JPH11284211A - Manufacture of zno transparent conductive film for thin film solar cell - Google Patents
Manufacture of zno transparent conductive film for thin film solar cellInfo
- Publication number
- JPH11284211A JPH11284211A JP10098228A JP9822898A JPH11284211A JP H11284211 A JPH11284211 A JP H11284211A JP 10098228 A JP10098228 A JP 10098228A JP 9822898 A JP9822898 A JP 9822898A JP H11284211 A JPH11284211 A JP H11284211A
- Authority
- JP
- Japan
- Prior art keywords
- transparent conductive
- conductive film
- zno
- film
- layer
- 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
- Y02E10/541—CuInSe2 material PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ＣＩＳ系薄膜太陽
電池の窓層として供されるＺｎＯ系透明導電膜及び該Ｚ
ｎＯ系透明導電膜の製造方法に関する。[0001] The present invention relates to a ZnO-based transparent conductive film used as a window layer of a CIS-based thin-film solar cell,
The present invention relates to a method for manufacturing an nO-based transparent conductive film.
【０００２】[0002]
【従来の技術】ＣＩＳ（二セレン化銅インジウムＣｕＩ
ｎＳｅ2 又は二硫化銅インジウムＣｕＩｎＳ2 ）系薄膜
太陽電池においては、窓層として供されるｎ形の導電性
を有する透明導電膜が必要である。この透明導電膜に要
求される性能としては、 (1) 上部電極として使用するので抵抗値が低いこと。
（横方向に電流が流れるのでシート抵抗が低いことが必
要で１０Ω／□以下が望ましい。） (2) 光が入射する窓層として働くので、透過率が高いこ
と。（透過率としては、９０％以上（波長８００ｎｍ）
あるいは表面反射量を差し引いて、４００〜１３００ｎ
ｍまでの波長範囲の面積が大きいことが望ましい。） (3) ＣＩＳ系薄膜太陽電池は積層構造であるので、接合
界面特性に損傷を与えないこと。等がある。2. Description of the Related Art CIS (copper indium diselenide CuI)
In an nSe 2 or indium copper disulfide (CuInS 2 ) -based thin-film solar cell, a transparent conductive film having n-type conductivity to serve as a window layer is required. The performance required of this transparent conductive film is as follows: (1) Since the transparent conductive film is used as an upper electrode, its resistance value is low.
(Since current flows in the horizontal direction, the sheet resistance needs to be low and is preferably 10 Ω / □ or less.) (2) Since it functions as a window layer through which light enters, high transmittance is required. (Transmittance is 90% or more (wavelength 800 nm)
Alternatively, by subtracting the amount of surface reflection, 400-1300 n
It is desirable that the area of the wavelength range up to m be large. (3) Since the CIS thin-film solar cell has a laminated structure, the junction interface characteristics should not be damaged. Etc.
【０００３】この透明導電膜としての酸化亜鉛（Ｚｎ
Ｏ）の製造方法としては、有機金属化学的気相成長法
（ＭＯＣＶＤ：Metal Organic Chemical Vapor Deposit
ion Method）とスパッタ法があり、それぞれの製造方法
の特徴を以下に示す。[0003] Zinc oxide (Zn) as this transparent conductive film
O) is produced by a metal organic chemical vapor deposition (MOCVD) method.
ion method) and sputtering method, and the features of each manufacturing method are described below.
【０００４】ＭＯＣＶＤ法においては、その利点とし
て、 ドーパント量を調整することで透明導電膜の抵抗率を
任意に変化させることができる。 化学反応を利用した透明導電膜の成長法であるために
柔らかいＣＩＳ系太陽電池の光吸収層に損傷を与えるこ
となく、穏やかな状態で硬質の酸化亜鉛（ＺｎＯ）を成
長させることができる。 透明導電膜表面の凹凸を制御したテクスチャー構造に
よる光閉じ込め効果により、部分的ではあるが反射防止
膜としての作用が期待できる。The advantage of the MOCVD method is that the resistivity of the transparent conductive film can be arbitrarily changed by adjusting the amount of the dopant. Since the method uses a chemical reaction to grow a transparent conductive film, hard zinc oxide (ZnO) can be grown in a gentle state without damaging the light absorbing layer of a soft CIS-based solar cell. Due to the light confinement effect of the texture structure in which the irregularities on the surface of the transparent conductive film are controlled, the effect as an antireflection film can be expected partially.
【０００５】また、その欠点としては、 透明導電膜の透過率と抵抗率を独立して調整すること
ができない。（この両者の交点が最適値となる。） 化学反応促進のために基板加熱が必要であり、この加
熱の熱応力による基板の弾性変形及びその変形による膜
の剥離等が発生し易い。 製造装置としてバッチ式の反応炉を使用するので、工
業化時には生産性が劣る可能性が高い。 大面積の薄膜太陽電池を製造する場合には、基板の加
熱の均一性及び原料ガスの流れの均一性を実現すること
が困難である。 抵抗率調整のためのドーパントとして特材ガスのＢ2
Ｈ6 ガス等を使用する必要があり、除害装置設置等のコ
ストアップの要因がある。Another drawback is that the transmittance and resistivity of the transparent conductive film cannot be adjusted independently. (The intersection of the two becomes an optimum value.) Heating of the substrate is required to promote the chemical reaction, and elastic deformation of the substrate due to the thermal stress of this heating and peeling of the film due to the deformation are likely to occur. Since a batch-type reaction furnace is used as a production apparatus, there is a high possibility that productivity will be poor during industrialization. When manufacturing a large-area thin-film solar cell, it is difficult to achieve uniform heating of the substrate and uniform flow of the source gas. B 2 of special material gas as a dopant for resistivity adjustment
It is necessary to use H 6 gas or the like, which causes an increase in cost such as installation of an abatement apparatus.
【０００６】スパッタ法においては、従来ＲＦスパッタ
法又はＤＣスパッタ法のいずれかの方法により、Ａｒガ
ス又はＯ2 ／Ａｒ混合ガスをスパッタガスとして、加熱
した基板上に一枚のＺｎＯ：Ａｌ等のターゲットを使用
して１ステップで単層のＺｎＯ：Ａｌ透明導電膜を作製
していた。ＤＣスパッタ法によるＣＩＳ系薄膜太陽電池
の製造方法に関する実施例は少なく、スパッタ法で得ら
れる高性能の窓層はいずれもＺｎＯ：Ａｌ等のターゲッ
トを使用したＲＦスパッタ法によるものである。しか
し、ＲＦスパッタ法は製膜速度が遅く、ＭＯＣＶＤ法と
比較しても製膜速度における利点はない。In the sputtering method, a single sheet of ZnO: Al or the like is formed on a heated substrate by using an Ar gas or an O 2 / Ar mixed gas as a sputtering gas by a conventional RF sputtering method or a DC sputtering method. Using a target, a single-layer ZnO: Al transparent conductive film was produced in one step. There are few examples of a method for manufacturing a CIS-based thin-film solar cell by DC sputtering, and high-performance window layers obtained by sputtering are all formed by RF sputtering using a target such as ZnO: Al. However, the RF sputtering method has a low film forming speed, and has no advantage in the film forming speed as compared with the MOCVD method.
【０００７】ＤＣスパッタ法の特徴を以下に示す。その
利点として、 大面積薄膜作製技術として確立しているので大面積の
薄膜太陽電池の製造には有利である。 透明導電膜の高速製膜が可能で、工業化時には高生産
性が可能である。 ＺｎＯターゲット中のＡｌ、Ｇａ等の合金元素量によ
り抵抗率の調整が可能なので、ＭＯＣＶＤ法で作製した
ＺｎＯ：Ｂの透明導電膜の膜厚に対して１／２〜２／３
に薄膜化すると、透過率を増大することも可能である。 ＺｎＯ透明導電膜の成長初期から均一な膜が成長でき
る。 反応性スパッタ法を利用することにより金属亜鉛ター
ゲットあるいは、Ａｌやそれ以外の種々のドーパント
（Ｂ、Ｉｎ、Ｇａ）等を合金化した亜鉛ターゲットと酸
素混合ガスを使用して抵抗値を制御したＺｎＯ透明導電
膜の成長が可能である。The characteristics of the DC sputtering method are as follows. As an advantage, it is advantageous for manufacturing large-area thin-film solar cells because it has been established as a large-area thin-film fabrication technology. High-speed film formation of a transparent conductive film is possible, and high productivity is possible during industrialization. Since the resistivity can be adjusted by the amount of alloying elements such as Al and Ga in the ZnO target, the thickness is 1/2 to 2/3 of the thickness of the ZnO: B transparent conductive film formed by the MOCVD method.
When the thickness is reduced, the transmittance can be increased. A uniform film can be grown from the initial growth of the ZnO transparent conductive film. ZnO in which the resistance value is controlled by using an oxygen mixed gas with a metal zinc target or a zinc target alloyed with Al or various other dopants (B, In, Ga) by utilizing the reactive sputtering method. A transparent conductive film can be grown.
【０００８】また、その欠点としては、 ＭＯＣＶＤ法と同程度の膜性能（キャリア濃度、移動
度）を有するＺｎＯ系透明導電膜を製造するには、２０
０°Ｃ以上の基板加熱を行う必要がある。 ＤＣスパッタ法はＲＦスパッタ法と比べてエネルギー
密度が高いので、接合界面又は光吸収層表面の損傷が起
こり易い。抵抗調整用の合金元素量はターゲット中の
濃度として一定であるので、抵抗率 を任意に調整できない。（但し、狭い範囲ならば、スパ
ッタガス中に酸素を混入することで微調整は可能であ
る。） 高性能のＣＩＳ系薄膜太陽電池を製造できる基板加熱
温度範囲では表面の凹凸を制御したテクスチャー構造が
作製できない。[0008] Another drawback is that, in order to produce a ZnO-based transparent conductive film having the same film performance (carrier concentration and mobility) as that of the MOCVD method, 20
It is necessary to heat the substrate to 0 ° C. or higher. Since the DC sputtering method has a higher energy density than the RF sputtering method, the bonding interface or the surface of the light absorption layer is easily damaged. Since the amount of the alloy element for resistance adjustment is constant as the concentration in the target, the resistivity cannot be arbitrarily adjusted. (However, fine adjustment is possible by mixing oxygen into the sputtering gas within a narrow range.) Texture structure with controlled surface irregularities in the substrate heating temperature range where high-performance CIS-based thin-film solar cells can be manufactured Cannot be produced.
【０００９】[0009]
【発明が解決しようとする課題】本発明は前記のような
問題点を解消するためになされたもので、本発明の目的
は、ＭＯＣＶＤ法で作製したＺｎＯ：Ｂ透明導電膜と同
等の性能のものを、ＲＦスパッタ法及びＤＣスパッタ法
により作製することにより、スパッタ衝撃の影響を低減
し、高速、且つ大面積で製膜することである。SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to provide a ZnO: B transparent conductive film having the same performance as that of a MOCVD method. An object of the present invention is to produce a film by an RF sputtering method and a DC sputtering method so as to reduce the influence of a sputtering impact and to form a film at a high speed and in a large area.
【００１０】[0010]
【課題を解決するための手段】本発明は、裏面電極層上
に、光吸収層（ｐ型）、界面層（バッファー層）、窓層
（ｎ型）及び上部電極の順に積層される薄膜太陽電池の
ＺｎＯ系透明導電膜において、前記窓層が、界面層上に
形成され界面保護膜として作用する第１の膜と、前記第
１の膜上に形成される第２のＺｎＯ系透明導電膜と、前
記第２の透明導電膜上に形成される第３のＺｎＯ系透明
導電膜とからなる積層体で、前記第１膜及び第２〜３の
透明導電膜がＺｎＯ：Ａｌ又はＺｎＯ：Ｇａからなる薄
膜太陽電池のＺｎＯ系透明導電膜である。According to the present invention, there is provided a thin-film solar cell having a light-absorbing layer (p-type), an interface layer (buffer layer), a window layer (n-type) and an upper electrode laminated in this order on a back electrode layer. In a ZnO-based transparent conductive film of a battery, a first film in which the window layer is formed on an interface layer and functions as an interface protective film, and a second ZnO-based transparent conductive film formed on the first film And a third ZnO-based transparent conductive film formed on the second transparent conductive film, wherein the first film and the second to third transparent conductive films are made of ZnO: Al or ZnO: Ga. It is a ZnO-based transparent conductive film of a thin-film solar cell comprising:
【００１１】本発明は、前記第１の膜が、膜厚が１００
ｎｍ以下である薄膜太陽電池のＺｎＯ系膜である。In the present invention, the first film preferably has a thickness of 100
nm or less for a thin-film solar cell.
【００１２】本発明は、前記第２の透明導電膜及び第３
の透明導電膜が、ドーパントとしてＡｌ、Ｇａ、Ｉｎ、
Ｂ又はこれらの組み合わせたものを含むＺｎＯからなる
薄膜太陽電池のＺｎＯ系透明導電膜である。According to the present invention, the second transparent conductive film and the third
Transparent conductive film, Al, Ga, In, as a dopant
It is a ZnO-based transparent conductive film of a thin-film solar cell made of ZnO containing B or a combination thereof.
【００１３】本発明は、裏面電極層上に、光吸収層（ｐ
形）、界面層（バッファー層）、窓層（ｎ形）及び上部
電極の順に積層される薄膜太陽電池のＺｎＯ系透明導電
膜の製造方法であって、界面層上にＲＦスパッタ法によ
り第１の膜（界面保護膜として作用する）を作製する工
程と、前記第１の膜上にスパッタ法により第２の透明導
電膜を作製する工程と、前記第２の透明導電膜上にスパ
ッタ法により第３の透明導電膜を作製する工程とからな
り、前記各工程において、ＺｎＯ：Ａｌ又はＺｎＯ：Ｇ
ａターゲットを用いる薄膜太陽電池のＺｎＯ系透明導電
膜の製造方法である。According to the present invention, a light absorption layer (p
A method for producing a ZnO-based transparent conductive film of a thin-film solar cell, which is laminated in this order, an interface layer (buffer layer), a window layer (n-type), and an upper electrode. Forming a film (acting as an interface protection film), forming a second transparent conductive film on the first film by sputtering, and forming a film on the second transparent conductive film by sputtering. Forming a third transparent conductive film. In each of the above steps, ZnO: Al or ZnO: G
This is a method for producing a ZnO-based transparent conductive film of a thin-film solar cell using a target.
【００１４】本発明は、裏面電極層上に、光吸収層（ｐ
型）、界面層（バッファー層）、窓層（ｎ型）及び上部
電極の順に積層される薄膜太陽電池のＺｎＯ系透明導電
膜の製造方法であって、界面層上にＲＦマグネトロンス
パッタ法により第１の膜（界面保護膜として作用する）
を作製する工程と、前記第１の膜上にＤＣマグネトロン
スパッタ法により第２の透明導電膜を作製する工程と、
前記第２の透明導電膜上にＤＣマグネトロンスパッタ法
により第３の透明導電膜を作製する工程とからなり、前
記各工程において、ＺｎＯ：Ａｌ又はＺｎＯ：Ｇａター
ゲットを用いる薄膜太陽電池のＺｎＯ系透明導電膜の製
造方法である。According to the present invention, a light absorption layer (p
), An interface layer (buffer layer), a window layer (n-type), and an upper electrode, which are stacked in this order, on the interface layer by RF magnetron sputtering. Film 1 (acting as an interface protective film)
And a step of forming a second transparent conductive film on the first film by DC magnetron sputtering,
Forming a third transparent conductive film on the second transparent conductive film by a DC magnetron sputtering method. In each of the steps, a ZnO-based transparent film of a thin-film solar cell using a ZnO: Al or ZnO: Ga target. This is a method for manufacturing a conductive film.
【００１５】本発明は、前記ＲＦスパッタ法又はＲＦマ
グネトロンスパッタ法においては、パワー密度が２．２
Ｗ／ｃｍ2 以下で、ＺｎＯ：Ａｌ又はＺｎＯ：Ｇａ透明
導電膜を作製する薄膜太陽電池のＺｎＯ系透明導電膜の
製造方法である。According to the present invention, in the RF sputtering method or the RF magnetron sputtering method, the power density is 2.2.
This is a method for producing a ZnO-based transparent conductive film of a thin-film solar cell for producing a ZnO: Al or ZnO: Ga transparent conductive film at W / cm 2 or less.
【００１６】[0016]
【発明の実施の形態】以下、本発明の実施の形態を説明
する。本発明は、薄膜太陽電池の窓層として供されるＺ
ｎＯ系透明導電膜及びその製造方法に関するものであっ
て、従来のＭＯＣＶＤ法で作製したＺｎＯ：Ｂ透明導電
膜と同等の性能で、かつ、耐湿性に優れたＺｎＯ系透明
導電膜を、ＲＦスパッタ及びＤＣスパッタ法により製膜
することにより、接合界面へのスパッタ衝撃の影響を低
減し、高速に、且つ大面積の太陽電池を作製することが
できる。Embodiments of the present invention will be described below. The present invention relates to a Z layer provided as a window layer of a thin-film solar cell.
The present invention relates to an nO-based transparent conductive film and a method for producing the same, and a ZnO-based transparent conductive film having the same performance as a ZnO: B transparent conductive film produced by a conventional MOCVD method and having excellent moisture resistance is formed by RF sputtering. In addition, by forming a film by the DC sputtering method, the influence of sputter impact on the bonding interface can be reduced, and a large-area solar cell can be manufactured at high speed.
【００１７】先ず、ＺｎＯ：Ａｌ又はＺｎＯ：Ｇａター
ゲットを用いて低出力（５００Ｗ以下）のＲＦスパッタ
法により、接合面へのスパッタ衝撃が少なく、接合界面
保護膜として作用する第１の導電膜を高抵抗バッファー
（界面）層上に形成し、その後、複数の処理工程に分け
て夫々ＺｎＯ：Ａｌ又はＺｎＯ：Ｇａターゲットを用い
て高速製膜が可能なＤＣスパッタ法により、窓層として
供される第２の導電膜及び第３の導電膜を形成すること
により、接合面へのスパッタ衝撃の影響を低減し、高速
に、且つ大面積の太陽電池を作製することができる。First, by using a ZnO: Al or ZnO: Ga target and using a low-power (500 W or less) RF sputtering method, the first conductive film which acts as a bonding interface protective film with little sputter impact on the bonding surface is formed. It is formed on a high resistance buffer (interface) layer, and then provided as a window layer by a DC sputtering method capable of high-speed film formation using a ZnO: Al or ZnO: Ga target in a plurality of processing steps. By forming the second conductive film and the third conductive film, the influence of sputtering impact on the bonding surface can be reduced, and a large-area solar cell can be manufactured at high speed.
【００１８】[0018]
【実施例】以下、本発明の実施例を図面に基づいて説明
する。本発明は、前記薄膜太陽電池の窓層として供され
る透明導電膜及び該透明導電膜の製造方法に関する。Embodiments of the present invention will be described below with reference to the drawings. The present invention relates to a transparent conductive film provided as a window layer of the thin-film solar cell and a method for producing the transparent conductive film.
【００１９】図１は本発明の透明導電膜を用いたＣＩＳ
系薄膜太陽電池の概略構成図である。薄膜太陽電池１は
基板２、裏面電極層３、光吸収層（ｐ型半導体）４、バ
ッファー層（界面層）５、窓層６及び上部電極７の順に
積層された積層構造体であり、特に、窓層６として供さ
れる透明導電膜に特徴を有し、前記窓層６は、界面層５
上に形成され界面保護膜として作用する第１の透明導電
膜と、前記第１の導電膜上に形成される第２の透明
導電膜と、前記第２の透明導電膜上に形成される第
３の透明導電膜とからなる積層体である。FIG. 1 shows a CIS using the transparent conductive film of the present invention.
It is a schematic structure figure of a system thin film solar cell. The thin-film solar cell 1 is a laminated structure in which a substrate 2, a back electrode layer 3, a light absorbing layer (p-type semiconductor) 4, a buffer layer (interface layer) 5, a window layer 6, and an upper electrode 7 are laminated in this order. And a transparent conductive film serving as a window layer 6.
A first transparent conductive film formed thereon and acting as an interface protection film; a second transparent conductive film formed on the first conductive film; and a second transparent conductive film formed on the second transparent conductive film. 3 is a laminate including the transparent conductive film.
【００２０】本発明の製造方法に使用される製造装置の
概略構成を図２に示す。製造装置は少なくとも、ＲＦス
パッタ処理部I 、ＤＣスパッタ処理部II、ＤＣスパッタ
処理部III 及びこれら各スパッタ処理部にスパッタリン
グ処理対象物である下記基板部材Ｘを搬送する搬送手段
（図示せず）から構成される。FIG. 2 shows a schematic configuration of a manufacturing apparatus used in the manufacturing method of the present invention. The manufacturing apparatus includes at least an RF sputtering unit I, a DC sputtering unit II, a DC sputtering unit III, and a conveying unit (not shown) for conveying a substrate member X to be sputtered to each of these sputtering units. Be composed.
【００２１】以下に本発明の製造方法を図１及び図２を
参照して説明する。先ず、図２に図示の前記製造装置で
ＺｎＯ透明導電膜を作製する前に、基板２上に裏面電極
層３、光吸収層（ｐ型半導体）４及びバッファー層（界
面層）５が形成されたもの（図１の斜線部分：以下、基
板部材Ｘという。）が準備される。The manufacturing method of the present invention will be described below with reference to FIGS. First, a back electrode layer 3, a light absorbing layer (p-type semiconductor) 4, and a buffer layer (interface layer) 5 are formed on a substrate 2 before producing a ZnO transparent conductive film by the manufacturing apparatus shown in FIG. (A hatched portion in FIG. 1; hereinafter, referred to as a substrate member X).
【００２２】先ず、最初の処理工程では、前記基板部材
Ｘが前記製造装置のＲＦスパッタ処理部I に搬送され、
ＲＦスパッタ処理部I において、ＺｎＯ：Ａｌあるいは
ＺｎＯ：Ｇａターゲット２１を用いてパワー密度が２．
２Ｗ／ｃｍ2 以下の低出力でＲＦスパッタリングを行う
ことにより、界面保護膜として作用する膜厚１００ｎｍ
以下の第１の導電膜が前記基板部材Ｘの高抵抗のバッ
ファー（界面）層５上に形成される。このＲＦスパッタ
処理工程では、スパッタ出力が低出力であるため、接合
界面へのスパッタ衝撃の影響が少ない。なお、前記ＲＦ
スパッタ処理工程では、ＲＦマグネトロンスパッタ法の
他に、各種ＲＦスパッタ法を適用し得る。First, in the first processing step, the substrate member X is transferred to the RF sputtering processing section I of the manufacturing apparatus,
In the RF sputtering processing part I, the power density is set to 2. using a ZnO: Al or ZnO: Ga target 21.
By performing RF sputtering at a low output of 2 W / cm 2 or less, a film thickness of 100 nm acting as an interface protective film
The following first conductive film is formed on the high-resistance buffer (interface) layer 5 of the substrate member X. In this RF sputtering process, since the sputter output is low, the impact of sputter impact on the bonding interface is small. The RF
In the sputtering process, various RF sputtering methods can be applied in addition to the RF magnetron sputtering method.
【００２３】次に、前記基板部材Ｘは前記製造装置の第
１ＤＣスパッタ処理部IIに搬送され、該第１ＤＣスパッ
タ処理部IIにおいて、ＺｎＯ：ＡｌあるいはＺｎＯ：Ｇ
ａターゲット２２を用いてＤＣスパッタリングを行うこ
とにより、第２の導電膜が前記基板部材Ｘの第１の導
電膜上に形成される。Next, the substrate member X is transported to the first DC sputter processing section II of the manufacturing apparatus, where ZnO: Al or ZnO: G
By performing DC sputtering using the target 22, a second conductive film is formed on the first conductive film of the substrate member X.
【００２４】更に、前記基板部材Ｘは前記製造装置の第
２ＤＣスパッタ処理部III に搬送され、該第２ＤＣスパ
ッタ処理部III において、ＺｎＯ：ＡｌあるいはＺｎ
Ｏ：Ｇａターゲット２３を用いてＤＣスパッタリングを
行うことにより、第３の導電膜が前記基板部材Ｘの第
２の導電膜上に形成される。なお、前記第２及び第３
のＤＣスパッタ処理工程では、ＤＣマグネトロンスパッ
タ法の他に、各種ＤＣスパッタ法又は全てのＲＦスパッ
タ法を適用し得る。Further, the substrate member X is transported to the second DC sputtering processing section III of the manufacturing apparatus, where ZnO: Al or Zn
By performing DC sputtering using the O: Ga target 23, a third conductive film is formed on the second conductive film of the substrate member X. Note that the second and third
In the DC sputtering process step, various DC sputtering methods or all RF sputtering methods can be applied in addition to the DC magnetron sputtering method.
【００２５】以上のように、本発明の製造方法において
は、前記ＺｎＯ系透明導電膜を作製するにあたり、ＲＦ
スパッタ法とＤＣスパッタ法とを併用するとともに、Ｄ
Ｃスパッタ法においては、第１ＤＣスパッタ処理部IIと
第２ＤＣスパッタ処理部IIIで、複数の処理工程に分け
て夫々ＺｎＯ：ＡｌあるいはＺｎＯ：Ｇａターゲットを
用いてＤＣスパッタ処理することにより、第２の導電膜
及び第３の導電膜を形成するので、同一膜層を得る
ための各スパッタ処理工程でのターゲット一枚当たりの
出力を低減（１／ターゲットの枚数）することができ、
スパッタ衝撃の影響が低減される。As described above, according to the manufacturing method of the present invention, when manufacturing the ZnO-based transparent conductive film, RF
In addition to using both sputtering and DC sputtering,
In the C sputtering method, the first DC sputtering processing section II and the second DC sputtering processing section III perform DC sputtering processing using a ZnO: Al or ZnO: Ga target in a plurality of processing steps, respectively. Since the conductive film and the third conductive film are formed, the output per target in each sputtering process for obtaining the same film layer can be reduced (1 / target number).
The effect of sputter impact is reduced.
【００２６】また、ＲＦスパッタ処理部I 、第１ＤＣス
パッタ処理部II及び第２ＤＣスパッタ処理部III におい
ては、夫々の処理部において作製される導電膜、及
びの膜厚に応じて基板部材Ｘの搬送速度が調節され
る。In the RF sputtering processing section I, the first DC sputtering processing section II, and the second DC sputtering processing section III, the substrate member X is transported in accordance with the thickness of the conductive film formed in each processing section and the thickness of the conductive film. The speed is adjusted.
【００２７】なお、前記実施例においては、ＤＣスパッ
タ処理を２工程に分けて行ったが、必要に応じてその工
程数を増加または減少してもよい。In the above embodiment, the DC sputtering process is performed in two steps. However, the number of steps may be increased or decreased as necessary.
【００２８】次に、本発明の製造方法により製膜された
窓層として供せられる透明導電膜を用いた太陽電池の特
性を以下に示す。本発明のＲＦスパッタ法及びＤＣスパ
ッタ法で作製した窓層の第１及び２層がＺｎＯ：Ａｌ、
第３層がＺｎＯ：Ｇａ透明導電膜からなる積層構造の太
陽電池（第３層のＤＣスパッタ電流：０．４Ａ）（Ａ）
と、本発明のＲＦスパッタ法及びＤＣスパッタ法で作製
した窓層の第１及び２層がＺｎＯ：Ａｌ、第３層がＺｎ
Ｏ：Ｇａ透明導電膜からなる積層構造の太陽電池（第３
層のＤＣスパッタ電流：０．６Ａ）（Ｂ）と、本発明の
ＲＦスパッタ法及びＤＣスパッタ法で作製した窓層の第
１〜３層がＺｎＯ：Ａｌ透明導電膜からなる積層構造の
太陽電池（Ｃ）と、ＤＣスパッタ法で作製した窓層が単
層のＺｎＯ：Ａｌ透明導電膜からなる太陽電池（Ｄ）の
太陽電池特性の比較結果を図３に示す。Next, the characteristics of the solar cell using the transparent conductive film provided as the window layer formed by the manufacturing method of the present invention are shown below. The first and second layers of the window layer produced by the RF sputtering method and the DC sputtering method of the present invention are ZnO: Al,
Solar cell having a laminated structure in which the third layer is made of a ZnO: Ga transparent conductive film (DC sputtering current of the third layer: 0.4 A) (A)
And the first and second window layers formed by the RF sputtering method and the DC sputtering method of the present invention are ZnO: Al, and the third layer is Zn.
O: A solar cell having a laminated structure composed of a Ga transparent conductive film (third structure)
Layer DC sputtering current: 0.6 A) (B), and a solar cell having a laminated structure in which the first to third layers of the window layer formed by the RF sputtering method and the DC sputtering method of the present invention are made of a ZnO: Al transparent conductive film. FIG. 3 shows a comparison result of solar cell characteristics between (C) and a solar cell (D) in which a window layer formed by a DC sputtering method has a single-layer ZnO: Al transparent conductive film.
【００２９】ＺｎＯ系透明導電膜の良否は、太陽電池特
性のうち、短絡電流密度（ＪSC）により膜自体の直列抵
抗値を、曲線因子（ＦＦ）により光吸収層表面又は接合
界面の界面接合特性に及ぼす影響を、夫々評価すること
ができる。前記図３の比較結果より、短絡電流密度（Ｊ
SC）、曲線因子（ＦＦ）及び、その積（ＪSC×ＦＦ）の
いずれも、単層のＺｎＯ：Ａｌ透明導電膜を用いた太陽
電池（Ｄ）に比べて、本発明の第１及び２層がＺｎＯ：
Ａｌ、第３層がＺｎＯ：Ｇａ透明導電膜からなる積層構
造の太陽電池（Ａ) 及び（Ｂ) 並びに第１〜３層がＺｎ
Ｏ：Ａｌからなる積層構造の透明導電膜を用いた太陽電
池（Ｃ）の方が良好な結果を示すことが判明した。The quality of the ZnO-based transparent conductive film is determined by determining the series resistance value of the film itself by the short-circuit current density (J SC ), the interface resistance of the light absorbing layer surface or the bonding interface by the fill factor (FF). The effect on the properties can be evaluated individually. From the comparison result of FIG. 3, the short-circuit current density (J
SC ), the fill factor (FF), and the product thereof (J SC × FF) are all different from the solar cell (D) using a single-layer ZnO: Al transparent conductive film in the first and second embodiments of the present invention. The layer is ZnO:
Al and the solar cells (A) and (B) having a laminated structure in which the third layer is composed of a ZnO: Ga transparent conductive film, and the first to third layers are composed of Zn.
It was found that the solar cell (C) using a transparent conductive film having a laminated structure of O: Al showed better results.
【００３０】この結果より、ＤＣスパッタ法で作製した
窓層が積層構造のＺｎＯ：Ｇａ透明導電膜を使用するこ
とにより、従来の単層又は積層のＺｎＯ：Ａｌ透明導電
膜における膜の問題点であった、直列抵抗成分が大きい
ために、短絡電流密度（ＪSC）が低いという欠点を改善
でき、更に、低いＤＣスパッタ電流で製膜できるため、
界面接合特性を劣化させる欠点も透明導電膜の膜厚を薄
膜化することで解決できる。From these results, it was found that the use of the ZnO: Ga transparent conductive film having a laminated structure as the window layer formed by the DC sputtering method caused a problem in the conventional single-layer or laminated ZnO: Al transparent conductive film. The disadvantage that the short circuit current density (J SC ) is low due to the large series resistance component can be improved, and the film can be formed with a low DC sputtering current.
The disadvantage of deteriorating the interface bonding characteristics can also be solved by reducing the thickness of the transparent conductive film.
【００３１】本発明で提案する窓層が積層構造のＺｎＯ
系透明導電膜を使用した太陽電池と単層のＺｎＯ：Ａｌ
透明導電膜を用いた太陽電池の変換効率〔％〕の比較結
果を図４に示す。The window layer proposed in the present invention has a laminated structure of ZnO.
Cell using single transparent conductive film and ZnO: Al of single layer
FIG. 4 shows a comparison result of the conversion efficiency [%] of the solar cell using the transparent conductive film.
【００３２】（ａ）は単層のＺｎＯ：Ａｌ透明導電膜を
用いた太陽電池の特性、（ｂ）は第１及び２層がＺｎ
Ｏ：Ａｌ、第３層がＺｎＯ：Ｇａからなる積層構造の透
明導電膜を用いた太陽電池の特性、（ｃ）は本発明の第
１乃至３層がＺｎＯ：Ｇａからなる積層構造の透明導電
膜を用いた太陽電池（Ｇａの含有量：第１層３．４％、
第２及び３層５．７％）、（ｄ）は本発明の第１乃至３
層がＺｎＯ：Ｇａからなる積層構造の透明導電膜を用い
た太陽電池（Ｇａの含有量：第１乃至３層５．７％）の
特性である。(A) shows the characteristics of a solar cell using a single-layer ZnO: Al transparent conductive film, and (b) shows the first and second layers formed of ZnO: Al.
Characteristics of a solar cell using a transparent conductive film having a laminated structure of O: Al and a third layer of ZnO: Ga, and (c) shows a transparent conductive film of a laminated structure of the first to third layers of ZnO: Ga of the present invention. Solar cell using film (Ga content: first layer 3.4%,
(2nd and 3rd layers 5.7%), (d) are the first to third layers of the present invention.
This is a characteristic of a solar cell (Ga content: first to third layers 5.7%) using a transparent conductive film having a layered structure of ZnO: Ga.
【００３３】前記図４の比較結果より、太陽電池の変換
効率では、単層のＺｎＯ：Ａｌ透明導電膜を用いた太陽
電池（ａ）と比べて、本発明のＺｎＯ：Ａｌ及びＺｎ
Ｏ：Ｇａの積層構造並びにＺｎＯ：Ｇａのみの積層構造
の太陽電池（ｂ）、（ｃ）、（ｄ）が良好な結果を示す
ことが判明した。According to the comparison result of FIG. 4, the conversion efficiency of the solar cell is higher than that of the solar cell (a) using the single-layer ZnO: Al transparent conductive film in comparison with the solar cell (a) of the present invention.
It was found that solar cells (b), (c), and (d) having a stacked structure of O: Ga and a stacked structure of only ZnO: Ga showed good results.
【００３４】[0034]
【発明の効果】以上のように、本発明は、低出力のＲＦ
スパッタ法によりＺｎＯ系透明導電膜の一部を製膜した
後、残りのＺｎＯ系透明導電膜部分をＤＣスパッタ法を
複数工程にわけてスパッタ処理することにより、スパッ
タ衝撃の影響を低減しつつ、ＭＯＣＶＤ法で作製したＺ
ｎ：Ｂ透明導電膜と同等の性能有する透明導電膜を、高
速、且つ大面積で製膜することができる。また、Ｚｎ
Ｏ：Ｇａ層を積層構造の中に取り入れることにより、耐
湿性を確保することができる。As described above, the present invention provides a low-power RF
After forming a part of the ZnO-based transparent conductive film by the sputtering method, the remaining ZnO-based transparent conductive film portion is subjected to the sputtering process by dividing the DC sputtering method into a plurality of steps, thereby reducing the influence of the sputtering impact. Z produced by MOCVD
A transparent conductive film having the same performance as the n: B transparent conductive film can be formed at a high speed and in a large area. Also, Zn
By incorporating the O: Ga layer into the laminated structure, moisture resistance can be ensured.
【００３５】更に、ＤＣスパッタ法で作製した積層構造
のＺｎＯ：Ｇａ透明導電膜を使用することにより、ＤＣ
スパッタ法における高速製膜が可能であるという長所を
生かしつつ、直列抵抗値を低減して、短絡電流密度（Ｊ
SC）を大きくすることができると共に、透明導電膜の膜
厚を薄膜化することにより、接合界面又は光吸収層表面
の損傷を防止して、界面接合特性を改善することが可能
となり、曲線因子（ＦＦ）を大きくできる。Further, by using a ZnO: Ga transparent conductive film having a laminated structure produced by DC sputtering,
While taking advantage of the fact that high-speed film formation by sputtering is possible, the series resistance is reduced and the short-circuit current density (J
SC ) can be increased, and by reducing the thickness of the transparent conductive film, damage to the bonding interface or the surface of the light absorbing layer can be prevented, and the interface bonding characteristics can be improved. (FF) can be increased.
【図１】本発明の製造方法で作製されるＺｎＯ系透明導
電膜を用いたＣＩＳ系薄膜太陽電池の概略構造図であ
る。FIG. 1 is a schematic structural diagram of a CIS-based thin-film solar cell using a ZnO-based transparent conductive film manufactured by a manufacturing method of the present invention.
【図２】本発明の製造方法に使用される製造装置の概略
構成図である。FIG. 2 is a schematic configuration diagram of a manufacturing apparatus used in the manufacturing method of the present invention.
【図３】本発明のＲＦスパッタ法及びＤＣスパッタ法で
作製した窓層の第１及び２層がＺｎＯ：Ａｌ、第３層が
ＺｎＯ：Ｇａ透明導電膜からなる積層構造の太陽電池
（第３層のＤＣスパッタ電流：０．４Ａ）（Ａ）と、本
発明のＲＦスパッタ法及びＤＣスパッタ法で作製した窓
層の第１及び２層がＺｎＯ：Ａｌ、第３層がＺｎＯ：Ｇ
ａ透明導電膜からなる積層構造の太陽電池（第３層のＤ
Ｃスパッタ電流：０．６Ａ）（Ｂ）と、本発明のＲＦス
パッタ法及びＤＣスパッタ法で作製した窓層の第１乃至
３層がＺｎＯ：Ａｌ透明導電膜からなる積層構造の太陽
電池（Ｃ）と、ＤＣスパッタ法で作製した窓層が単層の
ＺｎＯ：Ａｌ透明導電膜からなる太陽電池（Ｄ）の太陽
電池特性の比較結果を示す図である。FIG. 3 shows a solar cell (third layer) in which the first and second window layers formed by the RF sputtering method and the DC sputtering method of the present invention are made of ZnO: Al, and the third layer is made of a ZnO: Ga transparent conductive film. DC sputtering current of the layer: 0.4 A) (A), the first and second window layers prepared by the RF sputtering method and the DC sputtering method of the present invention were ZnO: Al, and the third layer was ZnO: G.
a Solar cell having a laminated structure composed of a transparent conductive film (D of the third layer)
(C sputtering current: 0.6 A) (B) and a solar cell (C) having a laminated structure in which the first to third layers of the window layer formed by the RF sputtering method and the DC sputtering method of the present invention are made of a ZnO: Al transparent conductive film. FIG. 7B) is a diagram showing comparison results of solar cell characteristics of a solar cell (D) in which a window layer formed by a DC sputtering method is made of a single-layer ZnO: Al transparent conductive film.
【図４】単層のＺｎＯ：Ａｌ透明導電膜を用いた太陽電
池の特性（ａ）と、第１及び２層がＺｎＯ：Ａｌ、第３
層がＺｎＯ：Ｇａからなる積層構造の透明導電膜を用い
た太陽電池の特性（ｂ）と、本発明の第１乃至３層がＺ
ｎＯ：Ｇａからなる積層構造の透明導電膜を用いた太陽
電池（Ｇａの含有量：第１層３．４％、第２及び３層
５．７％）（ｃ）と、本発明の第１乃至３層がＺｎＯ：
Ｇａからなる積層構造の透明導電膜を用いた太陽電池
（Ｇａの含有量：第１乃至３層５．７％）（ｄ）との変
換効率〔％〕の比較結果を示す図である。FIG. 4 shows the characteristics (a) of a solar cell using a single-layer ZnO: Al transparent conductive film, wherein the first and second layers have ZnO: Al,
The characteristics (b) of the solar cell using the transparent conductive film having a laminated structure in which the layer is made of ZnO: Ga, and the first to third layers of the present invention are made of Z
A solar cell using a transparent conductive film having a laminated structure of nO: Ga (Ga content: first layer 3.4%, second and third layers 5.7%) (c), and a first cell of the present invention. 3 to 3 layers of ZnO:
It is a figure which shows the comparison result of the conversion efficiency [%] with the solar cell (Ga content: 5.7% of 1st thru | or 3rd layers) (d) using the transparent conductive film of the laminated structure made of Ga.
１ 薄膜太陽電池 ２ 基板 ３ 裏面電極 ４ 光吸収層（ｐ型） ５ 界面層（バッファー層） ６ 窓層（ｎ型） 第１の導電膜（界面保護膜） 第２の導電膜 第３の導電膜 ７ 上部電極 I ＲＦスパッタ処理部 II 第１ＤＣスパッタ処理部 III 第２ＤＣスパッタ処理部 Ｘ 基板部材 DESCRIPTION OF SYMBOLS 1 Thin-film solar cell 2 Substrate 3 Back electrode 4 Light absorption layer (p-type) 5 Interface layer (buffer layer) 6 Window layer (n-type) 1st conductive film (interface protective film) 2nd conductive film 3rd conductive Film 7 Upper electrode I RF sputtering unit II First DC sputtering unit III Second DC sputtering unit X Substrate member
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１０年１２月２８日[Submission date] December 28, 1998
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項４[Correction target item name] Claim 4
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【請求項４】 裏面電極層上に、光吸収層（ｐ型）、界
面層（バッファー層）、窓層（ｎ型）及び上部電極の順
に積層される薄膜太陽電池のＺｎＯ系透明導電膜の製造
方法であって、界面層上にＲＦスパッタ法により第１の
膜（界面保護膜として作用する）を作製する工程と、前
記第１の膜上にスパッタ法により第２の透明導電膜を作
製する工程と、前記第２の透明導電膜上にスパッタ法に
より第３の透明導電膜を作製する工程とからなり、前記
各工程において、ＺｎＯ：Ａｌ又はＺｎＯ：Ｇａターゲ
ットを用いることを特徴とする薄膜太陽電池のＺｎＯ系
透明導電膜の製造方法。4. A ZnO-based transparent conductive film of a thin-film solar cell which is laminated on a back electrode layer in the order of a light absorbing layer (p-type), an interface layer (buffer layer), a window layer (n-type) and an upper electrode. A method for producing a first film (acting as an interfacial protective film) on an interface layer by RF sputtering, and producing a second transparent conductive film on the first film by sputtering. And a step of forming a third transparent conductive film on the second transparent conductive film by a sputtering method. In each of the above steps, a ZnO: Al or ZnO: Ga target is used. A method for producing a ZnO-based transparent conductive film for a thin-film solar cell.
【手続補正書】[Procedure amendment]
【提出日】平成１１年７月７日[Submission date] July 7, 1999
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】発明の名称[Correction target item name] Name of invention
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【発明の名称】 薄膜太陽電池のＺｎＯ系透明導電
膜の製造方法Patent application title: Method for producing ZnO-based transparent conductive film for thin-film solar cell
【手続補正２】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】特許請求の範囲[Correction target item name] Claims
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【特許請求の範囲】[Claims]
【手続補正３】[Procedure amendment 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】発明の詳細な説明[Correction target item name]
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【発明の属する技術分野】本発明は、ＣＩＳ系薄膜太陽
電池の窓層として供されるＺｎＯ系透明導電膜及び該Ｚ
ｎＯ系透明導電膜の製造方法に関する。[0001] The present invention relates to a ZnO-based transparent conductive film used as a window layer of a CIS-based thin-film solar cell,
The present invention relates to a method for manufacturing an nO-based transparent conductive film.
【０００２】[0002]
【従来の技術】ＣＩＳ（二セレン化銅インジウムＣｕＩ
ｎＳｅ2 又は二硫化銅インジウムＣｕＩｎＳ2 ）系薄膜
太陽電池においては、窓層として供されるｎ形の導電性
を有する透明導電膜が必要である。この透明導電膜に要
求される性能としては、 (1) 上部電極として使用するので抵抗値が低いこと。
（横方向に電流が流れるのでシート抵抗が低いことが必
要で１０Ω／□以下が望ましい。） (2) 光が入射する窓層として働くので、透過率が高いこ
と。（透過率としては、９０％以上（波長８００ｎｍ）
あるいは表面反射量を差し引いて、４００〜１３００ｎ
ｍまでの波長範囲の面積が大きいことが望ましい。） (3) ＣＩＳ系薄膜太陽電池は積層構造であるので、接合
界面特性に損傷を与えないこと。 等がある。2. Description of the Related Art CIS (copper indium diselenide CuI)
In an nSe 2 or indium copper disulfide (CuInS 2 ) -based thin-film solar cell, a transparent conductive film having n-type conductivity to serve as a window layer is required. The performance required of this transparent conductive film is as follows: (1) Since the transparent conductive film is used as an upper electrode, its resistance value is low.
(Since current flows in the horizontal direction, the sheet resistance needs to be low and is preferably 10 Ω / □ or less.) (2) Since it functions as a window layer through which light enters, high transmittance is required. (Transmittance is 90% or more (wavelength 800 nm)
Alternatively, by subtracting the amount of surface reflection, 400-1300 n
It is desirable that the area of the wavelength range up to m be large. (3) Since the CIS thin-film solar cell has a laminated structure, the junction interface characteristics should not be damaged. Etc.
【０００３】この透明導電膜としての酸化亜鉛（Ｚｎ
Ｏ）の製造方法としては、有機金属化学的気相成長法
（ＭＯＣＶＤ：Metal Organic Chemical Vapor Deposit
ion Method）とスパッタ法があり、それぞれの製造方法
の特徴を以下に示す。[0003] Zinc oxide (Zn) as this transparent conductive film
O) is produced by a metal organic chemical vapor deposition (MOCVD) method.
ion method) and sputtering method, and the features of each manufacturing method are described below.
【０００４】ＭＯＣＶＤ法においては、その利点とし
て、 ドーパント量を調整することで透明導電膜の抵抗率を
任意に変化させることができる。 化学反応を利用した透明導電膜の成長法であるために
柔らかいＣＩＳ系太陽電池の光吸収層に損傷を与えるこ
となく、穏やかな状態で硬質の酸化亜鉛（ＺｎＯ）を成
長させることができる。 透明導電膜表面の凹凸を制御したテクスチャー構造に
よる光閉じ込め効果により、部分的ではあるが反射防止
膜としての作用が期待できる。The advantage of the MOCVD method is that the resistivity of the transparent conductive film can be arbitrarily changed by adjusting the amount of the dopant. Since the method uses a chemical reaction to grow a transparent conductive film, hard zinc oxide (ZnO) can be grown in a gentle state without damaging the light absorbing layer of a soft CIS-based solar cell. Due to the light confinement effect of the texture structure in which the irregularities on the surface of the transparent conductive film are controlled, the effect as an antireflection film can be expected partially.
【０００５】また、その欠点としては、 透明導電膜の透過率と抵抗率を独立して調整すること
ができない。（この両者の交点が最適値となる。） 化学反応促進のために基板加熱が必要であり、この加
熱の熱応力による基板の弾性変形及びその変形による膜
の剥離等が発生し易い。 製造装置としてバッチ式の反応炉を使用するので、工
業化時には生産性が劣る可能性が高い。 大面積の薄膜太陽電池を製造する場合には、基板の加
熱の均一性及び原料ガスの流れの均一性を実現すること
が困難である。 抵抗率調整のためのドーパントとして特材ガスのＢ2
Ｈ6 ガス等を使用する必要があり、除害装置設置等のコ
ストアップの要因がある。Another drawback is that the transmittance and resistivity of the transparent conductive film cannot be adjusted independently. (The intersection of the two becomes an optimum value.) Heating of the substrate is required to promote the chemical reaction, and elastic deformation of the substrate due to the thermal stress of this heating and peeling of the film due to the deformation are likely to occur. Since a batch-type reaction furnace is used as a production apparatus, there is a high possibility that productivity will be poor during industrialization. When manufacturing a large-area thin-film solar cell, it is difficult to achieve uniform heating of the substrate and uniform flow of the source gas. B 2 of special material gas as a dopant for resistivity adjustment
It is necessary to use H 6 gas or the like, which causes an increase in cost such as installation of an abatement apparatus.
【０００６】スパッタ法においては、従来ＲＦスパッタ
法又はＤＣスパッタ法のいずれかの方法により、Ａｒガ
ス又はＯ 2 ／Ａｒ混合ガスをスパッタガスとして、加熱
した基板上に一枚のＺｎＯ：Ａｌ等のターゲットを使用
して１ステップで単層のＺｎＯ：Ａｌ透明導電膜を作製
していた。ＤＣスパッタ法によるＣＩＳ系薄膜太陽電池
の製造方法に関する実施例は少なく、スパッタ法で得ら
れる高性能の窓層はいずれもＺｎＯ：Ａｌ等のターゲッ
トを使用したＲＦスパッタ法によるものである。しか
し、ＲＦスパッタ法は製膜速度が遅く、ＭＯＣＶＤ法と
比較しても製膜速度における利点はない。In the sputtering method, a conventional RF sputtering
Ar gas by either the DC sputtering method or the DC sputtering method.
Or O Two / Ar mixed gas as sputtering gas and heating
A single target such as ZnO: Al on a substrate
To form a single-layer ZnO: Al transparent conductive film in one step
Was. CIS based thin film solar cell by DC sputtering method
There are few examples of the manufacturing method of
High performance window layers are made of targets such as ZnO: Al.
This is based on the RF sputtering method using a metal. Only
However, the RF sputtering method has a low film forming speed,
There is no advantage in the film formation speed by comparison.
【０００７】ＤＣスパッタ法の特徴を以下に示す。その
利点として、 大面積薄膜作製技術として確立しているので大面積の
薄膜太陽電池の製造には有利である。 透明導電膜の高速製膜が可能で、工業化時には高生産
性が可能である。 ＺｎＯターゲット中のＡｌ、Ｇａ等の合金元素量によ
り抵抗率の調整が可能なので、ＭＯＣＶＤ法で作製した
ＺｎＯ：Ｂの透明導電膜の膜厚に対して１／２〜２／３
に薄膜化すると、透過率を増大することも可能である。 ＺｎＯ透明導電膜の成長初期から均一な膜が成長でき
る。 反応性スパッタ法を利用することにより金属亜鉛ター
ゲットあるいは、Ａｌやそれ以外の種々のドーパント
（Ｂ、Ｉｎ、Ｇａ）等を合金化した亜鉛ターゲットと酸
素混合ガスを使用して抵抗値を制御したＺｎＯ透明導電
膜の成長が可能である。The characteristics of the DC sputtering method are as follows. As an advantage, it is advantageous for manufacturing large-area thin-film solar cells because it has been established as a large-area thin-film fabrication technology. High-speed film formation of a transparent conductive film is possible, and high productivity is possible during industrialization. Since the resistivity can be adjusted by the amount of alloying elements such as Al and Ga in the ZnO target, the thickness is 1/2 to 2/3 of the thickness of the ZnO: B transparent conductive film formed by the MOCVD method.
When the thickness is reduced, the transmittance can be increased. A uniform film can be grown from the initial growth of the ZnO transparent conductive film. ZnO in which the resistance value is controlled by using an oxygen mixed gas with a metal zinc target or a zinc target alloyed with Al or various other dopants (B, In, Ga) by utilizing the reactive sputtering method. A transparent conductive film can be grown.
【０００８】また、その欠点としては、 ＭＯＣＶＤ法と同程度の膜性能（キャリア濃度、移動
度）を有するＺｎＯ系透明導電膜を製造するには、２０
０°Ｃ以上の基板加熱を行う必要がある。 ＤＣスパッタ法はＲＦスパッタ法と比べてエネルギー
密度が高いので、接合界面又は光吸収層表面の損傷が起
こり易い。 抵抗調整用の合金元素量はターゲット中の濃度として
一定であるので、抵抗率を任意に調整できない。（但
し、狭い範囲ならば、スパッタガス中に酸素を混入する
ことで微調整は可能である。） 高性能のＣＩＳ系薄膜太陽電池を製造できる基板加熱
温度範囲では表面の凹凸を制御したテクスチャー構造が
作製できない。[0008] Another drawback is that, in order to produce a ZnO-based transparent conductive film having the same film performance (carrier concentration and mobility) as that of the MOCVD method, 20
It is necessary to heat the substrate to 0 ° C. or higher. Since the DC sputtering method has a higher energy density than the RF sputtering method, the bonding interface or the surface of the light absorption layer is easily damaged. Since the amount of the alloy element for resistance adjustment is constant as the concentration in the target, the resistivity cannot be arbitrarily adjusted. (However, fine adjustment is possible by mixing oxygen into the sputtering gas within a narrow range.) Texture structure with controlled surface irregularities in the substrate heating temperature range where high-performance CIS-based thin-film solar cells can be manufactured Cannot be produced.
【０００９】[0009]
【発明が解決しようとする課題】本発明は前記のような
問題点を解消するためになされたもので、本発明の目的
は、ＭＯＣＶＤ法で作製したＺｎＯ：Ｂ透明導電膜と同
等の性能のものを、ＲＦスパッタ法及びＤＣスパッタ法
により作製することにより、スパッタ衝撃の影響を低減
し、高速、且つ大面積で製膜することである。SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to provide a ZnO: B transparent conductive film having the same performance as that of a MOCVD method. An object of the present invention is to produce a film by an RF sputtering method and a DC sputtering method so as to reduce the influence of a sputtering impact and to form a film at a high speed and in a large area.
【００１０】[0010]
【課題を解決するための手段】本発明は、裏面電極層上
に、光吸収層（ｐ形）、界面層（バッファー層）、窓層
（ｎ形）及び上部電極の順に積層される薄膜太陽電池の
窓層の製造方法であって、界面層上に低出力のＲＦスパ
ッタ法により界面保護膜として作用する第１の膜を作製
する工程と、前記第１の膜上にスパッタ法により第２の
透明導電膜を作製する工程と、前記第２の透明導電膜上
にスパッタ法により第３の透明導電膜を作製する工程と
からなり、前記各工程において、ＺｎＯ：Ａｌ又はＺｎ
Ｏ：Ｇａターゲットを用いる薄膜太陽電池のＺｎＯ系透
明導電膜の製造方法である。According to the present invention, there is provided a thin-film solar cell having a light absorbing layer (p-type), an interface layer (buffer layer), a window layer (n-type) and an upper electrode laminated in this order on a back electrode layer. A method for manufacturing a window layer of a battery, comprising: forming a first film acting as an interface protective film on an interface layer by low-power RF sputtering; and forming a second film on the first film by sputtering. And a step of forming a third transparent conductive film on the second transparent conductive film by a sputtering method. In each of the steps, ZnO: Al or Zn
This is a method for producing a ZnO-based transparent conductive film of a thin-film solar cell using an O: Ga target.
【００１１】本発明は、裏面電極層上に、光吸収層（ｐ
形）、界面層（バッファー層）、窓層（ｎ形）及び上部
電極の順に積層される薄膜太陽電池の窓層の製造方法で
あって、界面層上に低出力のＲＦマグネトロンスパッタ
法により界面保護膜として作用する第１の膜を作製する
工程と、前記第１の膜上にＤＣマグネトロンスパッタ法
により第２の透明導電膜を作製する工程と、前記第２の
透明導電膜上にＤＣマグネトロンスパッタ法により第３
の透明導電膜を作製する工程とからなり、前記各工程に
おいて、ＺｎＯ：Ａｌ又はＺｎＯ：Ｇａターゲットを用
いる薄膜太陽電池のＺｎＯ系透明導電膜の製造方法であ
る。According to the present invention, a light absorption layer (p
A method for manufacturing a window layer of a thin-film solar cell in which an interface layer (buffer layer), a window layer (n-type), and an upper electrode are stacked in this order, wherein the interface is formed on the interface layer by RF magnetron sputtering with low output. A step of forming a first film acting as a protective film, a step of forming a second transparent conductive film on the first film by a DC magnetron sputtering method, and a step of forming a DC magnetron on the second transparent conductive film Third by sputtering
And a method for producing a ZnO-based transparent conductive film for a thin-film solar cell using a ZnO: Al or ZnO: Ga target in each of the above steps.
【００１２】本発明は、前記ＲＦスパッタ法又はＲＦマ
グネトロンスパッタ法においては、パワー密度が２．２
Ｗ／ｃｍ2 以下で、ＺｎＯ：Ａｌ又はＺｎＯ：Ｇａ透明
導電膜を作製する薄膜太陽電池のＺｎＯ系透明導電膜の
製造方法である。According to the present invention, in the RF sputtering method or the RF magnetron sputtering method, the power density is 2.2.
This is a method for producing a ZnO-based transparent conductive film of a thin-film solar cell for producing a ZnO: Al or ZnO: Ga transparent conductive film at W / cm 2 or less.
【００１３】[0013]
【発明の実施の形態】以下、本発明の実施の形態を説明
する。本発明は、薄膜太陽電池の窓層として供されるＺ
ｎＯ系透明導電膜及びその製造方法に関するものであっ
て、従来のＭＯＣＶＤ法で作製したＺｎＯ：Ｂ透明導電
膜と同等の性能で、かつ、耐湿性に優れたＺｎＯ系透明
導電膜を、ＲＦスパッタ及びＤＣスパッタ法により製膜
することにより、接合界面へのスパッタ衝撃の影響を低
減し、高速に、且つ大面積の太陽電池を作製することが
できる。Embodiments of the present invention will be described below. The present invention relates to a Z layer provided as a window layer of a thin-film solar cell.
The present invention relates to an nO-based transparent conductive film and a method for producing the same, and a ZnO-based transparent conductive film having the same performance as a ZnO: B transparent conductive film produced by a conventional MOCVD method and having excellent moisture resistance is formed by RF sputtering. In addition, by forming a film by the DC sputtering method, the influence of sputter impact on the bonding interface can be reduced, and a large-area solar cell can be manufactured at high speed.
【００１４】先ず、ＺｎＯ：Ａｌ又はＺｎＯ：Ｇａター
ゲットを用いて低出力（５００Ｗ又は２．２Ｗ／ｃｍ2
以下）のＲＦスパッタ法により、接合面へのスパッタ衝
撃が少なく、接合界面保護膜として作用する第１の導電
膜を高抵抗バッファー層（界面層）上に形成し、その
後、複数の処理工程に分けて夫々ＺｎＯ：Ａｌ又はＺｎ
Ｏ：Ｇａターゲットを用いて高速製膜が可能なＤＣスパ
ッタ法により、窓層として供される第２の導電膜及び第
３の導電膜を形成することにより、接合面へのスパッタ
衝撃の影響を低減し、高速に、且つ大面積の太陽電池を
作製することができる。First, using a ZnO: Al or ZnO: Ga target, a low output (500 W or 2.2 W / cm 2)
By the following RF sputtering method, a first conductive film that acts as a bonding interface protective film with less sputter impact on the bonding surface is formed on a high-resistance buffer layer (interface layer), and is then subjected to a plurality of processing steps. Separately ZnO: Al or Zn
By forming a second conductive film and a third conductive film serving as window layers by a DC sputtering method capable of high-speed film formation using an O: Ga target, the influence of sputter impact on the bonding surface can be reduced. It is possible to manufacture a large-area solar cell with reduced power consumption at high speed.
【００１５】[0015]
【実施例】以下、本発明の実施例を図面に基づいて説明
する。本発明は、前記薄膜太陽電池の窓層として供され
る透明導電膜及び該透明導電膜の製造方法に関する。Embodiments of the present invention will be described below with reference to the drawings. The present invention relates to a transparent conductive film provided as a window layer of the thin-film solar cell and a method for producing the transparent conductive film.
【００１６】図１は本発明の透明導電膜を用いたＣＩＳ
系薄膜太陽電池の概略構成図である。薄膜太陽電池１は
基板２、裏面電極層３、光吸収層（ｐ形半導体）４、バ
ッファー層（界面層）５、窓層６及び上部電極７の順に
積層された積層構造体であり、特に、窓層６として供さ
れるｎ形の半導体である透明導電膜に特徴を有し、前記
窓層６は、界面層５上に形成され界面保護膜として作用
する第１の透明導電膜と、前記第１の導電膜上に形
成される第２の透明導電膜と、前記第２の透明導電膜
上に形成される第３の透明導電膜とからなる積層体
である。FIG. 1 shows a CIS using the transparent conductive film of the present invention.
It is a schematic structure figure of a system thin film solar cell. The thin-film solar cell 1 is a laminated structure in which a substrate 2, a back electrode layer 3, a light absorbing layer (p-type semiconductor) 4, a buffer layer (interface layer) 5, a window layer 6, and an upper electrode 7 are laminated in this order. A transparent conductive film that is an n-type semiconductor provided as a window layer 6, wherein the window layer 6 is formed on the interface layer 5 and acts as an interface protective film; A stacked body including a second transparent conductive film formed on the first conductive film and a third transparent conductive film formed on the second transparent conductive film.
【００１７】本発明の製造方法に使用される製造装置の
概略構成を図２に示す。製造装置は少なくとも、ＲＦス
パッタ処理部I 、ＤＣスパッタ処理部II、ＤＣスパッタ
処理部III 及びこれら各スパッタ処理部にスパッタリン
グ処理対象物である下記基板部材Ｘを搬送する搬送手段
（図示せず）から構成される。FIG. 2 shows a schematic configuration of a manufacturing apparatus used in the manufacturing method of the present invention. The manufacturing apparatus includes at least an RF sputtering unit I, a DC sputtering unit II, a DC sputtering unit III, and a conveying unit (not shown) for conveying a substrate member X to be sputtered to each of these sputtering units. Be composed.
【００１８】以下に本発明の製造方法を図１及び図２を
参照して説明する。先ず、図２に図示の前記製造装置で
ＺｎＯ透明導電膜を作製する前に、基板２上に裏面電極
層３、光吸収層（ｐ形半導体）４及びバッファー層（界
面層）５が形成されたもの（図１の斜線部分：以下、基
板部材Ｘという。）が準備される。The manufacturing method of the present invention will be described below with reference to FIGS. First, a back electrode layer 3, a light absorbing layer (p-type semiconductor) 4, and a buffer layer (interface layer) 5 are formed on a substrate 2 before producing a ZnO transparent conductive film by the manufacturing apparatus shown in FIG. (A hatched portion in FIG. 1; hereinafter, referred to as a substrate member X).
【００１９】先ず、最初の処理工程では、前記基板部材
Ｘが前記製造装置のＲＦスパッタ処理部I に搬送され、
ＲＦスパッタ処理部I において、ＺｎＯ：Ａｌあるいは
ＺｎＯ：Ｇａターゲット２１を用いてパワー密度が２．
２Ｗ／ｃｍ2 以下の低出力でＲＦスパッタリングを行う
ことにより、界面保護膜として作用する膜厚１００ｎｍ
以下の第１の透明導電膜が前記基板部材Ｘの高抵抗の
バッファー層（界面層）５上に形成される。このＲＦス
パッタ処理工程では、スパッタ出力が低出力であるた
め、接合界面へのスパッタ衝撃の影響が少ない。なお、
前記ＲＦスパッタ処理工程では、ＲＦマグネトロンスパ
ッタ法の他に、各種ＲＦスパッタ法を適用し得る。First, in the first processing step, the substrate member X is transported to the RF sputtering processing section I of the manufacturing apparatus,
In the RF sputtering processing part I, the power density is set to 2. using a ZnO: Al or ZnO: Ga target 21.
By performing RF sputtering at a low output of 2 W / cm 2 or less, a film thickness of 100 nm acting as an interface protective film
The following first transparent conductive film is formed on the high-resistance buffer layer (interface layer) 5 of the substrate member X. In this RF sputtering process, since the sputter output is low, the impact of sputter impact on the bonding interface is small. In addition,
In the RF sputtering process, various RF sputtering methods can be applied in addition to the RF magnetron sputtering method.
【００２０】次に、前記基板部材Ｘは前記製造装置の第
１ＤＣスパッタ処理部IIに搬送され、該第１ＤＣスパッ
タ処理部IIにおいて、ＺｎＯ：ＡｌあるいはＺｎＯ：Ｇ
ａターゲット２２を用いてＤＣスパッタリングを行うこ
とにより、第２の透明導電膜が前記基板部材Ｘの第１
の透明導電膜上に形成される。Next, the substrate member X is transported to the first DC sputter processing section II of the manufacturing apparatus, where the substrate member X is ZnO: Al or ZnO: G.
a By performing DC sputtering using the target 22, the second transparent conductive film
Is formed on the transparent conductive film.
【００２１】更に、前記基板部材Ｘは前記製造装置の第
２ＤＣスパッタ処理部III に搬送され、該第２ＤＣスパ
ッタ処理部III において、ＺｎＯ：ＡｌあるいはＺｎ
Ｏ：Ｇａターゲット２３を用いてＤＣスパッタリングを
行うことにより、第３の透明導電膜が前記基板部材Ｘ
の第２の透明導電膜上に形成される。なお、前記第２
及び第３のＤＣスパッタ処理工程では、ＤＣマグネトロ
ンスパッタ法の他に、各種ＤＣスパッタ法又は全てのＲ
Ｆスパッタ法を適用し得る。Further, the substrate member X is transported to a second DC sputter processing section III of the manufacturing apparatus, where ZnO: Al or Zn
By performing DC sputtering using an O: Ga target 23, a third transparent conductive film is formed on the substrate member X.
Formed on the second transparent conductive film. Note that the second
In the third DC sputtering process, in addition to the DC magnetron sputtering method, various DC sputtering methods or all R sputtering methods are used.
An F sputtering method can be applied.
【００２２】以上のように、本発明の製造方法において
は、前記ＺｎＯ系透明導電膜を作製するにあたり、ＲＦ
スパッタ法とＤＣスパッタ法とを併用するとともに、Ｄ
Ｃスパッタ法においては、第１ＤＣスパッタ処理部IIと
第２ＤＣスパッタ処理部IIIで、複数の処理工程に分け
て夫々ＺｎＯ：ＡｌあるいはＺｎＯ：Ｇａターゲットを
用いてＤＣスパッタ処理することにより、第２の透明導
電膜及び第３の透明導電膜を形成するので、同一膜
層を得るための各スパッタ処理工程でのターゲット一枚
当たりの出力を低減（１／ターゲットの枚数）すること
ができ、スパッタ衝撃の影響が低減される。As described above, according to the manufacturing method of the present invention, in manufacturing the ZnO-based transparent conductive film, RF
In addition to using both sputtering and DC sputtering,
In the C sputtering method, the first DC sputtering processing section II and the second DC sputtering processing section III perform DC sputtering processing using a ZnO: Al or ZnO: Ga target in a plurality of processing steps, respectively. Since the transparent conductive film and the third transparent conductive film are formed, the output per target in each sputtering process step for obtaining the same film layer can be reduced (1 / target number), and the sputtering impact can be reduced. Is reduced.
【００２３】また、ＲＦスパッタ処理部I 、第１ＤＣス
パッタ処理部II及び第２ＤＣスパッタ処理部III におい
ては、夫々の処理部において作製される透明導電膜、
及びの膜厚に応じて基板部材Ｘの搬送速度が調節さ
れる。In the RF sputtering unit I, the first DC sputtering unit II, and the second DC sputtering unit III, a transparent conductive film formed in each processing unit;
The transport speed of the substrate member X is adjusted according to the film thickness of the substrate and the thickness of the substrate.
【００２４】なお、前記実施例においては、ＤＣスパッ
タ処理を２工程に分けて行ったが、必要に応じてその工
程数を増加または減少してもよい。In the above embodiment, the DC sputtering process is performed in two steps. However, the number of steps may be increased or decreased as necessary.
【００２５】次に、本発明の製造方法により製膜された
窓層として供せられる透明導電膜を用いた太陽電池の特
性を以下に示す。本発明のＲＦスパッタ法及びＤＣスパ
ッタ法で作製した窓層の第１及び２層がＺｎＯ：Ａｌ、
第３層がＺｎＯ：Ｇａ透明導電膜からなる積層構造の太
陽電池（第３層のＤＣスパッタ電流：０．４Ａ）（Ａ）
と、本発明のＲＦスパッタ法及びＤＣスパッタ法で作製
した窓層の第１及び２層がＺｎＯ：Ａｌ、第３層がＺｎ
Ｏ：Ｇａ透明導電膜からなる積層構造の太陽電池（第３
層のＤＣスパッタ電流：０．６Ａ）（Ｂ）と、本発明の
ＲＦスパッタ法及びＤＣスパッタ法で作製した窓層の第
１〜３層がＺｎＯ：Ａｌ透明導電膜からなる積層構造の
太陽電池（Ｃ）と、ＤＣスパッタ法で作製した窓層が単
層のＺｎＯ：Ａｌ透明導電膜からなる太陽電池（Ｄ）の
太陽電池特性の比較結果を図３に示す。Next, the characteristics of the solar cell using the transparent conductive film provided as the window layer formed by the manufacturing method of the present invention will be described below. The first and second layers of the window layer produced by the RF sputtering method and the DC sputtering method of the present invention are ZnO: Al,
Solar cell having a laminated structure in which the third layer is made of a ZnO: Ga transparent conductive film (DC sputtering current of the third layer: 0.4 A) (A)
And the first and second window layers formed by the RF sputtering method and the DC sputtering method of the present invention are ZnO: Al, and the third layer is Zn.
O: A solar cell having a laminated structure composed of a Ga transparent conductive film (third structure)
Layer DC sputtering current: 0.6 A) (B), and a solar cell having a laminated structure in which the first to third layers of the window layer formed by the RF sputtering method and the DC sputtering method of the present invention are made of a ZnO: Al transparent conductive film. FIG. 3 shows a comparison result of solar cell characteristics between (C) and a solar cell (D) in which a window layer formed by a DC sputtering method has a single-layer ZnO: Al transparent conductive film.
【００２６】ＺｎＯ系透明導電膜の良否は、太陽電池特
性のうち、短絡電流密度（ＪSC）により膜自体の直列抵
抗値を、曲線因子（ＦＦ）により光吸収層表面又は接合
界面の界面接合特性に及ぼす影響を、夫々評価すること
ができる。前記図３の比較結果より、短絡電流密度（Ｊ
SC）、曲線因子（ＦＦ）及び、その積（ＪSC×ＦＦ）の
いずれも、単層のＺｎＯ：Ａｌ透明導電膜を用いた太陽
電池（Ｄ）に比べて、本発明の第１及び２層がＺｎＯ：
Ａｌ、第３層がＺｎＯ：Ｇａ透明導電膜からなる積層構
造の太陽電池（Ａ) 及び（Ｂ) 並びに第１〜３層がＺｎ
Ｏ：Ａｌからなる積層構造の透明導電膜を用いた太陽電
池（Ｃ）の方が良好な結果を示すことが判明した。The quality of the ZnO-based transparent conductive film is evaluated by determining the series resistance value of the film itself by the short-circuit current density (J SC ), the interface resistance of the light absorbing layer surface or the bonding interface by the fill factor (FF), among the solar cell characteristics. The effect on the properties can be evaluated individually. From the comparison result of FIG. 3, the short-circuit current density (J
SC ), the fill factor (FF), and the product thereof (J SC × FF) are all different from the solar cell (D) using a single-layer ZnO: Al transparent conductive film in the first and second embodiments of the present invention. The layer is ZnO:
Al and the solar cells (A) and (B) having a laminated structure in which the third layer is composed of a ZnO: Ga transparent conductive film, and the first to third layers are composed of Zn.
It was found that the solar cell (C) using a transparent conductive film having a laminated structure of O: Al showed better results.
【００２７】この結果より、ＤＣスパッタ法で作製した
窓層が積層構造のＺｎＯ：Ｇａ透明導電膜を使用するこ
とにより、従来の単層又は積層のＺｎＯ：Ａｌ透明導電
膜における膜の問題点であった、直列抵抗成分が大きい
ために、短絡電流密度（ＪSC）が低いという欠点を改善
でき、更に、低いＤＣスパッタ電流で製膜できるため、
界面接合特性を劣化させる欠点も透明導電膜の膜厚を薄
膜化することで解決できる。From these results, it was found that the use of the ZnO: Ga transparent conductive film having the laminated structure as the window layer formed by the DC sputtering method caused the problem of the conventional single-layer or laminated ZnO: Al transparent conductive film. The disadvantage that the short circuit current density (J SC ) is low due to the large series resistance component can be improved, and the film can be formed with a low DC sputtering current.
The disadvantage of deteriorating the interface bonding characteristics can also be solved by reducing the thickness of the transparent conductive film.
【００２８】本発明で提案する窓層が積層構造のＺｎＯ
系透明導電膜を使用した太陽電池と単層のＺｎＯ：Ａｌ
透明導電膜を用いた太陽電池の変換効率〔％〕の比較結
果を図４に示す。The window layer proposed in the present invention has a laminated structure of ZnO.
Cell using single transparent conductive film and ZnO: Al of single layer
FIG. 4 shows a comparison result of the conversion efficiency [%] of the solar cell using the transparent conductive film.
【００２９】（ａ）は単層のＺｎＯ：Ａｌ透明導電膜を
用いた太陽電池の特性、（ｂ）は第１及び２層がＺｎ
Ｏ：Ａｌ、第３層がＺｎＯ：Ｇａからなる積層構造の透
明導電膜を用いた太陽電池の特性、（ｃ）は本発明の第
１乃至３層がＺｎＯ：Ｇａからなる積層構造の透明導電
膜を用いた太陽電池（Ｇａの含有量：第１層３．４％、
第２及び３層５．７％）、（ｄ）は本発明の第１乃至３
層がＺｎＯ：Ｇａからなる積層構造の透明導電膜を用い
た太陽電池（Ｇａの含有量：第１乃至３層５．７％）の
特性である。(A) shows the characteristics of a solar cell using a single-layer ZnO: Al transparent conductive film, and (b) shows that the first and second layers are made of Zn.
Characteristics of a solar cell using a transparent conductive film having a laminated structure of O: Al and a third layer of ZnO: Ga, and (c) shows a transparent conductive film of a laminated structure of the first to third layers of ZnO: Ga of the present invention. Solar cell using film (Ga content: first layer 3.4%,
(2nd and 3rd layers 5.7%), (d) are the first to third layers of the present invention.
This is a characteristic of a solar cell (Ga content: first to third layers 5.7%) using a transparent conductive film having a layered structure of ZnO: Ga.
【００３０】前記図４の比較結果より、太陽電池の変換
効率では、単層のＺｎＯ：Ａｌ透明導電膜を用いた太陽
電池（ａ）と比べて、本発明のＺｎＯ：Ａｌ及びＺｎ
Ｏ：Ｇａの積層構造並びにＺｎＯ：Ｇａのみの積層構造
の太陽電池（ｂ）、（ｃ）、（ｄ）が良好な結果を示す
ことが判明した。According to the comparison result shown in FIG. 4, the conversion efficiency of the solar cell is higher than that of the solar cell (a) using a single-layer ZnO: Al transparent conductive film in comparison with the solar cell (a) of the present invention.
It was found that solar cells (b), (c), and (d) having a stacked structure of O: Ga and a stacked structure of only ZnO: Ga showed good results.
【００３１】[0031]
【発明の効果】以上のように、本発明は、低出力のＲＦ
スパッタ法によりＺｎＯ系透明導電膜の一部を製膜した
後、残りのＺｎＯ系透明導電膜部分をＤＣスパッタ法を
複数工程にわけてスパッタ処理することにより、スパッ
タ衝撃の影響を低減しつつ、ＭＯＣＶＤ法で作製したＺ
ｎＯ：Ｂ透明導電膜と同等の性能を有する透明導電膜
を、高速、且つ大面積で製膜することができる。また、
ＺｎＯ：Ｇａ層を積層構造の中に取り入れることによ
り、耐湿性を確保することができる。As described above, the present invention provides a low-power RF
After forming a part of the ZnO-based transparent conductive film by the sputtering method, the remaining ZnO-based transparent conductive film portion is subjected to the sputtering process by dividing the DC sputtering method into a plurality of steps, thereby reducing the influence of the sputtering impact. Z produced by MOCVD
A transparent conductive film having performance equivalent to that of the nO: B transparent conductive film can be formed at high speed and in a large area. Also,
By incorporating the ZnO: Ga layer into the laminated structure, moisture resistance can be ensured.
【００３２】更に、ＤＣスパッタ法で作製した積層構造
のＺｎＯ：Ｇａ透明導電膜を使用することにより、ＤＣ
スパッタ法における高速製膜が可能であるという長所を
生かしつつ、直列抵抗値を低減して、短絡電流密度（Ｊ
SC）を大きくすることができると共に、透明導電膜の膜
厚を薄膜化することにより、接合界面又は光吸収層表面
の損傷を防止して、界面接合特性を改善することが可能
となり、曲線因子（ＦＦ）を大きくできる。Further, by using a ZnO: Ga transparent conductive film having a laminated structure produced by a DC sputtering method, a DC
While taking advantage of the fact that high-speed film formation by sputtering is possible, the series resistance is reduced and the short-circuit current density (J
SC ) can be increased, and by reducing the thickness of the transparent conductive film, damage to the bonding interface or the surface of the light absorbing layer can be prevented, and the interface bonding characteristics can be improved. (FF) can be increased.
Claims (6)
面層（バッファー層）、窓層（ｎ型）及び上部電極の順
に積層される薄膜太陽電池のＺｎＯ系透明導電膜におい
て、前記窓層が、界面層上に形成され界面保護膜として
作用する第１の膜と、前記第１の膜上に形成される第２
のＺｎＯ系透明導電膜と、前記第２の透明導電膜上に形
成される第３のＺｎＯ系透明導電膜とからなる積層体
で、前記第１膜及び第２〜３の透明導電膜がＺｎＯ：Ａ
ｌ又はＺｎＯ：Ｇａからなることを特徴とする薄膜太陽
電池のＺｎＯ系透明導電膜。1. A ZnO-based transparent conductive film of a thin-film solar cell in which a light absorbing layer (p-type), an interface layer (buffer layer), a window layer (n-type) and an upper electrode are laminated on a back electrode layer in this order. A first film formed on the interface layer and acting as an interface protective film, and a second film formed on the first film;
And a third ZnO-based transparent conductive film formed on the second transparent conductive film, wherein the first film and the second to third transparent conductive films are made of ZnO-based transparent conductive film. : A
1 or ZnO: A ZnO-based transparent conductive film for a thin-film solar cell, comprising Ga.
であることを特徴とする請求項１記載の薄膜太陽電池の
ＺｎＯ系透明導電膜。2. The ZnO-based transparent conductive film according to claim 1, wherein the first film has a thickness of 100 nm or less.
電膜は、ドーパントとしてＡｌ、Ｇａ、Ｉｎ、Ｂ又はこ
れらの組み合わせたものを含むＺｎＯからなることを特
徴とする請求項１記載の薄膜太陽電池のＺｎＯ系透明導
電膜。3. The method according to claim 1, wherein the second transparent conductive film and the third transparent conductive film are made of ZnO containing Al, Ga, In, B or a combination thereof as a dopant. ZnO-based transparent conductive film for thin-film solar cells.
面層（バッファー層）、窓層（型形）及び上部電極の順
に積層される薄膜太陽電池のＺｎＯ系透明導電膜の製造
方法であって、界面層上にＲＦスパッタ法により第１の
膜（界面保護膜として作用する）を作製する工程と、前
記第１の膜上にスパッタ法により第２の透明導電膜を作
製する工程と、前記第２の透明導電膜上にスパッタ法に
より第３の透明導電膜を作製する工程とからなり、前記
各工程において、ＺｎＯ：Ａｌ又はＺｎＯ：Ｇａターゲ
ットを用いることを特徴とする薄膜太陽電池のＺｎＯ系
透明導電膜の製造方法。4. A ZnO-based transparent conductive film of a thin-film solar cell which is laminated on a back electrode layer in the order of a light absorbing layer (p-type), an interface layer (buffer layer), a window layer (model) and an upper electrode. A method for producing a first film (acting as an interfacial protective film) on an interface layer by RF sputtering, and producing a second transparent conductive film on the first film by sputtering. And a step of forming a third transparent conductive film on the second transparent conductive film by a sputtering method. In each of the above steps, a ZnO: Al or ZnO: Ga target is used. A method for producing a ZnO-based transparent conductive film for a thin-film solar cell.
面層（バッファー層）、窓層（ｎ型）及び上部電極の順
に積層される薄膜太陽電池のＺｎＯ系透明導電膜の製造
方法であって、界面層上にＲＦマグネトロンスパッタ法
により第１の膜（界面保護膜として作用する）を作製す
る工程と、前記第１の膜上にＤＣマグネトロンスパッタ
法により第２の透明導電膜を作製する工程と、前記第２
の透明導電膜上にＤＣマグネトロンスパッタ法により第
３の透明導電膜を作製する工程とからなり、前記各工程
において、ＺｎＯ：Ａｌ又はＺｎＯ：Ｇａターゲットを
用いることを特徴とする薄膜太陽電池のＺｎＯ系透明導
電膜の製造方法。5. A ZnO-based transparent conductive film of a thin-film solar cell which is laminated on a back electrode layer in the order of a light absorbing layer (p-type), an interface layer (buffer layer), a window layer (n-type) and an upper electrode. A method of manufacturing a first film (acting as an interface protective film) on an interface layer by RF magnetron sputtering, and a method of forming a second transparent conductive film on the first film by DC magnetron sputtering. Forming a film;
Forming a third transparent conductive film on the transparent conductive film by a DC magnetron sputtering method, wherein each step uses a ZnO: Al or ZnO: Ga target. Method for producing transparent transparent conductive film.
ンスパッタ法においては、パワー密度が２．２Ｗ／ｃｍ
2 以下で、ＺｎＯ：Ａｌ又はＺｎＯ：Ｇａ透明導電膜を
作製することを特徴とする請求項４又は５記載の薄膜太
陽電池のＺｎＯ系透明導電膜の製造方法。6. A power density of 2.2 W / cm in the RF sputtering method or the RF magnetron sputtering method.
6. The method for producing a ZnO-based transparent conductive film of a thin-film solar cell according to claim 4, wherein a ZnO: Al or ZnO: Ga transparent conductive film is prepared in 2 or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10098228A JP3040373B2 (en) | 1998-03-27 | 1998-03-27 | Method of manufacturing ZnO-based transparent conductive film for thin film solar cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10098228A JP3040373B2 (en) | 1998-03-27 | 1998-03-27 | Method of manufacturing ZnO-based transparent conductive film for thin film solar cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11284211A true JPH11284211A (en) | 1999-10-15 |
| JP3040373B2 JP3040373B2 (en) | 2000-05-15 |
Family
ID=14214113
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10098228A Expired - Fee Related JP3040373B2 (en) | 1998-03-27 | 1998-03-27 | Method of manufacturing ZnO-based transparent conductive film for thin film solar cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3040373B2 (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003264307A (en) * | 2002-03-11 | 2003-09-19 | Sharp Corp | Thin film solar cell and its manufacturing method |
| US6822158B2 (en) * | 2002-03-11 | 2004-11-23 | Sharp Kabushiki Kaisha | Thin-film solar cell and manufacture method therefor |
| KR100682741B1 (en) | 2005-06-17 | 2007-02-15 | 한국과학기술연구원 | Fabrication method of zinc oxide based transparent conductive oxide thin film |
| JP2007527121A (en) * | 2004-03-05 | 2007-09-20 | ソリブロ アーベー | Method and apparatus for in-line process control of CIGS process |
| US7315662B2 (en) | 2000-08-25 | 2008-01-01 | N Gimat Co. | Electronic and optical devices and methods of forming these devices |
| WO2008059857A1 (en) * | 2006-11-17 | 2008-05-22 | Kaneka Corporation | Thin-film photoelectric conversion device |
| EP2028695A1 (en) * | 2007-07-12 | 2009-02-25 | Applied Materials, Inc. | Method for creating a transparent conductible oxide coating |
| WO2009041659A1 (en) | 2007-09-28 | 2009-04-02 | Fujifilm Corporation | Solar cell |
| WO2009041657A1 (en) | 2007-09-28 | 2009-04-02 | Fujifilm Corporation | Substrate for solar cell and solar cell |
| JP2009199986A (en) * | 2008-02-25 | 2009-09-03 | Sumitomo Metal Mining Co Ltd | Zinc oxide transparent conductive film lamination layer, transparent conductive substrate and device |
| WO2009110092A1 (en) * | 2008-03-07 | 2009-09-11 | 昭和シェル石油株式会社 | Laminated structuer of cis-type solar battery and integrated structure |
| JP2009259938A (en) * | 2008-04-15 | 2009-11-05 | Honda Motor Co Ltd | Method of manufacturing chalcopyrite thin film solar cell, and apparatus therefor |
| JP2009265629A (en) * | 2008-03-31 | 2009-11-12 | Kochi Univ Of Technology | Display substrate, and manufacturing method and display device therefor |
| JP2010199305A (en) * | 2009-02-25 | 2010-09-09 | Mitsubishi Heavy Ind Ltd | Method of manufacturing photoelectric conversion device |
| KR20130027991A (en) * | 2011-09-08 | 2013-03-18 | 서울옵토디바이스주식회사 | Ito for transparent electrode and method for the same |
| JP2013533637A (en) * | 2010-07-30 | 2013-08-22 | エルジー イノテック カンパニー リミテッド | Photovoltaic power generation apparatus and manufacturing method thereof |
| CN103681888A (en) * | 2013-12-24 | 2014-03-26 | 上海交通大学 | Silicon-based thin-film solar cell with doped ZnOnano-wires distributed on surface |
| JP2020204057A (en) * | 2019-06-14 | 2020-12-24 | 株式会社アルバック | Formation method of transparent conductive oxide film, sputtering apparatus and solar cell |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102804399A (en) * | 2009-06-16 | 2012-11-28 | Lg伊诺特有限公司 | Solar cell and method of fabricating the same |
| US8546797B2 (en) | 2009-10-20 | 2013-10-01 | Stanley Electric Co., Ltd. | Zinc oxide based compound semiconductor device |
| KR101154577B1 (en) * | 2010-07-30 | 2012-06-08 | 엘지이노텍 주식회사 | Solar cell and method of fabricating the same |
-
1998
- 1998-03-27 JP JP10098228A patent/JP3040373B2/en not_active Expired - Fee Related
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7315662B2 (en) | 2000-08-25 | 2008-01-01 | N Gimat Co. | Electronic and optical devices and methods of forming these devices |
| US6822158B2 (en) * | 2002-03-11 | 2004-11-23 | Sharp Kabushiki Kaisha | Thin-film solar cell and manufacture method therefor |
| JP2003264307A (en) * | 2002-03-11 | 2003-09-19 | Sharp Corp | Thin film solar cell and its manufacturing method |
| JP2007527121A (en) * | 2004-03-05 | 2007-09-20 | ソリブロ アーベー | Method and apparatus for in-line process control of CIGS process |
| KR100682741B1 (en) | 2005-06-17 | 2007-02-15 | 한국과학기술연구원 | Fabrication method of zinc oxide based transparent conductive oxide thin film |
| WO2008059857A1 (en) * | 2006-11-17 | 2008-05-22 | Kaneka Corporation | Thin-film photoelectric conversion device |
| EP2028695A1 (en) * | 2007-07-12 | 2009-02-25 | Applied Materials, Inc. | Method for creating a transparent conductible oxide coating |
| WO2009041659A1 (en) | 2007-09-28 | 2009-04-02 | Fujifilm Corporation | Solar cell |
| WO2009041657A1 (en) | 2007-09-28 | 2009-04-02 | Fujifilm Corporation | Substrate for solar cell and solar cell |
| JP4670877B2 (en) * | 2008-02-25 | 2011-04-13 | 住友金属鉱山株式会社 | Zinc oxide based transparent conductive film laminate, transparent conductive substrate and device |
| JP2009199986A (en) * | 2008-02-25 | 2009-09-03 | Sumitomo Metal Mining Co Ltd | Zinc oxide transparent conductive film lamination layer, transparent conductive substrate and device |
| WO2009110092A1 (en) * | 2008-03-07 | 2009-09-11 | 昭和シェル石油株式会社 | Laminated structuer of cis-type solar battery and integrated structure |
| JP2009265629A (en) * | 2008-03-31 | 2009-11-12 | Kochi Univ Of Technology | Display substrate, and manufacturing method and display device therefor |
| JP2009259938A (en) * | 2008-04-15 | 2009-11-05 | Honda Motor Co Ltd | Method of manufacturing chalcopyrite thin film solar cell, and apparatus therefor |
| JP2010199305A (en) * | 2009-02-25 | 2010-09-09 | Mitsubishi Heavy Ind Ltd | Method of manufacturing photoelectric conversion device |
| JP2013533637A (en) * | 2010-07-30 | 2013-08-22 | エルジー イノテック カンパニー リミテッド | Photovoltaic power generation apparatus and manufacturing method thereof |
| US9871159B2 (en) | 2010-07-30 | 2018-01-16 | Lg Innotek Co., Ltd. | Apparatus for generating electricity using solar power and method for manufacturing same |
| KR20130027991A (en) * | 2011-09-08 | 2013-03-18 | 서울옵토디바이스주식회사 | Ito for transparent electrode and method for the same |
| CN103681888A (en) * | 2013-12-24 | 2014-03-26 | 上海交通大学 | Silicon-based thin-film solar cell with doped ZnOnano-wires distributed on surface |
| JP2020204057A (en) * | 2019-06-14 | 2020-12-24 | 株式会社アルバック | Formation method of transparent conductive oxide film, sputtering apparatus and solar cell |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3040373B2 (en) | 2000-05-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3527815B2 (en) | Method for producing transparent conductive film of thin film solar cell | |
| JP3040373B2 (en) | Method of manufacturing ZnO-based transparent conductive film for thin film solar cell | |
| US6137048A (en) | Process for fabricating polycrystalline semiconductor thin-film solar cells, and cells produced thereby | |
| JP3249408B2 (en) | Method and apparatus for manufacturing thin film light absorbing layer of thin film solar cell | |
| US6534704B2 (en) | Solar cell | |
| US6169246B1 (en) | Photovoltaic devices comprising zinc stannate buffer layer and method for making | |
| JP2002057359A (en) | Laminated solar battery | |
| WO2006016577A1 (en) | Cis type compound semiconductor thin film solar cell and method for preparing light-absorbing layer of said solar cell | |
| US20130133734A1 (en) | Photovoltaic cell | |
| Takamoto et al. | Improved junction formation procedure for low temperature deposited CdSCdTe solar cells | |
| EP2403015B1 (en) | Thin film article and method for forming a reduced conductive area in transparent conductive films for photovoltaic modules | |
| CN101393942B (en) | Polycrystalline-silicon carbide lamination thin-film solar cell | |
| JP2014503125A (en) | Solar cell and manufacturing method thereof | |
| CN103469170B (en) | A kind of sputtering target for thin-film solar cells | |
| JP2003282902A (en) | Thin film solar cell | |
| JP2003282600A (en) | Method and device for manufacturing light-absorbing layer | |
| JPH10190030A (en) | Photovoltaic element | |
| JPH10150212A (en) | Precursor for semiconductor thin film formation use and manufacture of semiconductor thin film | |
| KR20100085769A (en) | Cds/cdte thin film solar cells and manufacturing method thereof | |
| JP4215697B2 (en) | Photoelectric conversion device and manufacturing method thereof | |
| JP2975693B2 (en) | Method for producing chalcopyrite-type compound thin film | |
| JP2000012883A (en) | Manufacture of solar cell | |
| CN103474514B (en) | The preparation method of copper indium gallium selenium solar cell | |
| JP2000174306A (en) | Manufacture of compound semiconductor thin film | |
| JPH0456172A (en) | Method for forming thin cuinse2 film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313115 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080303 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090303 Year of fee payment: 9 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090303 Year of fee payment: 9 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090303 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100303 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100303 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110303 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110303 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120303 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120303 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130303 Year of fee payment: 13 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130303 Year of fee payment: 13 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140303 Year of fee payment: 14 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |