JP3162864B2 - A method for producing a polycrystalline semiconductor thin film. - Google Patents
A method for producing a polycrystalline semiconductor thin film.Info
- Publication number
- JP3162864B2 JP3162864B2 JP05232393A JP5232393A JP3162864B2 JP 3162864 B2 JP3162864 B2 JP 3162864B2 JP 05232393 A JP05232393 A JP 05232393A JP 5232393 A JP5232393 A JP 5232393A JP 3162864 B2 JP3162864 B2 JP 3162864B2
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- Prior art keywords
- film
- layer
- amorphous
- hydrogen
- semiconductor thin
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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
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、特に光起電力装置の半
導体層に用いられる多結晶半導体薄膜の製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a polycrystalline semiconductor thin film used for a semiconductor layer of a photovoltaic device.
【０００２】[0002]
【従来の技術】図１は、ｉ層として多結晶Ｇｅ膜を備え
た光起電力装置の模式的断面図である。2. Description of the Related Art FIG. 1 is a schematic sectional view of a photovoltaic device having a polycrystalline Ge film as an i-layer.
【０００３】この光起電力装置は、次の様に形成され
る。[0003] This photovoltaic device is formed as follows.
【０００４】ガラス基板１上に、 膜厚が２０００Å〜
１μｍのＡｇまたはＡｌから成る裏面電極２、支持体と
して膜厚が約５００Åの非晶質Ｇｅ膜から成るｎ層３、
膜厚が約１０００Åの非晶質Ｇｅ膜から成るｉ層４を順
次積層する。On a glass substrate 1, a film thickness of 2000-
A back electrode 2 made of 1 μm Ag or Al, an n-layer 3 made of an amorphous Ge film having a thickness of about 500 ° as a support,
An i-layer 4 made of an amorphous Ge film having a thickness of about 1000 ° is sequentially laminated.
【０００５】ここで、上記ｎ層３、ｉ層４を公知のプラ
ズマＣＶＤ法で形成した。i層４の形成条件は、圧力
０．２ｔｏｒｒ、ＲＦパワ−１０Ｗ、ＧｅＨ4／Ｈ2：４
０ＳＣＣＭである。Here, the n layer 3 and the i layer 4 were formed by a known plasma CVD method. The conditions for forming the i-layer 4 were as follows: a pressure of 0.2 torr, an RF power of 10 W, and GeH 4 / H 2 : 4.
0 SCCM.
【０００６】そして、ゴ−ルドイメ−ジ炉によりＮ2雰
囲気中で熱アニ−ルを４時間行い、上記非晶質Ｇｅ膜か
ら成るｉ層４を固相成長させた。[0006] Then, GORE - Rudoime - thermal annealing in an N 2 atmosphere by di furnace - performed 4 hours Le, and the i layer 4 made of the amorphous Ge film was solid-phase crystallization.
【０００７】ただし、固相成長温度としては、断面ＳＥ
Ｍにより粒径２００Å以上の結晶粒が認められた温度を
採用した。[0007] However, the solid phase growth temperature is the cross-section SE.
The temperature at which a crystal grain having a particle size of 200 ° or more was recognized by M was adopted.
【０００８】その後、膜厚が約２００Åの非晶質Ｓｉ膜
からなるｐ層５をプラズマＣＶＤ法で形成し、膜厚が２
０００〜６０００ÅのＩＴＯ等の透明電極膜６を順次積
層する。Thereafter, a p-layer 5 made of an amorphous Si film having a thickness of about 200 ° is formed by a plasma CVD method.
A transparent electrode film 6 of ITO or the like having a thickness of 2,000 to 6000 ° is sequentially laminated.
【０００９】図２に、非晶質Ｇｅ膜における膜中水素量
と固相成長温度の関係を示す。FIG. 2 shows the relationship between the hydrogen content in the amorphous Ge film and the solid phase growth temperature.
【００１０】図２より、膜中水素量２．５％の非晶質Ｇ
ｅ膜の固相成長温度は３８０℃で、膜中水素量９．５％
の非晶質Ｇｅ膜の固相成長温度は４６０℃である。FIG. 2 shows that amorphous G having a hydrogen content of 2.5%
e The solid phase growth temperature of the film is 380 ° C, and the hydrogen content in the film is 9.5%.
The solid phase growth temperature of the amorphous Ge film is 460 ° C.
【００１１】膜中水素量は基板温度の制御（室温〜４０
０℃）によって、制御することができる。すなわち、基
板温度を３５０℃に設定することによって、膜中水素量
２．５％、基板温度を８０℃に設定することによって、
膜中水素量９．５％とすることができる。The amount of hydrogen in the film is controlled by controlling the substrate temperature (from room temperature to 40
0 ° C.). That is, by setting the substrate temperature to 350 ° C., the hydrogen content in the film is set to 2.5%, and the substrate temperature is set to 80 ° C.,
The hydrogen content in the film can be 9.5%.
【００１２】表１は、膜中水素量２．５％の非晶質Ｇｅ
膜の固相成長によって得られた多結晶Ｇｅ膜（ｉ層４）
を備えた光起電力装置Ａと、膜中水素量９．５％の非晶
質Ｇｅ膜の固相成長によって得られた多結晶Ｇｅ膜（ｉ
層４）を備えた光起電力装置Ｂの出力特性を示す。Table 1 shows that amorphous Ge having a hydrogen content of 2.5% in the film was used.
Polycrystalline Ge film obtained by solid phase growth of film (i-layer 4)
And a polycrystalline Ge film (i) obtained by solid-phase growth of an amorphous Ge film having a hydrogen content of 9.5% in the film.
4 shows output characteristics of a photovoltaic device B having a layer 4).
【００１３】ただし、測定値は、基準光源（ＡＭ１．
５）、１００ｍＷ／ｃｍ2照射下の条件に基づくもので
ある。However, the measured values are based on the reference light source (AM1.
5) Based on conditions under irradiation of 100 mW / cm 2 .
【００１４】[0014]
【表１】 [Table 1]
【００１５】表１より明らかなように、光活性層として
膜中水素量９．５％の非晶質Ｇｅ膜の固相成長膜を備え
た光起電力装置Ｂの方が全体的により良い出力特性を示
している。As is apparent from Table 1, the photovoltaic device B provided with a solid-phase grown film of an amorphous Ge film having a hydrogen content of 9.5% as a photoactive layer has a better overall output. The characteristics are shown.
【００１６】これは、水素による補償効果により膜特性
が良くなった結果である。This is a result of improving the film characteristics due to the compensation effect of hydrogen.
【００１７】しかし、唯一、Ｖｏｃについては、光起電
力装置Ｂの方が３０ｍＶも低い。However, only Voc is lower by 30 mV in the photovoltaic device B.
【００１８】これは、膜中水素量の多い非晶質半導体薄
膜の方がアニ−ル温度が高くなるために、Ｖｏｃが低下
したものと思われる。This is probably because the amorphous semiconductor thin film having a large amount of hydrogen in the film has a higher annealing temperature, and thus has a lower Voc.
【００１９】因みに、ＰＨＩＬＯＳＯＰＨＩＣＡＬ Ｍ
ＡＧＡＺＩＮＥ，Ｖｏｌ６０，１９８９，ｐ３−９にお
いては、結晶成長温度が５００℃以上というような高温
になるとの記載がある。By the way, PHILOSOPICAL M
AGAZINE, Vol 60, 1989, p3-9, states that the crystal growth temperature is as high as 500 ° C. or higher.
【００２０】[0020]
【発明が解決しようとする課題】そこで本発明は上記に
鑑みて、結晶成長温度を低下させることにより、非晶質
半導体薄膜を結晶化させた多結晶半導体薄膜の特性を改
善することを課題とする。In view of the above, an object of the present invention is to improve the characteristics of a polycrystalline semiconductor thin film obtained by crystallizing an amorphous semiconductor thin film by lowering the crystal growth temperature. I do.
【００２１】[0021]
【課題を解決するための手段】支持体上に形成された水
素を含有する非晶質半導体薄膜に、熱処理を施すことに
よって、多結晶化せしめる多結晶半導体薄膜の製造方法
において、上記非晶質半導体薄膜の支持体側に膜中水素
含有量の少ない領域を設けたことを特徴とする。According to a method for producing a polycrystalline semiconductor thin film in which a hydrogen-containing amorphous semiconductor thin film formed on a support is polycrystallized by subjecting it to a heat treatment, A region having a small hydrogen content in the film is provided on the support side of the semiconductor thin film.
【００２２】[0022]
【作用】本発明によれば、支持体側に膜中水素含有量の
少ない領域を設けたので、熱処理を施して上記非晶質半
導体膜を多結晶化させる際に、従来より低温で結晶成長
が始まるとともに、膜中水素量の多い領域により、水素
による補償等の効果がもたらされる。According to the present invention, since a region having a low hydrogen content in the film is provided on the support side, when the heat treatment is performed to polycrystallize the amorphous semiconductor film, crystal growth can be performed at a lower temperature than in the past. At the beginning, the region with a large amount of hydrogen in the film brings about effects such as compensation by hydrogen.
【００２３】[0023]
【実施例】本発明における光起電力装置の構造は、従来
例と同様に図１で示されている。DESCRIPTION OF THE PREFERRED EMBODIMENTS The structure of a photovoltaic device according to the present invention is shown in FIG.
【００２４】図３は本発明の一実施例に用いる非晶質Ｇ
ｅ膜（ｉ層４）中の水素プロファイル（１）を示す。FIG. 3 shows an amorphous G used in one embodiment of the present invention.
3 shows a hydrogen profile (1) in an e-film (i-layer 4).
【００２５】膜中の水素量は、成膜時の基板温度によっ
て制御される。The amount of hydrogen in the film is controlled by the substrate temperature during film formation.
【００２６】支持体（ｎ層３）との界面からの距離が０
〜２５０Åの成膜過程では、基板温度を３５０℃とし、
２５０Å〜５００Åの成膜過程では、基板温度を２５０
℃とし、５００Å〜７５０Åの成膜過程では、基板温度
を１５０℃とし、７５０〜１０００Åの成膜過程では、
基板温度を８０℃としたとき、上記水素プロファイル
（１）を有する非晶質Ｇｅ膜（ｉ層４）が得られた。The distance from the interface with the support (n layer 3) is 0
In the film formation process of ~ 250 °, the substrate temperature was 350 ° C,
In the film formation process of 250 ° to 500 °, the substrate temperature is set to 250 ° C.
° C, the substrate temperature is set to 150 ° C in the film forming process of 500 ° to 750 °, and in the film forming process of 750 to 1000 °,
When the substrate temperature was set to 80 ° C., an amorphous Ge film (i-layer 4) having the hydrogen profile (1) was obtained.
【００２７】上記非晶質Ｇｅ膜（ｉ層４）は、プラズマ
ＣＶＤ法で形成した。このときの条件は、圧力０．２ｔ
ｏｒｒ、ＲＦパワ−１０Ｗ、ＧｅＨ4／Ｈ2：４０ＳＣＣ
Ｍである。The amorphous Ge film (i-layer 4) was formed by a plasma CVD method. The condition at this time is a pressure of 0.2 t.
orr, RF power 10W, GeH 4 / H 2 : 40SCC
M.
【００２８】次に、ゴ−ルドイメ−ジ炉によりＮ2雰囲
気中で熱アニ−ルを行い、上記非晶質Ｇｅ膜を固相成長
させ、多結晶Ｇｅ膜を製造した。このときの固相成長温
度を調べたところ、３７５℃であった。これは、水素の
ほとんど入っていない非晶質Ｇｅ膜の場合とほぼ同じ温
度であった。Next, GORE - Rudoime - thermal annealing in an N 2 atmosphere by di furnace - performs Le, the amorphous Ge film was solid-phase growth, to produce a poly-Ge layer. When the solid phase growth temperature at this time was examined, it was 375 ° C. This was almost the same temperature as that of the amorphous Ge film containing almost no hydrogen.
【００２９】このときも、断面ＳＥＭにより粒径２００
Å以上の結晶粒が認められる温度を採用した。At this time, the particle size was 200
The temperature at which more than Å crystal grains were observed was adopted.
【００３０】表２は、本発明の方法によって作成した多
結晶Ｇｅ膜と従来の方法によって作成した多結晶Ｇｅ膜
との特性の比較表である。Table 2 is a comparison table of characteristics between a polycrystalline Ge film formed by the method of the present invention and a polycrystalline Ge film formed by a conventional method.
【００３１】[0031]
【表２】 [Table 2]
【００３２】表２より明らかなように、本発明の製造方
法の方が、従来の製造方法よりも結晶化温度を低くする
ことができるとともに、粒径が大きく、移動度も大きい
膜を作成することができる。As is clear from Table 2, the production method of the present invention can lower the crystallization temperature and produce a film having a large particle size and a high mobility, as compared with the conventional production method. be able to.
【００３３】次に、表３は上記のように製造した多結晶
Ｇｅ膜から成るｉ層４を備えた光起電力装置Ｃの出力特
性を示す。Next, Table 3 shows the output characteristics of the photovoltaic device C provided with the i-layer 4 made of the polycrystalline Ge film manufactured as described above.
【００３４】ただし、測定値は、基準光源（ＡＭ１．
５）、１００ｍＷ／ｃｍ2照射下の条件に基づくもので
ある。However, the measured values are based on the reference light source (AM1.
5) Based on conditions under irradiation of 100 mW / cm 2 .
【００３５】[0035]
【表３】 [Table 3]
【００３６】表１と表３を比較すると、光起電力装置Ｃ
では、低温で膜中水素量の多い非晶質Ｇｅ膜（ｉ層４）
を固相成長させた結果、出力特性が大きく改善されたこ
とがわかる。Comparison between Tables 1 and 3 shows that the photovoltaic device C
Then, an amorphous Ge film having a large amount of hydrogen in the film at a low temperature (i-layer 4)
As a result, the output characteristics were greatly improved.
【００３７】図４は、本発明の他の実施例に用いる非晶
質Ｇｅ膜（ｉ層４）中の水素プロファイル（２）を示
す。FIG. 4 shows a hydrogen profile (2) in an amorphous Ge film (i-layer 4) used in another embodiment of the present invention.
【００３８】成膜の開始時（支持体（ｎ層３）界面から
の距離が０Å）での基板温度を３５０℃に設定し、成膜
の終了時（支持体界面からの距離が１０００Å）の基板
温度が８０℃に設定し、この間の基板温度を徐々に下げ
ていくことによって、水素プロファイル（２）を有する
非晶質Ｇｅ膜が得られた。At the start of the film formation (the distance from the interface of the support (n-layer 3) is 0 °), the substrate temperature is set to 350 ° C., and at the end of the film formation (the distance from the interface of the support is 1000 °). By setting the substrate temperature to 80 ° C. and gradually lowering the substrate temperature during this period, an amorphous Ge film having a hydrogen profile (2) was obtained.
【００３９】上記非晶質Ｇｅ膜（ｉ層４）は、プラズマ
ＣＶＤ法で形成した。このときの条件は、圧力０．２ｔ
ｏｒｒ、ＲＦパワ−１０Ｗ、ＧｅＨ4／Ｈ2：４０ＳＣＣ
Ｍである。The amorphous Ge film (i-layer 4) was formed by a plasma CVD method. The condition at this time is a pressure of 0.2 t.
orr, RF power 10W, GeH 4 / H 2 : 40SCC
M.
【００４０】次に、ゴ−ルドイメ−ジ炉によりＮ2雰囲
気中で熱アニ−ルを行い、上記非晶質Ｇｅ膜（ｉ層４）
を固相成長させ、多結晶Ｇｅ膜を製造した。このときの
固相成長温度を調べたところ、３８０℃であった。これ
は、水素のほとんど入っていない非晶質Ｇｅ膜の場合と
ほぼ同じ温度であった。Next, thermal annealing is performed in a N 2 atmosphere by a gold image furnace to form the amorphous Ge film (i-layer 4).
Was subjected to solid phase growth to produce a polycrystalline Ge film. When the solid phase growth temperature at this time was examined, it was 380 ° C. This was almost the same temperature as that of the amorphous Ge film containing almost no hydrogen.
【００４１】このときも、断面ＳＥＭにより粒径２００
Å以上の結晶粒が認められる温度を採用した。At this time, the particle size was 200
The temperature at which more than Å crystal grains were observed was adopted.
【００４２】表４は、上記のように製造した多結晶Ｇｅ
膜から成るｉ層４を備えた光起電力装置Ｄの出力特性を
示す。Table 4 shows the polycrystalline Ge produced as described above.
The output characteristic of the photovoltaic device D provided with the i-layer 4 made of a film is shown.
【００４３】ただし、測定値は基準光源（ＡＭ１．
５）、１００ｍＷ／ｃｍ2照射下の条件に基づくもので
ある。However, the measured values are based on the reference light source (AM1.
5) Based on conditions under irradiation of 100 mW / cm 2 .
【００４４】[0044]
【表４】 [Table 4]
【００４５】表１と表４を比較すると、光起電力装置Ｄ
では、低温で膜中水素量の多い非晶質Ｇｅ膜（ｉ層４）
を固相成長させた結果、出力特性が大きく改善された。Comparison between Table 1 and Table 4 shows that the photovoltaic device D
Then, an amorphous Ge film having a large amount of hydrogen in the film at a low temperature (i-layer 4)
As a result of the solid phase growth, the output characteristics were greatly improved.
【００４６】しかも、光起電力装置Ｄにおいては連続的
に水素量が変化しているために、固相成長後の膜のＦ．
Ｆ．の大きな改善が認められた。Moreover, in the photovoltaic device D, since the amount of hydrogen changes continuously, the F.V.
F. Significant improvement was observed.
【００４７】尚、光活性層であるｉ層４の主構成材料と
してＧｅをとりあげたが、Ｓｉ等でも同様の効果が得ら
れる。Although Ge is used as a main constituent material of the i-layer 4 as the photoactive layer, the same effect can be obtained with Si or the like.
【００４８】また、ガラス基板１上に、透明電極６、ｐ
層５、ｉ層４、ｎ層３、裏面電極２をこの順に積層され
た構造の光起電力装置に用いることも可能である。この
とき支持体はｐ層５となる。Further, a transparent electrode 6, p
It is also possible to use a photovoltaic device having a structure in which the layer 5, the i-layer 4, the n-layer 3, and the back electrode 2 are stacked in this order. At this time, the support becomes the p-layer 5.
【００４９】[0049]
【発明の効果】本発明によれば、非晶質半導体膜の支持
体側に膜中水素含有量の少ない領域を設けることによ
り、結晶化温度を低温化でき、特性の良好な多結晶半導
体薄膜が得られる。According to the present invention, a crystallization temperature can be lowered by providing a region having a low hydrogen content in a film on the support side of an amorphous semiconductor film, and a polycrystalline semiconductor thin film having good characteristics can be obtained. can get.
【図１】多結晶Ｇｅ膜を備えた光起電力装置の模式的断
面図を示す。FIG. 1 is a schematic sectional view of a photovoltaic device provided with a polycrystalline Ge film.
【図２】膜中水素量と非晶質Ｇｅ膜の固相成長温度の変
化図を示す。FIG. 2 is a diagram showing changes in the amount of hydrogen in the film and the solid phase growth temperature of the amorphous Ge film.
【図３】本発明の一実施例である非晶質Ｇｅ膜の水素プ
ロファイル（１）を示す。FIG. 3 shows a hydrogen profile (1) of an amorphous Ge film according to one embodiment of the present invention.
【図４】本発明の他の実施例である非晶質Ｇｅ膜の水素
プロファイル（２）を示す。FIG. 4 shows a hydrogen profile (2) of an amorphous Ge film according to another embodiment of the present invention.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭62−122171（ＪＰ，Ａ) 特開 平５−55140（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01L 21/205 H01L 31/04 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-62-122171 (JP, A) JP-A-5-55140 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) H01L 21/205 H01L 31/04
Claims (1)
晶質半導体薄膜に、熱処理を施すことによって、多結晶
化せしめる多結晶半導体薄膜の製造方法において、上記
非晶質半導体薄膜の支持体側に膜中水素含有量の少ない
領域を設けたことを特徴とする多結晶半導体薄膜の製造
方法。1. A method for producing a polycrystalline semiconductor thin film, which comprises subjecting a hydrogen-containing amorphous semiconductor thin film formed on a support to heat treatment so as to be polycrystallized, comprises the step of supporting the amorphous semiconductor thin film. A method for producing a polycrystalline semiconductor thin film, wherein a region having a low hydrogen content in a film is provided on a body side.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05232393A JP3162864B2 (en) | 1993-03-12 | 1993-03-12 | A method for producing a polycrystalline semiconductor thin film. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05232393A JP3162864B2 (en) | 1993-03-12 | 1993-03-12 | A method for producing a polycrystalline semiconductor thin film. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06267860A JPH06267860A (en) | 1994-09-22 |
| JP3162864B2 true JP3162864B2 (en) | 2001-05-08 |
Family
ID=12911591
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05232393A Expired - Lifetime JP3162864B2 (en) | 1993-03-12 | 1993-03-12 | A method for producing a polycrystalline semiconductor thin film. |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3162864B2 (en) |
-
1993
- 1993-03-12 JP JP05232393A patent/JP3162864B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06267860A (en) | 1994-09-22 |
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