比べた時、１２０％の優れた変換効率が得られた。The reflectance of the substrate on which the reflective layer and the transparent conductive layer were formed was measured with a spectrophotometer. When the reflectance of Comparative Example 1 was set to 100% at a wavelength of 800 nm, 12
The reflectance was as high as 0%. After completion of AM 1.5 (1
When the characteristics were evaluated under light irradiation of (00 mW / cm2), an excellent conversion efficiency of 120% was obtained when the conversion efficiency of Comparative Example 1 was set to 100% in terms of photoelectric conversion efficiency.
【００６２】さらにこのサンプルを温度８５℃、湿度８
５％の環境試験箱による１０００時間の環境試験を行っ
た。変換効率の変化は０．０３％低下しただけで全く問
題なかった。Further, this sample was subjected to a temperature of 85 ° C. and a humidity of 8
An environmental test was conducted for 1000 hours using a 5% environmental test box. The change in the conversion efficiency was reduced by only 0.03% without any problem.
【００６３】（実施例３）真空排気およびガス供給後、
ヒータユニット２３６、２３７、２３８、２２４、２２
５を４００℃になるよう温度を制御して加熱した。設定
温度に約１５分で設定温度に到達した後約１５分この状
態を保った後ヒータを消し約１５分放置した。この後再
度４００℃になるよう制御して加熱し約１０分後設定温
度に到達した後約１５分この状態を保った以外は実施例
１と同じ条件で作製した。Example 3 After evacuation and gas supply,
Heater units 236, 237, 238, 224, 22
5 was heated to 400 ° C. while controlling the temperature. After reaching the set temperature in about 15 minutes, this state was maintained for about 15 minutes, then the heater was turned off and left for about 15 minutes. Thereafter, heating was performed again by controlling the temperature to 400 ° C., and after reaching the set temperature after about 10 minutes, this state was maintained for about 15 minutes.
【００６４】途中反射層と透明導電層の形成された基板
を分光光度計で反射率を測定したところ８００ｎｍの波
長で比較例１の反射率を１００％として比べた時、１２
０％の高い反射率であった。また完成後ＡＭ１.５（１
００ｍＷ／ｃｍ2）の光照射下にて特性評価を行ったと
ころ、光電変換効率で比較例１の変換効率を１００％と
して比べた時、１２０％の優れた変換効率が得られた。The reflectance of the substrate on which the reflective layer and the transparent conductive layer were formed was measured with a spectrophotometer. When the reflectance of Comparative Example 1 was set to 100% at a wavelength of 800 nm, 12
The reflectance was as high as 0%. After completion of AM 1.5 (1
When the characteristics were evaluated under light irradiation of (00 mW / cm2), an excellent conversion efficiency of 120% was obtained when the conversion efficiency of Comparative Example 1 was set to 100% in terms of photoelectric conversion efficiency.
【００６５】さらにこのサンプルを温度８５℃、湿度８
５％の環境試験箱による１０００時間の環境試験を行っ
た。変換効率の変化は０．０３％低下しただけで全く問
題なかった。Further, this sample was subjected to a temperature of 85 ° C. and a humidity of 8
An environmental test was conducted for 1000 hours using a 5% environmental test box. The change in the conversion efficiency was reduced by only 0.03% without any problem.
【００６６】（実施例４）真空排気およびガス供給後、
ヒータユニット２３６、２３７、２３８、２２４、２２
５を４００℃になるよう温度を制御して１時間加熱した
以外は実施例１と同じ条件で作製した。Example 4 After evacuation and gas supply,
Heater units 236, 237, 238, 224, 22
5 was heated under the same conditions as in Example 1 except that the temperature was controlled to 400 ° C. and heated for 1 hour.
【００６７】途中反射層と透明導電層の形成された基板
を分光光度計で反射率を測定したところ８００ｎｍの波
長で比較例１の反射率を１００％として比べた時、１２
０％の高い反射率であった。また完成後ＡＭ１.５（１
００ｍＷ／ｃｍ2）の光照射下にて特性評価を行ったと
ころ、光電変換効率で比較例１の変換効率を１００％と
して比べた時、１１７％の優れた変換効率が得られた。The reflectance of the substrate on which the reflective layer and the transparent conductive layer were formed was measured with a spectrophotometer. When the reflectance of Comparative Example 1 was set to 100% at a wavelength of 800 nm, the reflectance was 12%.
The reflectance was as high as 0%. After completion of AM 1.5 (1
When the characteristics were evaluated under light irradiation of (00 mW / cm2), an excellent conversion efficiency of 117% was obtained when the conversion efficiency of Comparative Example 1 was set to 100% in terms of photoelectric conversion efficiency.
【００６８】さらにこのサンプルを温度８５℃、湿度８
５％の環境試験箱による１０００時間の環境試験を行っ
た。変換効率の変化は０．０４％低下しただけで全く問
題なかった。Further, this sample was subjected to a temperature of 85 ° C. and a humidity of 8
An environmental test was conducted for 1000 hours using a 5% environmental test box. The change in the conversion efficiency was only 0.04% and was no problem at all.
【００６９】（比較例１）真空排気およびガス供給後、
ヒータユニット２２４、２２５のみそれぞれ１５０℃、
２５０℃に加熱し、予備加熱を行わないで搬送を開始
し、活性酸素処理室２０６、２０７両方に、酸素ガスは
同量供給するが直流電力を供給せず、反射層の表面を活
性酸素にさらすことなく作製した以外は実施例１と同じ
条件で作製した。(Comparative Example 1) After evacuation and gas supply,
Only 150 ° C. for heater units 224 and 225
Heating was performed to 250 ° C., and transport was started without preheating, and the same amount of oxygen gas was supplied to both the active oxygen processing chambers 206 and 207, but no DC power was supplied, and the surface of the reflective layer was converted to active oxygen. It was produced under the same conditions as in Example 1 except that it was not exposed.
【００７０】途中反射層と透明導電層の形成された基板
を分光光度計で反射率を測定し８００ｎｍの波長を１０
０％として反射率の比較対象とした。また完成後ＡＭ
１.５（１００ｍＷ／ｃｍ2）の光照射下にて特性評価を
行い得られた 光電変換効率を１００％として比較対象
とした。The reflectance of the substrate on which the reflective layer and the transparent conductive layer were formed was measured with a spectrophotometer, and the wavelength of 800 nm
0% was used as a comparison object of the reflectance. AM after completion
The characteristics were evaluated under light irradiation of 1.5 (100 mW / cm 2), and the obtained photoelectric conversion efficiency was set to 100%, which was used as a comparison object.
【００７１】（比較例２）真空排気およびガス供給後、
ヒータユニット２２４、２２５のみそれぞれ１５０℃、
２５０℃に加熱し、予備加熱を行わないで搬送を開始し
た以外は実施例１と同じ条件で作製した。Comparative Example 2 After evacuation and gas supply,
Only 150 ° C. for heater units 224 and 225
It was manufactured under the same conditions as in Example 1 except that the heating was performed at 250 ° C. and the conveyance was started without performing the preliminary heating.
【００７２】完成後ＡＭ１.５（１００ｍＷ／ｃｍ2）の
光照射下にて特性評価を行ったところ、光電変換効率で
比較例１の変換効率を１００％として比べた時、１１４
％の変換効率しか得られなかった。After the completion, the characteristics were evaluated under light irradiation of AM 1.5 (100 mW / cm 2). When the conversion efficiency of the photoelectric conversion efficiency of Comparative Example 1 was set to 100%, 114% was obtained.
% Conversion efficiency.
【００７３】（比較例３）真空排気およびガス供給後、
ヒータユニット２２４、２２５のみそれぞれ１５０℃、
２５０℃に加熱し１２時間保った後搬送を開始した以外
は実施例１と同じ条件で作製した。(Comparative Example 3) After evacuation and gas supply,
Only 150 ° C. for heater units 224 and 225
It was manufactured under the same conditions as in Example 1 except that the conveyance was started after heating to 250 ° C. and holding for 12 hours.
【００７４】完成後ＡＭ１.５（１００ｍＷ／ｃｍ2）の
光照射下にて特性評価を行ったところ、光電変換効率で
比較例１の変換効率を１００％として比べた時、１１４
％の変換効率しか得られなかった。After completion, the characteristics were evaluated under light irradiation of AM 1.5 (100 mW / cm 2). As a result, when the conversion efficiency of Comparative Example 1 was set to 100%, the photoelectric conversion efficiency was 114%.
% Conversion efficiency.
【００７５】（比較例４）活性酸素発生室２０６の直流
電力を４００Wとした以外は比較例１と同じ条件で作製
した。完成後ＡＭ１.５（１００ｍＷ／ｃｍ2）の光照射
下にて特性評価を行ったところ、光電変換効率で比較例
１の変換効率を１００％として比べた時、８８％の変換
効率しか得られなかった。(Comparative Example 4) A device was produced under the same conditions as in Comparative Example 1 except that the DC power in the active oxygen generating chamber 206 was changed to 400 W. When the characteristics were evaluated under light irradiation of AM 1.5 (100 mW / cm 2) after completion, only 88% conversion efficiency was obtained when the conversion efficiency of Comparative Example 1 was set to 100% in terms of photoelectric conversion efficiency. Was.
【００７６】（比較例５）ガスゲート２２６へのアルゴ
ンガスの供給を停止し、反射層作製室２０５へのアルゴ
ンガスの供給量を５ｓｃｃｍに低減した以外は実施例１
と同じ条件で作製した。完成後ＡＭ１.５（１００ｍＷ
／ｃｍ2）の光照射下にて特性評価を行ったところ、光
電変換効率で比較例１の変換効率を１００％として比べ
た時、８０％の変換効率しか得られなかった。Comparative Example 5 Example 1 was repeated except that the supply of the argon gas to the gas gate 226 was stopped and the supply amount of the argon gas to the reflective layer production chamber 205 was reduced to 5 sccm.
It was produced under the same conditions as described above. After completion AM1.5 (100mW
/ Cm 2), the characteristics were evaluated. As a result, only 80% conversion efficiency was obtained when the conversion efficiency of Comparative Example 1 was set to 100% in terms of photoelectric conversion efficiency.
【００７７】どの程度の酸素混入で影響が出るかを調べ
るため反射層作製室へのアルゴンガスに酸素ガスを意図
的に混合して透明導電層まで作製し反射率を作製した。
合計流量を３５ｓｃｃｍとし酸素ガス量を２ｓｃｃｍ、
４ｓｃｃｍ、８ｓｃｃｍと変化させた結果、それぞれの
反射率は８００ｎｍの波長で比較例を１００％としたと
きに１２０％、１１５％、８５％となった。４ｓｃｃｍ
以上、つまりは約１０％以上の酸素混入で著しく反射率
が低下した。In order to examine how much oxygen would affect the mixing, an oxygen gas was intentionally mixed with an argon gas to the reflecting layer forming chamber to form a transparent conductive layer, and the reflectance was formed.
The total flow rate is 35 sccm, the oxygen gas amount is 2 sccm,
As a result of changing to 4 sccm and 8 sccm, the respective reflectances were 120%, 115%, and 85% when the comparative example was 100% at a wavelength of 800 nm. 4sccm
Above, that is, the reflectivity was remarkably reduced by oxygen mixing of about 10% or more.
【００７８】[0078]
【発明の効果】本発明によって作製される反射層及び透
明導電層を用いる事により、入射する光を有効に利用で
きるため半導体への光の吸収が増加し高い変換効率が得
られ、より小面積での光電変換素子の利用が可能とな
る。また長時間にわたり連続した光電変換素子の作製が
可能で、安価でかつ信頼性の高い光電変換素子の系統電
力用としての本格的な普及に寄与する。By using the reflective layer and the transparent conductive layer produced according to the present invention, the incident light can be used effectively, so that the absorption of light into the semiconductor increases and a high conversion efficiency can be obtained. The use of the photoelectric conversion element is possible. In addition, it is possible to manufacture a photoelectric conversion element continuously for a long time, which contributes to full-scale spread of a low-cost and highly reliable photoelectric conversion element for system power use.
【図１】本発明の光電変換素子の一例FIG. 1 shows an example of the photoelectric conversion element of the present invention.
【図２】本発明の光電変換素子の反射層及び透明導電層
を作製するに好適なスパッタリング装置の一例FIG. 2 shows an example of a sputtering apparatus suitable for producing a reflective layer and a transparent conductive layer of the photoelectric conversion element of the present invention.
１００ 活性酸素処理される領域 １０１ 基板 １０２ 反射層 １０３ 透明導電層 １０４ 半導体接合層 １０５ ｎ型ａ−Ｓｉ １０６ ｉ型ａ−Ｓｉ １０７ ｐ型μｃ−ＳＩ １０８ 反射防止膜 １０９ 集電電極 １１０ 出力端子 １１１ 保護樹脂 ２０１ 送り出し室 ２０２ ロール状基板 ２０３ ガイドローラ ２０４ 基板 ２０５ 反射層作製室 ２０６、２０７ 活性酸素処理室 ２０８、２０９ 透明電極層作製室 ２１０ 巻き取り室 ２１１ 巻き取りロール ２１２ ステアリングローラ ２１３ 合紙ロール ２１４ 反射層用ターゲット ２１５、２１６ グロー放電用カソード電極 ２１７、２１８ 透明導電層用ターゲット ２１９〜２２３ 直流電源 ２２４、２２５ 基板加熱用ヒータ ２２６ ガスゲート ２２７、２２８、２２９ しきり板 ２３０〜２３４ ガス導入管 ２３５ マグネットローラ ２３６〜２３８ 予備加熱用ヒータ ２３９ 真空ポンプ ２４０ 拡散ポンプ REFERENCE SIGNS LIST 100 Area to be treated with active oxygen 101 Substrate 102 Reflective layer 103 Transparent conductive layer 104 Semiconductor bonding layer 105 n-type a-Si 106 i-type a-Si 107 p-type μc-SI 108 Antireflection film 109 Current collecting electrode 110 Output terminal 111 Protective resin 201 Sending-out chamber 202 Roll-shaped substrate 203 Guide roller 204 Substrate 205 Reflective layer producing chamber 206, 207 Active oxygen processing chamber 208, 209 Transparent electrode layer producing chamber 210 Winding chamber 211 Winding roll 212 Steering roller 213 Interleaf roll 214 Reflective layer target 215, 216 Glow discharge cathode electrode 217, 218 Transparent conductive layer target 219-223 DC power supply 224, 225 Substrate heating heater 226 Gas gate 227, 228, 229 Stripping plate 230-234 Gas Immigration 235 magnet roller 236-238 preheating heater 239 vacuum pump 240 diffusion pump
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｈ０１Ｌ 31/04 Ｈ０１Ｌ 31/04 Ｖ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI H01L 31/04 H01L 31/04 V
Claims (22)
減圧し、該成膜室を所定の成膜温度以上に加熱した後、
冷却または放冷し、該成膜室を所定の成膜温度に設定
し、基板上に金属反射層を形成する工程と、該金属反射
層表面に活性酸素を接触させる工程と、透明導電層を形
成する工程とを有することを特徴とする堆積膜製造方
法。After the film forming chamber is opened to the atmosphere, the pressure in the film forming chamber is reduced, and the film forming chamber is heated to a predetermined film forming temperature or higher.
Cooling or cooling, setting the film forming chamber to a predetermined film forming temperature, forming a metal reflective layer on the substrate, contacting the surface of the metal reflective layer with active oxygen, Forming a deposited film.
形成するように連結されていることを特徴とする請求項
１記載の堆積膜製造方法。2. The method according to claim 1, wherein the plurality of film forming chambers are connected so as to form a single vacuum chamber.
基板送り出し室から複数の成膜室を貫通して基板巻き取
り室で巻き取るようにセットし、該成膜室を減圧し、該
成膜室を所定の成膜温度以上に加熱した後、該成膜室を
所定の成膜温度に設定し、長尺基板上に金属反射層を形
成する工程と、該金属反射層表面に活性酸素を接触させ
る工程と、透明導電層を形成する工程とを有することを
特徴とする堆積膜製造方法。3. After the film forming chamber is opened to the atmosphere, the long substrate is set so as to pass through the plurality of film forming chambers from the substrate unloading chamber and to be wound by the substrate winding chamber, and the film forming chamber is depressurized. Heating the film forming chamber to a predetermined film forming temperature or higher, setting the film forming chamber to a predetermined film forming temperature, and forming a metal reflective layer on a long substrate; A method of producing a deposited film, comprising: a step of bringing active oxygen into contact with a substrate; and a step of forming a transparent conductive layer.
する温度は400℃から500℃の範囲で、且つ時間は15分か
ら120分の範囲であることを特徴とする請求項1又は3記
載の堆積膜製造方法。4. The method according to claim 1, wherein a temperature for heating the film forming chamber before forming the metal reflection layer is in a range of 400 ° C. to 500 ° C., and a time is in a range of 15 minutes to 120 minutes. 3. The method for producing a deposited film according to 3.
ことを特徴とする請求項１又は３記載の堆積膜製造方
法。5. The method according to claim 1, wherein the heating and the cooling or the cooling are performed a plurality of times.
化学的気相成長法、イオンプレーティング法、及びイオ
ンビーム法のいずれかにより行われることを特徴とする
請求項１又は３記載の堆積膜製造方法。6. The film is formed by a sputtering method, a vacuum evaporation method,
4. The method according to claim 1, wherein the method is performed by any one of a chemical vapor deposition method, an ion plating method, and an ion beam method.
の成膜室へ混入する酸素ガスのガス分圧が１０％以下で
あることを特徴とする請求項1又は3記載の堆積膜製造方
法。7. The method for producing a deposited film according to claim 1, wherein the partial pressure of oxygen gas mixed into the film formation chamber for the metal layer from the space contacted with active oxygen is 10% or less. .
膜室との間にガスゲート又はピンチバルブを有すること
を特徴とする請求項1又は3記載の堆積膜製造方法。8. The method for producing a deposited film according to claim 1, further comprising a gas gate or a pinch valve between a space contacting with active oxygen and a film forming chamber for forming the metal layer.
ることを特徴とする請求項３記載の堆積膜製造方法。9. The method according to claim 3, wherein the long substrate is formed while being continuously transported.
膜終了後に長尺基板を搬送して、引き続く成膜室で成膜
を行うことを特徴とする請求項３記載の堆積膜製造方
法。10. The deposition according to claim 3, wherein the transport of the long substrate is stopped during the film formation, and the long substrate is transported after the completion of the film formation, and the film is formed in a subsequent film formation chamber. Film manufacturing method.
属層及び透明導電層を成膜する工程と、半導体層を形成
する工程とを有することを特徴とする光起電力素子製造
方法。11. A method for manufacturing a photovoltaic device, comprising: a step of forming a metal layer and a transparent conductive layer on a long substrate by the method according to claim 3; and a step of forming a semiconductor layer. .
熱する温度は400℃から500℃の範囲で、且つ時間は15分
から120分の範囲であることを特徴とする請求項11記載
の光起電力素子製造方法。12. The method according to claim 11, wherein the temperature for heating the film forming chamber before forming the metal reflection layer is in the range of 400 ° C. to 500 ° C., and the time is in the range of 15 minutes to 120 minutes. Photovoltaic element manufacturing method.
うことを特徴とする請求項11記載の光起電力素子製造方
法。13. The method according to claim 11, wherein heating and cooling or cooling are performed a plurality of times.
法、化学的気相成長法、イオンプレーティング法、及び
イオンビーム法のいずれかにより行われることを特徴と
する請求項11記載の光起電力素子製造方法。14. The photovoltaic device according to claim 11, wherein the film is formed by any one of a sputtering method, a vacuum evaporation method, a chemical vapor deposition method, an ion plating method, and an ion beam method. Element manufacturing method.
層の成膜室へ混入する酸素ガスのガス分圧が１０％以下
であることを特徴とする請求項11記載の光起電力素子製
造方法。15. The method for manufacturing a photovoltaic device according to claim 11, wherein the partial pressure of oxygen gas mixed into the film formation chamber for the metal layer from the space brought into contact with active oxygen is 10% or less. .
成膜室との間にガスゲート又はピンチバルブを有するこ
とを特徴とする請求項11記載の光起電力素子製造方法。16. The method according to claim 11, wherein a gas gate or a pinch valve is provided between the space to be brought into contact with active oxygen and the metal layer deposition chamber.
することを特徴とする請求項11記載の光起電力素子製造
方法。17. The method according to claim 11, wherein the film is formed while continuously transporting the long substrate.
膜終了後に長尺基板を搬送して、引き続く成膜室で成膜
を行うことを特徴とする請求項11記載の光起電力素子製
造方法。18. The light according to claim 11, wherein the transport of the long substrate is stopped during the film formation, and the long substrate is transported after the completion of the film formation, and the film is formed in a subsequent film formation chamber. A method for manufacturing an electromotive element.
ばれる一種であることを特徴とする請求項11記載の光起
電力素子製造方法。19. The method according to claim 11, wherein the metal reflection layer is one type selected from Al, Ag, and Cu.
から選ばれる少なくとも一種の酸化物であることを特徴
とする請求項11記載の光起電力素子製造方法。20. The transparent conductive layer is made of Zn, Ti, In, Sn.
12. The method for producing a photovoltaic element according to claim 11, wherein the method is at least one oxide selected from the group consisting of:
第１の透明導電層の成膜温度よりも高い温度で成膜する
第２の透明導電層からなることを特徴とする請求項11記
載の光起電力素子製造方法。21. A transparent conductive layer comprising: a first transparent conductive layer; and a second transparent conductive layer formed at a temperature higher than a temperature at which the first transparent conductive layer is formed. Item 12. The method for producing a photovoltaic element according to Item 11.
を特徴とする請求項11記載の光起電力素子製造方法。22. The method according to claim 11, wherein the semiconductor layer is a non-single-crystal semiconductor.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12218497A JP3787410B2 (en) | 1997-05-13 | 1997-05-13 | Deposited film manufacturing method and photovoltaic device manufacturing method |
| US09/076,237 US5998730A (en) | 1997-05-13 | 1998-05-12 | Production method for deposited film, production method for photoelectric conversion element, production apparatus for deposited film, production apparatus for photoelectric conversion element |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12218497A JP3787410B2 (en) | 1997-05-13 | 1997-05-13 | Deposited film manufacturing method and photovoltaic device manufacturing method |
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| Publication Number | Publication Date |
|---|---|
| JPH10310862A true JPH10310862A (en) | 1998-11-24 |
| JP3787410B2 JP3787410B2 (en) | 2006-06-21 |
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ID=14829665
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12218497A Expired - Fee Related JP3787410B2 (en) | 1997-05-13 | 1997-05-13 | Deposited film manufacturing method and photovoltaic device manufacturing method |
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| Country | Link |
|---|---|
| JP (1) | JP3787410B2 (en) |
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