JPS61120480A - Photoelectric converter - Google Patents
Photoelectric converterInfo
- Publication number
- JPS61120480A JPS61120480A JP59240649A JP24064984A JPS61120480A JP S61120480 A JPS61120480 A JP S61120480A JP 59240649 A JP59240649 A JP 59240649A JP 24064984 A JP24064984 A JP 24064984A JP S61120480 A JPS61120480 A JP S61120480A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- amorphous
- photoelectric conversion
- layers
- alloy
- 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
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000010409 thin film Substances 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 229910000676 Si alloy Inorganic materials 0.000 claims abstract description 4
- 239000013078 crystal Substances 0.000 claims abstract description 4
- 238000003475 lamination Methods 0.000 claims abstract 3
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims abstract 3
- 230000000737 periodic effect Effects 0.000 claims abstract 2
- 239000000956 alloy Substances 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 2
- 229910052710 silicon Inorganic materials 0.000 claims 2
- 239000010703 silicon Substances 0.000 claims 2
- 229910021417 amorphous silicon Inorganic materials 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 4
- 238000010030 laminating Methods 0.000 abstract description 3
- 229910020328 SiSn Inorganic materials 0.000 abstract 2
- 239000010408 film Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
- -1 GaAS Chemical class 0.000 description 1
- 241000935061 Larrea Species 0.000 description 1
- 229910006854 SnOx Inorganic materials 0.000 description 1
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 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
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/548—Amorphous silicon PV cells
Abstract
Description
【発明の詳細な説明】
〔発明の利用分野〕
本発明は光電変換装置に係り、特にバンドギャップの狭
い非単結晶材料を用いた薄膜光電変換装置に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a photoelectric conversion device, and particularly to a thin film photoelectric conversion device using a non-single crystal material with a narrow band gap.
従来、アモルファスシリコン（ａ−８ｉ）を主材料とす
る光起電力装置が良く知られているが、バンドギャップ
が約ｉ、７ｅｖと広いため可視波長域から長波長域に成
分が多い太陽光に対しては高い充電変換効率が得られて
いない。このため、よりバンドギャップの狭いアモルフ
ァス材料が求めラレアモルファスシリコン・ゲル甘ニュ
ーム（ａ−８ｉ（）ｅ）、アモルファスシリコン＠ｉｉ
Ｉ！＜ａ−３ｉ５ｎ）等が提案されている。たとえば、
ＪａｐａｎＪ、Ａｐｐｌ 、 ｐｈｙｓ、、 Ｍｏｌ
２１ 、５ｕｐｐ１．２１−２ 、’ り２９７〜３０
２に示されるようにａ−８ｉセルとａ −８ｉＧｅセル
を組合せたダブルセルもしくはトリプルセルが、作製さ
れ、ａ−７９ｉシングルセルに比べて、より高い光電変
換効率が得られている。しかしながら、ＧｅＯ量が増え
るに従って光導電度が低下し、望ましいバンドギャップ
である１、４〜１．５ｅｖではａ−８ｉに比べて１桁か
ら２桁も低くなる。このため、ダブルセル、トリプルセ
ルにおいてもシングルセルに比べて、その光電変換効率
の飛躍的な向上はなかった。Conventionally, photovoltaic devices mainly made of amorphous silicon (A-8i) are well known, but because of their wide bandgap of about i,7ev, they are difficult to absorb sunlight that has many components in the visible wavelength range to the long wavelength range. However, high charging conversion efficiency has not been achieved. For this reason, amorphous materials with narrower band gaps are required, such as Larrea amorphous silicon gel sweet newum (a-8i()e), amorphous silicon@ii
I! <a-3i5n) etc. have been proposed. for example,
JapanJ, Appl, phys, Mol
21, 5upp1.21-2,'ri297-30
As shown in Fig. 2, a double cell or a triple cell combining an a-8i cell and an a-8i Ge cell was fabricated, and a higher photoelectric conversion efficiency was obtained than that of an a-79i single cell. However, as the amount of GeO increases, the photoconductivity decreases, and at a desirable band gap of 1.4 to 1.5 ev, it is one to two orders of magnitude lower than that of a-8i. For this reason, even in double cells and triple cells, there was no dramatic improvement in photoelectric conversion efficiency compared to single cells.
一方、アモルファス合金材料の性質を変える方法として
、異なる材料の薄膜を多層に重ね合わせることが試みら
れている。たとえば、日本学術振興会光電相互変換第ｉ
ｚｓ姿員会、第１１１回研究会資料第４２６号に示され
る工うに、ａ−３ｉトアモルファスゲルマニューム（ａ
−Ｇｅ）の多層薄膜を形成し、光学的、電気的特性につ
いて検討し膜質の改造の確認が行われている。１．かし
Ｇｅｔ多量に含むため、光導電度が低下し、光電変換効
率の大巾な向上は期待できない。On the other hand, as a method of changing the properties of amorphous alloy materials, attempts have been made to stack thin films of different materials in multiple layers. For example, the Japan Society for the Promotion of Science Photoelectricity Interconversion Part I
The a-3i amorphous germanium (a
A multilayer thin film of -Ge) has been formed, and its optical and electrical properties have been examined to confirm modification of the film quality. 1. Since it contains a large amount of Get, the photoconductivity decreases and a significant improvement in photoelectric conversion efficiency cannot be expected.
本発明の目的は、ａ−３ｉ膜よりバンドギャップが小さ
く、光導電特性の良好な薄膜を有する光電変換効率の良
い光電変換装置を提供することにるる。An object of the present invention is to provide a photoelectric conversion device having a thin film with a smaller bandgap and better photoconductive properties than an a-3i film and with good photoelectric conversion efficiency.
本発明者は、；１−３ｉもしくはＢ−８ｉ（）ｅなどの
シリコン合金とこれと異なるａ−８ｉＧｅ、ａ−８ｉｎ
ｎ等のＶ族合金、もしくはＧａＡＳなどの■−Ｖ族化合
物、もしくはＩｎＰなどの■−■低化合物を多層に積層
した半導体膜がバンドギャップが小さく、また光導電特
性もよいことを見出した。The present inventor has discovered that silicon alloys such as;1-3i or B-8i()e, and different a-8iGe, a-8in
It has been found that a semiconductor film formed by laminating multiple layers of a V group alloy such as n, a ■-V group compound such as GaAS, or a ■-■ low compound such as InP has a small band gap and good photoconductive properties.
特１ｃ ａ −３ｉと！−８ｉＧｅｉ、 ａ−８ｉとａ
−３Ｌ９ｎの工うにＳｉを共通に含む半導体の多層膜
は界面準位やトラップが生じることが少なく、単なるａ
−ｆ３ｉＱｅ膜やａ−３ｉ３ｎより光導電特性の良い半
導体薄膜を得ることができた。Special 1c a-3i! -8iGei, a-8i and a
-3L9n semiconductor multilayer films that commonly contain Si rarely generate interface states or traps, and are simply a
A semiconductor thin film with better photoconductive properties than the -f3iQe film and the a-3i3n film could be obtained.
以下、本発明の実施例を図面を用いて説明する。 Embodiments of the present invention will be described below with reference to the drawings.
実施例１ 第１図を用いて説明する。Example 1 This will be explained using FIG. 1.
８０８基板ｌの上にプラズマＣＶＤ法により非単結晶薄
膜を積層した。まず、ａ−７９ｉの第１ｐ層２ｔ−３０
０人の厚さに形成した。次にａ−３ｉの超薄膜ｉ層３１
とａ−８ｉ３ｎの超薄膜ｉ層３２を交互に、それぞれ２
００人と１００人の膜厚で積層して、膜厚４５００ 人
の第１１層３１ｒ形成した。A non-single crystal thin film was laminated on the 808 substrate l by plasma CVD. First, the first p layer 2t-30 of a-79i
It was formed to a thickness of 0 people. Next, the ultra-thin i-layer 31 of a-3i
and a-8i3n ultra-thin i-layers 32 alternately.
The 11th layer 31r having a thickness of 4,500 layers was formed by laminating layers with a thickness of 0.00 layers and a thickness of 100 layers.
このとき３ｉと３ｎの組成はＳ ｉ （Ｌ７１１ Ｓ
ｆｌＬｌｓとした。次に微結晶３ｉの第１ｎ層４を２０
０人の厚さに形成し、以上のｐｉｎ層で第１光起電力素
子とした。次に、ａ−３ｉの第２ｐ層５ｔ−３００人、
ａ−３ｉの第２１層６を１５００人、微結晶ＳｔＯ第２
ｎ層７ｔ−１０ＯＡの厚さに形成し、以上のｐｉｎ層で
第２光起電力素子とした。最後に透明電極８としテＩ
Ｔ Ｏ（Ｉｎｄｉｕｍ ’ｌ’ｉｎ Ｑｘｉｄｅ ）
ｔ−２００ＯＡ、真空蒸着法で形成した。本構造と、第
１１層３を本発明のものと同程度の光吸収係数になる４
５００人のａ−８ｉＳｎにしたものを比較した。At this time, the composition of 3i and 3n is S i (L711 S
It was set as flLLs. Next, the first n layer 4 of the microcrystal 3i is
The pin layer was formed to have a thickness of 0.0 mm, and the above pin layer was used as a first photovoltaic element. Next, the second p layer 5t-300 people of a-3i,
21st layer 6 of a-3i 1500 people, microcrystalline StO 2nd
An n layer was formed to a thickness of 7t-10OA, and the above pin layer constituted a second photovoltaic element. Finally, as transparent electrode 8,
T O (Indium 'l'in Qxide)
t-200OA, formed by vacuum evaporation method. With this structure, the 11th layer 3 has a light absorption coefficient similar to that of the present invention.
A comparison was made between 500 people using A-8iSn.
太陽光下での光電変換効率は、ａ−８ｎｇｎのみのもの
では４．９％であったのに対し本特許構造では７．１−
と飛躍的な向上が見られた。The photoelectric conversion efficiency under sunlight was 4.9% with only a-8ngn, but with this patented structure, it was 7.1-
A dramatic improvement was seen.
実施例２
ガラス基板上に３ｂドープのＳ ｎ Ｏｘ透明電極を形
成し、この上にｐｉｎｍ太陽電池を形成した。Example 2 A 3b-doped SnOx transparent electrode was formed on a glass substrate, and a pinm solar cell was formed thereon.
ガラス基板、透明電極は省略し、この上に形成し九ｐｉ
ｎ層のバンド構造を第２図に示した。透明電極上にａ−
３ｉＣのｐ層９１に：ｌ Ｏ０人形成した。The glass substrate and transparent electrode are omitted, and a 9-pi
The band structure of the n-layer is shown in FIG. a- on the transparent electrode
3iC p layer 91 was formed with: lO0.
次にａ−８ｉの超薄膜ｉ層１０とａ−３ｉ（）ｅの超薄
膜ｉ層１１〜１６を交互に８０人ずつ全体で５０００人
になるように形成した。このときａ−３ｉは同一形成条
件で作製した。ａ−３ｉＧｅは１１から順に１６１でＧ
ｅの比率を増加させ、バンドギャップにして１．６５ｅ
Ｖから１．４ｅＶまで変化させた。次に微結晶３ｉの１
層１７を形成し、最後に、図では省略したが、Ａ／、の
電極を真空蒸着法で形成した。この素子の光電変換効率
は７．６−で、ａ−８ｉＧｅのみでｉｆ＠を形成した場
合の光電変換効率５．５ ’１４に比べて非常に良い特
性でめった。Next, the ultra-thin film i-layer 10 of a-8i and the ultra-thin film i-layers 11 to 16 of a-3i()e were alternately formed by 80 people each for a total of 5000 people. At this time, a-3i was produced under the same formation conditions. a-3iGe is 161 in order from 11 to G
Increase the ratio of e and make the band gap 1.65e
The voltage was varied from V to 1.4 eV. Next, 1 of microcrystal 3i
A layer 17 was formed, and finally, although not shown in the figure, electrodes A/ and 2 were formed by vacuum evaporation. The photoelectric conversion efficiency of this device was 7.6-, which was very good compared to the photoelectric conversion efficiency of 5.5'14 when if@ was formed only with a-8iGe.
なお、上記の実施例では超薄膜材料として、一方はａ−
８ｉ、もう一方はａ−３ｉ３ｎ又はａ−３ｉＱｅの例を
示したが、ａ−３ｉの替りにａ−８ｎ合金、：１−３ｉ
３ｎ又はａ−３ｉＱｅの替りに■−■もしくは■−■化
合物を用いても、同様なメリットが得られることは明ら
かである。In addition, in the above example, one of the ultra-thin film materials was a-
8i, the other is a-3i3n or a-3iQe, but instead of a-3i, a-8n alloy: 1-3i
It is clear that similar advantages can be obtained by using a ■-■ or ■-■ compound in place of 3n or a-3iQe.
本発明に：れば光導電特性が良く、かつ光吸収波長範囲
の広い光電変換装置を得ることができ、これによって、
たとえば光電変換効率を飛躍的に高めることができる。According to the present invention, it is possible to obtain a photoelectric conversion device with good photoconductive properties and a wide light absorption wavelength range.
For example, photoelectric conversion efficiency can be dramatically increased.
第１図は本発明の第１の実施例を説明するための図、第
２因は第２の実施例のバンド構造を示す図である。
１・・・ＳＵＳ基板、２・・・第１ｐ層、３・・・第１
１層、４・・・第１ｎ層、５・・・第２ｐ層、６・・・
第２１層、７・・・第２ｎ層、８・・・透明電極、９・
・・ｐ層、１０・・・ａ−８ｉの超薄膜ｉ層、１１〜１
６−ａ−８ｉＧｅの超薄膜ｉ層、１７・・・ｎ層、３１
・・・ａ−８ｉの超薄■ １ 図
Ｊ／
ｔ
蔦 ２ 品FIG. 1 is a diagram for explaining the first embodiment of the present invention, and the second factor is a diagram showing the band structure of the second embodiment. DESCRIPTION OF SYMBOLS 1... SUS board, 2... 1st p layer, 3... 1st
1st layer, 4... 1st n layer, 5... 2nd p layer, 6...
21st layer, 7... 2nd n layer, 8... transparent electrode, 9...
...p layer, 10...a-8i ultra-thin film i layer, 11-1
6-a-8iGe ultra-thin i-layer, 17...n-layer, 31
...a-8i ultra-thin ■ 1 Figure J/t Ivy 2 items
Claims (1)
において、非単結晶シリコンもしくはシリコン合金層と
、周期律表上のIV族合金、もしくはIII−Ｖ族化合物、
もしくはII−VI族化合物が積層され、該積層物が少くと
も二層以上に重ねられた構造を有することを特徴とする
光電変換装置。 ２、上記積層物を構成する薄膜のいずれか、もしくは両
方で、バンドギャップが積層順に変化していることを特
徴とする特許請求の範囲第１項記載の光電変換装置。 ３、上記積層物が、一方は非単結晶シリコンもしくはシ
リコン合金、もう一方もシリコンを含有するIV族合金で
あることを特徴とする特許請求の範囲第１項もしくは第
２項記載の光電変換装置。[Claims] 1. In a photoelectric conversion device using a non-single crystal thin film containing silicon, a non-single crystal silicon or silicon alloy layer, a group IV alloy or a group III-V compound on the periodic table,
Alternatively, a photoelectric conversion device characterized in that it has a structure in which group II-VI compounds are laminated, and the laminated product is stacked in at least two layers. 2. The photoelectric conversion device according to claim 1, wherein the band gap of one or both of the thin films constituting the laminate changes in the order of lamination. 3. The photoelectric conversion device according to claim 1 or 2, wherein one of the laminates is non-single crystal silicon or a silicon alloy, and the other is a group IV alloy containing silicon. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59240649A JPS61120480A (en) | 1984-11-16 | 1984-11-16 | Photoelectric converter |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59240649A JPS61120480A (en) | 1984-11-16 | 1984-11-16 | Photoelectric converter |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61120480A true JPS61120480A (en) | 1986-06-07 |
Family
ID=17062631
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59240649A Pending JPS61120480A (en) | 1984-11-16 | 1984-11-16 | Photoelectric converter |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61120480A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4926229A (en) * | 1987-11-20 | 1990-05-15 | Canon Kabushiki Kaisha | Pin junction photovoltaic element with P or N-type semiconductor layer comprising non-single crystal material containing Zn, Se, H in an amount of 1 to 4 atomic % and a dopant and I-type semiconductor layer comprising non-single crystal Si(H,F) material |
| US5008726A (en) * | 1987-11-20 | 1991-04-16 | Canon Kabushiki Kaisha | PIN junction photovoltaic element containing Zn, Se, Te, H in an amount of 1 to 4 atomic % |
| JP2011018884A (en) * | 2009-07-07 | 2011-01-27 | Korea Iron & Steel Co Ltd | Photovoltaic device and manufacturing method thereof |
| JP2012094588A (en) * | 2010-10-25 | 2012-05-17 | Sharp Corp | Solar cell |
| KR20140066219A (en) * | 2011-09-23 | 2014-05-30 | 갈리움 엔터프라이지즈 피티와이 엘티디 | Varying bandgap solar cell |
| JP2014209651A (en) * | 2014-06-24 | 2014-11-06 | セイコーエプソン株式会社 | Photoelectric conversion device, electronic apparatus, photoelectric conversion device manufacturing method and electronic apparatus manufacturing method |
| JP2016066825A (en) * | 2016-02-03 | 2016-04-28 | セイコーエプソン株式会社 | Photoelectric conversion device |
-
1984
- 1984-11-16 JP JP59240649A patent/JPS61120480A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4926229A (en) * | 1987-11-20 | 1990-05-15 | Canon Kabushiki Kaisha | Pin junction photovoltaic element with P or N-type semiconductor layer comprising non-single crystal material containing Zn, Se, H in an amount of 1 to 4 atomic % and a dopant and I-type semiconductor layer comprising non-single crystal Si(H,F) material |
| US5008726A (en) * | 1987-11-20 | 1991-04-16 | Canon Kabushiki Kaisha | PIN junction photovoltaic element containing Zn, Se, Te, H in an amount of 1 to 4 atomic % |
| JP2011018884A (en) * | 2009-07-07 | 2011-01-27 | Korea Iron & Steel Co Ltd | Photovoltaic device and manufacturing method thereof |
| JP2012094588A (en) * | 2010-10-25 | 2012-05-17 | Sharp Corp | Solar cell |
| KR20140066219A (en) * | 2011-09-23 | 2014-05-30 | 갈리움 엔터프라이지즈 피티와이 엘티디 | Varying bandgap solar cell |
| JP2014531758A (en) * | 2011-09-23 | 2014-11-27 | ガリウム エンタープライジズ ピーティーワイ リミテッド | Variable band gap solar cell |
| JP2014209651A (en) * | 2014-06-24 | 2014-11-06 | セイコーエプソン株式会社 | Photoelectric conversion device, electronic apparatus, photoelectric conversion device manufacturing method and electronic apparatus manufacturing method |
| JP2016066825A (en) * | 2016-02-03 | 2016-04-28 | セイコーエプソン株式会社 | Photoelectric conversion device |
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