JPS61244072A - Amorphous silicon photoelectric conversion element - Google Patents
Amorphous silicon photoelectric conversion elementInfo
- Publication number
- JPS61244072A JPS61244072A JP60084535A JP8453585A JPS61244072A JP S61244072 A JPS61244072 A JP S61244072A JP 60084535 A JP60084535 A JP 60084535A JP 8453585 A JP8453585 A JP 8453585A JP S61244072 A JPS61244072 A JP S61244072A
- Authority
- JP
- Japan
- Prior art keywords
- photoelectric conversion
- amorphous silicon
- atoms
- conversion element
- layer
- 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 title claims abstract description 35
- 229910021417 amorphous silicon Inorganic materials 0.000 title claims abstract description 27
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 18
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 18
- 230000003287 optical effect Effects 0.000 claims abstract description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 125000004431 deuterium atom Chemical group 0.000 claims abstract description 4
- 125000005843 halogen group Chemical group 0.000 claims abstract description 4
- 125000004429 atom Chemical group 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims 6
- 229910052805 deuterium Inorganic materials 0.000 claims 1
- 239000002356 single layer Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 8
- 238000000354 decomposition reaction Methods 0.000 abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 4
- 230000035945 sensitivity Effects 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001569 carbon dioxide Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 150000004678 hydrides Chemical class 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 16
- 239000000758 substrate Substances 0.000 description 12
- 239000002184 metal Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 150000004820 halides Chemical class 0.000 description 5
- 206010070834 Sensitisation Diseases 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000008313 sensitization Effects 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- 206010034972 Photosensitivity reaction Diseases 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000036211 photosensitivity Effects 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- -1 silicon hydride monodeuteride Chemical compound 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052990 silicon hydride Inorganic materials 0.000 description 1
- 238000002834 transmittance 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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/036—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0376—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including amorphous semiconductors
-
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/20—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Light Receiving Elements (AREA)
- Photovoltaic Devices (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、光エネルギーを電気エネルギーに、あるいは
光の情報を電気的情報に変換する光電変換素子に関し、
特に、短波長増感のアモルファスシリコン光電変換素子
に関するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a photoelectric conversion element that converts optical energy into electrical energy or optical information into electrical information.
In particular, it relates to short wavelength sensitized amorphous silicon photoelectric conversion elements.
（従来の技術）
アモルファスシリコン（以下ａ−８ｉと記す）を用いた
光電変換素子には、サンドインチ型とコブレナー型の２
つの型式がある。このうちコプレナー型は、サンドイン
チ型と比較して応答速度が遅いので、高速の光電変換素
子を目的とする場合、通常、サンドインチ型が使用され
る。(Prior art) There are two types of photoelectric conversion elements using amorphous silicon (hereinafter referred to as a-8i): sandwich type and coblenner type.
There are two models. Among these, the coplanar type has a slower response speed than the sandwich type, so the sandwich type is usually used when a high-speed photoelectric conversion element is intended.
一般に、光電変換素子に用いられる、不純物を添加して
いない水素化アモルファスシリコン（以下ａ−３ｉ：Ｈ
と記す）は、光学的バンドギャップが約１．７ ｅＶで
ある。そのため、ａ−８ｉ：Ｈの分光感度は約６００ｎ
ｍ付近にピークを持つことになる。Hydrogenated amorphous silicon (hereinafter a-3i: H
) has an optical bandgap of approximately 1.7 eV. Therefore, the spectral sensitivity of a-8i:H is approximately 600n
It will have a peak around m.
６００ｎｍ以下の短波長光を利用する目的で、短波長側
に増感を持たせるための材料として、従来、炭素原子を
ａ−Ｓｉ：Ｈにドーピングし、光学的バンドギャップを
炭素原子によって１．９〜２．４ ｅＶに広げたａ−Ｓ
ｉ：Ｃ：Ｈが用いられている。For the purpose of utilizing short wavelength light of 600 nm or less, a-Si:H has been conventionally doped with carbon atoms as a material to provide sensitization on the short wavelength side, and the optical band gap is increased to 1. a-S expanded from 9 to 2.4 eV
i:C:H is used.
参考文献；
（１） Ａｎｄｅｒｓｏｎ、 Ｄ、Ａ、、５ｐｅａｒ、
１１．Ｅ、： ＩＥｌｅｃｔｒｉｃａｌａｎｄ ｏｐ
ｔｉｃａｌ ｐｒｏｐｅｒｔｉｅｓ ｏｆ ａｍｏｒｐ
ｈｏｕｓｓｉｌｉｃｏｎ ｃａｒｂｉｄｅ、 ５ｉｌｉ
ｃｏｎ ｎ１ｔｒｉｄｅ ａｎｄｇｅｒｉ＋ａｎｉｕＩ
ｌｃａｒｂｉｄｅ ｐｒｅｐａｒｅｄ ｂｙ ｔｈｅ
ｇｌｏｗｄｉｓｃｈａｒｇｅ ｔｅｃｈｎｉｑｕａ、
Ｐｈ１ｌｏｓ、 Ｍａｇ、、３５ ： １（２） Ｓｕ
ｓｓｍａｎｎ、 Ｒ，Ｓ、、 Ｏｇｄｅｎ、 Ｒ，：
Ｐｈｏｔｏｌｕ＋５ｉ−ｎｅｓｃａｎｃａ ａｎｄ ｏ
ｐｔｉｃａｌ ｐｒｏｐｅｒｔｉｅｓ ｏｆｐｌａｓｍ
ａ−ｄｅｐｏｓｉｔｅｄ ａｍｏｒｐｈｏｕｓ ５
ｉｘＣ□−。References; (1) Anderson, D.A., 5pear,
11. E: IElectricaland op
tical properties of amorp
houssilicon carbide, 5ili
con n1tride andgeri+aniuI
lcarbide prepared by the
glow discharge techniqua,
Ph1los, Mag, 35: 1(2) Su
ssmann, R.S., Ogden, R.:
Photolu+5i-nescanca and o
physical properties of plasma
a-deposited amorphous 5
ixC□-.
ａｌｌａｙｓ、 Ｐｈ１ｌｏｓ、 Ｍａｇ、 Ｂ、 ４
４ ： １３７（１９８１）（発明が解決しようとする
問題点）
しかしながら炭素原子によって光学的バンドギャップを
広げたａ−８ｉ：Ｃ：Ｈはａ−８ｉ：Ｈと比較してダン
グリングボンドが多く、局在準位密度が高い、そのため
暗伝導では、活性型伝導の他にホッピング伝導を起こし
易く、大きなσ２．／σ４を得ることが難しい、このこ
とは光電変換素子にとって機能上問題となる。また、光
電変換素子の電極としてＩＴＯやＳｎＯ，のような透明
導電膜を用いる場合、ａ−８ｉ：Ｃ：Ｈの炭素源となる
ｃＨ４等がＩＴＯやＳｎＯ，の酸素原子を還元し、Ｓｎ
、 Ｉｎを生成させ、これがａ−８ｉ：Ｃ：Ｈ層へ入り
込んで光電変換特性の低下を来したり、さらに透明導電
膜の劣化を招くことになる。allays, Ph1los, Mag, B, 4
4: 137 (1981) (Problems to be Solved by the Invention) However, a-8i:C:H, whose optical band gap is widened by carbon atoms, has more dangling bonds than a-8i:H. The localized level density is high, so in dark conduction, hopping conduction is likely to occur in addition to active conduction, resulting in a large σ2. /σ4 is difficult to obtain, which poses a functional problem for the photoelectric conversion element. In addition, when using a transparent conductive film such as ITO or SnO as an electrode of a photoelectric conversion element, cH4, etc., which is a carbon source of a-8i:C:H, reduces the oxygen atoms of ITO or SnO, and
, In enters into the a-8i:C:H layer, resulting in deterioration of photoelectric conversion characteristics and further deterioration of the transparent conductive film.
そこで本発明は、従来技術の欠点を除去した、短波長増
感のある光電変換素子を提供するものである。Therefore, the present invention provides a photoelectric conversion element with short wavelength sensitization that eliminates the drawbacks of the prior art.
（問題点を解決するための手段）
ａ−８ｉを母体とし、これに構成原子として水素原子、
ハロゲン原子、重水素原子の少なくとも１種を含む単層
のａ−８ｉ層の両主面にそれぞれ電極を設けてなる光電
変換素子において、ａ−８ｉ層を形成する際に、ＳｉＨ
４等に、グロー放電分解により酸素原子及び窒素原子を
発生する例えば二酸化炭素と窒素を混合して使用し、ａ
−８ｉ層中にそれらの原子を含有させる。(Means for solving the problem) A-8i is used as a matrix, and hydrogen atoms and hydrogen atoms are added to it as constituent atoms.
In a photoelectric conversion element in which electrodes are provided on both main surfaces of a single a-8i layer containing at least one of halogen atoms and deuterium atoms, when forming the a-8i layer, SiH
For example, a mixture of carbon dioxide and nitrogen is used to generate oxygen atoms and nitrogen atoms by glow discharge decomposition.
- Contain those atoms in the 8i layer.
（作 用）
上記のような酸素原子及び窒素原子の含有により局在準
位密度の小さいａ−５ｉ層が形成され、光学的バンドギ
ャップが２．０ｅＶ以上の領域で、光導電性を有する。(Function) Due to the inclusion of oxygen atoms and nitrogen atoms as described above, an a-5i layer with a small local level density is formed, and has photoconductivity in a region where the optical band gap is 2.0 eV or more.
また、σ２．／σ１が１０”以上と高い値を示す、さら
に酸素原子及び窒素原子を含むことで耐熱性が向上し、
また窒素を混合することで、より低い高周波電力で酸素
原子及び窒素原子を含ませることが可能となり、膜質の
良好なａ−Ｓｉ層を形成することができる。Also, σ2. /σ1 shows a high value of 10” or more, and contains oxygen atoms and nitrogen atoms, which improves heat resistance.
Further, by mixing nitrogen, oxygen atoms and nitrogen atoms can be included with lower radio frequency power, and an a-Si layer with good film quality can be formed.
（実施例）
以下図面を参照しながら実施例を詳細に説明する。第１
図及び第２図は、それぞれ本発明のａ−８ｉ光電変換素
子の構成を示したものである。(Example) Examples will be described in detail below with reference to the drawings. 1st
The figure and FIG. 2 each show the structure of the a-8i photoelectric conversion element of the present invention.
まず第１図に示す光電変換素子１００は、支持基板とし
てのガラスあるいは透明高分子フィルム等の透明基板１
０１の一方の面に下部電極１０２を設け、その上にａ−
８ｉ層１０３を積層し、さらに上部電極１０４を設けて
いる。この種のタイプのものは、光入射面として透明基
板１０１の他方の面１０５又は上部電極の表面１０６の
いずれかを選択することができる。First, the photoelectric conversion element 100 shown in FIG.
A lower electrode 102 is provided on one side of 01, and a-
8i layers 103 are stacked, and an upper electrode 104 is further provided. In this type of device, either the other surface 105 of the transparent substrate 101 or the surface 106 of the upper electrode can be selected as the light incident surface.
第２図に示す光電変換素子２００は、支持基板として、
Ａｔ、Ｆｅ、Ｎｘｅ Ｃｒなどの金属基板、あるいはセ
ラミック基板等の一方の面を導電処理した不透明基板２
０１が使用され、その上にａ−８ｉ層２０３を積層し、
さらに上部電極２０４を設けている。この種のタイプの
ものは、不透明基板２０１が下部電極を兼ねている。ま
た光入射面としては上部電極の表面２０６に限定される
。The photoelectric conversion element 200 shown in FIG. 2 includes, as a support substrate,
Opaque substrate 2 with conductive treatment on one side of a metal substrate such as At, Fe, Nxe Cr, or a ceramic substrate
01 is used, a-8i layer 203 is laminated on it,
Further, an upper electrode 204 is provided. In this type of device, the opaque substrate 201 also serves as the lower electrode. Further, the light incident surface is limited to the surface 206 of the upper electrode.
光電変換素子１００．２００のａ−８ｉ層１０３．２０
３は、ａ−８ｉを母体とし、これに水素原子、ハロゲン
原子、重水素原子の少なくとも１種を含むものに、さら
に酸素原子及び窒素原子を含有させたものである。この
ａ−８ｉ層は、シリコンの水素化物１重水素化物、ある
いはハロゲン化物と二酸化炭素（以下Ｃｏよと記す）及
び窒素（以下Ｎ２と記す）の混合ガスのグロー放電分解
で形成される。このようにして作製されたａ−８ｉ層は
、光学的バンドギャップが２．０ｅＶ以上の領域で光導
電性を有する。A-8i layer 103.20 of photoelectric conversion element 100.200
No. 3 has a-8i as a base material, which contains at least one of hydrogen atoms, halogen atoms, and deuterium atoms, and further contains oxygen atoms and nitrogen atoms. This a-8i layer is formed by glow discharge decomposition of a mixed gas of a silicon hydride monodeuteride or a halide, carbon dioxide (hereinafter referred to as Co), and nitrogen (hereinafter referred to as N2). The a-8i layer produced in this way has photoconductivity in a region where the optical band gap is 2.0 eV or more.
第３図にこのａ−Ｓｉ層の赤外吸収特性を示す、横軸は
波長、縦軸は透過率をそれぞれ示す、第３図より酸素原
子及び窒素原子が含有されていることが確認できる。FIG. 3 shows the infrared absorption characteristics of this a-Si layer. The horizontal axis shows the wavelength, and the vertical axis shows the transmittance. From FIG. 3, it can be confirmed that oxygen atoms and nitrogen atoms are contained.
第４図は、ａ−８ｉ層１０３．２０３の分光感度特性を
示したものであり、横軸は波長、縦軸は光電流をそれぞ
れ示す、第４図よりこのａ−８ｉ層が５００ｎｍ付近に
光感度のピークを有しており、短波長増感がなされてい
ることが判る。また、光学的バンドギャップを変えるこ
とで光感度のピーク波長を変えることができる。Figure 4 shows the spectral sensitivity characteristics of the a-8i layer 103.203, where the horizontal axis shows the wavelength and the vertical axis shows the photocurrent. It has a peak in photosensitivity, indicating that short wavelength sensitization has been achieved. Furthermore, the peak wavelength of photosensitivity can be changed by changing the optical bandgap.
ａ−３ｉ層１０３．２０３にＡＭ１（擬似太陽光）１０
０ｍＷ／ｄを照射したときの光導電率σ、ｈは、光学的
バンドギャップが２．０ｅＶ以上の領域において、Ｓｉ
Ｈ，等に混合するＣＯ２及びＮ８のガス量によりｌｏ−
６〜１０−’（Ω３）−１の間で変化する。一方、暗導
電率σ、は、前記のＣｏ２及びＮ２の混合ガス量でＬｔ
ｌＯ−” 〜１０−”（Ｑｍ）−’ｔ’アルノテ、１７
ｔｈ／＋７４が１０３より大きくなり、高いσｐｈ／’
σ、を有している。これは、ａ−８ｉ層の酸素及び窒素
源としてＣｏ、、Ｎ、を用いることにより局在準位密度
の小さいａ−８ｉ層を作製できるためと考えられる。AM1 (pseudo sunlight) 10 on a-3i layer 103.203
The photoconductivity σ, h when irradiated with 0 mW/d is
lo- depending on the amount of CO2 and N8 gas mixed with H, etc.
It varies between 6 and 10-'(Ω3)-1. On the other hand, the dark conductivity σ is Lt with the above-mentioned mixed gas amount of Co2 and N2.
lO-” ~10-”(Qm)-'t'alnote, 17
th/+74 becomes larger than 103, high σph/'
It has σ. This is considered to be because the a-8i layer with a small local level density can be formed by using Co, , N as the oxygen and nitrogen sources for the a-8i layer.
混合するＮ２は、Ｃｏ２とＮ２の励起準位が近いためＮ
２の励起エネルギーがｃｏ、の励起に移行し、Ｃｏ８の
分解に触媒として関与する。またａ−８ｉ層にＮ２より
窒素原子が含有されることでさらに局在準位密度が低下
し、耐熱性も向上する。The N2 to be mixed is N2 because the excited levels of Co2 and N2 are close to each other.
The excitation energy of 2 is transferred to the excitation of co, which participates as a catalyst in the decomposition of Co8. Further, by containing more nitrogen atoms than N2 in the a-8i layer, the localized level density is further reduced, and heat resistance is also improved.
ａ−８ｉ層１０３．２０３は、■族原子、■族原子をド
ーピングし、それぞれｐ型、ｎ型としても光電変換素子
として使用することができる。ドーピングする■族原子
としては、 Ｂ、 ＡＪ、 Ｇａ、 Ｉｎ、 Ｔｆｆｉ
等が好適なものとして挙げられ、また■族原子としては
、Ｐ、Ａｓ、Ｓｂｇ Ｂｉ等が好適なものとして挙げら
れる。ドーピングする量としては、通常の場合１０”
〜１０−”ａｔｏｍｉｃ％とするのが望ましい。The a-8i layer 103.203 can be doped with a group II atom or a group II atom, and can be used as a photoelectric conversion element as a p-type or an n-type, respectively. Group ■ atoms to be doped include B, AJ, Ga, In, Tffi
Suitable examples include P, As, Sbg Bi, and the like as group (I) atoms. The amount of doping is usually 10”
It is desirable to set it to 10-" atomic%.
ａ−５ｉ層への不純物のドーピング方法としては、シリ
コンの水素化物、重水素化物あるいはハロゲン化物とＣ
ｏ、、 Ｎ、を用いてグロー放電分解を行なう際に、■
族、■族等の不純物の水素化物１重水素化物あるいはハ
ロゲン化物（Ｂ＊Ｈｉ、ＢｓＤｓ。As a method for doping impurities into the a-5i layer, silicon hydride, deuteride, or halide and C
When performing glow discharge decomposition using o,, N, ■
Hydride monodeuteride or halide (B*Hi, BsDs.
ＢＦ、、 ＰＨ，、ＰＤ３． ＰＦ、等）を反応器内に
導入することによって達成される。不純物の含有量は、
反応器内へ導入する不純物の水素化物１重水素化物ある
いはハロゲン化物等のガス量を制御する等によって達成
される。BF,, PH,, PD3. PF, etc.) into the reactor. The content of impurities is
This is achieved by controlling the amount of impurity gas such as hydride, monodeuteride or halide introduced into the reactor.
ａ−８ｉ層１０３．２０３の膜厚は、使用する光の波長
等によって決定されるが、通常の場合０．１〜５μ腸、
好ましくは０．３〜２μｍである。The film thickness of the a-8i layer 103.203 is determined by the wavelength of the light used, etc., but in normal cases it is 0.1 to 5μ,
Preferably it is 0.3 to 2 μm.
光電変換素子１００の構成において、光を入射する面と
して透明基板１０１の面１０５あるいは上部電極、１０
４の表面１０６が選択される。透明基板面１０５から光
を入射させる場合は、下部電極１０２はａ−８ｉ層１０
３との接合をショットキー接合とすることが望ましい、
その場合の下部電極は、ｐｔ等の金属の蒸着あるいはス
パッタリング等により形成される。In the configuration of the photoelectric conversion element 100, the surface 105 of the transparent substrate 101 or the upper electrode 10 is used as the surface on which light is incident.
4 surface 106 is selected. When light is incident from the transparent substrate surface 105, the lower electrode 102 is formed by the a-8i layer 10.
It is desirable that the junction with 3 be a Schottky junction,
In this case, the lower electrode is formed by vapor deposition or sputtering of metal such as PT.
下部電極の膜厚としては、光の透過を考慮して通常５０
〜３００人、好ましくは５０〜１００人である。The thickness of the lower electrode is usually 50 mm in consideration of light transmission.
~300 people, preferably 50-100 people.
また、下部電極１０２とａ−８ｉ層１０３との接合を、
ショットキー接合の代りにＩＴＯ，ＳｎＯ，等の透明導
電膜を用いてヘテロ接合としてもよい。透明導電膜を用
いた場合、ａ−８ｉ層１０３を形成する際にグロー放電
分解により酸素原子及び窒素原子を発生するガスを混合
するため、透明導電膜のＩＴＯやＳｎＯ，の酸素原子の
還元が抑制され、透明導電膜の劣化を抑えることができ
、ａ−ＳＬ：Ｃ：Ｈで見られるような光電変換特性の低
下は起こらない。In addition, the bond between the lower electrode 102 and the a-8i layer 103 is
Instead of a Schottky junction, a transparent conductive film such as ITO, SnO, etc. may be used to form a heterojunction. When a transparent conductive film is used, a gas that generates oxygen atoms and nitrogen atoms by glow discharge decomposition is mixed when forming the a-8i layer 103, so the reduction of oxygen atoms in ITO, SnO, and the like of the transparent conductive film is reduced. The deterioration of the transparent conductive film can be suppressed, and the deterioration of photoelectric conversion characteristics as seen in a-SL:C:H does not occur.
上部電極１０４としては、Ａ（Ｉｇ Ｎｉ、Ｃｒなどの
金属膜を用いるのが望ましい、これらの金属膜は蒸着あ
るいはスパッタリング等により形成される。As the upper electrode 104, it is desirable to use a metal film such as A (Ig Ni, Cr, etc.), and these metal films are formed by vapor deposition, sputtering, or the like.
光電変換素子１００に上部電極の表面１０６から光を入
射する場合は、前述とは逆に、下部電極１０２をＡ−等
の金属膜で形成し、上部電極１０４としてショットキー
接合を形成するＰｔ、Ａｕ、Ｐｄ等の金属薄膜か、ペテ
ロ接合を形成するＩＴＯ等の透明導電膜を用いるとよい
。When light enters the photoelectric conversion element 100 from the surface 106 of the upper electrode, contrary to the above, the lower electrode 102 is formed of a metal film such as A-, and the upper electrode 104 is formed of Pt, which forms a Schottky junction. It is preferable to use a metal thin film such as Au or Pd, or a transparent conductive film such as ITO that forms a Peter junction.
また、光電変換素子２００においては、光は上部電極表
面２０６からのみ入射するので、上部電極２０４は、光
の透過を考慮してショットキー接合、あるいはヘテロ接
合を形成する金属薄膜あるいは透明導電膜とすることが
望ましい。Furthermore, in the photoelectric conversion element 200, since light enters only from the upper electrode surface 206, the upper electrode 204 is made of a metal thin film or a transparent conductive film that forms a Schottky junction or a heterojunction in consideration of light transmission. It is desirable to do so.
次に、実施例をあげて具体的に説明する。Next, a specific explanation will be given by giving examples.
実施例１
ガラス基板（２５閣×５０鵬、ｔ＝１．ｏ■）上に下部
電極としてＩＴＯ膜を形成し、その上に酸素原子を含有
する水素化アモルファスシリコン（ａ −Ｓ ｉ：０：
Ｈ）をグロー放電分解により約５０００人堆積した。Example 1 An ITO film was formed as a lower electrode on a glass substrate (25 × 50 × t = 1.o■), and hydrogenated amorphous silicon containing oxygen atoms (a-Si:0:
Approximately 5,000 pieces of H) were deposited by glow discharge decomposition.
ａ−５ｉ層の作製条件は以下の通りである。The conditions for producing the a-5i layer are as follows.
作製方法 プラズマＣＶＤ法
原料ガス ５ＩＨ４ｉｎ Ｈｌ １０％１００ｓ１０
０５ｃ、 １００％２５〜１００ｓｅｃ■Ｎ、
１００％ ２５−２５−１Ｏ０ｓｃ Ｏｚ
／ Ｎ ｚ １
基板温度 ２５０℃
反応器内圧力１．０Ｔｏｒｒ
高周波出力 ８Ｗ
ａ−８ｉ層上に上部電極としてＡＪを蒸着により形成し
た。Production method: Plasma CVD method Raw material gas: 5IH4in Hl 10%100s10
05c, 100% 25~100sec■N,
100% 25-25-1O0sc Oz
/ N z 1 Substrate temperature: 250° C. Reactor internal pressure: 1.0 Torr High frequency output: 8 W AJ was formed as an upper electrode on the a-8i layer by vapor deposition.
第５図は、このようにして作製された光電変換素子にお
ける酸素原子及び窒素原子を含むａ−８ｉ層の光学的バ
ンドギャップ、光導電率σＰｈ、Ｐｈ型率σ、を示した
ものである。横軸は（ＣＯ，＋ Ｎ、）／ＳｉＨ，のガ
ス流量比を、縦軸は導電率、光学的バンドギャップをそ
れぞれ示す、第５図によれば。FIG. 5 shows the optical bandgap, photoconductivity σPh, and Ph type ratio σ of the a-8i layer containing oxygen atoms and nitrogen atoms in the photoelectric conversion element thus produced. According to FIG. 5, the horizontal axis shows the gas flow rate ratio of (CO, +N, )/SiH, and the vertical axis shows the electrical conductivity and optical band gap.
光学的バンドギャップは２．０〜２．４５ ｅＶの範囲
にある。ＡＭｌ（擬似太陽光）１００ｍＷ／ａＪを照射
したときの光導電率σ、は（Ｃｏ、＋Ｎ、）／ＳｉＨ４
のガス流量比の増加に伴い１０−８より１０−”（Ω３
）−１へと減少する。一方、暗導電率σ、はｌＯ−２〜
ｉｏ””（００ｍ）−１の範囲にあり、ａｐＪ６ｍが１
０３より大きいことが判った。The optical bandgap is in the range 2.0-2.45 eV. Photoconductivity σ when irradiated with AMl (simulated sunlight) 100 mW/aJ is (Co, +N,)/SiH4
As the gas flow rate ratio increases, 10-” (Ω3
)-1. On the other hand, the dark conductivity σ is lO-2~
io"" (00m)-1 range, and apJ6m is 1
It turned out to be larger than 03.
実施例２
光電変換素子の構成は実施例１と同様とし、酸素原子及
び窒素原子を含む５−８ｉ層へ■族原子、■族原子のド
ーピングを行なった。ドーピングする不純物としてはＢ
、Ｐを選択した。酸素原子及び窒素原子を含むａ−３ｉ
層の形成条件は以下に示す通りである。Example 2 The structure of a photoelectric conversion element was the same as that of Example 1, and the 5-8i layer containing oxygen atoms and nitrogen atoms was doped with group II atoms and group II atoms. B as an impurity for doping
, P was selected. a-3i containing oxygen atoms and nitrogen atoms
The conditions for forming the layer are as shown below.
作製方法 プラズマＣＶＤ法
原料ガス ＳｉＨ，ｉｎ Ｈ，１０％１００ｓ１００
５ｅ、 １００％２５ｓｅｃｍＮ、
１００％ ２５ｓｅｃ１Ｂ、Ｈ，ｉｎ Ｈ
，２０００ｐｐｍ １０〜１５０ｓｃｃｍＰＨ，ｉｎ
Ｈ，２０００ｐｐｍ １０〜２５０ｓｃｃｍ第６図
は、このようにして製作された酸素原子及び窒素原子を
含むａ−８ｉ層のＡＭ１（擬似太陽光）１００ｍＷ／ｄ
照射時の光導゛電率σ２．及び暗導電率σ１を示したも
のである。横軸はＢ ｓ Ｈｓ ／ Ｓ ｉＨ４＋ Ｇ
Ｏ，＋ Ｎ、、ＰＨ，／ＳｉＨ，＋ＧＯ，＋Ｎ、（７
）ガス流量比を、縦軸は導電率をそれぞれ示す、第６図
より、それぞれガス流量比が増加するに伴い、光導電率
σ２５、暗導電率σ、が大きくなることが判明した。つ
まり、酸素原子及び窒素原子を含むａ−８ｉ層は荷電子
制御が可能であることが判り、Ｐｅｎ接合も可能である
。Production method: Plasma CVD method Raw material gas: SiH, in H, 10%100s100
5e, 100% 25secN,
100% 25sec1B, H, in H
,2000ppm 10~150sccmPH,in
H, 2000ppm 10-250sccm Figure 6 shows the AM1 (simulated sunlight) 100mW/d of the a-8i layer containing oxygen atoms and nitrogen atoms manufactured in this way.
Photoconductivity during irradiation σ2. and dark conductivity σ1. The horizontal axis is B s Hs / SiH4+ G
O, + N, PH, /SiH, +GO, +N, (7
) From FIG. 6, in which the gas flow rate ratio and the vertical axis represent the conductivity, it was found that as the gas flow rate ratio increases, the photoconductivity σ25 and the dark conductivity σ increase. In other words, it was found that charge electron control is possible in the a-8i layer containing oxygen atoms and nitrogen atoms, and Pen junction is also possible.
実施例３
ＩＴＯの代りに、ショットキー接合とするためｐｔを約
１００人蒸着し、実施例１，２と同様に光電変換素子を
作製した。これらの素子においても良好な結果が得られ
た。Example 3 Instead of ITO, about 100 pts were deposited to form a Schottky junction, and a photoelectric conversion element was produced in the same manner as in Examples 1 and 2. Good results were also obtained with these devices.
実施例４
ＳｉＨ，の代りに重水素化物５ｉＤ４．ハロゲン化物Ｓ
ｉＦ、を用いて同様の光電変換素子を作製した。Example 4 Deuteride 5iD4. instead of SiH. Halide S
A similar photoelectric conversion element was fabricated using iF.
これらの素子においても良好な結果が得られた。Good results were also obtained with these devices.
（発明の効果）
以上説明したように、本発明によれば、光学的バンドギ
ャップが２．０ｅＶ以上の領域で光導電性を有し、かつ
σ２．／σ、＞ｔｏ’と高い値を示すとともに、優れた
光電変換特性と短波長増感を有する光電変換素子を実現
することができる。(Effects of the Invention) As explained above, according to the present invention, the optical band gap has photoconductivity in a region of 2.0 eV or more, and σ2. It is possible to realize a photoelectric conversion element that exhibits a high value of /σ, >to', and has excellent photoelectric conversion characteristics and short wavelength sensitization.
第１図及び第２図は、それぞれ本発明の光電変換素子の
構成図、第３図は、赤外吸収特性図、第４図は、同分光
特性図、第５図は、本発明における酸素原子及び窒素原
子を含むａ−３Ｌ膜の（ＣＯ□”Ｎｓ）／ＳｉＨ４のガ
ス流量比と光学的バンドギャップ及び光導電率σ２１．
暗導電率σ、の関係を示す図、第６図は、酸素原子及び
窒素原子を含むａ−８ｉ膜への■族原子、■族原子をド
ーピングしたときの光導電率σ２５、暗導電率σ６を示
す図である。
１００．２００・・・光電変換素子、 １０１・・・透
明基板、１０２ ・・・下部電極、 １０３，２０３
− ａ−８ｉ層、１０４．２０４・・・上部電極、
２０１・・・不透明基板。
特許出願人 株式会社 リ コ −リコ一応用電子
研究所株式会社
第１図
第２図
第３図
液長（回内
第４図
λ（ｎｍ）1 and 2 are block diagrams of the photoelectric conversion element of the present invention, FIG. 3 is an infrared absorption characteristic diagram, FIG. 4 is a spectral characteristic diagram, and FIG. 5 is an oxygen absorption characteristic diagram of the present invention. Gas flow rate ratio of (CO□”Ns)/SiH4, optical band gap and photoconductivity σ21. of a-3L film containing atoms and nitrogen atoms.
Figure 6 shows the relationship between the dark conductivity σ and the photoconductivity σ25 and the dark conductivity σ6 when an a-8i film containing oxygen atoms and nitrogen atoms is doped with group II atoms and group II atoms. FIG. 100.200... Photoelectric conversion element, 101... Transparent substrate, 102... Lower electrode, 103,203
- a-8i layer, 104.204... upper electrode,
201... Opaque substrate. Patent applicant Rico Co., Ltd. - Rico Applied Electronics Research Institute Co., Ltd. Figure 1 Figure 2 Figure 3 Liquid length (pronation Figure 4 λ (nm)
Claims (5)
て水素原子、ハロゲン原子、重水素原子の少なくとも１
種を含む単層のアモルファスシリコン層の両主面にそれ
ぞれ電極を設けてなる光電変換素子において、前記アモ
ルファスシリコン層が酸素原子及び窒素原子を含み、か
つ光学的バンドギャップが２．０ｅＶ以上の領域で、光
導電性を有することを特徴とするアモルファスシリコン
光電変換素子。(1) Amorphous silicon is used as the base material, and at least one constituent atom is a hydrogen atom, a halogen atom, or a deuterium atom.
In a photoelectric conversion element in which electrodes are provided on both principal surfaces of a single-layer amorphous silicon layer containing seeds, a region where the amorphous silicon layer contains oxygen atoms and nitrogen atoms and has an optical band gap of 2.0 eV or more. An amorphous silicon photoelectric conversion element characterized by having photoconductivity.
族原子を含むことを特徴とする特許請求の範囲第（１）
項記載のアモルファスシリコン光電変換素子。(2) The amorphous silicon layer contains group III atoms and V atoms.
Claim No. (1) characterized in that it contains a group atom.
The amorphous silicon photoelectric conversion element described in .
ｄが、ＡＭ１（擬似太陽光）１００ｍＷ／ｃｍ＾２入射
時にσ＿ｐ＿ｈ／σ＿ｄ＞１０＾３であることを特徴と
する特許請求の範囲第（１）項記載のアモルファスシリ
コン光電変換素子。(3) σ_p_h/σ_ of the amorphous silicon layer
The amorphous silicon photoelectric conversion element according to claim 1, wherein d is σ_p_h/σ_d>10^3 when AM1 (simulated sunlight) is incident at 100 mW/cm^2.
に接する電極との接合がショットキー接合であることを
特徴とする特許請求の範囲第（１）項記載のアモルファ
スシリコン光電変換素子。(4) The amorphous silicon photoelectric conversion element according to claim (1), wherein a junction between one main surface of the amorphous silicon layer and an electrode in contact therewith is a Schottky junction.
に接する電極との接合がヘテロ接合であることを特徴と
する特許請求の範囲第（１）項記載のアモルファスシリ
コン光電変換素子。(5) The amorphous silicon photoelectric conversion element according to claim (1), wherein a junction between one main surface of the amorphous silicon layer and an electrode in contact therewith is a heterojunction.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60084535A JPS61244072A (en) | 1985-04-22 | 1985-04-22 | Amorphous silicon photoelectric conversion element |
| US07/309,688 US5140397A (en) | 1985-03-14 | 1989-02-10 | Amorphous silicon photoelectric device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60084535A JPS61244072A (en) | 1985-04-22 | 1985-04-22 | Amorphous silicon photoelectric conversion element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61244072A true JPS61244072A (en) | 1986-10-30 |
Family
ID=13833332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60084535A Pending JPS61244072A (en) | 1985-03-14 | 1985-04-22 | Amorphous silicon photoelectric conversion element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61244072A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5511329A (en) * | 1978-07-08 | 1980-01-26 | Shunpei Yamazaki | Semiconductor device |
| JPS5983916A (en) * | 1982-11-01 | 1984-05-15 | Kanegafuchi Chem Ind Co Ltd | Amorphous multielement semiconductor |
| JPS6041269A (en) * | 1984-03-16 | 1985-03-04 | Shunpei Yamazaki | Semiconductor device |
-
1985
- 1985-04-22 JP JP60084535A patent/JPS61244072A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5511329A (en) * | 1978-07-08 | 1980-01-26 | Shunpei Yamazaki | Semiconductor device |
| JPS5983916A (en) * | 1982-11-01 | 1984-05-15 | Kanegafuchi Chem Ind Co Ltd | Amorphous multielement semiconductor |
| JPS6041269A (en) * | 1984-03-16 | 1985-03-04 | Shunpei Yamazaki | Semiconductor device |
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