JPH0878714A - Photoelectromotive device and manufacture of photoelectromotive device - Google Patents
Photoelectromotive device and manufacture of photoelectromotive deviceInfo
- Publication number
- JPH0878714A JPH0878714A JP6213796A JP21379694A JPH0878714A JP H0878714 A JPH0878714 A JP H0878714A JP 6213796 A JP6213796 A JP 6213796A JP 21379694 A JP21379694 A JP 21379694A JP H0878714 A JPH0878714 A JP H0878714A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- transparent electrode
- sio
- sno
- photovoltaic device
- 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.)
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Classifications
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- 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]
【産業上の利用分野】本発明は、アモルファスシリコン
（以下、ａ−Ｓｉという）を用いた光起電力装置及びそ
の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photovoltaic device using amorphous silicon (hereinafter referred to as a-Si) and a manufacturing method thereof.
【０００２】[0002]
【従来の技術】光電変換層としてアモルファスシリコン
（以下、ａ−Ｓｉという）膜を有する光起電力装置にあ
っては、コストと特性との両面に基づいて、ソーダガラ
ス（青板ガラス）基板上に常圧ＣＶＤ法にて形成したＳ
ｎＯ2 膜を透明電極として利用している。そして、Ｓｎ
Ｏ2 膜の形成時に青板ガラス基板よりＮａ+ ，Ｋ+ 等の
アルカリイオンがＳｎＯ2 中に拡散して、透明電極とし
ての特性が劣化することを防止するために、ＳｎＯ2 膜
の形成前に、青板ガラス基板上に厚さ1000〜2000Å程度
のＳｉＯ2 層を、スパッタ法、または、ＳｉＨ4 ＋Ｏ2
の熱ＣＶＤ法等にて形成しておくことが一般的である。
また、このＳｎＯ2 膜とこの上方に設けるａ−Ｓｉ膜と
の間に、ａ−Ｓｉ膜を形成する際のプラズマ放電による
酸素の還元を防止する目的にて、プラズマ耐性に優れた
ＺｎＯ層を挿入することもなされている。2. Description of the Related Art In a photovoltaic device having an amorphous silicon (hereinafter referred to as a-Si) film as a photoelectric conversion layer, a soda glass (blue plate glass) substrate is formed on the basis of cost and characteristics. S formed by atmospheric pressure CVD method
The nO 2 film is used as a transparent electrode. And Sn
Before the formation of the SnO 2 film, in order to prevent alkali ion such as Na + , K +, etc. from diffusing into SnO 2 from the soda-lime glass substrate at the time of forming the O 2 film and deteriorating the characteristics as a transparent electrode. , A SiO 2 layer with a thickness of about 1000 to 2000 Å on a soda-lime glass substrate by sputtering or SiH 4 + O 2
It is generally formed by the thermal CVD method or the like.
In addition, a ZnO layer excellent in plasma resistance is provided between the SnO 2 film and the a-Si film provided above the SnO 2 film in order to prevent oxygen reduction due to plasma discharge when forming the a-Si film. It has also been inserted.
【０００３】[0003]
【発明が解決しようとする課題】上述したような、透明
電極（ＳｎＯ2 膜）の基板側におけるＳｉＯ2 層の形
成、及び、透明電極（ＳｎＯ2 膜）とａ−Ｓｉ膜との間
のＺｎＯ層の挿入により、製造されるａ−Ｓｉ光起電力
装置の性能は著しく改善されたが、製造プロセスが煩雑
であるので、低コスト化という観点からは問題があり、
また、製造プロセスの煩雑さに起因して歩留りが低いと
いう難点がある。[SUMMARY OF THE INVENTION] as described above, formation of the SiO 2 layer in the substrate side of the transparent electrode (SnO 2 film), and, ZnO between the transparent electrode (SnO 2 film) and a-Si film By inserting the layers, the performance of the manufactured a-Si photovoltaic device was significantly improved, but since the manufacturing process is complicated, there is a problem from the viewpoint of cost reduction,
Further, there is a drawback that the yield is low due to the complexity of the manufacturing process.
【０００４】本発明は斯かる事情に鑑みてなされたもの
であり、製造プロセスの簡素化を図ることができて従来
に比べて低コスト化を実現でき、しかも、歩留りの向上
を図ることができる光起電力装置及びその製造方法を提
供することを目的とする。The present invention has been made in view of such circumstances, and the manufacturing process can be simplified, the cost can be reduced as compared with the conventional one, and the yield can be improved. It is an object of the present invention to provide a photovoltaic device and a manufacturing method thereof.
【０００５】[0005]
【課題を解決するための手段】本願の請求項１に係る光
起電力装置は、ガラス基板上に、ＳｎＯ2 を主成分とす
る透明電極，アモルファスシリコン膜をこの順に有する
光起電力装置において、前記ガラス基板と前記透明電極
との間、及び／または、前記透明電極と前記アモルファ
スシリコン膜との間に、ＳｉＯ2 層を設けたことを特徴
とする。A photovoltaic device according to claim 1 of the present application is a photovoltaic device having a transparent electrode containing SnO 2 as a main component and an amorphous silicon film in this order on a glass substrate. A SiO 2 layer is provided between the glass substrate and the transparent electrode and / or between the transparent electrode and the amorphous silicon film.
【０００６】本願の請求項２に係る光起電力装置は、請
求項１において、前記ＳｉＯ2 層と前記透明電極との間
に、前記ＳｉＯ2 層側から前記透明電極側に向かうにつ
れてＳｎＯ2 の含有率を連続的または階段状に増加させ
たＳｉＯ2 ／ＳｎＯ2 混在層を設けたことを特徴とす
る。The photovoltaic device according to claim 2 of the present application is the photovoltaic device according to claim 1, in which SnO 2 is added between the SiO 2 layer and the transparent electrode as it goes from the SiO 2 layer side toward the transparent electrode side. It is characterized in that a SiO 2 / SnO 2 mixed layer whose content rate is increased continuously or stepwise is provided.
【０００７】本願の請求項３に係る光起電力装置の製造
方法は、ＳｉＯ2 層を有する光起電力装置を製造する方
法において、Ｓｉ（ＮＣＯ）4 ＋Ｈ2 Ｏの低温ＣＶＤ法
により前記ＳｉＯ2 層を形成することを特徴とする。A method of manufacturing a photovoltaic device according to claim 3 of the present application is the method of manufacturing a photovoltaic device having a SiO 2 layer, wherein the SiO 2 is formed by a low temperature CVD method of Si (NCO) 4 + H 2 O. It is characterized by forming a layer.
【０００８】本願の請求項４に係る光起電力装置の製造
方法は、ガラス基板上に、ＳｎＯ2を主成分とする透明
電極，アモルファスシリコン膜をこの順に有する光起電
力装置を製造する方法において、前記ガラス基板と前記
透明電極との間、及び／または、前記透明電極と前記ア
モルファスシリコン膜との間に、Ｓｉ（ＮＣＯ）4 ＋Ｈ
2 Ｏの低温ＣＶＤ法によりＳｉＯ2 層を形成することを
特徴とする。The method for manufacturing a photovoltaic device according to claim 4 of the present application is the method for manufacturing a photovoltaic device having a transparent electrode containing SnO 2 as a main component and an amorphous silicon film in this order on a glass substrate. , Si (NCO) 4 + H between the glass substrate and the transparent electrode and / or between the transparent electrode and the amorphous silicon film.
The feature is that the SiO 2 layer is formed by a low temperature CVD method of 2 O.
【０００９】本願の請求項５に係る光起電力装置の製造
方法は、請求項４において、前記ＳｉＯ2 層と前記透明
電極との間に、Ｈ2 Ｏ雰囲気中で、ＳｎＣｌ4 またはＳ
ｎ（ＣＨ3 ）4 とＳｉ（ＮＣＯ）4 との流量比を連続的
または階段状に変化させて、前記ＳｉＯ2 層側から前記
透明電極側に向かうにつれてＳｎＯ2 の含有率が高くな
るＳｉＯ2 ／ＳｎＯ2 混在層を形成することを特徴とす
る。The method for manufacturing a photovoltaic device according to claim 5 of the present application is the method according to claim 4, wherein SnCl 4 or S is added between the SiO 2 layer and the transparent electrode in an H 2 O atmosphere.
n (CH 3) 4 and Si (NCO) the flow ratio of 4 by changing continuously or stepwise, the content of SnO 2 increases toward the transparent electrode side from the SiO 2 layer side SiO 2 / SnO 2 mixed layer is formed.
【００１０】[0010]
【作用】本発明の光起電力装置では、ガラス基板と透明
電極（ＳｎＯ2 膜）との間、及び／または、透明電極と
ａ−Ｓｉ膜との間に、ＳｉＯ2 層を設けている。ガラス
基板と透明電極との間のＳｉＯ2 層は、アルカリイオン
のガラス基板から透明電極への拡散を防止する。また、
透明電極とａ−Ｓｉ膜との間のＳｉＯ2 層は、後にプラ
ズマＣＶＤ法によりａ−Ｓｉ膜を形成する際の透明電極
に対するプラズマ放電の影響を低減する。また、これら
のＳｉＯ2 層と透明電極（ＳｎＯ2 膜）との間にその混
合比を層厚方向に変化させたＳｉＯ2 ／ＳｎＯ2 混在層
を設けると、透明電極との付着力が強くなって安定した
透明電極が得られる。In the photovoltaic device of the present invention, the SiO 2 layer is provided between the glass substrate and the transparent electrode (SnO 2 film) and / or between the transparent electrode and the a-Si film. The SiO 2 layer between the glass substrate and the transparent electrode prevents the diffusion of alkali ions from the glass substrate to the transparent electrode. Also,
The SiO 2 layer between the transparent electrode and the a-Si film reduces the influence of plasma discharge on the transparent electrode when the a-Si film is subsequently formed by the plasma CVD method. Further, when a SiO 2 / SnO 2 mixed layer whose mixing ratio is changed in the layer thickness direction is provided between the SiO 2 layer and the transparent electrode (SnO 2 film), the adhesive force with the transparent electrode becomes strong. A stable and stable transparent electrode can be obtained.
【００１１】本発明の光起電力装置の製造方法では、ガ
ラス基板と透明電極との間、及び／または、透明電極と
ａ−Ｓｉ膜との間に、Ｓｉ（ＮＣＯ）4 ＋Ｈ2 Ｏの低温
ＣＶＤ法を用いてＳｉＯ2 層を形成する。Ｓｉ（ＮＣ
Ｏ）4 は、室温程度の低温環境でもＨ2 Ｏと反応してＳ
ｉＯ2 を形成できるので、Ｈ2 Ｏ雰囲気でのＣＶＤ法に
より透明電極（ＳｎＯ2 膜）を形成するプロセス設備と
同一のプロセス設備を使用できる。よって、製造プロセ
スの簡素化を実現して、従来例に比べて低コスト化を図
れる。また、同一のプロセス設備を使用できるので、プ
ロセス設備を変更する際に生じる歩留りの低下も抑制で
きる。また、毒性が強くて取扱いに注意を要するＳｉＨ
4 に代えて、原料ガスとして毒性が弱いＳｉ（ＮＣＯ）
4 を使用するので、安全性も高い。In the method for manufacturing a photovoltaic device of the present invention, Si (NCO) 4 + H 2 O at a low temperature is provided between the glass substrate and the transparent electrode and / or between the transparent electrode and the a-Si film. A SiO 2 layer is formed by using the CVD method. Si (NC
O) 4 reacts with H 2 O even in a low temperature environment such as room temperature to give S
Since iO 2 can be formed, the same process equipment as the process equipment for forming the transparent electrode (SnO 2 film) by the CVD method in the H 2 O atmosphere can be used. Therefore, the manufacturing process can be simplified and the cost can be reduced as compared with the conventional example. Further, since the same process equipment can be used, it is possible to suppress a decrease in yield that occurs when changing the process equipment. Also, SiH is highly toxic and requires careful handling.
Instead of 4 , Si (NCO), which has low toxicity as a source gas
Since 4 is used, it is highly safe.
【００１２】[0012]
【実施例】以下、本発明をその実施例を示す図面に基づ
いて具体的に説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below with reference to the drawings showing the embodiments.
【００１３】図１は、本発明の光起電力装置の一実施例
の構成を示す断面図である。図１において、１はガラス
基板としての青板ガラスであり、青板ガラス１上には、
第１のＳｉＯ2 層２（膜厚：約1000Å），第１の界面層
３（膜厚：約 300Å），ＳｎＯ2 膜からなる透明電極４
（膜厚：約8000Å）がこの順に積層形成されている。第
１の界面層３は、ＳｉＯ2 ／ＳｎＯ2 の混在層であり、
その混合率は第１のＳｉＯ2 層２側から透明電極４側に
向かってＳｎＯ2 の割合が連続的または階段状に増加し
ている。FIG. 1 is a sectional view showing the structure of an embodiment of the photovoltaic device of the present invention. In FIG. 1, 1 is a soda-lime glass as a glass substrate, and on the soda-lime glass 1,
First SiO 2 layer 2 (thickness: about 1000 Å), first interface layer 3 (thickness: about 300 Å), transparent electrode 4 made of SnO 2 film
(Film thickness: about 8000Å) is laminated in this order. The first interface layer 3 is a mixed layer of SiO 2 / SnO 2 ,
As for the mixing ratio, the ratio of SnO 2 increases continuously or stepwise from the first SiO 2 layer 2 side toward the transparent electrode 4 side.
【００１４】また、透明電極４上には、第２の界面層５
（膜厚：約 300Å），第２のＳｉＯ 2 層６（膜厚：約10
00Å）がこの順に積層形成されている。第２の界面層５
は、ＳｉＯ2 ／ＳｎＯ2 の混在層であり、その混合率は
透明電極４側から第２のＳｉＯ2 層６側に向かってＳｎ
Ｏ2 の割合が連続的または階段状に減少している。A second interface layer 5 is formed on the transparent electrode 4.
(Film thickness: about 300Å), second SiO 2Layer 6 (film thickness: about 10
00Å) is laminated in this order. Second interface layer 5
Is SiO2/ SnO2It is a mixed layer of
The second SiO from the transparent electrode 4 side2Sn toward layer 6
O2The ratio of is decreasing continuously or stepwise.
【００１５】第２のＳｉＯ2 層６上には、ボロンドープ
のａ−ＳｉＣ：Ｈよりなるｐ型半導体層7a（膜厚： 100
〜 300Å）, ａ−Ｓｉ：Ｈよりなるｉ型半導体層7b（膜
厚：3000〜5000Å）及びリンドープのμＣーＳｉ：Ｈよ
りなるｎ型半導体層7c（膜厚： 100〜 300Å）の積層体
である光電変換層としてのａ−Ｓｉ膜７と、Ａｌ，Ａｇ
等からなる裏面電極８（膜厚：約1000Å）とがこの順に
積層形成されている。On the second SiO 2 layer 6, a p-type semiconductor layer 7a (film thickness: 100) made of boron-doped a-SiC: H is formed.
~ 300Å), an i-type semiconductor layer 7b (thickness: 3000 to 5000Å) made of a-Si: H and an n-type semiconductor layer 7c (thickness: 100 to 300Å) made of phosphorus-doped μC-Si: H. A-Si film 7 as a photoelectric conversion layer, and Al, Ag
A back electrode 8 (thickness: about 1000 Å) made of the same material is laminated in this order.
【００１６】次に、このような構成の光起電力装置の製
造手順について、その工程を示す図２，図３を参照して
説明する。Next, a manufacturing procedure of the photovoltaic device having such a structure will be described with reference to FIGS.
【００１７】まず、常圧ＣＶＤ装置内に青板ガラス１を
搬入して、炉内温度を約 500℃にした状態で、ガス状の
Ｓｉ（ＮＣＯ）4 とＨ2 Ｏとを導入し、青板ガラス１上
に第１のＳｉＯ2 層２を形成する（図２（ａ））。次
に、Ｓｉ（ＮＣＯ）4 ，Ｈ2 Ｏに加えてＳｎＣｌ4 を導
入して、第１のＳｉＯ2 層２上に第１の界面層３を形成
する（図２（ｂ））。この際、Ｓｉ（ＮＣＯ）4 の流量
をゼロまで除々に減らしていくと共に、ＳｎＣｌ4 の流
量をゼロから除々に増やしていくことにより、第１のＳ
ｉＯ2 層２側でＳｉＯ2 の含有率が高く第１のＳｉＯ2
層２から離れるにつれてＳｉＯ2 の含有率が低くなる第
１の界面層（ＳｉＯ2 ／ＳｎＯ2 混在層）３を形成す
る。ここで、第１のＳｉＯ2 層２及び第１の界面層３の
膜厚は、あまり薄いとそれぞれの効果（青板ガラス１か
らのアルカリイオンの散乱の防止効果，付着力の向上効
果）がなく、逆に厚すぎるとコスト的に無駄となるの
で、第１のＳｉＯ2 層２，第１の界面層３の厚さはそれ
ぞれ、500 〜3000Å，100 〜500Å程度が最適である。First, the soda lime glass 1 was carried into the atmospheric pressure CVD apparatus, and in the state where the temperature inside the furnace was about 500 ° C., gaseous Si (NCO) 4 and H 2 O were introduced to the soda lime glass. A first SiO 2 layer 2 is formed on the substrate 1 (FIG. 2A). Next, SnCl 4 is introduced in addition to Si (NCO) 4 and H 2 O to form the first interface layer 3 on the first SiO 2 layer 2 (FIG. 2B). At this time, the flow rate of Si (NCO) 4 is gradually reduced to zero, and the flow rate of SnCl 4 is gradually increased from zero, so that the first S
The SiO 2 content is high on the side of the iO 2 layer 2 and the first SiO 2
A first interface layer (SiO 2 / SnO 2 mixed layer) 3 in which the content of SiO 2 decreases as the distance from the layer 2 increases is formed. Here, if the film thicknesses of the first SiO 2 layer 2 and the first interface layer 3 are too thin, the respective effects (the effect of preventing the scattering of alkali ions from the blue plate glass 1 and the effect of improving the adhesive force) will be lost. On the other hand, if it is too thick, it becomes useless in terms of cost. Therefore, the optimum thicknesses of the first SiO 2 layer 2 and the first interface layer 3 are about 500 to 3000Å and 100 to 500Å, respectively.
【００１８】その後、同一の常圧ＣＶＤ装置内で、Ｓｎ
Ｃｌ4 ，Ｈ2 Ｏに加えて、抵抗制御用のフッ素系ガスと
してＣＦ3 ＣＨ2 Ｆを使用して、透明電極４となるフッ
素をドープしたＳｎＯ2 膜を形成する（図２（ｃ））。Then, Sn is deposited in the same atmospheric pressure CVD apparatus.
In addition to Cl 4 and H 2 O, CF 3 CH 2 F is used as a fluorine-based gas for resistance control to form a fluorine-doped SnO 2 film to be the transparent electrode 4 (FIG. 2C). .
【００１９】次いで、フッ素系ガスの導入を停止し、Ｓ
ｉ（ＮＣＯ）4 の導入を開始して、第２の界面層５を形
成する（図２（ｄ））。この際、ＳｎＣｌ4 の流量をゼ
ロまで除々に減らしていくと共に、Ｓｉ（ＮＣＯ）4 の
流量をゼロから除々に増やしていくことにより、透明電
極４側でＳｎＯ2 の含有率が高く透明電極４から離れる
につれてＳｎＯ2 の含有率が低くなる第２の界面層（Ｓ
ｉＯ2 ／ＳｎＯ2 混在層）５を形成する。次に、Ｓｉ
（ＮＣＯ）4 ，Ｈ2 Ｏのみを導入して第２のＳｉＯ2 層
６を形成する（図３（ｅ））。ここで、第２のＳｉＯ2
層６の膜厚は、あまり薄いと効果（透明電極４をプラズ
マダメージから守る効果，透明電極４からのフッ素拡散
の防止効果）がなく、逆に厚すぎると抵抗が高くなっ
て、光電変換特性を劣化させるので、その膜厚は 100〜
300Å程度が最適である。Then, the introduction of the fluorine-based gas is stopped, and S
The introduction of i (NCO) 4 is started to form the second interface layer 5 (FIG. 2 (d)). At this time, the flow rate of SnCl 4 is gradually reduced to zero and the flow rate of Si (NCO) 4 is gradually increased from zero, whereby the content of SnO 2 on the transparent electrode 4 side is high and the transparent electrode 4 second interface layer the content of SnO 2 decreases with increasing distance from (S
iO 2 / SnO 2 mixed layer) 5 is formed. Next, Si
The second SiO 2 layer 6 is formed by introducing only (NCO) 4 and H 2 O (FIG. 3E). Here, the second SiO 2
If the thickness of the layer 6 is too thin, there is no effect (the effect of protecting the transparent electrode 4 from plasma damage, the effect of preventing fluorine diffusion from the transparent electrode 4). The film thickness is 100 ~
300 Å is optimal.
【００２０】次いで、以上のようにして作成したＳｎＯ
2 膜付きのガラスを、十分に洗浄して乾燥させた後、プ
ラズマＣＶＤ装置内に搬入し、ＳｉＨ4 ガスを主成分と
する原料ガスを用いて、上述したｐ型半導体層7aとなる
ボロンドープａ−ＳｉＣ：Ｈ層, ｉ型半導体層7bとなる
ノンドープａ−Ｓｉ：Ｈ層及びｎ型半導体層7cとなるリ
ンドープμＣーＳｉ：Ｈ層を順次堆積して、ＰＩＮ型の
ａ−Ｓｉ膜７よりなる光電変換層を形成する（図３
（ｆ））。最後に、ａ−Ｓｉ膜７上に、裏面電極８とな
るＡｌ，Ａｇ等の金属膜を真空蒸着法により形成する
（図３（ｇ））。Next, the SnO prepared as described above
(2 ) The glass with the film is thoroughly washed and dried, then carried into a plasma CVD apparatus, and using a source gas containing SiH 4 gas as a main component, a boron-doped a that becomes the above-mentioned p-type semiconductor layer 7a. -SiC: H layer, non-doped a-Si: H layer to be the i-type semiconductor layer 7b, and phosphorus-doped μC-Si: H layer to be the n-type semiconductor layer 7c are sequentially deposited, and the PIN-type a-Si film 7 is formed. A photoelectric conversion layer is formed (Fig. 3
(F)). Finally, on the a-Si film 7, a metal film of Al, Ag or the like to be the back surface electrode 8 is formed by the vacuum evaporation method (FIG. 3G).
【００２１】ここで、第１，第２の界面層３，５（Ｓｉ
Ｏ2 ／ＳｎＯ2 混在層）の存在意義について述べる。上
述した本実施例（第１，第２界面層３，５を設けた例）
とこの本実施例にあって第１，第２の界面層３，５を設
けない例とをそれぞれ製造してそれらの光起電力装置と
しての特性を比較した。光起電力装置の初期特性におい
ては明確な差異は見られなかったが、温湿度サイクルテ
スト後においては、界面層を設けた例では設けない例に
比較して特性，歩留りが共に２割以上優れていた。この
原因は、第１，第２の界面層３，５の存在により、第
１，第２のＳｉＯ 2 層２，６との付着力が強くて安定し
た透明電極４が得られたことに起因している。Here, the first and second interface layers 3 and 5 (Si
O2/ SnO2The meaning of existence of the mixed layer) is described. Up
This embodiment described above (an example in which the first and second interface layers 3 and 5 are provided)
In this embodiment, the first and second interface layers 3 and 5 are provided.
And the photovoltaic devices and
The characteristics were compared. Odor characteristics of photovoltaic devices
Although no clear difference was seen in the
After the strike, in the example of not providing the interface layer
In comparison, both characteristics and yield were 20% or more superior. this
The cause is due to the existence of the first and second interface layers 3 and 5.
1, second SiO 2Strong adhesion to layers 2 and 6 and stable
This is due to the fact that the transparent electrode 4 was obtained.
【００２２】次に、従来例との比較について述べる。ガ
ラス基板と透明電極との間にアルカリイオン拡散防止用
のＳｉＯ2 層をスパッタ法にて設け、また、透明電極と
ａ−Ｓｉ膜との間にプラズマ耐性用のＺｎＯ層を同じく
スパッタ法にて設けた構成をなす従来例と、上述した本
実施例とについて、その光起電力装置としての特性を同
一条件にて比較した場合、両者はほぼ同程度の特性を示
した。Next, a comparison with the conventional example will be described. A SiO 2 layer for preventing alkali ion diffusion is provided between the glass substrate and the transparent electrode by a sputtering method, and a ZnO layer for plasma resistance is also provided between the transparent electrode and the a-Si film by the sputtering method. When the characteristics of the photovoltaic device of the conventional example having the configuration provided and the above-described present example are compared under the same conditions, the two show approximately the same characteristics.
【００２３】しかしながら、本実施例の場合には、透明
電極（ＳｎＯ2 膜）とＳｉＯ2 層との形成を同一のＣＶ
Ｄ装置内で行えるので、従来のようなＣＶＤ装置，スパ
ッタ装置間の半製品の移動がなく、歩留りは従来より明
らかに向上する。具体的には、本実施例では上述の従来
例に比べて、歩留りを２割以上改善することができた。However, in the case of this embodiment, the transparent electrode (SnO 2 film) and the SiO 2 layer are formed in the same CV.
Since it can be performed in the D apparatus, there is no movement of the semi-finished product between the CVD apparatus and the sputtering apparatus as in the conventional case, and the yield is obviously improved as compared with the conventional case. Specifically, in this embodiment, the yield could be improved by 20% or more as compared with the above-mentioned conventional example.
【００２４】なお、上述した実施例では、ＳｎＯ2 形成
用の原料ガスとしてＳｎＣｌ4 を使用したが、これに代
えてＳｎ（ＣＨ3 ）4 を使用するようにしても良い。Although SnCl 4 was used as the source gas for forming SnO 2 in the above-mentioned embodiment, Sn (CH 3 ) 4 may be used instead.
【００２５】[0025]
【発明の効果】以上のように、本発明では、透明電極
（ＳｎＯ2 膜）とＳｉＯ2 層との間にＳｉＯ2 ／ＳｎＯ
2 混在層を設けているので、付着力が強くて安定した透
明電極を得ることができ、この結果、温湿度サイクルテ
ストに対する耐久性を大幅に向上できる。As described above, according to the present invention, SiO 2 / SnO is provided between the transparent electrode (SnO 2 film) and the SiO 2 layer.
Since two mixed layers are provided, it is possible to obtain a stable transparent electrode having a strong adhesive force, and as a result, it is possible to significantly improve the durability against the temperature and humidity cycle test.
【００２６】また、Ｓｉ（ＮＣＯ）4 ＋Ｈ2 Ｏの低温Ｃ
ＶＤ法によりＳｉＯ2 層を形成するので、透明電極（Ｓ
ｎＯ2 膜）とＳｉＯ2 層とを同一のプロセス設備を使用
して連続的に形成することができ、製造コストの低下を
図れると共に、歩留りの向上を図ることが可能となる。In addition, low temperature C of Si (NCO) 4 + H 2 O
Since the SiO 2 layer is formed by the VD method, the transparent electrode (S
The nO 2 film) and the SiO 2 layer can be continuously formed by using the same process equipment, so that the manufacturing cost can be reduced and the yield can be improved.
【図１】本発明の光起電力装置の構成を示す断面図であ
る。FIG. 1 is a sectional view showing a configuration of a photovoltaic device of the present invention.
【図２】本発明の光起電力装置の製造方法を工程を示す
断面図である。FIG. 2 is a cross-sectional view showing steps in a method for manufacturing a photovoltaic device according to the present invention.
【図３】本発明の光起電力装置の製造方法を工程を示す
断面図である。FIG. 3 is a cross-sectional view showing steps in a method for manufacturing a photovoltaic device of the present invention.
１ 青板ガラス（ガラス基板） ２ 第１のＳｉＯ2 層 ３ 第１の界面層（ＳｉＯ2 ／ＳｎＯ2 混在層） ４ 透明電極（ＳｎＯ2 膜） ５ 第２の界面層（ＳｉＯ2 ／ＳｎＯ2 混在層） ６ 第２のＳｉＯ2 層 ７ ａ−Ｓｉ膜 ８ 裏面電極1 Blue glass (glass substrate) 2 First SiO 2 layer 3 First interface layer (SiO 2 / SnO 2 mixed layer) 4 Transparent electrode (SnO 2 film) 5 Second interface layer (SiO 2 / SnO 2 mixed) Layer) 6 second SiO 2 layer 7 a-Si film 8 back electrode
Claims (5)
る透明電極，アモルファスシリコン膜をこの順に有する
光起電力装置において、前記ガラス基板と前記透明電極
との間、及び／または、前記透明電極と前記アモルファ
スシリコン膜との間に、ＳｉＯ2 層を設けたことを特徴
とする光起電力装置。1. A photovoltaic device having a transparent electrode containing SnO 2 as a main component and an amorphous silicon film on a glass substrate in this order, between the glass substrate and the transparent electrode and / or the transparent electrode. A photovoltaic device comprising a SiO 2 layer provided between an electrode and the amorphous silicon film.
に、前記ＳｉＯ2 層側から前記透明電極側に向かうにつ
れてＳｎＯ2 の含有率を連続的または階段状に増加させ
たＳｉＯ2 ／ＳｎＯ2 混在層を設けたことを特徴とする
請求項１記載の光起電力装置。 2. A SiO 2 / SnO layer between the SiO 2 layer and the transparent electrode, wherein the content of SnO 2 is continuously or stepwise increased from the SiO 2 layer side toward the transparent electrode side. 2. The photovoltaic device according to claim 1, wherein two mixed layers are provided.
する方法において、Ｓｉ（ＮＣＯ）4 ＋Ｈ2 Ｏの低温Ｃ
ＶＤ法により前記ＳｉＯ2 層を形成することを特徴とす
る光起電力装置の製造方法。3. A method of manufacturing a photovoltaic device having a SiO 2 layer, the low temperature C of Si (NCO) 4 + H 2 O.
A method for manufacturing a photovoltaic device, comprising forming the SiO 2 layer by a VD method.
る透明電極，アモルファスシリコン膜をこの順に有する
光起電力装置を製造する方法において、前記ガラス基板
と前記透明電極との間、及び／または、前記透明電極と
前記アモルファスシリコン膜との間に、Ｓｉ（ＮＣＯ）
4 ＋Ｈ2 Ｏの低温ＣＶＤ法によりＳｉＯ2 層を形成する
ことを特徴とする光起電力装置の製造方法。4. A method for manufacturing a photovoltaic device having a transparent electrode containing SnO 2 as a main component and an amorphous silicon film in this order on a glass substrate, wherein a space between the glass substrate and the transparent electrode and / Alternatively, Si (NCO) is formed between the transparent electrode and the amorphous silicon film.
A method for manufacturing a photovoltaic device, comprising forming a SiO 2 layer by a low temperature CVD method of 4 + H 2 O.
に、Ｈ2 Ｏ雰囲気中で、ＳｎＣｌ4 またはＳｎ（Ｃ
Ｈ3 ）4 とＳｉ（ＮＣＯ）4 との流量比を連続的または
階段状に変化させて、前記ＳｉＯ2 層側から前記透明電
極側に向かうにつれてＳｎＯ2 の含有率が高くなるＳｉ
Ｏ2 ／ＳｎＯ2 混在層を形成することを特徴とする請求
項４記載の光起電力装置の製造方法。Between wherein said transparent electrode and the SiO 2 layer, in H 2 O atmosphere, SnCl 4 or Sn (C
The flow rate ratio between H 3 ) 4 and Si (NCO) 4 is changed continuously or stepwise so that the content of SnO 2 increases from the SiO 2 layer side toward the transparent electrode side.
The method for manufacturing a photovoltaic device according to claim 4, wherein an O 2 / SnO 2 mixed layer is formed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21379694A JP3291401B2 (en) | 1994-09-07 | 1994-09-07 | Photovoltaic device and method of manufacturing photovoltaic device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21379694A JP3291401B2 (en) | 1994-09-07 | 1994-09-07 | Photovoltaic device and method of manufacturing photovoltaic device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0878714A true JPH0878714A (en) | 1996-03-22 |
| JP3291401B2 JP3291401B2 (en) | 2002-06-10 |
Family
ID=16645198
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21379694A Expired - Fee Related JP3291401B2 (en) | 1994-09-07 | 1994-09-07 | Photovoltaic device and method of manufacturing photovoltaic device |
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| Country | Link |
|---|---|
| JP (1) | JP3291401B2 (en) |
Cited By (5)
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|---|---|---|---|---|
| WO2003036657A1 (en) * | 2001-10-19 | 2003-05-01 | Asahi Glass Company, Limited | Substrate with transparent conductive oxide film and production method therefor, and photoelectric conversion element |
| WO2008120498A1 (en) * | 2007-03-29 | 2008-10-09 | Mitsubishi Heavy Industries, Ltd. | Photoelectric conversion device and method for manufacturing the same |
| DE10134901B4 (en) * | 2000-07-21 | 2010-11-11 | Sharp K.K. | Transmissive thin-film solar cell module with a transparent substrate, a translucent section and a translucent sealing layer |
| WO2013035746A1 (en) * | 2011-09-05 | 2013-03-14 | 旭硝子株式会社 | Glass substrate having alkali barrier layer attached thereto, and glass substrate having transparent conductive oxide film attached thereto |
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|---|---|---|---|---|
| DE10134901B4 (en) * | 2000-07-21 | 2010-11-11 | Sharp K.K. | Transmissive thin-film solar cell module with a transparent substrate, a translucent section and a translucent sealing layer |
| WO2003036657A1 (en) * | 2001-10-19 | 2003-05-01 | Asahi Glass Company, Limited | Substrate with transparent conductive oxide film and production method therefor, and photoelectric conversion element |
| US7179527B2 (en) | 2001-10-19 | 2007-02-20 | Asahi Glass Company, Limited | Substrate with transparent conductive oxide film, process for its production and photoelectric conversion element |
| US7364808B2 (en) | 2001-10-19 | 2008-04-29 | Asahi Glass Company, Limited | Substrate with transparent conductive oxide film, process for its production and photoelectric conversion element |
| US7883789B2 (en) | 2001-10-19 | 2011-02-08 | Asahi Glass Company, Limited | Substrate with transparent conductive oxide film, process for its production and photoelectric conversion element |
| WO2008120498A1 (en) * | 2007-03-29 | 2008-10-09 | Mitsubishi Heavy Industries, Ltd. | Photoelectric conversion device and method for manufacturing the same |
| JPWO2008120498A1 (en) * | 2007-03-29 | 2010-07-15 | 三菱重工業株式会社 | Photoelectric conversion device and manufacturing method thereof |
| AU2008233856B2 (en) * | 2007-03-29 | 2012-11-01 | Mitsubishi Heavy Industries, Ltd. | Photovoltaic device and process for producing same. |
| WO2013035746A1 (en) * | 2011-09-05 | 2013-03-14 | 旭硝子株式会社 | Glass substrate having alkali barrier layer attached thereto, and glass substrate having transparent conductive oxide film attached thereto |
| CN109065659A (en) * | 2018-08-08 | 2018-12-21 | 浙江师范大学 | N doping tungsten oxide heterojunction solar battery and preparation method thereof |
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|---|---|
| JP3291401B2 (en) | 2002-06-10 |
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