JPH04286167A - Photosensor - Google Patents
PhotosensorInfo
- Publication number
- JPH04286167A JPH04286167A JP3049536A JP4953691A JPH04286167A JP H04286167 A JPH04286167 A JP H04286167A JP 3049536 A JP3049536 A JP 3049536A JP 4953691 A JP4953691 A JP 4953691A JP H04286167 A JPH04286167 A JP H04286167A
- Authority
- JP
- Japan
- Prior art keywords
- semiconductor
- amorphous silicon
- photovoltaic device
- conductivity type
- intrinsic amorphous
- 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.)
- Pending
Links
- 239000004065 semiconductor Substances 0.000 claims abstract description 70
- 229910021417 amorphous silicon Inorganic materials 0.000 claims abstract description 55
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- 239000012535 impurity Substances 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims description 19
- 238000009792 diffusion process Methods 0.000 abstract description 12
- 230000006866 deterioration Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 36
- 239000007789 gas Substances 0.000 description 28
- 230000003287 optical effect Effects 0.000 description 22
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000010586 diagram Methods 0.000 description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 8
- 229910000077 silane Inorganic materials 0.000 description 8
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 7
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- QUZPNFFHZPRKJD-UHFFFAOYSA-N germane Chemical compound [GeH4] QUZPNFFHZPRKJD-UHFFFAOYSA-N 0.000 description 5
- 229910052986 germanium hydride Inorganic materials 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、非晶質半導体を備えた
光起電力装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photovoltaic device comprising an amorphous semiconductor.
【０００２】0002
【従来の技術】非晶質シリコンで代表される非晶質半導
体は、プラズマＣＶＤ法や蒸着法などの比較的簡便な方
法で良好な膜を形成し得ることから、薄膜半導体の有望
な材料と考えられている。[Prior Art] Amorphous semiconductors, represented by amorphous silicon, are promising materials for thin film semiconductors because good films can be formed using relatively simple methods such as plasma CVD and vapor deposition. It is considered.
【０００３】特に、前記非晶質半導体は、その形成の際
に主原料であるシリコン化合物ガスに導電型決定不純物
を含有する反応ガスを添加することにより、容易に導電
性を備えさせ得るため、例えば、光起電力装置の基本構
造であるｐ型層やｎ型層を、一つの反応炉で前記反応ガ
スを切り替えることで連続して形成できることとなる。
この様な非晶質シリコンや非晶質シリコンアロイに関し
ては、特開昭６３−２２２４２５号に詳細に記載されて
いる。In particular, the amorphous semiconductor can be easily made conductive by adding a reactive gas containing a conductivity type determining impurity to the silicon compound gas, which is the main raw material, during its formation. For example, a p-type layer and an n-type layer, which are the basic structure of a photovoltaic device, can be formed continuously in one reactor by switching the reaction gas. Such amorphous silicon and amorphous silicon alloy are described in detail in JP-A-63-222425.
【０００４】0004
【発明が解決しようとする課題】然し乍ら、斯様な特徴
を有する非晶質半導体でありながら、その一方で、例え
ば先に導電型決定不純物を含有する半導体を形成し、次
に真性の非晶質半導体を形成したならば、前記半導体に
含まれるその導電型決定不純物がその非晶質半導体に拡
散し、該非晶質半導体は汚染されてしまう。[Problem to be Solved by the Invention] However, although an amorphous semiconductor has such characteristics, it is difficult to form a semiconductor containing conductivity type determining impurities first, and then form an intrinsic amorphous semiconductor. If a crystalline semiconductor is formed, impurities that determine the conductivity type contained in the semiconductor diffuse into the amorphous semiconductor, thereby contaminating the amorphous semiconductor.
【０００５】この様な汚染は、真性の前記非晶質半導体
の膜質を劣化させ、引いてはこれを有する光起電力装置
の特性を劣化させる。[0005] Such contamination deteriorates the film quality of the intrinsic amorphous semiconductor, which in turn deteriorates the characteristics of a photovoltaic device having the same.
【０００６】特に、斯る汚染は、真性の前記非晶質半導
体として比較的高温で形成されることを要する非晶質シ
リコンアロイを採用した場合においては著しい。[0006] Such contamination is particularly severe when an amorphous silicon alloy, which is an intrinsic amorphous semiconductor and needs to be formed at a relatively high temperature, is used.
【０００７】そこで、本発明の目的とするところは、前
記非晶質半導体への前記導電型決定不純物等の拡散を抑
制しえる光起電力装置を提供することにある。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a photovoltaic device capable of suppressing the diffusion of the conductivity type determining impurity into the amorphous semiconductor.
【０００８】[0008]
【課題を解決するための手段】本発明光起電力装置の特
徴とするところは、基板上に形成された導電型決定不純
物を含有する半導体上に被着形成された真性の非晶質半
導体を具備する光起電力装置に於て、前記半導体と前記
非晶質半導体との間に、少なくともその一部に含有水素
量が２０原子％以上の真性非晶質シリコンを介在させた
ことにある。[Means for Solving the Problems] The photovoltaic device of the present invention is characterized by using an intrinsic amorphous semiconductor formed on a semiconductor containing conductivity type determining impurities formed on a substrate. In the photovoltaic device, intrinsic amorphous silicon having a hydrogen content of 20 atomic % or more is interposed between the semiconductor and the amorphous semiconductor, at least in part thereof.
【０００９】[0009]
【作用】本発明で使用する前記真性非晶質シリコンは、
膜中の前記含有水素量が２０原子％以上と多いことから
、その膜自体前記導電型決定不純物等の拡散が小さく、
これによる汚染が少なくてすむ。[Operation] The intrinsic amorphous silicon used in the present invention is
Since the amount of hydrogen contained in the film is as high as 20 atomic % or more, the film itself has little diffusion of the conductivity type determining impurities, etc.
This results in less contamination.
【００１０】0010
【実施例】図１は、本発明光起電力装置の第１の実施例
を示す素子構造図である。図中の（１）は石英やガラス
などからなる透光性絶縁基板、（２）は酸化錫や酸化イ
ンジュウムなどからなる透明導電膜、（３）は導電型決
定不純物を含有するｐ型の非晶質シリコンからなる半導
体、（４）は本発明の特徴である前記含有水素量が２０
原子％以上の真性非晶質シリコン、（５）は真性非晶質
シリコン（４）に被着形成された非晶質シリコンゲルマ
ニュームからなる真性の非晶質半導体、（６）はｎ型の
非晶質シリコンからなる半導体、そして（７）はアルミ
ニュームなどからなる金属膜である。真性非晶質シリコ
ン（４）以外は従来周知のものである。DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 is an element structure diagram showing a first embodiment of a photovoltaic device according to the present invention. In the figure, (1) is a transparent insulating substrate made of quartz or glass, (2) is a transparent conductive film made of tin oxide, indium oxide, etc., and (3) is a p-type non-conductive film containing conductivity type determining impurities. Semiconductor (4) made of crystalline silicon has a hydrogen content of 20%, which is a feature of the present invention.
atomic percent or more of intrinsic amorphous silicon, (5) is an intrinsic amorphous semiconductor consisting of amorphous silicon germanium deposited on intrinsic amorphous silicon (4), and (6) is an n-type non-crystalline semiconductor. A semiconductor is made of crystalline silicon, and (7) is a metal film made of aluminum or the like. The materials other than intrinsic amorphous silicon (4) are conventionally known.
【００１１】この光起電力装置の製作は次のように行っ
た。透光性絶縁基板（１）上にＩＴＯ膜（Ｉｎｄｉｕｍ
Ｔｉｎ Ｏｘｉｄｅ）膜（２）を電子ビーム蒸着
法によって形成した後、プラズマＣＶＤ法により半導体
（３）を形成する。前記半導体（３）の形成条件として
、反応ガスは、シランガス１０ｃｃ／ｍｉｎと、メタン
ガス１０ｃｃ／ｍｉｎの混合ガスに、導電型決定不純物
をドーピングするためのジボランガス（Ｂ２Ｈ６）を前
記シランガスとメタンガスの総流量の０．５％以下とな
るように添加したものを使用し、基板温度としては２０
０℃、放電時のガスの圧力を０．１Ｔｏｒｒ、放電電力
を３０Ｗとなるように設定した。尚、その膜厚は１００
Åで、前記光学的禁止帯幅は１．９ｅＶ程度である。This photovoltaic device was manufactured as follows. An ITO film (Indium
After forming a tin oxide film (2) by electron beam evaporation, a semiconductor (3) is formed by plasma CVD. As a condition for forming the semiconductor (3), the reaction gas is a mixed gas of 10 cc/min of silane gas and 10 cc/min of methane gas, and diborane gas (B2H6) for doping with conductivity type determining impurities is added at a total flow rate of the silane gas and methane gas. The substrate temperature is 20% or less.
The temperature was set at 0° C., the gas pressure during discharge was set at 0.1 Torr, and the discharge power was set at 30 W. In addition, the film thickness is 100
Å, and the optical forbidden band width is about 1.9 eV.
【００１２】次に、前記真性非晶質シリコン（４）は、
プラズマＣＶＤ法によって形成し、その形成条件として
は、シランガス及び水素ガスをそれぞれ２０ｃｃ／ｍｉ
ｎ，１００ｃｃ／ｍｉｎとなるように設定し、放電電力
１０Ｗ、放電時のガス圧力を０．１Ｔｏｒｒに保った。
そして、膜内の含有水素量を制御するために、基板温度
を１００℃一定として形成し、その膜厚は１００Åとし
た。これにより形成された前記非晶質シリコン（４）は
、光学的禁止帯幅が１．８５ｅＶであり、またその含有
水素量が２３原子％程度であった。Next, the intrinsic amorphous silicon (4) is
It is formed by plasma CVD method, and the formation conditions are as follows: 20 cc/mi of silane gas and hydrogen gas each.
n, 100 cc/min, the discharge power was 10 W, and the gas pressure during discharge was maintained at 0.1 Torr. In order to control the amount of hydrogen contained in the film, the substrate temperature was kept constant at 100° C., and the film thickness was 100 Å. The amorphous silicon (4) thus formed had an optical forbidden band width of 1.85 eV and a hydrogen content of about 23 at %.
【００１３】真性非晶質シリコン（４）に引き続き真性
非晶質半導体（５）をプラズマＣＶＤ法によって形成し
た。
その形成条件としては、シランガス，ＧｅＨ４ガス及び
水素ガスをそれぞれ２０ｃｃ／ｍｉｎ，４ｃｃ／ｍｉｎ
，９６ｃｃ／ｍｉｎとなるように設定し、放電電力１０
Ｗ、放電時のガス圧力を０．１Ｔｏｒｒに保った。
又、基板温度は２５０℃一定として形成し、その膜厚を
３０００Å、その光学的禁止帯幅を１．４ｅＶとなるよ
うにした。Following the intrinsic amorphous silicon (4), an intrinsic amorphous semiconductor (5) was formed by plasma CVD. The formation conditions include silane gas, GeH4 gas, and hydrogen gas at 20 cc/min and 4 cc/min, respectively.
, 96cc/min, and discharge power 10
W, the gas pressure during discharge was maintained at 0.1 Torr. Further, the substrate temperature was kept constant at 250° C., the film thickness was 3000 Å, and the optical bandgap width was 1.4 eV.
【００１４】次に、非晶質半導体（５）に引き続き、導
電性の半導体（６）であるｎ型非晶質シリコンを形成し
た。
この形成条件は、プラズマＣＶＤ法による場合、シラン
ガス１０ｃｃ／ｍｉｎに フォスフィンガスを前記シ
ランガスに対して１０％以下になるように添加し、その
膜厚が２００Åとなるように形成する。この場合の基板
温度は２００℃で、放電電力３０Ｗとし、放電時のガス
圧力は０．１Ｔｏｒｒである。斯る条件によって形成さ
れた膜の光学的禁止帯幅は１．９ｅＶであった。そして
、最後に蒸着法によりアルミニュームを形成して電極（
７）とし、素子を完成させた。Next, following the amorphous semiconductor (5), n-type amorphous silicon, which is a conductive semiconductor (6), was formed. When using the plasma CVD method, the formation conditions are such that phosphine gas is added to silane gas at 10 cc/min so that the amount of phosphine gas is 10% or less relative to the silane gas, and the film thickness is 200 Å. In this case, the substrate temperature was 200° C., the discharge power was 30 W, and the gas pressure during discharge was 0.1 Torr. The optical band gap of the film formed under these conditions was 1.9 eV. Finally, aluminum is formed by vapor deposition and the electrode (
7), and the device was completed.
【００１５】図２は、実施例光起電力装置（２１）にお
ける前記導電型決定不純物、即ち実施例の場合にあって
はボロン（Ｂ）の膜厚方向に対する分布特性図で、二次
イオン分析によって前記ｎ型の非晶質シリコン側から分
析した。更に同図には、実施例光起電力装置の他に、該
光起電力装置の本発明の特徴である前記非晶質シリコン
を具備せず他の条件は全て同一として形成した従来の光
起電力装置（２２）の特性も同時に示しているとともに
、図中にｐ型の半導体（３）及び真性非晶質シリコン（
４）の界面位置をも示している。FIG. 2 is a distribution characteristic diagram of the conductivity type determining impurity, that is, boron (B) in the case of the example, in the film thickness direction in the photovoltaic device (21) of the example. The analysis was performed from the n-type amorphous silicon side. Furthermore, in addition to the example photovoltaic device, the figure also shows a conventional photovoltaic device formed without the amorphous silicon, which is a feature of the present invention, and with all other conditions being the same. The characteristics of the power device (22) are also shown, and the figure also shows a p-type semiconductor (3) and intrinsic amorphous silicon (
4) is also shown.
【００１６】同図によれば、本発明光起電力装置（２１
）の場合にあっては、前記導電型決定不純物の拡散が極
めて小さく、その分布は非常に急峻である。一方、従来
の光起電力装置（２２）の場合では前記導電型決定不純
物の拡散が大きく、ｐ型層とｉ型層の界面が不明瞭とな
っている。According to the figure, the photovoltaic device of the present invention (21
), the diffusion of the conductivity type determining impurity is extremely small and its distribution is extremely steep. On the other hand, in the case of the conventional photovoltaic device (22), the conductivity type determining impurity is largely diffused, and the interface between the p-type layer and the i-type layer is unclear.
【００１７】本実施例光起電力装置にあっては、その代
表的な電気的特性は、開放電圧０．６４Ｖ，短絡電流２
２．０ｍＡ／ｃｍ２，曲率因子０．５７，変換効率８．
０％であった。一方、従来例光起電力装置にあっては、
前記代表値のそれぞれは、０．６０Ｖ，２１．０ｍＡ／
ｃｍ２，０ ．５０，６．３％であった。本実施例光起
電力装置に於ては、前記開放電圧、前記短絡電流のいず
れもが向上している。Typical electrical characteristics of the photovoltaic device of this embodiment are an open voltage of 0.64 V and a short circuit current of 2.
2.0mA/cm2, curvature factor 0.57, conversion efficiency 8.
It was 0%. On the other hand, in the conventional photovoltaic device,
Each of the above representative values is 0.60V, 21.0mA/
cm2,0. It was 50.6.3%. In the photovoltaic device of this example, both the open circuit voltage and the short circuit current are improved.
【００１８】次に本発明光起電力装置の第２の実施例と
して、図３にダブルグレーデッド型光起電力装置の素子
構造図を、図４に当該光起電力装置の真性半導体部分の
みのバンドプロファイル図を示す。Next, as a second embodiment of the photovoltaic device of the present invention, FIG. 3 shows an element structure diagram of a double graded photovoltaic device, and FIG. 4 shows a diagram of only the intrinsic semiconductor portion of the photovoltaic device. A band profile diagram is shown.
【００１９】このダブルグレーデッド構造とは、ｐ型や
ｎ型の各導電型の半導体に挟まれた真性半導体をその膜
厚方向に沿って、光学的禁止帯幅を変化させたもので、
特にその途中で前記光学的禁止帯幅の最小値となる部分
を設け、その最小値の部分の前後でその部分から遠ざか
るに従って、前記光学的禁止帯幅を緩やかに増加させた
構造をいう。This double graded structure is one in which the optical band gap width of an intrinsic semiconductor sandwiched between semiconductors of each conductivity type, p-type and n-type, is changed along the film thickness direction.
In particular, it refers to a structure in which a portion where the optical forbidden band width has a minimum value is provided in the middle, and the optical forbidden band width gradually increases as the distance from the minimum value portion increases.
【００２０】両図中の符号は以下の内容を示す。（３１
）はガラスや石英等からなる透光性絶縁基板、（３２）
は酸化錫や酸化インジュウムなどからなる透明導電膜、
（３３）は導電型決定不純物を含有する一導電型の半導
体でこの実施例では、ｐ型非晶質シリコンを使用し、（
３４）は本発明の特徴である含有水素量２０原子％以上
を含有せしめた真性非晶質シリコンを一部に含む層であ
るとともに、その光学的禁止帯幅を膜厚の方向に沿って
減少させたものである、（３５）は前記非晶質シリコン
（３４）の光学的禁止帯幅と連続となるように形成され
た真性の非晶質半導体で、実施例では非晶質シリコンゲ
ルマニュームで、斯る膜にあっては前記光学的禁止帯幅
を前記ダブルグレーデッド構造となるように膜形成途中
で前記光学的禁止帯幅が最小となる部分を有するように
変化させてある、（３６）は他導電型のｎ型非晶質シリ
コンからなる半導体、（３７）は電極である。[0020] Reference numerals in both figures indicate the following contents. (31
) is a transparent insulating substrate made of glass, quartz, etc., (32)
is a transparent conductive film made of tin oxide, indium oxide, etc.
(33) is a semiconductor of one conductivity type containing a conductivity type determining impurity, and in this example, p-type amorphous silicon is used;
34) is a layer partially containing intrinsic amorphous silicon with a hydrogen content of 20 atomic % or more, which is a feature of the present invention, and the optical bandgap width is decreased in the direction of the film thickness. (35) is an intrinsic amorphous semiconductor formed so as to be continuous with the optical band gap of the amorphous silicon (34), and in the example, it is made of amorphous silicon germanium. In such a film, the optical band gap width is changed so as to have a portion where the optical band gap width is minimum during film formation so as to obtain the double graded structure. ) is a semiconductor made of n-type amorphous silicon of another conductivity type, and (37) is an electrode.
【００２１】この光起電力装置の製作は以下のように行
った。まず、透光性絶縁基板（３１）上にＩＴＯ膜（３
２）及び半導体（３３）を第１の実施例と同様な方法に
て形成し、次に真性非晶質シリコン（３４）を形成する
。該非晶質シリコン（３４）の前記光学的禁止帯幅を制
御する方法としては、種々の方法があるが、本実施例で
は、膜内の前記含有水素量を変化させて行った。従って
、本例では、本発明の特徴である含有水素量２０原子％
以上の非晶質シリコンを形成するのと同時に、前記光学
的禁止帯幅の制御を同時に行うこととなる。This photovoltaic device was manufactured as follows. First, an ITO film (3) is placed on a transparent insulating substrate (31).
2) and a semiconductor (33) are formed in the same manner as in the first embodiment, and then intrinsic amorphous silicon (34) is formed. There are various methods for controlling the optical band gap of the amorphous silicon (34), but in this example, the amount of hydrogen contained in the film was changed. Therefore, in this example, the content of hydrogen is 20 at%, which is a feature of the present invention.
At the same time as forming the above amorphous silicon, the optical band gap is controlled at the same time.
【００２２】その形成条件としては、プラズマＣＶＤ法
においてシランガス及び水素ガスをそれぞれ２０ｃｃ／
ｍｉｎ，１００ｃｃ／ｍｉｎとなるように設定し、放電
電力１０Ｗ、放電時のガス圧力を０．１Ｔｏｒｒに保っ
た。そして、膜内の含有水素量を制御するために、非晶
質シリコン（３４）の成膜とともに基板温度を５０℃か
ら２５０℃へと漸次昇温させた。The formation conditions are as follows: silane gas and hydrogen gas are supplied at 20 cc/each in the plasma CVD method.
The discharge power was set to 10 W, and the gas pressure during discharge was maintained at 0.1 Torr. Then, in order to control the amount of hydrogen contained in the film, the substrate temperature was gradually raised from 50° C. to 250° C. while forming the amorphous silicon (34) film.
【００２３】特に、昇温過程としては、前記非晶質シリ
コン（３４）が１００Åの膜厚（３４ａ）にまで形成さ
れる過程で前記基板温度を５０℃から１５０℃と変化さ
せ、さらにその後の１００Åの膜厚（３４ｂ）を形成す
る間に１５０℃から２５０℃へと変化させた。実験によ
れば、基板温度と前記含有水素量とは良い相関があり、
例えば２５０℃，１５０℃さらに５０℃のそれぞれの基
板温度では、前記含有水素量は１５、２０，２５原子％
とそれぞれ変化し、これにともない前記光学的禁止帯幅
も１．７，１．８，１．９ｅＶとそれぞれ変化した。In particular, in the temperature raising process, the substrate temperature is changed from 50°C to 150°C in the process of forming the amorphous silicon (34) to a thickness of 100 Å (34a), and then The temperature was changed from 150° C. to 250° C. while forming a film thickness (34b) of 100 Å. According to experiments, there is a good correlation between the substrate temperature and the amount of hydrogen contained.
For example, at substrate temperatures of 250°C, 150°C, and 50°C, the hydrogen content is 15, 20, and 25 atomic %.
Along with this, the optical band gap also changed to 1.7, 1.8, and 1.9 eV, respectively.
【００２４】斯様な非晶質シリコン（３４）の形成に引
き続き非晶質半導体（３５）を形成する。この非晶質半
導体（３５）の形成条件は、前記プラズマＣＶＤ法を使
用し、その反応ガスとしては、シランガス２０ｃｃ／ｍ
ｉｎにＧｅＨ４ガスを０〜４ｃｃ／ｍｉｎの範囲で添加
し，これらガスに水素ガスを添加することにより、その
総流量が１２０ｃｃ／ｍｉｎになるように調整した。Following the formation of such amorphous silicon (34), an amorphous semiconductor (35) is formed. The conditions for forming this amorphous semiconductor (35) are as follows: the plasma CVD method described above is used, and the reaction gas is silane gas at 20 cc/m
GeH4 gas was added to the inlet at a rate of 0 to 4 cc/min, and hydrogen gas was added to these gases to adjust the total flow rate to 120 cc/min.
【００２５】特に、ＧｅＨ４ガスの添加量の変化は、非
晶質シリコンゲルマニュームの光学的禁止帯幅によく対
応する。即ち、前記光学的禁止帯幅が、最小値となる部
分にあっては、ＧｅＨ４ガスの添加量が前記範囲内で最
大となるようにし、前記部分の前後では該ＧｅＨ４ガス
を漸減させた。放電電力は、１０Ｗ、放電時ガス圧を０
．１Ｔｏｒｒに保ち、基板温度は２５０℃とした。In particular, the change in the amount of GeH4 gas added corresponds well to the optical forbidden band width of amorphous silicon germanium. That is, in the portion where the optical forbidden band width is the minimum value, the amount of GeH4 gas added was set to be the maximum within the range, and the amount of GeH4 gas was gradually decreased before and after the portion. The discharge power was 10W, and the gas pressure during discharge was 0.
．． The temperature was maintained at 1 Torr, and the substrate temperature was 250°C.
【００２６】これにより、図４に示す如く初期の膜厚５
００Åの範囲の非晶質半導体（３５ａ）を前記光学的禁
止帯幅が１．７ｅＶから１．４ｅＶとなるように漸減さ
せ、これに引き続く２５００Åの範囲の非晶質シリコン
（３５ｂ）では前記光学的禁止帯幅が１．４ｅＶから１
．７ｅＶになるように漸増させた。これにより、ダブル
グレーデッド構造が構成し得る。As a result, the initial film thickness 5 is reduced as shown in FIG.
The optical band gap of the amorphous semiconductor (35a) in the range of 00 Å is gradually decreased from 1.7 eV to 1.4 eV, and then the optical bandgap width of the amorphous silicon (35b) in the range of 2500 Å is target bandgap width from 1.4eV to 1
．． The voltage was gradually increased to 7 eV. This allows a double graded structure to be constructed.
【００２７】次に、ｎ型非晶質シリコンである他導電型
半導体（３６）を第１の実施例と同様の形成条件によっ
て成膜した。そして、最後に、アルミニュームやクロム
などからなる金属膜の電極（３７）を形成し、素子を完
成した。Next, a semiconductor of another conductivity type (36) made of n-type amorphous silicon was formed under the same formation conditions as in the first embodiment. Finally, a metal film electrode (37) made of aluminum, chromium, etc. was formed to complete the device.
【００２８】本発明光起電力装置にあっては、真性非晶
質シリコン（３４ａ）の膜厚と、これに含まれる含有水
素量が重要である。In the photovoltaic device of the present invention, the thickness of the intrinsic amorphous silicon (34a) and the amount of hydrogen contained therein are important.
【００２９】図５は、真性非晶質シリコン（３４ａ）の
膜厚が前記光起電力装置の特性に与える影響を示す特性
図である。前記特性としては、光起電力装置の曲率因子
を採用した。前記曲率因子は、１の値に近いもの程良好
な特性であることを意味する。FIG. 5 is a characteristic diagram showing the influence of the film thickness of the intrinsic amorphous silicon (34a) on the characteristics of the photovoltaic device. As the characteristic, the curvature factor of the photovoltaic device was adopted. The closer the curvature factor is to 1, the better the characteristics.
【００３０】同図によれば約４０Åから約１２０Åの範
囲内で０．６０を越える良好な特性を示している。この
理由としては、前記膜厚が約４０Å以下の場合ではその
膜厚が薄すぎるため、前記非晶質半導体（３５）が前記
半導体（３３）からの導電型決定不純物、実施例ではボ
ロン（Ｂ）の拡散による影響を受け、前記非晶質半導体
（３５）内の内部電界が弱くなってしまうためであり、
一方前記膜厚が約１２０Å以上の場合では、前記拡散に
よる影響は小さくなるものの該非晶質半導体が前記半導
体（３３）から遠くなり過ぎ、前記非晶質半導体（３５
）内に有効な電界が発生しないことによるものである。According to the figure, good characteristics exceeding 0.60 are shown within the range of about 40 Å to about 120 Å. The reason for this is that when the film thickness is about 40 Å or less, the film thickness is too thin, and the amorphous semiconductor (35) is contaminated with conductivity type determining impurities from the semiconductor (33), boron (B) in the example. ), the internal electric field within the amorphous semiconductor (35) weakens.
On the other hand, when the film thickness is about 120 Å or more, although the influence of the diffusion becomes small, the amorphous semiconductor becomes too far away from the semiconductor (33), and the amorphous semiconductor (35) becomes too far away from the semiconductor (33).
) is due to the fact that no effective electric field is generated within the range.
【００３１】次に、前記真性非晶質シリコン（３４ａ）
の含有水素量に関するものとして、図６に、前記含有水
素量を変化させた場合の、該非晶質シリコン（３４ａ）
への前記導電型決定不純物の拡散距離の変化を示してい
る。尚、その含有水素量の変化は、前記基板温度を制御
することによって行い、非晶質シリコン（３４ａ）の膜
厚は図５より得られた好適な範囲内にある１００Å一定
としている。Next, the intrinsic amorphous silicon (34a)
Regarding the content of hydrogen in the amorphous silicon (34a), FIG. 6 shows the content of the amorphous silicon (34a) when the content of hydrogen is changed.
3 shows a change in the diffusion distance of the conductivity type determining impurity. The amount of hydrogen contained is changed by controlling the substrate temperature, and the thickness of the amorphous silicon (34a) is kept constant at 100 Å, which is within the preferable range obtained from FIG.
【００３２】従って、横軸は、前記基板温度のスケール
に加えて、その各基板温度によって形成した場合の膜中
の含有水素量のスケールをも同時に対応させ示している
。Therefore, in addition to the scale of the substrate temperature, the horizontal axis also corresponds to the scale of the amount of hydrogen contained in the film formed at each substrate temperature.
【００３３】これによれば、前記拡散距離が１００Å以
下となるように前記導電型決定不純物の拡散を有効に阻
止するためには、２０原子％以上の含有水素量を有する
非晶質シリコンを使用することが好ましいことが判る。According to this, in order to effectively prevent the diffusion of the conductivity type determining impurity so that the diffusion distance is 100 Å or less, amorphous silicon having a hydrogen content of 20 atomic % or more is used. It turns out that it is preferable to do so.
【００３４】第２の実施例のダブルグレーデッド構造の
光起電力装置の代表的な光起電力特性としては、開放電
圧０．７０Ｖ、短絡電流２１．５ｍＡ／ｃｍ２、曲率因
子０．６１、変換効率９．２％であった。一方、本発明
の特徴である含有水素量が２０原子以上の真性非晶質シ
リコンを具備しない従来のダブルグレーデッド構造の光
起電力装置にあっては、開放電圧０．６６Ｖ、短絡電流
２０．２ｍＡ／ｃｍ２、曲率因子０．５９、変換効率７
．９％あり、本発明光起電力装置がその特性向上の面で
優れていることが確認できている。Typical photovoltaic characteristics of the double graded structure photovoltaic device of the second embodiment include an open circuit voltage of 0.70 V, a short circuit current of 21.5 mA/cm2, a curvature factor of 0.61, and a conversion factor of 0.61. The efficiency was 9.2%. On the other hand, in a conventional double graded structure photovoltaic device that does not include intrinsic amorphous silicon with a hydrogen content of 20 atoms or more, which is a feature of the present invention, the open circuit voltage is 0.66 V and the short circuit current is 20. 2mA/cm2, curvature factor 0.59, conversion efficiency 7
．． 9%, confirming that the photovoltaic device of the present invention is excellent in improving its characteristics.
【００３５】尚、第２の実施例で前記非晶質シリコン（
３４ｂ）として示し含有水素量２０％未満となる部分は
、従来の光起電力装置用バッファ層に相当するもので、
本発明の効果を呈するための必須のものではない。従っ
て、本発明の効果を呈するためには、前記非晶質シリコ
ン（３４）として少なくともその一部に前記含有水素量
が２０原子％以上の真性非晶質シリコンを有しておれば
良い。更には又、斯様な含有水素量を有する真性非晶質
シリコンであれば、実施例で使用した様な前記光学的禁
止帯幅が膜厚に沿って変化するものである必要は必ずし
もなく、膜厚方向に沿って均一なものであってもよい。In the second embodiment, the amorphous silicon (
The portion shown as 34b) with a hydrogen content of less than 20% corresponds to a conventional buffer layer for a photovoltaic device,
It is not essential for exhibiting the effects of the present invention. Therefore, in order to exhibit the effects of the present invention, at least a portion of the amorphous silicon (34) should contain intrinsic amorphous silicon containing 20 at % or more of hydrogen. Furthermore, if it is an intrinsic amorphous silicon having such a hydrogen content, the optical forbidden band width does not necessarily need to change along the film thickness as used in the examples. It may be uniform along the film thickness direction.
【００３６】第２の実施例では、非晶質シリコン（３４
ｂ）と非晶質シリコンゲルマニューム（３５）との接触
部において、それらの前記光学的禁止帯幅を連続とする
ように設計し形成したが、本発明はこれに限られるもの
ではなく、例え前記接触部が不連続となっても、本発明
の効果である前記導電型決定不純物等の拡散の抑制効果
を得ることができる。但し、光キャリアの収集等の向上
を図るためには、本実施例の様に前記光学的禁止帯幅が
連続となるように構成する方が好ましい。In the second embodiment, amorphous silicon (34
b) and the amorphous silicon germanium (35) are designed and formed so that the optical bandgap width thereof is continuous, but the present invention is not limited to this. Even if the contact portion is discontinuous, the effect of suppressing the diffusion of the conductivity type determining impurity, etc., which is the effect of the present invention, can be obtained. However, in order to improve collection of optical carriers, etc., it is preferable to configure the optical forbidden band width to be continuous as in this embodiment.
【００３７】両実施例では、導電型の半導体として非晶
質半導体で説明したがこれに限られず、多結晶半導体や
単結晶半導体であってもよく、更に、実施例では、導電
型の半導体の間に配置された半導体については、真性の
非晶質シリコンゲルマニュームを使用したが、これ以外
に非晶質シリコンカーバイド等であってよい。In both embodiments, an amorphous semiconductor is used as a conductive type semiconductor, but it is not limited to this, and may be a polycrystalline semiconductor or a single crystal semiconductor. Although intrinsic amorphous silicon germanium is used as the semiconductor disposed in between, other materials such as amorphous silicon carbide may be used.
【００３８】前述した実施例では、基板からｐ型半導体
、真性非晶質半導体及びｎ型半導体を順次形成した構造
であるが、これに対し基板側からｎ型半導体、真性非晶
質半導体及びｐ型半導体を順次形成し得る場合にあって
は、前記ｎ型半導体と前記真性非晶質半導体の界面に、
本発明の特徴である含有水素量２０原子％以上の非晶質
シリコンを介在せしめればよい。In the above-mentioned embodiment, the p-type semiconductor, the intrinsic amorphous semiconductor, and the n-type semiconductor are sequentially formed from the substrate. In the case where type semiconductors can be formed sequentially, at the interface between the n-type semiconductor and the intrinsic amorphous semiconductor,
Amorphous silicon having a hydrogen content of 20 at % or more, which is a feature of the present invention, may be interposed.
【００３９】[0039]
【発明の効果】本発明光起電力装置によれば、導電型決
定不純物の拡散が抑制し得ることから光起電力装置とし
ての特性の向上が果たし得る。According to the photovoltaic device of the present invention, the characteristics of the photovoltaic device can be improved because diffusion of conductivity type determining impurities can be suppressed.
【００４０】更に、本発明で使用する含有水素量が２０
原子％以上の真性非晶質シリコンは、その形成条件が、
通常穏やかな形成状態の範囲内となることから、この真
性非晶質シリコンの形成に先だって形成されている導電
型決定不純物を含有する半導体へのその形成の際の損傷
を少なくでき、該損傷に基づく前記導電型決定不純物の
拡散が抑制しえるという効果も備えている。Furthermore, the amount of hydrogen used in the present invention is 20
Intrinsic amorphous silicon of atomic percent or more is formed under the following conditions:
Since the formation state is normally within the range of mild conditions, damage to the semiconductor containing conductivity type determining impurities formed prior to the formation of this intrinsic amorphous silicon can be reduced, and the damage can be reduced. It also has the effect of suppressing the diffusion of the conductivity type determining impurities.
【図１】本発明光起電力装置の素子構造断面図である。FIG. 1 is a sectional view of an element structure of a photovoltaic device according to the present invention.
【図２】前記光起電力装置に於ける導電型決定不純物の
分布特性図である。FIG. 2 is a distribution characteristic diagram of conductivity type determining impurities in the photovoltaic device.
【図３】本発明光起電力装置の第２の実施例の素子構造
断面図である。FIG. 3 is a sectional view of the element structure of a second embodiment of the photovoltaic device of the present invention.
【図４】前記光起電力装置におけるｉ型半導体部分のバ
ンドプロファイル図である。FIG. 4 is a band profile diagram of an i-type semiconductor portion in the photovoltaic device.
【図５】非晶質シリコンの膜厚に対する前記光起電力装
置の曲率因子との関係を示す特性図である。FIG. 5 is a characteristic diagram showing the relationship between the film thickness of amorphous silicon and the curvature factor of the photovoltaic device.
【図６】非晶質シリコンの含有水素量に対する導電型決
定不純物の拡散距離の関係を示す特性図である。FIG. 6 is a characteristic diagram showing the relationship between the diffusion distance of conductivity type determining impurities and the amount of hydrogen contained in amorphous silicon.
１──基板 ３──半導体 ４──真性非晶質シリコン ５──非晶質半導体 1──Substrate 3──Semiconductor 4──Intrinsic amorphous silicon 5──Amorphous semiconductor
Claims (1)
を含有する半導体上に被着形成された真性の非晶質半導
体を具備する光起電力装置に於て、前記半導体と前記非
晶質半導体との間に、少なくともその一部に含有水素量
が２０原子％以上の真性非晶質シリコンを介在させたこ
とを特徴とする光起電力装置。1. In a photovoltaic device comprising an intrinsic amorphous semiconductor formed on a semiconductor containing conductivity type determining impurities formed on a substrate, the semiconductor and the amorphous 1. A photovoltaic device characterized in that intrinsic amorphous silicon having a hydrogen content of 20 atomic % or more is interposed between the semiconductor and at least a portion thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3049536A JPH04286167A (en) | 1991-03-14 | 1991-03-14 | Photosensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3049536A JPH04286167A (en) | 1991-03-14 | 1991-03-14 | Photosensor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04286167A true JPH04286167A (en) | 1992-10-12 |
Family
ID=12833898
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3049536A Pending JPH04286167A (en) | 1991-03-14 | 1991-03-14 | Photosensor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04286167A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09223807A (en) * | 1996-02-14 | 1997-08-26 | Mitsubishi Heavy Ind Ltd | Amorphous semiconductor solar cell |
| US7030413B2 (en) | 2000-09-05 | 2006-04-18 | Sanyo Electric Co., Ltd. | Photovoltaic device with intrinsic amorphous film at junction, having varied optical band gap through thickness thereof |
| US7135349B2 (en) | 2003-11-27 | 2006-11-14 | Samsung Electronics Co., Ltd. | Photodiode and method of fabricating the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63274184A (en) * | 1987-05-06 | 1988-11-11 | Hitachi Ltd | Photoelectric transducer and manufacture thereof |
| JPS63304673A (en) * | 1987-06-03 | 1988-12-12 | Sanyo Electric Co Ltd | Photovoltaic device |
| JPH0352271A (en) * | 1989-07-20 | 1991-03-06 | Sanyo Electric Co Ltd | Photovoltaic device |
-
1991
- 1991-03-14 JP JP3049536A patent/JPH04286167A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63274184A (en) * | 1987-05-06 | 1988-11-11 | Hitachi Ltd | Photoelectric transducer and manufacture thereof |
| JPS63304673A (en) * | 1987-06-03 | 1988-12-12 | Sanyo Electric Co Ltd | Photovoltaic device |
| JPH0352271A (en) * | 1989-07-20 | 1991-03-06 | Sanyo Electric Co Ltd | Photovoltaic device |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09223807A (en) * | 1996-02-14 | 1997-08-26 | Mitsubishi Heavy Ind Ltd | Amorphous semiconductor solar cell |
| US7030413B2 (en) | 2000-09-05 | 2006-04-18 | Sanyo Electric Co., Ltd. | Photovoltaic device with intrinsic amorphous film at junction, having varied optical band gap through thickness thereof |
| US7135349B2 (en) | 2003-11-27 | 2006-11-14 | Samsung Electronics Co., Ltd. | Photodiode and method of fabricating the same |
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