JPH0664935B2 - Transparent conductive film and method for forming the same - Google Patents
Transparent conductive film and method for forming the sameInfo
- Publication number
- JPH0664935B2 JPH0664935B2 JP60231061A JP23106185A JPH0664935B2 JP H0664935 B2 JPH0664935 B2 JP H0664935B2 JP 60231061 A JP60231061 A JP 60231061A JP 23106185 A JP23106185 A JP 23106185A JP H0664935 B2 JPH0664935 B2 JP H0664935B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- sno
- transparent conductive
- conductive film
- ito
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、例えば太陽電池に用いられる透明導電膜およ
びその形成方法に関するものである。Description: TECHNICAL FIELD The present invention relates to a transparent conductive film used for, for example, a solar cell and a method for forming the transparent conductive film.
（従来の技術） 例えば太陽電池の受光側電極としては従来より透明導電
膜が、用いられている。すなわち、ガラス基板上にスパ
ッタリング法や真空蒸着法等によってITO(Indium Tin O
xide)層を形成し、さらにその上にSnO2層を形成して透
明電極を構成している。ITO層は比抵抗は低いともに透
過率が高いので透明導電膜として優れた特性を有してい
るが、化学的安定性に欠けるため、その上に半導体層を
直接形成することはできない。そこでITO層の上に化学
的に安定なSnO2層を堆積して透明導電膜を構成してい
る。(Prior Art) For example, a transparent conductive film has been conventionally used as a light-receiving side electrode of a solar cell. That is, ITO (Indium Tin Oxide) is formed on a glass substrate by sputtering or vacuum deposition.
xide) layer is formed, and a SnO 2 layer is further formed thereon to form a transparent electrode. Since the ITO layer has a low specific resistance and a high transmittance, it has excellent characteristics as a transparent conductive film, but since it lacks chemical stability, a semiconductor layer cannot be directly formed on it. Therefore, a chemically stable SnO 2 layer is deposited on the ITO layer to form a transparent conductive film.
（発明が解決しようとする問題点） 上述した従来の透明導電膜においてはITO層上にSnO2層
を形成しているが、このSnO2層の形成過程においてITO
層の比抵抗が高くなるとともに透過率が低くなる欠点が
ある。これはITO層を構成するIn2O3：SnO2の内のIn2O3
の組成が過剰の酸素の存在下で変性し、比抵抗が高くな
り、透過率が低くなるためである。したがって、従来比
抵抗が低く、透過率が高い透明導電膜を形成することは
きわめて困難であり、特にSnO2層形成時の酸化条件の制
御が非常に難かしいという欠点があつた。In the (invention try to Problem solving) conventional transparent conductive film described above to form a SnO 2 layer on the ITO layer but, ITO in the formation process of the SnO 2 layer
There is a drawback that the specific resistance of the layer increases and the transmittance decreases. In 2 O which constitutes the ITO layer 3: In 2 O 3 of the SnO 2
This is because the composition of (3) is modified in the presence of excess oxygen, the specific resistance becomes high, and the transmittance becomes low. Therefore, it is extremely difficult to form a transparent conductive film having a low specific resistance and a high transmittance, and it is very difficult to control the oxidation conditions particularly when the SnO 2 layer is formed.
本発明の目的は上述した欠点を除去し、比抵抗が低く、
透過率の高い透明導電膜を提供することともにこのよう
な透明導電膜を簡単に製造することができる方法を提供
しようとするものである。The object of the present invention is to eliminate the above-mentioned drawbacks, low specific resistance,
It is an object of the present invention to provide a transparent conductive film having a high transmittance and a method capable of easily manufacturing such a transparent conductive film.
（問題点を解決するための手段） 本発明は、基板と、その上に形成した金属酸化物の透明
導電層と、その上に形成したSnO2層とを具える透明導電
膜において、前記透明導電層とSnO2層との間に、０＜ｘ
＜１とするSnO2-x層を設けたことを特徴とするものであ
る。(Means for Solving Problems) The present invention provides a transparent conductive film comprising a substrate, a transparent conductive layer of a metal oxide formed thereon, and a SnO 2 layer formed thereon, wherein the transparent 0 <x between the conductive layer and the SnO 2 layer
It is characterized in that a SnO 2−x layer having <1 is provided.
さらに本発明は、上述した透明導電膜を形成するに当た
り、基板上に金属酸化物より成る透明導電層を形成する
工程と、この透明導電層上に、酸化条件を変えながら、
０＜ｘ＜１とするSnO2-x層とSnO2層とを順次に形成する
工程とを具えることを特徴とするものである。Furthermore, the present invention, in forming the above-mentioned transparent conductive film, a step of forming a transparent conductive layer made of a metal oxide on the substrate, and while changing the oxidation conditions on the transparent conductive layer,
It is characterized by comprising a step of sequentially forming a SnO 2-x layer and a SnO 2 layer with 0 <x <1.
（作用） 上述した本発明の透明導電膜によれば、ITOのような金
属酸化物より成る透明導電層とSnO2層との間にSnO
2-x（０＜ｘ＜１）層を設けたため、このSnO2-x層はSnO
2層を形成する際にはパツシベーシヨン層としての機能
を果たし、ITO層の比抵抗が増大したり、透過率が低下
したりすることはなくなる。また、本発明の形成方法に
よれば、SnO2-x層とSnO2層とを、単に酸化条件を変える
だけで順次に形成するため、形成工程そのものが簡単と
なる。(Function) According to the above-described transparent conductive film of the present invention, SnO 2 is provided between the SnO 2 layer and the transparent conductive layer made of a metal oxide such as ITO.
Since the 2-x (0 <x <1) layer is provided, this SnO 2-x layer is SnO
When the two layers are formed, they function as a passivation layer, and the resistivity of the ITO layer does not increase and the transmittance does not decrease. Further, according to the forming method of the present invention, the SnO 2-x layer and the SnO 2 layer are sequentially formed by simply changing the oxidation conditions, so that the forming process itself is simplified.
（実施例） 第１図は本発明の透明導電膜の一実施例の構成を示す断
面図である。透明なガラス基板１の上に厚さ約２０００
ÅのITO層２を形成し、その上に厚さ約２００ÅのSnO
2-x（０＜ｘ＜１）層３を形成し、さらにその上に厚さ
約２００ÅのSnO2層４を形成したものである。中間のSn
O2-x層３は、０＜ｘ＜0.5、特に０＜ｘ＜0.2の組成とす
ることが好適である。(Embodiment) FIG. 1 is a sectional view showing the structure of an embodiment of the transparent conductive film of the present invention. About 2000 on the transparent glass substrate 1
Å ITO layer 2 is formed and SnO about 200 Å is formed on it.
A 2-x (0 <x <1) layer 3 is formed, and a SnO 2 layer 4 having a thickness of about 200Å is further formed thereon. Middle Sn
The O 2−x layer 3 preferably has a composition of 0 <x <0.5, particularly 0 <x <0.2.
次に、このような透明導電膜の形成方法について説明す
る。先ずソーダガラス基板１の表面を清浄とした後、ス
パツタリング法や真空蒸着法等によつてITO層２を所望
の厚さに形成する。次にこのようにITO層２を形成した
ガラス基板１を真空蒸着装置内に設置し、真空引きした
後加熱装置により基板１を所望の温度に加熱する、その
後、真空蒸着装置内に酸素ガスを導入する。この場合、
真空槽内は１×10-3Torr以下の一定の圧力に保持される
ようにする。また、真空槽内には予じめSnO2またはSnO2
とSn2O3，Sb2O5，SnF2，SnF4等との混合物の焼結体を蒸
発源として設置しておき、この蒸発源を電子ビーム加
熱、抵抗加熱、高周波誘導加熱等によつて加熱する。Sn
O2は加熱されると、SnO2→SnO＋Ｏと分解される。加熱
されたITO層２上に達したSnOは、酸素圧力、加熱温度、
蒸着速度、また蒸発源とガラス基板との間にイオン化機
構がある場合にはそのイオン化電力等の酸化条件を制御
することにより再び酸化されてSnO2-x（０＜ｘ＜１）と
なり、SnO2-x層３がITO層２上に堆積形成される。この
場合、ｘの値は、真空槽内の酸素分圧、導入酸素の流量
等を測定し、これらのパラメータを経験的に決めること
により所望の値とすることができる。SnO2-x層３が所望
の厚さに形成されたら再び酸化条件を制御し、SnO2-x層
３の上にSnO2層４を形成する。このSnO2層４の厚さが所
望の厚さとなつたら、蒸着を終了する。このように、本
発明の形成方法によればITO層２を形成したガラス基板
１を真空蒸着装置に設置したまま、酸化条件を制御する
だけでSnO2-x層３とSnO2層４とを順次に連続して形成す
ることができるため、工程は簡単になるとともに酸化条
件の制御も容易となる。Next, a method for forming such a transparent conductive film will be described. First, the surface of the soda glass substrate 1 is cleaned, and then the ITO layer 2 is formed to a desired thickness by a sputtering method, a vacuum evaporation method, or the like. Next, the glass substrate 1 on which the ITO layer 2 is thus formed is placed in a vacuum vapor deposition apparatus, and after vacuuming, the substrate 1 is heated to a desired temperature by a heating apparatus. Then, oxygen gas is fed into the vacuum vapor deposition apparatus. Introduce. in this case,
The inside of the vacuum chamber should be maintained at a constant pressure of 1 × 10 -3 Torr or less. In addition, the SnO 2 or SnO 2
And Sn 2 O 3, Sb 2 O 5, SnF 2, leave installed SnF sintered body of a mixture of such 4 as an evaporation source, the evaporation source electron beam heating, resistance heating, high frequency induction heating, etc. To heat. Sn
When O 2 is heated, it decomposes as SnO 2 → SnO + O. The SnO reaching the heated ITO layer 2 has oxygen pressure, heating temperature,
If there is an ionization mechanism between the evaporation rate and the evaporation source and the glass substrate, it is oxidized again by controlling the oxidation conditions such as the ionization power to become SnO 2−x (0 <x <1). A 2-x layer 3 is deposited on the ITO layer 2. In this case, the value of x can be set to a desired value by measuring the oxygen partial pressure in the vacuum chamber, the flow rate of introduced oxygen, etc. and empirically determining these parameters. After the SnO 2-x layer 3 is formed to a desired thickness, the oxidation conditions are controlled again to form the SnO 2 layer 4 on the SnO 2-x layer 3. When the SnO 2 layer 4 has a desired thickness, the vapor deposition is completed. As described above, according to the forming method of the present invention, the SnO 2-x layer 3 and the SnO 2 layer 4 can be formed only by controlling the oxidation conditions while the glass substrate 1 on which the ITO layer 2 is formed is installed in the vacuum deposition apparatus. Since they can be formed successively in succession, the process is simplified and the control of oxidation conditions is facilitated.
上述したようにして形成した本発明の透明導電膜の比抵
抗の平均値を、ITO層だけを形成した透明導電膜およびI
TO層およびSnO2層を形成した透明導電膜の比抵抗の平均
値と対比して次表に示す。The average value of the specific resistance of the transparent conductive film of the present invention formed as described above is calculated as follows:
The following table compares with the average value of the specific resistance of the transparent conductive film on which the TO layer and the SnO 2 layer are formed.
上表から明らかなように本発明の透明導電膜の比抵抗は
ITO層のみを有する透明導電膜の比抵抗よりも若干高い
が、ITO層の上にSnO2層を形成した従来の透明導電膜と
比較した場合半分以下となつている。 As is clear from the above table, the specific resistance of the transparent conductive film of the present invention is
Although it is slightly higher than the specific resistance of the transparent conductive film having only the ITO layer, it is less than half that of the conventional transparent conductive film in which the SnO 2 layer is formed on the ITO layer.
第２図は上述した３つの透明導電膜の分光透過率を示す
ものであり、本発明のITO/SnO2-x/SnO2構造を有する透
明導電膜の分光透過率は、ITO層のみを有する導電膜
と、ITO/SnO2構造を有する従来の導電膜とのほぼ中間の
値を示すことがわかる。FIG. 2 shows the spectral transmittances of the above-mentioned three transparent conductive films, and the transparent conductive film having the ITO / SnO 2-x / SnO 2 structure of the present invention has only the ITO layer. It can be seen that the value is almost intermediate between the conductive film and the conventional conductive film having the ITO / SnO 2 structure.
第３図は上述した３種類の透明導電膜を用いて製作した
水素化アモルフアスシリコンの太陽電池の、AM(Air Mas
s)1.5(100mv/cm2)の照射条件での光電変換特性を示すも
のである。このグラフから明らかなように、ITO/SnO2-x
/SnO2構造を有する本発明の透明導電膜を用いた太陽電
池では、透明導電膜の比抵抗が低く、透過率が高いため
きわめて優れた光電変換特性を示し、大きな光電変換効
率が得られることがわかる。一方、ITO層のみより成る
透明導電膜を用いた太陽電池では、ITO層そのものの比
抵抗は低く、透過率は高かつたにも拘らず、化学的安定
性に乏しいため、その上に水素化アモルフアスシリコン
を堆積させた太陽電池の光電変換特性は、ITO/SnO2構造
を有する透明導電膜を用いた太陽電池の光電変換特性よ
りも劣るものであつた。Figure 3 shows the AM (Air Mas) of a hydrogenated amorphous silicon solar cell manufactured using the three types of transparent conductive films described above.
s) shows the photoelectric conversion characteristics under the irradiation condition of 1.5 (100 mv / cm 2 ). As you can see from this graph, ITO / SnO 2-x
In the solar cell using the transparent conductive film of the present invention having a / SnO 2 structure, the transparent conductive film has a low specific resistance and a high transmittance and thus exhibits extremely excellent photoelectric conversion characteristics, and a large photoelectric conversion efficiency can be obtained. I understand. On the other hand, in a solar cell using a transparent conductive film consisting of only the ITO layer, the ITO layer itself has a low specific resistance and a high transmittance, but has poor chemical stability. The photoelectric conversion characteristics of solar cells deposited with amorphous silicon were inferior to those of solar cells using a transparent conductive film having an ITO / SnO 2 structure.
本発明は上述した実施例に限定されるものではなく、種
々の変更や変形を加えることができる。例えばSnO2-x層
やSnO2層にはSb,F,P等の比抵抗を低下させる元素を添加
することができる。また、本発明の透明導電膜は太陽電
池に用いるだけでなく、例えば自動車のデフロストガラ
スの透光性ヒータとして用いることもできる。さらに基
板に被着する透明導電層はITO層とする必要はなく、他
の透明導電層とすることもできる。また、SnO2-x層は均
一な組成のものとする必要はなく、例えばITO層からSnO
2層にかけてｘの値が１から０まで連続的に変化するよ
うなものでもよい。The present invention is not limited to the above-described embodiments, and various changes and modifications can be added. For example, elements such as Sb, F, and P that reduce the specific resistance can be added to the SnO 2-x layer and the SnO 2 layer. Further, the transparent conductive film of the present invention can be used not only for a solar cell but also as a translucent heater for defrosted glass of an automobile, for example. Furthermore, the transparent conductive layer adhered to the substrate does not need to be the ITO layer, and can be another transparent conductive layer. Further, the SnO 2-x layer does not need to have a uniform composition, for example, from the ITO layer to SnO 2
The value of x may continuously change from 1 to 0 over two layers.
（発明の効果） 上述した本発明の透明導電膜によればSnO2-x層をITO層
とSnO2層との間に介在させたため、比抵抗を低くするこ
とができるとともに透過率を高くすることができる。ま
た、SnO2層は化学的に安定であるため、本発明の透明導
電膜を用いた太陽電池の光電変換特性はきわめて優れた
ものとなるとともに経時変化も少ないなめ良好な光電変
換特性を長期間に亘つて維持することができる。さら
に、熱的安定性も高く、加熱による抵抗値の変化も小さ
い。(Effects of the Invention) According to the above-described transparent conductive film of the present invention, the SnO 2-x layer is interposed between the ITO layer and the SnO 2 layer, so that the specific resistance can be lowered and the transmittance can be increased. be able to. In addition, since the SnO 2 layer is chemically stable, the photoelectric conversion characteristics of the solar cell using the transparent conductive film of the present invention will be extremely excellent and the change over time will be small, and good photoelectric conversion characteristics will be maintained for a long time. Can be maintained for Furthermore, the thermal stability is high and the change in resistance value due to heating is small.
また、本発明の形成方法によれば、ITO層を形成した基
板を真空槽内に入れたままで、酸化条件を制御すること
によりSnO2-x層とSnO2層を順次に形成することができる
ので工程が簡単となるとともに特性も優れたものとな
る。Further, according to the forming method of the present invention, the SnO 2-x layer and the SnO 2 layer can be sequentially formed by controlling the oxidation condition while the substrate on which the ITO layer is formed is kept in the vacuum chamber. Therefore, the process is simplified and the characteristics are excellent.
第１図は本発明の透明導電膜の構成を示す断面図、 第２図は本発明の透明導電膜の分光透過率を、従来の透
明導電膜と対比して示すグラフ、 第３図は本発明の透明導電膜を用いて製作した太陽電池
の光電変換特性を、従来の透明導電膜を用いて製作した
太陽電池と対比して示すグラフである。 １…ガラス基板、２…ITO層 ３…SnO2-x層、４…SnO2層FIG. 1 is a sectional view showing the structure of the transparent conductive film of the present invention, FIG. 2 is a graph showing the spectral transmittance of the transparent conductive film of the present invention in comparison with a conventional transparent conductive film, and FIG. It is a graph which shows the photoelectric conversion characteristic of the solar cell manufactured using the transparent conductive film of the invention in comparison with the solar cell manufactured using the conventional transparent conductive film. 1 ... Glass substrate, 2 ... ITO layer 3 ... SnO 2-x layer, 4 ... SnO 2 layer
Claims (3)
明導電層と、その上に形成したSnO2層とを具える透明導
電膜において、前記透明導電層とSnO2層との間に、０＜
ｘ＜１とするSnO2-x層を設けたことを特徴とする透明導
電膜。1. A transparent conductive film comprising a substrate, a transparent conductive layer of metal oxide formed thereon, and a SnO 2 layer formed thereon, wherein the transparent conductive layer and the SnO 2 layer are between the transparent conductive layer and the SnO 2 layer. And 0 <
A transparent conductive film provided with a SnO 2-x layer with x <1.
または双方にSb，Ｆ，Ｐ等の、比抵抗を低減する元素を
添加したことを特徴とする特許請求の範囲第１項記載の
透明導電膜。2. The element, such as Sb, F, or P, which reduces specific resistance, is added to either or both of the SnO 2 layer and the SnO 2-x layer. The transparent conductive film according to the item.
形成する工程と、 この透明導電層上に、酸化条件を変えながら、０＜ｘ＜
１とするSnO2-x層とSnO2層とを順次に形成する工程とを
具えることを特徴とする透明導電膜の形成方法。3. A step of forming a transparent conductive layer made of a metal oxide on a substrate, and 0 <x <while changing the oxidizing conditions on the transparent conductive layer.
1. A method for forming a transparent conductive film, comprising the step of sequentially forming the SnO 2-x layer and the SnO 2 layer as 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60231061A JPH0664935B2 (en) | 1985-10-18 | 1985-10-18 | Transparent conductive film and method for forming the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60231061A JPH0664935B2 (en) | 1985-10-18 | 1985-10-18 | Transparent conductive film and method for forming the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6293804A JPS6293804A (en) | 1987-04-30 |
| JPH0664935B2 true JPH0664935B2 (en) | 1994-08-22 |
Family
ID=16917671
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60231061A Expired - Fee Related JPH0664935B2 (en) | 1985-10-18 | 1985-10-18 | Transparent conductive film and method for forming the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0664935B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07112076B2 (en) * | 1987-05-07 | 1995-11-29 | 日本板硝子株式会社 | Transparent conductive film body having a two-layer structure |
| JPH0751745B2 (en) * | 1988-08-11 | 1995-06-05 | 日本真空技術株式会社 | Method for producing transparent conductive film |
| GB2252332A (en) * | 1991-01-31 | 1992-08-05 | Glaverbel | Glass coated with two tin oxide coatings |
| JP4844014B2 (en) * | 2005-05-31 | 2011-12-21 | ソニー株式会社 | ORGANIC EL ELEMENT, DISPLAY DEVICE, AND METHOD FOR MANUFACTURING ORGANIC EL ELEMENT |
| US20120028011A1 (en) * | 2010-07-27 | 2012-02-02 | Chong Pyung An | Self-passivating mechanically stable hermetic thin film |
| EP3748697A4 (en) | 2018-01-29 | 2021-09-29 | Kabushiki Kaisha Toshiba | Solar cell, multi-junction solar cell, solar cell module and solar power system |
| WO2019146120A1 (en) * | 2018-01-29 | 2019-08-01 | 株式会社 東芝 | Solar cell, multijunction solar cell, solar cell module, and photovoltaic power generation system |
-
1985
- 1985-10-18 JP JP60231061A patent/JPH0664935B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6293804A (en) | 1987-04-30 |
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