JPH0691272B2 - Method for manufacturing amorphous solar cell - Google Patents
Method for manufacturing amorphous solar cellInfo
- Publication number
- JPH0691272B2 JPH0691272B2 JP58052663A JP5266383A JPH0691272B2 JP H0691272 B2 JPH0691272 B2 JP H0691272B2 JP 58052663 A JP58052663 A JP 58052663A JP 5266383 A JP5266383 A JP 5266383A JP H0691272 B2 JPH0691272 B2 JP H0691272B2
- Authority
- JP
- Japan
- Prior art keywords
- silicon layer
- disilane
- type
- type silicon
- solar cell
- 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 - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 5
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 43
- 229910052710 silicon Inorganic materials 0.000 claims description 42
- 239000010703 silicon Substances 0.000 claims description 42
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 claims description 30
- 230000015572 biosynthetic process Effects 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 10
- 230000003287 optical effect Effects 0.000 claims description 8
- 239000003085 diluting agent Substances 0.000 claims description 7
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 description 18
- 239000007789 gas Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 229910021417 amorphous silicon Inorganic materials 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 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
- 230000006399 behavior Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 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
- 229910004012 SiCx Inorganic materials 0.000 description 1
- 229910004304 SiNy Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- VEDJZFSRVVQBIL-UHFFFAOYSA-N trisilane Chemical compound [SiH3][SiH2][SiH3] VEDJZFSRVVQBIL-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition 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
【発明の詳細な説明】 本発明は非晶質太陽電池の高効率化に関する。The present invention relates to increasing the efficiency of amorphous solar cells.
非晶質太陽電池の高効率化が各種の手段で試みられてい
る。これらの手段に少数キャリヤの逆拡散防止及び電極
との間の接触抵抗の減少、背面電極による反射光の有効
利用等がある。本発明はこれらの高効率化の手段を提供
するものである。Attempts have been made to improve the efficiency of amorphous solar cells by various means. These means include prevention of back diffusion of minority carriers, reduction of contact resistance with the electrode, effective use of reflected light by the back electrode. The present invention provides means for increasing these efficiencies.
即ち、高い電気伝導性を有し、かつ広いバンドギャップ
すなわち光学禁止帯巾を有するｎ型シリコン層を背面電
極に接して形成したpin型非晶質太陽電池を提供するも
のである。That is, the present invention provides a pin type amorphous solar cell in which an n-type silicon layer having high electrical conductivity and a wide bandgap, that is, an optical band gap is formed in contact with a back electrode.
第１図に本発明の非晶質太陽電池の模式断面図を示し
た。第１図にもとずいて本発明を説明すると、１は透明
な基板であり、透明電極２が形成せしめられている。こ
の透明電極上にｐ型、ｉ型の順序に非晶質シリコン層3,
4が形成せられる。ついで、ジシラン、ｎ型の導電性付
与物質及び希釈ガスよりなる混合ガスを用いて、ｎ型の
非晶質シリコン層５を形成速度を２Å/sec以下に制御し
てグロー放電により形成せしめる。ついで背面電極６を
形成し、本発明の太陽電池を得る。ここで、100は入射
光を示す。第２図は本発明の別の具体例である。すなわ
ち、基板10の上に背面電極11、ｎ型シリコン層12、ｉ型
非晶質シリコン層13、ｐ型非晶質シリコン層14、透明電
極15が形成されており、光100が透明電極15に入射する
非晶質太陽電池である。本発明においてｎ型シリコン層
は1x10-3S/cm以上、高いものは1S/cmを越える電気伝導
性を有するので背面電極に接して配置された場合、該背
面電極との電気的接触性が顕著に良好になり、直列抵抗
成分による効率の低下が大幅に改善される。さらに広い
バンドギャップ、すなわち1.80eVを越える光学禁制帯巾
を保有するという特徴も有する。この結果ｉ−ｎ界面で
のヘテロ接合が期待され、キャリヤーの逆拡散に対して
該接合は効果的に障壁として作用する。あるいは、背面
電極で反射された光は、該電極に接するｎ型層の光学禁
制帯巾が大きいので、該ｎ型層で吸収されることなく、
光活性領域であるｉ型層にまで到達して吸収され、フォ
トキャリヤー生成に有効に寄与するのである。このよう
に本発明におけるｎ型シリコン層は光発電領域と電極と
の間の電気的接続を良好にし、キャリヤーの逆拡散を防
止し、反射光を有効利用する等の顕著な作用効果によ
り、発明の目的を達成するものである。FIG. 1 shows a schematic sectional view of the amorphous solar cell of the present invention. The present invention will be described with reference to FIG. 1. Reference numeral 1 is a transparent substrate on which a transparent electrode 2 is formed. Amorphous silicon layer 3, on the transparent electrode in the order of p-type and i-type,
4 is formed. Then, a mixed gas of disilane, an n-type conductivity imparting substance and a diluent gas is used to form the n-type amorphous silicon layer 5 by glow discharge while controlling the formation rate to 2 Å / sec or less. Then, the back electrode 6 is formed to obtain the solar cell of the present invention. Here, 100 indicates incident light. FIG. 2 shows another embodiment of the present invention. That is, the back electrode 11, the n-type silicon layer 12, the i-type amorphous silicon layer 13, the p-type amorphous silicon layer 14, and the transparent electrode 15 are formed on the substrate 10, and the light 100 transmits the transparent electrode 15. It is an amorphous solar cell that is incident on. In the present invention, the n-type silicon layer has an electrical conductivity of 1 × 10 −3 S / cm or more, and the higher one has an electrical conductivity of more than 1 S / cm. Therefore, when the n-type silicon layer is placed in contact with the back electrode, the electrical contact with the back electrode is high. This is remarkably good, and the reduction in efficiency due to the series resistance component is greatly improved. It also has the feature of possessing a wider band gap, that is, an optical band gap exceeding 1.80 eV. As a result, a heterojunction at the in interface is expected, and the junction effectively acts as a barrier against carrier back diffusion. Alternatively, the light reflected by the back electrode is not absorbed by the n-type layer because the optical band gap of the n-type layer in contact with the electrode is large.
It reaches the i-type layer, which is the photoactive region, and is absorbed, and contributes effectively to the generation of photocarriers. As described above, the n-type silicon layer in the present invention improves electrical connection between the photovoltaic region and the electrode, prevents back diffusion of carriers, and effectively utilizes reflected light. To achieve the purpose of.
本発明においてはｎ型シリコン層の形成速度を２Å/sec
以下にせねばならない。２Å/secを越えると、後記実施
例に示すように、得られる非晶質太陽電池の光電変換効
率ηが急激に低下して仕舞い、本発明の目的を達成する
ことができない。ジシランは通常の条件ではその形成速
度が大きいことで知られているが、これをことさら２Å
/sec以下という、異常ともいえる小さい形成速度とする
ためには、グロー放電室内へ供給するジシラン流量を意
図的に低く抑えねばならない。ジシラン流量について、
一義的、具体的に表わすことは、放電設備の形状、電極
の形状、ガスの流れ方等により最適な流量範囲が異るこ
とから困難であるが実施例には好ましい流量の事例の一
つを示した。しかして、本発明において、流量決定の具
体的な方法は、ジシラン単位重量（ｇ）あたり10KJ以上
の大きいグロー放電エネルギー（我々はこれを「供給エ
ネルギー」と呼んでいる）を与えて、シリコン層を形成
し、その形成速度が２Å/sec以下となるような流量を決
定すればよい。というのは本発明者らが見出したよう
に、該10KJ以上と云う、大なる特定の放電エネルギーの
範囲においては、ｎ型シリコン層の形成速度は、もは
や、グロー放電エネルギー（電力）には殆ど影響され
ず、ジシラン流量によってのみ決まるという驚くべき現
象があるからである。In the present invention, the formation rate of the n-type silicon layer is set to 2Å / sec.
You have to: When it exceeds 2 Å / sec, the photoelectric conversion efficiency η of the obtained amorphous solar cell is drastically reduced and it ends up, as shown in Examples below, and the object of the present invention cannot be achieved. Disilane is known to have a high rate of formation under normal conditions, but this is especially
The flow rate of disilane supplied into the glow discharge chamber must be intentionally kept low in order to achieve an abnormally low formation rate of / sec or less. About disilane flow rate,
It is difficult to express uniquely and specifically because the optimum flow rate range varies depending on the shape of the discharge equipment, the shape of the electrodes, the way gas flows, etc. Indicated. Therefore, in the present invention, a specific method for determining the flow rate is to give a large glow discharge energy of 10 KJ or more per unit weight (g) of disilane (which we call “supply energy”) to obtain a silicon layer. Is formed, and the flow rate at which the formation speed is 2 Å / sec or less may be determined. This is because, as found by the present inventors, in the range of a large specific discharge energy of 10 KJ or more, the formation rate of the n-type silicon layer is almost no more than the glow discharge energy (electric power). This is because there is a surprising phenomenon that it is not affected and is determined only by the disilane flow rate.
本発明において、グロー放電エネルギーの算出は次の
（Ｉ）式で行なう。In the present invention, the glow discharge energy is calculated by the following equation (I).
たとえば設例として、Heで10vol％に希釈したジシラン
（Si2H6）0.02l/分、H2で1vol％に希釈したPH30.002l/
分およびH20.06l/分を混合した原料に100Wのグロー放電
電力を加える場合を考えると、該エネルギーは次のよう
に算出される。 For example, as an example, disilane (Si 2 H 6 ) diluted with He to 10 vol% 0.02 l / min, PH 3 diluted with H 2 to 1 vol% 0.002 l / min
Considering the case where 100 W glow discharge power is applied to a raw material obtained by mixing min. And H 2 0.06 l / min, the energy is calculated as follows.
原料ガス流量＝0.02＋0.002＋0.06＝0.082l/分 原料ガスの平均分子量＝｛（62.2×2/82）＋（４×18/82）＋（34×0.02/82）＋
（２×61.98/82）｝＝3.914gr ジシランの重量分率（62.2×2/82）/3.914＝0.388 これらを（Ｉ）式に代入して 103をKJと表わせば該エネルギーは162KJ/g−Si2H6と表
わすことができる。しかして本発明においては上記で規
定されるエネルギー値において50〜500KJ/g−SI2H6と云
う範囲でn50KJ/g−Si2H6より小さいとｎ型シリコン層は
その電気伝導性が低下してしまう。また、500KJ/g−Si2
H6を越える程あまり大きいエネルギーを加える必要はな
い。なぜならかかる過大なエネルギーの供与はｎ型シリ
コン層のバンドギャップや光学禁制帯巾を広くしたり、
導電率を大きくしたりする改善効果以上に、グロー放電
設備上の問題点や経済上の問題点をクローズアップする
からである。すなわちあまり過大のエネルギーの供与は
原料ガスと放電のバランスを不安定にし易く、安定した
ｎ型シリコン層の形成を困難にする。また必要以上のエ
ネルギーを加えること自体、経済上の損失につながるう
えに、さらに高価な大型のグロー放電電源を設備せねば
ならないという問題も起る。しかして、本発明は基本的
なコンセプトとして、50KJ/g−SI2H6以上という、通常
の当業者の常識からいえば、生成する薄膜を損傷せしめ
る恐れがあるような、きわめて高パワーの分解エネルギ
ー（供給エネルギー）を、敢えて採用するものであるこ
とに注意しなければならない。しかしながら、ことモノ
シランとジシランとでは、当業者の常識に反し、全く異
なった挙動を示すものであることを本発明者らは初めて
見出したのである。特にモノシランの挙動をもってジシ
ランの挙動を推し量ることは、決してできないことを特
に指摘したい。Source gas flow rate = 0.02 + 0.002 + 0.06 = 0.082 l / min Average molecular weight of source gas = {(62.2 x 2/82) + (4 x 18/82) + (34 x 0.02 / 82) +
(2 × 61.98 / 82)} = 3.914gr Disilane weight fraction (62.2 × 2/82) /3.914=0.388 Substituting these into equation (I) When 10 3 is expressed as KJ, the energy can be expressed as 162 KJ / g-Si 2 H 6 . Thus 50~500KJ / g-SI 2 H 6 and refers range n50KJ / g-Si 2 H 6 is smaller than the n-type silicon layer in the energy value as defined above in the present invention is its electrical conductivity decreases Resulting in. In addition, 500KJ / g-Si 2
It is not necessary to add too much energy to exceed H 6 . Because such excessive energy donation widens the band gap and optical forbidden band of the n-type silicon layer,
This is because the problems of the glow discharge facility and the problems of economy are highlighted, beyond the improvement effect of increasing the conductivity. That is, if too much energy is applied, the balance between the source gas and the discharge tends to be unstable, making it difficult to form a stable n-type silicon layer. In addition, adding more energy than necessary leads to an economic loss, and there is a problem in that a larger expensive glow discharge power source must be installed. Therefore, the present invention has a basic concept of 50 KJ / g-SI 2 H 6 or more, which is, based on common sense of ordinary skill in the art, an extremely high power decomposition that may damage the thin film to be formed. It must be noted that energy (supply energy) is intentionally adopted. However, the present inventors have found for the first time that the monosilane and the disilane have completely different behaviors, contrary to the common sense of those skilled in the art. In particular, it should be pointed out that the behavior of disilane cannot be estimated by the behavior of monosilane.
さらに本発明においてはｎ型シリコン層の形成温度を10
0〜400℃の間に適宜選択して行なうことが好ましい。後
記実施例第１表にｎ型シリコン層の形成温度と光学禁制
帯巾の関係を示した。第１表から明らかなごとく形成温
度が低下すると光学禁制帯巾は、2.0eVを越えて大きく
なると共に導電率はやや低下する傾向があるものの150
℃においても導電率は9.1×10-2（Ω・cm）-1と良好な
値を示し、背面電極とは充分良好な電気的接続が得られ
て、本発明において有効に使用できる。Further, in the present invention, the formation temperature of the n-type silicon layer is set to 10
It is preferable that the temperature is appropriately selected between 0 and 400 ° C. The relationship between the formation temperature of the n-type silicon layer and the optical forbidden band is shown in Table 1 of Example described later. As is clear from Table 1, the optical forbidden band increases beyond 2.0 eV as the forming temperature decreases, and the conductivity tends to decrease slightly.
The conductivity shows a good value of 9.1 × 10 -2 (Ω · cm) -1 even at ° C, and a sufficiently good electrical connection with the back electrode can be obtained, which can be effectively used in the present invention.
しかしながら、むやみに該温度を低下せしめることは好
ましくない。けだし100℃以下のように低い温度におい
ては、導電率の低下が非常に大きいうえに、シリコン層
の剥離や黄色のシリコン粉末が生じるようになり、本発
明の目的を達しえないからである。また形成温度が高く
なると導電率は向上するが、あまり高くしすぎると光学
禁制帯巾は狭められる。それ故400℃以下でシリコン層
を形成することが好ましい。また400℃を越えるような
温度においては、シリコン層の問題だけでなく、基板や
電極の耐熱性、グロー放電中におけるプラズマによる損
傷の問題も無視できなくなる。即ち、基板や電極に欠陥
が生じるようになれば光電変換効率は当然のことながら
低下するので、前述の如く形成温度を極端に高くしすぎ
ることは好ましくない。However, it is not preferable to unnecessarily reduce the temperature. This is because, at a low temperature such as 100 ° C. or less, the decrease in conductivity is extremely large, the silicon layer is peeled off, and yellow silicon powder is generated, so that the object of the present invention cannot be achieved. Further, when the formation temperature is high, the conductivity is improved, but when it is too high, the optical band gap is narrowed. Therefore, it is preferable to form the silicon layer at 400 ° C. or lower. At temperatures above 400 ° C., not only the problem of the silicon layer, but also the problems of heat resistance of the substrate and electrodes and damage by plasma during glow discharge cannot be ignored. That is, if defects occur in the substrate or the electrodes, the photoelectric conversion efficiency naturally lowers. Therefore, it is not preferable to make the forming temperature extremely high as described above.
つぎに本発明の非晶質太陽電池を製造する具体的態様を
述べる。グロー放電可能な反応室中に透明電極を有する
透明基板を設置し、減圧下100〜400℃の温度に加熱維持
する。シランにｐ型導電性物質を混合して反応室へ導入
し、グロー放電を行ない透明電極上にｐ型シリコン層を
形成する。ついでシランのグロー放電によりｉ型シリコ
ン層を形成する。ｐ型やｉ型シリコン層の形成時に希釈
ガスを用いることは何ら差しつかえない。ついで本発明
のｎ型シリコン層を形成する。即ち、ジシラン、ｎ型導
電性付与物質、希釈ガスからなる混合ガスをｎ型シリコ
ン層の形成速度が２Å/sec以下となる流量で導入し、形
成温度100〜400℃、形成圧力0.5−5Torr、グロー放電エ
ネルギー50〜500KJ/g−Si2H6の条件でグロー放電するこ
とによりｎ型シリコン層を形成する。つぎに背面電極を
形成して第１図に示すごとき本発明の太陽電池を得る。
また、ステンレス基板の如き不透明な基板の場合には、
基板側が背面電極となるので第２図に示すように基板側
からｎ型、ｉ型、ｐ型の順にシリコン層を形成し、ｐ型
シリコン層上に透明電極を形成することにより、本発明
の太陽電池を得る。Next, a specific mode for producing the amorphous solar cell of the present invention will be described. A transparent substrate having a transparent electrode is placed in a reaction chamber capable of glow discharge and heated and maintained at a temperature of 100 to 400 ° C. under reduced pressure. A p-type conductive substance is mixed with silane and introduced into the reaction chamber, and glow discharge is performed to form a p-type silicon layer on the transparent electrode. Then, an i-type silicon layer is formed by glow discharge of silane. There is no problem in using a diluent gas when forming the p-type or i-type silicon layer. Then, the n-type silicon layer of the present invention is formed. That is, a mixed gas composed of disilane, an n-type conductivity imparting substance and a diluent gas is introduced at a flow rate such that the formation rate of the n-type silicon layer is 2Å / sec or less, the formation temperature is 100 to 400 ° C., the formation pressure is 0.5-5 Torr, An n-type silicon layer is formed by glow discharge under the conditions of glow discharge energy of 50 to 500 KJ / g-Si 2 H 6 . Next, a back electrode is formed to obtain the solar cell of the present invention as shown in FIG.
Also, in the case of an opaque substrate such as a stainless substrate,
Since the substrate side serves as a back electrode, as shown in FIG. 2, by forming a silicon layer in the order of n-type, i-type and p-type from the substrate side, and forming a transparent electrode on the p-type silicon layer, the present invention can be formed. Get a solar cell.
ｎ型シリコン層の形成においては、上記態様において、
希釈ガスの流量を増加せしめることが好ましい。希釈ガ
スの流量の増加は導電率を向上させ、光電変換効率の改
善につながる。希釈ガスとしてはH2、He、Ar等が用いら
れる。ジシランに対して用いる希釈ガスの総量はジシラ
ン１容量部あたり10容量部以上が好ましい。In forming the n-type silicon layer, in the above aspect,
It is preferable to increase the flow rate of the diluent gas. The increase in the flow rate of the dilution gas improves the conductivity and leads to the improvement in photoelectric conversion efficiency. H 2 , He, Ar or the like is used as the diluent gas. The total amount of diluent gas used for disilane is preferably 10 parts by volume or more per 1 part by volume of disilane.
本発明においてシランとは一般式SinH2n+2で表わされる
化合物を示すが、用いるに好ましい物質はｎ＝２〜４で
ある。ｎ＝１がモノシランであるが、これは決して本発
明の目的に使用することはできない。この中でｎ＝２の
物質が本発明で使用するジシランである。勿論ジシラン
は高純度であることが好ましい。グロー放電中でジシラ
ンと同様に挙動するトリシラン、テトラシラン等（一般
式においてｎ＝３、４）が含まれていることは何らさし
つかえないが、これらの含有量は５％以下であることが
好ましい。In the present invention, silane refers to a compound represented by the general formula Si n H 2n + 2 , and preferred substances to be used are n = 2 to 4. Although n = 1 is monosilane, it can never be used for the purposes of the present invention. Of these, the substance of n = 2 is the disilane used in the present invention. Of course, disilane preferably has a high purity. It does not matter at all that trisilane, tetrasilane, etc. (n = 3, 4 in the general formula) that behaves like disilane in glow discharge are contained, but the content of these is preferably 5% or less.
ｎ型の導電性付与物質はたとえばPH3やAsH3であり、通
常H2やHeで希釈された状態で用いられる。これらの物質
のジシランに対する使用割合はジシラン100容量部に対
して0.1〜５容量部である。またｎ型シリコン層の厚み
は50〜500Åで用いられる。つけ加えて述べるとｐ型の
導電性付与物質はB2H6が用いられる。ｐ型およびｉ型シ
リコン層の厚みはそれぞれ50〜500Å、3000〜7500Å程
度である。The n-type conductivity imparting substance is, for example, PH 3 or AsH 3, which is usually used in a state diluted with H 2 or He. The use ratio of these substances to disilane is 0.1 to 5 parts by volume based on 100 parts by volume of disilane. The thickness of the n-type silicon layer is 50 to 500Å. In addition, B 2 H 6 is used as the p-type conductivity imparting substance. The p-type and i-type silicon layers have thicknesses of about 50 to 500Å and 3000 to 7500Å, respectively.
なお、本発明において、ｐ型層に炭素や窒素を含んだａ
−SiCxやａ−SiNyを用いることは差しつかえないことで
あり、光電変換効率の改善ができる。In addition, in the present invention, a in which the p-type layer contains carbon or nitrogen
It is safe to use -SiCx or a-SiNy, and the photoelectric conversion efficiency can be improved.
基板や電極の材料については特に制限がなく、従来用い
られている材料が有効に用いられる。たとえば、基板と
しては、絶縁性、又は導電性、透明又は不透明、いずれ
の性質を有するものでもよい。具体的には、ガラス、石
英、アルミナ、シリコン、ステンレススチール、アルミ
ニウム、モリブデン、耐熱性高分子等の物質で形成され
る。一方、電極材料としては、光入射側には当然のこと
ながら透明あるいは透光性の材料を用いなければならな
いがこれ以外の制限は特にない。銀、アルミニウム、モ
リブデン、ニクロム、ITO、酸化錫、ステンレススチー
ル等の薄板や薄膜が有用である。There are no particular restrictions on the materials of the substrate and electrodes, and conventionally used materials can be effectively used. For example, the substrate may have any of insulating, conductive, transparent, and opaque properties. Specifically, it is made of a material such as glass, quartz, alumina, silicon, stainless steel, aluminum, molybdenum, and heat resistant polymer. On the other hand, as the electrode material, a transparent or translucent material must be used as a matter of course on the light incident side, but there is no particular limitation other than this. Thin plates and thin films of silver, aluminum, molybdenum, nichrome, ITO, tin oxide, stainless steel, etc. are useful.
上記の製造法の実施の具体的態様においては一つのグロ
ー放電室でpin型太陽電池を形成する例を示した。而し
てこれらのpin型シリコン層はそれぞれ連結された別個
のグロー放電室で形成することができることはもちろん
である。In the specific embodiment of the implementation of the above manufacturing method, an example in which a pin type solar cell is formed in one glow discharge chamber has been shown. Thus, it goes without saying that these pin-type silicon layers can be formed in separate glow discharge chambers connected to each other.
さらに本発明のｎ型シリコン層はpin型太陽電池ばかり
でなく、ショットキー接合太陽電池においても、背面電
極との良好なコンタクト材として有用である。Further, the n-type silicon layer of the present invention is useful as a good contact material with the back electrode not only in the pin-type solar cell but also in the Schottky junction solar cell.
このように本発明は新規のpin型アモルファス太陽電池
を提供するものである。なお、本発明は其以外にpin接
合型のみならずショットキー接合型、MIS接合型にも有
用な技術を提供するものである。Thus, the present invention provides a novel pin type amorphous solar cell. In addition, the present invention provides a technique useful not only for the pin junction type but also for the Schottky junction type and the MIS junction type.
以下、実施例をあげて本発明をさらに具体的に説明す
る。Hereinafter, the present invention will be described more specifically with reference to examples.
実施例１ 基板加熱手段、真空排気手段、ガス導入手段及び基板を
設置することのできる平行平板電極を有するグロー放電
室をもつ容量結合型高周波プラズマCVD（Chemical Vapo
r Deposition）装置の該基板設置部へITOで電極を形成
したガラス基板を設置した。油拡散ポンプにより10-7To
rr以下に真空排気しながら基板設置部の温度（形成温
度）が250℃になるように加熱した。He希釈のジシラン
（希釈比Si2H6/He＝1/9）、H2希釈のB2H6（希釈比B2H6
／H2＝1/999）をそれぞれ50cc/分、10cc/分を導入し圧
力1Torrで30秒間グロー放電を行なって、ｐ型シリコン
層を形成した。ついで該He希釈のジシランを500cc/分の
流量で導入し、圧力5Torrでグロー放電エネルギー約17K
J/g−Si2H6でｉ型シリコン層を形成した。ｉ型シリコン
層の形成に要した時間は２分である。ついで該He希釈の
ジシラン、H2希釈のPH3（希釈比PH3／H2＝1/99）及びH2
をそれぞれ10〜50cc/分、１〜5cc/分及び30〜150cc/分
の流量（それぞれの流量比は10:1:30＝一定）で該グロ
ー放電室へ導入し圧力を1Torrに調節した。グロー放電
電力130W、即ちグロー放電エネルギーとして約210KJ/g
−Si2H6で１分40秒間グロー放電を行ないｎ型シリコン
層を形成した。つぎに真空蒸着によりアルミニウムを蒸
着し背面電極とした。ｐ型シリコン層側からAMIの光を
ソーラーシュミレータで照射して、光電変換効率を測定
した。光電変換効率ηは、7.1％であった。この結果を
第３図に示した。第３図からわかるようにジシラン流量
Ｖが35cc/min（＝２Å/sec）を越えると、光電変換効率
ηの低下が急減に大きくなった。また、２Å/sec以下で
は、最大の光電変換効率はη＝7.1％でほぼ一定であっ
た。なお、第４図はジシラン流量Ｖとｎ型シリコン層の
形成速度Ｒの関係であって、第４図から上記35cc/minの
ジシラン流量での形成速度は２Å/seであることがわか
る。Example 1 Capacitively coupled high-frequency plasma CVD (Chemical Vapor CVD) having a substrate heating means, a vacuum evacuation means, a gas introduction means, and a glow discharge chamber having parallel plate electrodes on which a substrate can be installed
A glass substrate having electrodes formed of ITO was placed on the substrate placement part of the r Deposition apparatus. 10 -7 To by oil diffusion pump
While evacuating to less than rr, the substrate was heated to a temperature of 250 ° C. (formation temperature). He-diluted disilane (dilution ratio Si 2 H 6 / He = 1/9), H 2 diluted B 2 H 6 (dilution ratio B 2 H 6
/ H 2 = 1/999) was introduced at 50 cc / min and 10 cc / min respectively, and glow discharge was performed at a pressure of 1 Torr for 30 seconds to form a p-type silicon layer. Then, the He-diluted disilane was introduced at a flow rate of 500 cc / min, and the glow discharge energy was about 17 K at a pressure of 5 Torr.
An i-type silicon layer was formed with J / g-Si 2 H 6 . The time required to form the i-type silicon layer is 2 minutes. Next, the He diluted disilane, H 2 diluted PH 3 (dilution ratio PH 3 / H 2 = 1/99) and H 2
Were introduced into the glow discharge chamber at flow rates of 10 to 50 cc / min, 1 to 5 cc / min, and 30 to 150 cc / min (respective flow rate ratios were 10: 1: 30 = constant), and the pressure was adjusted to 1 Torr. Glow discharge power 130W, that is, about 210KJ / g as glow discharge energy
Glow discharge was performed for 1 minute and 40 seconds with -Si 2 H 6 to form an n-type silicon layer. Next, aluminum was deposited by vacuum deposition to form a back electrode. The light of AMI was irradiated from the p-type silicon layer side with a solar simulator to measure the photoelectric conversion efficiency. The photoelectric conversion efficiency η was 7.1%. The results are shown in FIG. As can be seen from FIG. 3, when the flow rate V of disilane exceeds 35 cc / min (= 2Å / sec), the decrease in photoelectric conversion efficiency η rapidly decreases. At 2 Å / sec or less, the maximum photoelectric conversion efficiency was η = 7.1%, which was almost constant. Note that FIG. 4 shows the relationship between the flow rate V of disilane and the formation rate R of the n-type silicon layer. From FIG. 4, it is understood that the formation rate at the flow rate of disilane of 35 cc / min is 2Å / se.
実施例２〜６ 実施例１において用いた高周波プラズマCVD装置を用い
て、コーニング社製7059ガラス基板上に、ｎ型シリコン
層を形成温度を変えたこと以外には実施例１と同じ条件
で作成した。形成温度及び得られたｎ型シリコン膜の特
性を第１表に示した。Examples 2 to 6 Using the high-frequency plasma CVD apparatus used in Example 1, the n-type silicon layer was formed on the Corning 7059 glass substrate under the same conditions as in Example 1 except that the formation temperature was changed. did. The formation temperature and the characteristics of the obtained n-type silicon film are shown in Table 1.
第１図及び第２図は本発明による太陽電池の一例を示す
模式断面図である。第３図はジシラン流量Ｖと光電変換
効率ηの関係を示すグラフであり第４図はジシラン流量
Ｖとｎ型シリコン層の形成速度Ｒとの関係を示すグラフ
である。 第１図及び第２図において図中の数字は、 100……入射光、1,10……基板、6,11……背面電極、5,1
2……本発明のｎ型シリコン層を表わす。1 and 2 are schematic cross-sectional views showing an example of the solar cell according to the present invention. FIG. 3 is a graph showing the relationship between the disilane flow rate V and the photoelectric conversion efficiency η, and FIG. 4 is a graph showing the relationship between the disilane flow rate V and the formation rate R of the n-type silicon layer. In Figures 1 and 2, the numbers in the figures are 100 ... Incident light, 1,10 ... Substrate, 6,11 ... Back electrode, 5,1
2 represents the n-type silicon layer of the present invention.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 信学技報 81 Ｎｏ．213 ＣＰＭ81− 80，Ｐ．７−９ 信学技法 Ｖｏｌ．81，Ｎｏ．255 第 29〜36頁 ─────────────────────────────────────────────────── ─── Continued Front Page (56) References Technical Report 81 No. 213 CPM 81-80, P.I. 7-9 Religious Technique Vol. 81, No. 255 Pages 29-36
Claims (1)
ガスからなる混合ガスをグロー放電分解して形成するｎ
型シリコン層を有するpin型非晶質太陽電池の製造方法
であって、（ｉ）該ｎ型シリコン層は、上記混合ガス中
のジシランの供給量を制御してジシラン単位質量あたり
50kJ〜500kJの放電のためのエネルギーを加えて成膜す
ることにより、２Å/sec以下の形成速度で光学バンドギ
ャップが1.8eV以上となるごとくして形成するものであ
り、かつ（ii）該ｎ型シリコン層が背面電極に接して配
置されるように形成することを特徴とする非晶質太陽電
池の製造方法。1. An n formed by glow discharge decomposition of a mixed gas consisting of disilane, an n-type conductivity-imparting substance and a diluent gas.
A method for manufacturing a pin-type amorphous solar cell having a type silicon layer, comprising: (i) controlling the amount of disilane supplied in the mixed gas by controlling the supply amount of disilane per unit mass of disilane.
The film is formed by applying energy for discharge of 50 kJ to 500 kJ so that the optical band gap becomes 1.8 eV or more at a formation rate of 2 Å / sec or less, and (ii) n A method of manufacturing an amorphous solar cell, which comprises forming a type silicon layer so as to be in contact with a back electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58052663A JPH0691272B2 (en) | 1983-03-30 | 1983-03-30 | Method for manufacturing amorphous solar cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58052663A JPH0691272B2 (en) | 1983-03-30 | 1983-03-30 | Method for manufacturing amorphous solar cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59178777A JPS59178777A (en) | 1984-10-11 |
| JPH0691272B2 true JPH0691272B2 (en) | 1994-11-14 |
Family
ID=12921102
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58052663A Expired - Lifetime JPH0691272B2 (en) | 1983-03-30 | 1983-03-30 | Method for manufacturing amorphous solar cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0691272B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5055141A (en) * | 1990-01-19 | 1991-10-08 | Solarex Corporation | Enhancement of short-circuit current by use of wide bandgap n-layers in p-i-n amorphous silicon photovoltaic cells |
-
1983
- 1983-03-30 JP JP58052663A patent/JPH0691272B2/en not_active Expired - Lifetime
Non-Patent Citations (2)
| Title |
|---|
| 信学技報８１Ｎｏ．２１３ＣＰＭ８１−８０，Ｐ．７−９ |
| 信学技法Ｖｏｌ．８１，Ｎｏ．２５５第２９〜３６頁 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59178777A (en) | 1984-10-11 |
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