JPS6316914B2 - - Google Patents
Info
- Publication number
- JPS6316914B2 JPS6316914B2 JP58087194A JP8719483A JPS6316914B2 JP S6316914 B2 JPS6316914 B2 JP S6316914B2 JP 58087194 A JP58087194 A JP 58087194A JP 8719483 A JP8719483 A JP 8719483A JP S6316914 B2 JPS6316914 B2 JP S6316914B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- boron
- solar cell
- distribution
- formation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000010409 thin film Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 238000013459 approach Methods 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 claims description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 15
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 14
- 229910052796 boron Inorganic materials 0.000 description 14
- 239000007789 gas Substances 0.000 description 8
- 239000000370 acceptor Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 4
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination 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
- H01L31/18—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
- H01L31/202—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 including only elements of Group IV of the Periodic Table
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photovoltaic Devices (AREA)
Description
〔発明の属する技術分野〕
本発明は、グロー放電分解による非晶質シリコ
ン等の非晶質半導体薄膜を用いてｐ−ｉ−ｎ接合
を形成して光電変換領域とした薄膜太陽電池の製
造方法に関する。
〔従来技術とその問題点〕
モノシラン（以下SiH4）のグロー放電分解法
による水素化非晶質シリコン（以下ａ−Si：Ｈ）
の生成方法が開発されて以来、ａ−Si：Ｈの各種
電子デバイスへの応用研究が活発に進められてい
る。その中で低価格太陽電池への応用研究が注目
されている。太陽電池材料としてａ−Si：Ｈを見
た場合、低温成長、簡単な製造工程など、数多く
の特徴を持つているにも係わらず、市販の単結晶
シリコン太陽電池に比べて、変換効率が低いのが
現状である。従つて、ａ−Si：Ｈで発電用低価格
太陽電池を実現させるためには、変換効率の向上
が急務である。
ところで、ａ−Si：Ｈを用いたｐ−ｉ−ｎ型の
太陽電池の特性要因の一つとして、ｉ層中のｐ型
不純物（例えばほう素）の分布が重要であること
が、明らかになつて来た。
第１図は従来から用いられている、グロー放電
分解法によるａ−Si太陽電池の生成装置の概略図
である。平行平板電極１，２を真空槽３の中に設
置し、該電極間に電源４より高周波電界又は直流
電界を加えることで、真空槽３に導入口５より導
入されたSiH4ガス等を分解し、電極２の上に置
かれた基板６にａ−Si：Ｈ膜を形成する。ｐ型層
を形成する場合には、例えばSiH4とジボラン
（B2H6）との混合ガス、ｉ層を形成する場合には
SiH4のみ、ｎ型層を形成する場合にはSiH4とホ
スフイン（PH3）との混合ガスを各々用いること
で簡単に生成が可能である。
以上の様な方法でｐ層、ｉ層、ｎ層の順に形成
したｐ−ｉ−ｎ型太陽電池のｉ層中には、第２図
の曲線Ａで示す様なｐ層に近いｉ層中で傾斜を持
つたほう素分布がIMAにより観測された。この
ほう素分布は、ｐ層形成時に真空槽内の壁等に付
着したほう素原子がｉ層形成の初期に膜中に取り
込まれた結果であると考えられる。このｉ層中の
ほう素は補償原子として働き、しかもｐ−ｉ界面
でのキヤリア再結合を減少させ、特性に良い影響
を与えている。
しかし、上述の装置を用いる方法は、基本的に
多量生産に適しておらず第３図に示すようにｐ層
形成室１１、ｉ層形成室１２、ｎ層形成室１３が
前後および中間に予備加熱、基板集積、冷却等の
役目をする予備室１４を備えて配置され、基板を
のせたトレイ１５が矢印１６の方向に流される連
続形成装置が用いられる。ここでは必然的にｐ層
形成室１１、ｉ層形成室１２、ｎ層形成室１３と
分離されるために、前述の傾斜を持つたほう素分
布は観測されず、全体に低いほう素濃度となつて
いる（第２図中の曲線Ｂ）。一方、ｉ層成長中に
例えばB2H6を適量導入した場合は曲線Ｃの様に
なる。これら三種類のほう素分布をｉ層中に持つ
た太陽電池の特性比較をまとめてみると、第１表
の様になり、ほう素分布型Ａが優れていることが
分かつた。
[Technical field to which the invention pertains] The present invention relates to a method for manufacturing a thin film solar cell by forming a pin junction using an amorphous semiconductor thin film such as amorphous silicon by glow discharge decomposition to form a photoelectric conversion region. Regarding. [Prior art and its problems] Hydrogenated amorphous silicon (hereinafter referred to as a-Si:H) by glow discharge decomposition method of monosilane (hereinafter referred to as SiH 4 )
Since the development of a production method for a-Si:H, research on the application of a-Si:H to various electronic devices has been actively conducted. Among these, applied research to low-cost solar cells is attracting attention. When looking at a-Si:H as a solar cell material, although it has many features such as low-temperature growth and a simple manufacturing process, it has lower conversion efficiency than commercially available single-crystal silicon solar cells. is the current situation. Therefore, in order to realize a low-cost solar cell for power generation using a-Si:H, it is urgently necessary to improve the conversion efficiency. By the way, it is clear that the distribution of p-type impurities (e.g. boron) in the i-layer is important as one of the characteristic factors of pin-type solar cells using a-Si:H. I'm getting used to it. FIG. 1 is a schematic diagram of a conventionally used apparatus for generating a-Si solar cells using a glow discharge decomposition method. Parallel plate electrodes 1 and 2 are installed in a vacuum chamber 3, and by applying a high frequency electric field or a DC electric field from a power source 4 between the electrodes, SiH 4 gas etc. introduced into the vacuum chamber 3 from the inlet 5 is decomposed. Then, an a-Si:H film is formed on the substrate 6 placed on the electrode 2. For example, a mixed gas of SiH 4 and diborane (B 2 H 6 ) is used to form a p-type layer, and a mixed gas of SiH 4 and diborane (B 2 H 6 ) is used to form an i-layer.
When forming an n-type layer using only SiH 4 , it can be easily generated by using a mixed gas of SiH 4 and phosphine (PH 3 ). In the i-layer of a p-i-n type solar cell formed in the order of p-layer, i-layer, and n-layer by the method described above, there is a layer in the i-layer close to the p-layer as shown by curve A in Figure 2. A boron distribution with a slope was observed by IMA. This boron distribution is considered to be the result of boron atoms attached to the walls of the vacuum chamber during the formation of the p-layer being incorporated into the film at the beginning of the formation of the i-layer. The boron in this i-layer acts as a compensating atom, and also reduces carrier recombination at the p-i interface, which has a positive effect on the characteristics. However, the method using the above-mentioned apparatus is basically not suitable for mass production, and as shown in FIG. A continuous forming apparatus is used in which a tray 15 carrying substrates is flown in the direction of an arrow 16, and is provided with a preliminary chamber 14 for heating, substrate accumulation, cooling, etc. Here, since the p-layer formation chamber 11, i-layer formation chamber 12, and n-layer formation chamber 13 are inevitably separated, the boron distribution with the above-mentioned slope is not observed, and the boron concentration is low overall. (Curve B in Figure 2). On the other hand, if, for example, an appropriate amount of B 2 H 6 is introduced during the growth of the i-layer, a curve like C is obtained. A comparison of the characteristics of solar cells having these three types of boron distribution in the i-layer is summarized in Table 1, and it was found that boron distribution type A is superior.
本発明は、連続非晶質半導体形成装置を用いて
特性の良好なｐ−ｉ−ｎ型薄膜太陽電池を製造す
る方法を提供することを目的とする。
〔発明の要点〕
本発明はｉ層形成時の反応ガスにアクセプタ元
素を含むガスを混合し、かつ放電電力を変化せし
めることによりｐ層に近づくにつれてアクセプタ
濃度の高くなるｉ層を得ることによつて上述の目
的を達成した。
〔発明の実施例〕
第４図は本発明による第一の実施例の概念図を
示している。ｉ層形成室１２中に、三つに分割さ
れた平行平板電板電極２１，３１，４１および２
２，３２，４２が設置され、各々に独立した電源
４が接続されている。このｉ層形成室１２内に
は、例えば流量1200sccmのSiH4（10％）＋H2混合
ガスと流量450sccmのB2H6（1ppm）＋H2混合ガス
を導入する。すでにｐ層が形成された基板をのせ
たトレイ１５がコンベアで運ばれ、最初の電極２
１，２２間で止められ、RF（13.56MHz）50Wの
グロー放電によりｉ層を約500Åの厚さに形成す
る。第二の電極３１，３２間では、RF30Wで約
1000Å、第三の電極４１，４２間ではRF20Wで
約2500Å形成する。ｉ層中のほう素濃度と放電電
力との間には第５図に示すような関係があるの
で、形成されたｉ層中のほう素分布は第２図の曲
線Ａで示されたのとほぼ同じであり、その太陽電
池の特性を同等にすぐれたものであつた。
第６図は本発明による第二の実施例の概念図を
示している。基本的には第一の実施例と同じであ
るが、三つに分割された電極２１，３１，４１お
よび２２，３２，４２は同一の電源４に接続され
ている。ただし、上部電極と下部電極との距離が
異なつており、電極２１，２２から電極４１，４
２の方へ次第に広くなつている。従つて実効的な
電力密度が途々に変化する様になつている。この
装置で形成された太陽電池の特性は第一の実施例
の場合と同様にｉ層中のほう素分布が最適化さ
れ、優れたものであつた。
〔発明の効果〕
以上二つの実施例で見たように、ｐ−ｉ−ｎ型
非晶質太陽電池のｉ層形成中に、反応ガス適量の
アクセプタ元素を導入し、実効的な放電電力を変
化させることで、ｉ層中のアクセプタ濃度分布が
ｐ層に近づくにつれて高くなるように制御し、そ
れにより、連続形成装置でも特性の良い太陽電池
の製造が可能となつた。本発明は、アクセプタと
してほう素以外の族元素を用いることもでき、
広く薄膜太陽電池の特性向上に対して極めて有効
である。
An object of the present invention is to provide a method for manufacturing a pin-type thin film solar cell with good characteristics using a continuous amorphous semiconductor forming apparatus. [Summary of the Invention] The present invention mixes a gas containing an acceptor element with the reaction gas during i-layer formation, and changes the discharge power to obtain an i-layer in which the acceptor concentration increases as it approaches the p-layer. The above objectives were achieved. [Embodiment of the Invention] FIG. 4 shows a conceptual diagram of a first embodiment of the invention. In the i-layer forming chamber 12, parallel plate electrodes 21, 31, 41 and 2 are divided into three parts.
2, 32, and 42 are installed, and an independent power source 4 is connected to each. For example, a SiH 4 (10%) + H 2 mixed gas with a flow rate of 1200 sccm and a B 2 H 6 (1 ppm) + H 2 mixed gas with a flow rate of 450 sccm are introduced into the i-layer forming chamber 12 . A tray 15 carrying a substrate on which a p-layer has already been formed is carried by a conveyor, and the first electrode 2
The i-layer was formed to a thickness of about 500 Å by RF (13.56 MHz) 50 W glow discharge. Between the second electrodes 31 and 32, approximately
1000 Å, and about 2500 Å between the third electrodes 41 and 42 with RF 20W. Since there is a relationship between the boron concentration in the i-layer and the discharge power as shown in Figure 5, the boron distribution in the formed i-layer is as shown by curve A in Figure 2. The characteristics of the solar cell were almost the same, and the characteristics of the solar cell were equally excellent. FIG. 6 shows a conceptual diagram of a second embodiment according to the present invention. This embodiment is basically the same as the first embodiment, but the three divided electrodes 21, 31, 41 and 22, 32, 42 are connected to the same power source 4. However, the distance between the upper electrode and the lower electrode is different, and the distance from electrodes 21 and 22 to electrodes 41 and 4 is different.
It gradually becomes wider towards 2. Therefore, the effective power density is gradually changing. The characteristics of the solar cell formed with this device were excellent, with the boron distribution in the i-layer being optimized, as in the case of the first example. [Effects of the Invention] As seen in the above two examples, an appropriate amount of acceptor element is introduced into the reactive gas during the formation of the i-layer of a pin-type amorphous solar cell, and effective discharge power can be increased. By changing the acceptor concentration distribution in the i-layer, the acceptor concentration distribution in the i-layer is controlled to increase as it approaches the p-layer, thereby making it possible to manufacture solar cells with good characteristics even with a continuous formation apparatus. The present invention can also use group elements other than boron as acceptors,
It is extremely effective for widely improving the characteristics of thin film solar cells.
第１図は従来のａ−Si：Ｈのバツチ式形成装置
の断面図、第２図はａ−Si：Ｈ太陽電池のほう素
分布線図、第３図は従来のａ−Si：Ｈの連続形成
装置の断面図、第４図は本発明の一実施例に用い
るａ−Si：Ｈ連続形成装置の部分断面図、第５図
はａ−Si：Ｈ薄膜のほう素濃度と放電電力の関係
線図、第６図は本発明の別の実施例に用いるａ−
Si：Ｈ連続形成装置の部分断面図である。
１１……ｐ層形成室、１２……ｉ層形成室、１
３……ｎ層形成室、２１，３１，４１，２２，３
２，４２……電極。
Figure 1 is a cross-sectional view of a conventional a-Si:H batch forming apparatus, Figure 2 is a boron distribution diagram of an a-Si:H solar cell, and Figure 3 is a conventional a-Si:H batch formation device. FIG. 4 is a partial cross-sectional view of the continuous a-Si:H forming device used in one embodiment of the present invention, and FIG. 5 shows the boron concentration and discharge power of the a-Si:H thin film. The relationship diagram, FIG. 6, is a-
FIG. 2 is a partial cross-sectional view of a continuous Si:H forming apparatus. 11...p-layer formation chamber, 12...i-layer formation chamber, 1
3...N layer formation chamber, 21, 31, 41, 22, 3
2,42...electrode.
Claims (1)
解によつてｐ−ｉ−ｎ接合を有する非晶質半導体
薄膜を形成する際に、ｉ層形成時の反応ガスにア
クセプタ元素を含むガスを混合し、かつ放電電力
を変化せしめることによりｐ層に近づくにつれて
アクセプタ濃度の高くなるｉ層を得ることを特徴
とする薄膜太陽電池の製造方法。1. When forming an amorphous semiconductor thin film having a p-i-n junction as a photoelectric conversion region by glow discharge decomposition of a reactive gas, a gas containing an acceptor element is mixed with the reactive gas during i-layer formation, A method for manufacturing a thin-film solar cell, characterized in that the i-layer has an increasing acceptor concentration as it approaches the p-layer by varying the discharge power.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58087194A JPS59213176A (en) | 1983-05-18 | 1983-05-18 | Manufacture of thin film solar battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58087194A JPS59213176A (en) | 1983-05-18 | 1983-05-18 | Manufacture of thin film solar battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59213176A JPS59213176A (en) | 1984-12-03 |
| JPS6316914B2 true JPS6316914B2 (en) | 1988-04-11 |
Family
ID=13908169
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58087194A Granted JPS59213176A (en) | 1983-05-18 | 1983-05-18 | Manufacture of thin film solar battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59213176A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4692558A (en) * | 1983-05-11 | 1987-09-08 | Chronar Corporation | Counteraction of semiconductor impurity effects |
| JPH0232569A (en) * | 1988-07-22 | 1990-02-02 | Mitsubishi Electric Corp | Amorphous solar cell |
| US5736431A (en) * | 1995-02-28 | 1998-04-07 | Semiconductor Energy Laboratory Co., Ltd. | Method for producing thin film solar battery |
| JPH11246971A (en) | 1998-03-03 | 1999-09-14 | Canon Inc | Production of microcrystal silicon series thin film and producing device therefor |
| TW201108448A (en) * | 2009-04-06 | 2011-03-01 | Ulvac Inc | Method and system for manufacturing photoelectric conversion device |
| RU2698491C1 (en) * | 2019-03-06 | 2019-08-28 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Чеченский государственный университет" | Manufacturing method of solar energy converter with high efficiency |
-
1983
- 1983-05-18 JP JP58087194A patent/JPS59213176A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59213176A (en) | 1984-12-03 |
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