JPH046880A - Amorphous silicon carbide film, formation thereof and photovoltaic device using same - Google Patents
Amorphous silicon carbide film, formation thereof and photovoltaic device using sameInfo
- Publication number
- JPH046880A JPH046880A JP2404325A JP40432590A JPH046880A JP H046880 A JPH046880 A JP H046880A JP 2404325 A JP2404325 A JP 2404325A JP 40432590 A JP40432590 A JP 40432590A JP H046880 A JPH046880 A JP H046880A
- Authority
- JP
- Japan
- Prior art keywords
- film
- silicon carbide
- amorphous silicon
- carbide film
- photovoltaic device
- 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.)
- Granted
Links
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910021417 amorphous silicon Inorganic materials 0.000 title claims abstract description 29
- 230000015572 biosynthetic process Effects 0.000 title description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 150000001722 carbon compounds Chemical class 0.000 claims abstract description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 3
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 230000031700 light absorption Effects 0.000 abstract description 7
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 238000010586 diagram Methods 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/548—Amorphous silicon PV cells
Landscapes
- Photovoltaic Devices (AREA)
Abstract
Description
［０００１］
本発明は、非晶質シリコンカーバイド膜及びこの膜の形
成方法並びに光起電力装置に関する。
［０００２］[0001] The present invention relates to an amorphous silicon carbide film, a method for forming the film, and a photovoltaic device. [0002]
非晶質半導体、特に、非晶質シリコンを用いた光起電力
装置は、電卓等の民生用として既に実用化されている。
［０００３］
このような光起電力装置は、通常、ｐｉｎ接合を有して
おり、そして、多くの光を光活性層であるｉ型層に入射
するべく、光入射側に設けられるｐ型層は、バンドギャ
ップの広い非晶質シリコンカーバイド（以下、ａ−３ｉ
Ｃと称す）膜から構成されている。例えば、米国！＃許
第４．３８５．１９９号に詳しい。
［０００４］Photovoltaic devices using amorphous semiconductors, particularly amorphous silicon, have already been put into practical use for consumer products such as calculators. [0003] Such a photovoltaic device usually has a pin junction, and a p-type layer provided on the light incidence side in order to input a large amount of light into the i-type layer, which is a photoactive layer. is amorphous silicon carbide with a wide band gap (hereinafter referred to as a-3i
It is composed of a membrane (referred to as C). For example, the United States! #For details on permission No. 4.385.199. [0004]
しかし乍ら、従来のａ−３ｉＣ膜においても、十分に光
を透過しているとは言えなかった。
［０００５］
また、光起電力装置の寿命を伸ばすべく、ｉ型層中の水
素濃度を低減させることが成されており、そのために、
ｉ型層を高温で形成している。
［０００６］
然るに、ｉ型層を高温で形成するに先立って、ｐ型層が
形成されている場合、従来のｐ型層としてのａ−３ｉＣ
膜は、耐熱性に乏しく、ｉ型層の形成時にこの層に悪影
響を与えていた。また、ｉ型層の形成に先立ってｎ型層
が形成される場合においても、同様に、ｉ型層形成時、
この層に悪影響を与えてしまう。
［０００７］However, even in the conventional a-3iC film, it could not be said that light was sufficiently transmitted. [0005] Furthermore, in order to extend the life of the photovoltaic device, efforts have been made to reduce the hydrogen concentration in the i-type layer, and for that purpose,
The i-type layer is formed at high temperature. [0006] However, if a p-type layer is formed before forming an i-type layer at high temperature, a-3iC as a conventional p-type layer
The film had poor heat resistance, which adversely affected the i-type layer during its formation. Furthermore, even in the case where the n-type layer is formed prior to the formation of the i-type layer, when forming the i-type layer,
This will have a negative impact on this layer. [0007]
本発明の非晶質シリコンカーバイド膜は、炭素原子１個
に対して、平均２個以上のシリコン原子が結合したこと
を特徴とする。
［０００８］
また、本発明の非晶質シリコンカーバイド膜の形成方法
は、放電電極により発生されたプラズマ放電を磁界によ
り特定の領域に閉じ込めた反応室内において、上記プラ
ズマ放電領域から離れた位置に膜形成用基板を配置する
工程と、上記反応室内に、シリコン化合物ガス及びこの
ガス量より多い炭素化合物ガスを導入し上記プラズマ放
電によって分解する工程と、分解されたガスにより上記
基板上に膜を形成する工程と、を備えたことを特徴とす
る。
［０００９］
更に、本発明の非晶質シリコンカーバイド膜の形成方法
は、上記基板上に上記非晶質シリコンカーバイド膜が形
成された後、この非晶質シリコンカーバイド膜中にｐ型
不純物を添加することを特徴とする。
［００１０１
更に、本発明の光起電力装置は、受光面電極上に、上述
の非晶質シリコンカーバイド膜をｐ型層として備えるこ
とを特徴とする。
［００１１］
更には、本発明の光起電力装置は、基板の導電性表面に
形成されるｎ型層が、膜中のシリコン原子の２０〜５０
％が炭素原子と結合した非晶質シリコンカーバイド膜か
らなることを特徴とする。
［００１２］The amorphous silicon carbide film of the present invention is characterized in that an average of two or more silicon atoms are bonded to one carbon atom. [0008] Further, the method for forming an amorphous silicon carbide film of the present invention includes forming a film at a position away from the plasma discharge region in a reaction chamber in which plasma discharge generated by a discharge electrode is confined in a specific region by a magnetic field. a step of arranging a substrate for formation, a step of introducing a silicon compound gas and a carbon compound gas in an amount greater than the amount of this gas into the reaction chamber and decomposing it by the plasma discharge, and forming a film on the substrate with the decomposed gas. It is characterized by comprising a step of. [0009] Further, the method for forming an amorphous silicon carbide film of the present invention includes doping p-type impurities into the amorphous silicon carbide film after the amorphous silicon carbide film is formed on the substrate. It is characterized by [00101] Further, the photovoltaic device of the present invention is characterized in that the above-mentioned amorphous silicon carbide film is provided as a p-type layer on the light-receiving surface electrode. [0011] Further, in the photovoltaic device of the present invention, the n-type layer formed on the conductive surface of the substrate has 20 to 50 silicon atoms in the film.
% is composed of an amorphous silicon carbide film bonded with carbon atoms. [0012]
本発明のａ−５ｉＣ膜は、炭素原子１個に対して、平均
２個以上のシリコン原子が結合しているので、光吸収の
少ないａ−３ｉＣ膜となる。
［００１３］
また、本発明の方法によれば、シリコン原子と水素原子
が直接結合する割合が少ないので、耐熱性に優れたａ−
３ｉＣ膜となる。
［００１４］
更に、このようなａ−３ｉＣ膜を用いた光起電力装置に
あっては、光の収集効率に優れ、高出力を得られる。
［００１５］Since the a-5iC film of the present invention has an average of two or more silicon atoms bonded to one carbon atom, it becomes an a-3iC film with low light absorption. [0013] Furthermore, according to the method of the present invention, since the proportion of direct bonding between silicon atoms and hydrogen atoms is small, a-
This becomes a 3iC film. [0014]Furthermore, a photovoltaic device using such an a-3iC film has excellent light collection efficiency and can obtain high output. [0015]
本発明は、光吸収が少なく、また耐熱特性に優れたａ−
３ｉＣ膜を提供するものであり、炭素原子１個に対して
、平均２個以上のシリコン原子が結合したことを特徴と
する。
［００１６］
図１は、本発明のａ−３ｉＣ膜を形成するためのＲＦグ
ロー放電装置を示している。
［００１７］
この装置は、低圧状態となると共に原料ガスが導入され
る反応室１内に、対向配置で一対の放電電極２．３が設
けられ、これら放電電極２．３間には、高周波電力ＲＦ
が印加されている。一方の電極２上には、膜形成用の基
板４が配され、また、他方の電極３に近接して、放電電
極２．３にて形成されるプラズマを閉じ込めるための電
磁石５が設けられている。この電磁石５は、これに流れ
る電流、所謂、磁場電流（Ｉ ｍｇ）を任意に変更でき
るようになっている。
［００１８］
本発明のａ−５ｉＣ膜は、この装置を用いて形成される
。表１にａ−５ｉＣ膜の一形成条件を示す。なお、同表
には、通常のプラズマＣＶＤ法による従来のａ−５ｉＣ
膜の形成条件をも示している。
［００１９］The present invention provides a-
It provides a 3iC film, which is characterized by an average of two or more silicon atoms bonded to one carbon atom. [0016] FIG. 1 shows an RF glow discharge apparatus for forming the a-3iC film of the present invention. [0017] In this device, a pair of discharge electrodes 2.3 are provided in a reaction chamber 1 which is placed in a low pressure state and into which a raw material gas is introduced, and which are disposed opposite to each other. RF
is applied. A substrate 4 for film formation is disposed on one electrode 2, and an electromagnet 5 for confining the plasma formed at the discharge electrode 2.3 is disposed close to the other electrode 3. There is. The electromagnet 5 is configured such that the current flowing therein, so-called magnetic field current (I mg), can be changed arbitrarily. [0018] The a-5iC film of the present invention is formed using this apparatus. Table 1 shows conditions for forming the a-5iC film. In addition, in the same table, conventional a-5iC by ordinary plasma CVD method
The conditions for forming the film are also shown. [0019]
【表１】
［００２０］
図２は、この条件にて形成されたａ−３ｉＣ膜の光吸収
特性を示している。
同図において、本発明方法によるものは、夫々電磁石５
の磁場電流をＯＡ、ＩＡ及び２Ａとした場合を示してお
り、また、従来方法のものは破線にて示している。
［００２１］
同図から明らかなように、本発明により形成されたａ−
３ｉＣ膜は、いかなる波長の光に対しても、その吸収係
数が小さい。
［００２２］
図３及び図４は、本発明方法と従来方法とにより形成さ
れたａ−３ｉＣ膜のＸｐｓ（Ｘ線光電子分光法）スペク
トル特性（実線が本発明方法によるもの）及び本発明に
より形成されたａ−５ｉＣ膜の赤外線吸収特性を示して
いる。
［００２３］
これら各特性から見て、本発明方法により形成されたａ
−３ｉＣ膜は、従来方法により形成されたａ−３ｉＣ膜
と比べて、炭素原子とシリコン原子とが直接結合してい
る割合が多い。また、本発明により形成されたａ−３ｉ
Ｃ膜は、炭素原子と水素原子、及びシリコン原子と水素
原子が、夫々直接結合している割合が少ないことが分か
る。
［００２４］
即ち、本発明のａ−５ｉＣ膜は、炭素原子とシリコン原
子とが直接結合する割合が多い。より具体的に言うと、
膜中において、炭素原子１個に対し、平均２個以上のシ
リコン原子が結合しているため、上述の如く、光吸収係
数の小さいａ −３ｉＣ膜となる。
［００２５］
更に、本発明のａ−５ｉＣ膜は、シリコン原子と水素原
子とが結合する割合が少ないので、耐熱性に優れたａ−
３ｉＣ膜となる。
［００２６］
ところで、本発明のａ−３ｉＣ膜を光起電力装置のｐ型
層として用いる場合、ａ−３ｉＣ膜中にｐ型不純物をド
ープする必要がある。
［００２７］
通常、ｐ型不純物は、膜形成時にＢ ２ Ｈ６等のｐ型
不純物化合物ガスを用いてドープするが、本発明者等は
、本発明のａ−５ｉＣ膜にあっては、膜形成後に、ａ−
３ｉＣ膜中にｐ型不純物をドープするのが好ましいこと
を見出しな。
［００２８］
即ち、上述の方法でａ−５ｉＣ膜を形成した後、この膜
をＢ２Ｈ６ガスを含むプラズマ放電中にて処理すること
により、ａ−３ｉＣ膜中に、ｐ型不純物としてボロン（
Ｂ）をドープする。
［００２９］
図５（Ａ）は、斯る方法によりａ−３ｉＣ膜中にＢをド
ープした場合のプラズマ処理時間とａ−３ｉＣ膜の暗導
電率との関係を示している。また、同図（Ｂ）は、ａ−
３ｉＣ膜中の形成時に、Ｂ ２ Ｈ６ガスを用いてａ−
３ｉＣ膜中にＢをドープした場合のＢＨのＳｉＨ４に対
する比率と暗導電率との関係を示す。
［００３０］
なお、同図（Ａ）及び（Ｂ）のａ−３ｉＣ膜は、共に表
１に示す条件で、膜厚２００Ａに形成されたものであり
、また、Ｂ２Ｈ６ガスによるプラズマ処理の条件は、以
下の表２の通りである。
［００３１７[0020] FIG. 2 shows the light absorption characteristics of the a-3iC film formed under these conditions. In the same figure, those according to the method of the present invention each have an electromagnet 5
The case where the magnetic field current is OA, IA, and 2A is shown, and the conventional method is shown with a broken line. [0021] As is clear from the figure, the a-
The 3iC film has a small absorption coefficient for light of any wavelength. [0022] FIGS. 3 and 4 show the Xps (X-ray photoelectron spectroscopy) spectral characteristics of a-3iC films formed by the method of the present invention and the conventional method (the solid line is by the method of the present invention) and the characteristics of the a-3iC films formed by the method of the present invention. The figure shows the infrared absorption characteristics of the a-5iC film. [0023] In view of these characteristics, a formed by the method of the present invention
The -3iC film has a higher proportion of carbon atoms and silicon atoms directly bonded than the a-3iC film formed by the conventional method. Also, a-3i formed according to the present invention
It can be seen that in the C film, the proportion of direct bonds between carbon atoms and hydrogen atoms and between silicon atoms and hydrogen atoms is small. [0024] That is, in the a-5iC film of the present invention, carbon atoms and silicon atoms have a high proportion of direct bonds. More specifically,
Since an average of two or more silicon atoms are bonded to one carbon atom in the film, the a -3iC film has a small light absorption coefficient, as described above. [0025] Furthermore, since the a-5iC film of the present invention has a low bonding ratio between silicon atoms and hydrogen atoms, the a-5iC film has excellent heat resistance.
This becomes a 3iC film. [0026] By the way, when the a-3iC film of the present invention is used as a p-type layer of a photovoltaic device, it is necessary to dope a p-type impurity into the a-3iC film. [0027] Normally, p-type impurities are doped using a p-type impurity compound gas such as B 2 H6 during film formation, but the present inventors have discovered that in the a-5iC film of the present invention, the film formation Later, a-
It has been discovered that it is preferable to dope p-type impurities into the 3iC film. [0028] That is, after forming an a-5iC film by the method described above, this film is treated in a plasma discharge containing B2H6 gas, so that boron (
B) dope. [0029] FIG. 5A shows the relationship between the plasma processing time and the dark conductivity of the a-3iC film when B is doped into the a-3iC film using this method. In addition, in the same figure (B), a-
During formation in the 3iC film, a-
The relationship between the ratio of BH to SiH4 and the dark conductivity when B is doped into a 3iC film is shown. [0030] The a-3iC films in (A) and (B) of the same figure were both formed to a thickness of 200A under the conditions shown in Table 1, and the conditions of plasma treatment with B2H6 gas were as follows. , as shown in Table 2 below. [00317
【表２】
［００３２］
図５（Ａ）及び（Ｂ）から明らかなように、ｐ型のａ−
ＳｉＣ膜を形成するに当り、ａ−３ｉＣ膜を形成した後
に、ｐ型不純物としてのＢを膜中にドープすることによ
り、ａ−３ｉＣ膜の暗導電率を、膜形成と同時にＢをド
ープする場合に比べて、大きく向上させることができる
。
［００３３］
図６は、上述のａ−３ｉＣ膜を用いた本発明の光起電力
装置の一実施例を示しており、ガラス等の透明基板１０
上に形成されたＩＴ○、ＳｎＯ３等の透明電極膜１１上
に、本発明のｐ型ａ−３ｉＣ膜１２、プラズマＣＶＤ法
を用いて３５０℃の温度で膜厚的２０００ Ａに形成し
なｉ型ａ−３ｉ膜１３、ｎ型ａ−３ｉ膜１４及び裏面電
極膜１５を、この順に形成したものである。
［００３４］
ところで、この例によれば、上記ｐ型ａ−３ｉＣ膜１２
は、膜形成後にＢをドープするために、Ｂの濃度がｉ型
ａ−３ｉ膜１４側で高く、透明電極膜１１側で低くなる
ため、ｐ型ａ−３ｉＣ膜１３と透明電極膜１１とのオー
ミック特性が悪くなる。
［００３５］
そこで、図７は、この課題を解決した本発明の光起電力
装置の他の実施例を示しており、透明電極膜１１とｐ型
ａ−３ｉＣ膜１２との間に、従来゛の方法、即ち、膜形
成と同時にｐ型不純物をドープした第２ｐ型ａ−３ｉＣ
膜１６を挿入したものである。なお、第２ｐ型ａ−３ｉ
Ｃ膜１６の膜厚は、３０Ａ以下が好ましい。
［００３６］
この構造によれば、透明電極膜１１とｐ型層−３ｉＣ膜
１２との間のオーミック特性は、第２ｐ型ａ−３ｉＣ膜
１６にて改善される。
［００３７］
これら構成の光起電力装置によれば、光入射側のｐ型層
−３ｉＣ膜１２は、光吸収係数が小さく、また暗導電率
が大きいので、図８に実線で示すように、破線で示す従
来の光起電力装置より光収集効率が向上し、また、ｉ型
層−３ｉ膜１３にて発生した光キャリアの取出し時にお
けるｐ型層−３ｉＣ膜１２での電気的損失を低減するこ
とができ、出力特性の優れた光起電力装置を形成するこ
とができる。
［００３８］
ところで、上述の光起電力装置は、本願のａ−３ｉＣ膜
を、基板１０上に先に形成されるｐ型層−３ｉＣ膜１２
として用いた形態のものであるが、本発明のａ−３ｉＣ
膜は、その耐熱性を生かして、ｎ型層を先に基板上に形
成する形態の光起電力装置のｎ型層として用いても好適
である。
［００３９］
図９は、二〇種光起電力装置の一実施例を示す断面図で
ある。裏面に背面反射用の金属膜２２が被着されたガラ
ス等の透明基板２１の表面に、５ｎ０２等の透明電極膜
２３、膜厚１０〜５０ Ａ （７） ｎ型層−３ｉ膜２
４、本発明の特徴である膜厚５０〜２００Ａのｎ型層−
３ｉＣ膜２５、プラズマＣＶＤ法を用いて３００℃の温
度により形成され水素含有量が１０％以下である膜厚４
０００〜８０００Ａノｉ型ａ−３ｉ膜２６、膜厚１００
〜２００Ａのｐ型層−３ｉ膜２７及びＩＴ○等の透明電
極膜２８を、この順に形成したものである。
［００４０］
ｎ型層−５ｉＣ膜２５は、図１に示すＲＦグロー放電装
置を用いて形成される。
表３にこのｎ型層−３ｉＣ膜２５の一形成条件を示す。
［００４１］[Table 2] [0032] As is clear from FIGS. 5(A) and (B), p-type a-
In forming the SiC film, after forming the a-3iC film, by doping B as a p-type impurity into the film, the dark conductivity of the a-3iC film can be increased by doping B at the same time as film formation. This can be greatly improved compared to the case. [0033] FIG. 6 shows an embodiment of the photovoltaic device of the present invention using the above-mentioned a-3iC film, in which a transparent substrate 10 such as glass is used.
On the transparent electrode film 11 of IT○, SnO3, etc. formed thereon, the p-type a-3iC film 12 of the present invention is formed to a film thickness of 2000 A at a temperature of 350° C. using a plasma CVD method. A type a-3i film 13, an n-type a-3i film 14, and a back electrode film 15 are formed in this order. [0034] According to this example, the p-type a-3iC film 12
Because B is doped after film formation, the concentration of B is higher on the i-type a-3i film 14 side and lower on the transparent electrode film 11 side. The ohmic characteristics of will deteriorate. [0035] Therefore, FIG. 7 shows another embodiment of the photovoltaic device of the present invention that solves this problem. The second p-type a-3iC doped with p-type impurities at the same time as film formation.
A membrane 16 is inserted. In addition, the second p-type a-3i
The thickness of the C film 16 is preferably 30A or less. [0036] According to this structure, the ohmic characteristics between the transparent electrode film 11 and the p-type layer-3iC film 12 are improved by the second p-type a-3iC film 16. [0037] According to the photovoltaic device having these configurations, the p-type layer-3iC film 12 on the light incidence side has a small light absorption coefficient and a large dark conductivity, so as shown by the solid line in FIG. Light collection efficiency is improved compared to the conventional photovoltaic device shown by the broken line, and electrical loss in the p-type layer-3iC film 12 is reduced when taking out photocarriers generated in the i-type layer-3i film 13. It is possible to form a photovoltaic device with excellent output characteristics. [0038] By the way, in the above-mentioned photovoltaic device, the a-3iC film of the present application is used as a p-type layer-3iC film 12 formed previously on the substrate 10.
a-3iC of the present invention.
Taking advantage of its heat resistance, the film is also suitable for use as an n-type layer in a photovoltaic device in which the n-type layer is first formed on a substrate. [0039] FIG. 9 is a sectional view showing an example of a Type 20 photovoltaic device. A transparent electrode film 23 such as 5n02 with a film thickness of 10 to 50 A is formed on the surface of a transparent substrate 21 made of glass or the like on which a metal film 22 for rear reflection is adhered to the back surface. (7) N-type layer-3i film 2
4. An n-type layer with a thickness of 50 to 200 A, which is a feature of the present invention.
3iC film 25, film thickness 4 formed using plasma CVD method at a temperature of 300°C and having a hydrogen content of 10% or less
000-8000A noi type a-3i film 26, film thickness 100
A p-type layer-3i film 27 of ~200A and a transparent electrode film 28 of IT○ etc. are formed in this order. [0040] The n-type layer-5iC film 25 is formed using the RF glow discharge device shown in FIG. Table 3 shows conditions for forming this n-type layer-3iC film 25. [0041]
【表３】
但し、ＣＨ４：Ｈ，ガスにより１０％に希釈ＰＨ，：
Ｈ，ガスにより１％に希釈
［００４２］
この条件により形成されたｎ型ａ−３ｉＣ膜２５も、本
発明のｐ型ａ−３ｉＣ膜と同様に、シリコン原子と炭素
原子との結合（Ｓｉ−Ｃ結合）を多く含み、耐熱性に優
れたものであるため、ｎ型ａ−３ｉＣ膜２５の形成後に
ｉ型ａ−３ｉ膜２６を高温で形成したとしても、ｉ型ａ
−５ｉ膜２６に悪影響を与えることがない。
［００４３］
ところで、ｎ型ａ−３ｉＣ膜２５の形成条件は、表３に
示したように、非常に過激な条件であるため、透明電極
膜２３上に直接ｎ型ａ−３ｉＣ膜２５を形成した場合透
明電極膜２３がダメージを受け、更に、透明電極膜２３
の構成元素が不純物としてｎ型ａ−３ｉＣ膜２５中に混
入してこの膜の特性を劣化させる。これを防止するため
に、本実施例では、ｎ型ａ−３ｉＣ膜２５の形成前に、
透明電極膜２３上にｎ型ａ−５ｉ膜２４を形成している
。
［００４４］
図１０は、斯る光起電力装置における変換効率のｉ型ａ
−５ｉ膜２６形成温度依存性を示している。なお、この
光起電力装置のｎ型ａ−３ｉＣ膜２５は、水素量８％、
Ｃ原子と結合しているＳｉ原子の比率が２０％のもので
ある。また、同図にはｎ型ａ−３ｉＣ膜２５に代えて、
通常の方法により形成したｎ型ａ−３ｉ膜２４と同様の
ｎ型ａ−３ｉ膜を用いた従来の光起電力装置の依存性も
併せて、破線で示している。
［００４５］
同図から見て、従来の光起電力装置は、ｉ型層の形成温
度が高くなるほど、変換効率が低下するのに対し、本発
明の光起電力装置は、その光電変換効率がｉ型ａ−３ｉ
膜２６の形成温度にほとんど影響されないことが分かる
。
［００４６］
ところで、図９に示す光起電力装置の光電変換効率は、
ｎ型ａ−３ｉＣ膜２５中のＣ原子と結合するＳｉ原子の
比率の影響を受ける。図１１は、ｎ型ａ−５ｉＣ膜２５
中のＣ原子と結合するＳｉ原子の比率と光電変換効率と
の関係を示している［００４７］
同図から分かるように、Ｃ原子と結合するＳｉ原子の比
率が２０〜５０％の場合、非常に優れた光電変換効率を
得られる。
［００４８］
更に、図１２は、ｎ型ａ−３ｉＣ膜２５中の水素量と光
電変換効率との関係を示している。
［００４９］
この図によれば、光起電力装置の光電変換効率は、ｎ型
ａ−５ｉＣ膜２５中の水素量に影響を受けることが分か
り、光電変換効率を向上させるには、水素量を１０％以
下とするのが好ましい。
［００５０］
［発明の効果］
本発明の非晶質シリコンカーバイド膜は、光吸収特性に
優れたものとなる。
［００５１］
また、本発明の非晶質シリコンカーバイド膜は、これを
ｐ型層とする場合、ｐ型不純物が非晶質シリコンカーバ
イド膜形成後にドープされるので、膜の導電率を向上さ
せることができる。
［００５２３
更に、本発明の光起電力装置は、上述したｐ型の非晶質
シリコンカーバイド膜を光入射側に備えた構成であるの
で、光の収集効率が向上し、優れた特性を備える。
［００５３］
更には、本発明の光起電力装置は、ｉ型層の形成に先だ
って形成されるｎ型層を耐熱性に優れた本発明の非晶質
シリコンカーバイド膜から構成したので、優れた特性を
備える。[Table 3] However, CH4:H, diluted to 10% with gas, PH:
Diluted to 1% with H, gas [0042] Similarly to the p-type a-3iC film of the present invention, the n-type a-3iC film 25 formed under these conditions also has a bond between silicon atoms and carbon atoms (Si- C bonds) and has excellent heat resistance, even if the i-type a-3i film 26 is formed at high temperature after the n-type a-3iC film 25 is formed, the i-type a
-5i film 26 is not adversely affected. [0043] By the way, the conditions for forming the n-type a-3iC film 25 are very extreme as shown in Table 3, so the n-type a-3iC film 25 is not formed directly on the transparent electrode film 23. In this case, the transparent electrode film 23 is damaged, and furthermore, the transparent electrode film 23 is damaged.
The constituent elements mix into the n-type a-3iC film 25 as impurities and deteriorate the characteristics of this film. In order to prevent this, in this embodiment, before forming the n-type a-3iC film 25,
An n-type a-5i film 24 is formed on the transparent electrode film 23. [0044] FIG. 10 shows the conversion efficiency of type i a in such a photovoltaic device.
-5i film 26 formation temperature dependence is shown. Note that the n-type a-3iC film 25 of this photovoltaic device has a hydrogen content of 8%,
The ratio of Si atoms bonded to C atoms is 20%. Also, in the same figure, instead of the n-type a-3iC film 25,
The dependence of a conventional photovoltaic device using an n-type a-3i film similar to the n-type a-3i film 24 formed by a conventional method is also shown by a broken line. [0045] As seen from the figure, in the conventional photovoltaic device, the conversion efficiency decreases as the formation temperature of the i-type layer increases, whereas in the photovoltaic device of the present invention, the photoelectric conversion efficiency decreases. i type a-3i
It can be seen that the temperature at which the film 26 is formed is hardly affected. [0046] By the way, the photoelectric conversion efficiency of the photovoltaic device shown in FIG.
It is affected by the ratio of Si atoms bonded to C atoms in the n-type a-3iC film 25. FIG. 11 shows an n-type a-5iC film 25
[0047] As can be seen from the figure, when the ratio of Si atoms bonded to C atoms is 20 to 50%, the ratio of Si atoms bonded to C atoms is very high. Excellent photoelectric conversion efficiency can be obtained. [0048] Furthermore, FIG. 12 shows the relationship between the amount of hydrogen in the n-type a-3iC film 25 and the photoelectric conversion efficiency. [0049] According to this figure, it can be seen that the photoelectric conversion efficiency of the photovoltaic device is affected by the amount of hydrogen in the n-type a-5iC film 25, and in order to improve the photoelectric conversion efficiency, the amount of hydrogen must be increased. It is preferably 10% or less. [0050] [Effects of the Invention] The amorphous silicon carbide film of the present invention has excellent light absorption characteristics. [0051] Furthermore, when the amorphous silicon carbide film of the present invention is used as a p-type layer, p-type impurities are doped after the amorphous silicon carbide film is formed, so that the conductivity of the film can be improved. I can do it. [00523] Furthermore, since the photovoltaic device of the present invention has the above-mentioned p-type amorphous silicon carbide film on the light incident side, the light collection efficiency is improved and it has excellent characteristics. [0053] Furthermore, the photovoltaic device of the present invention has excellent properties because the n-type layer formed prior to the formation of the i-type layer is composed of the amorphous silicon carbide film of the present invention having excellent heat resistance. have characteristics.
【図１】
本発明のａ−３ｉＣ膜を形成するためのＲＦグロー放電
装置を示す模式的断面図である。FIG. 1 is a schematic cross-sectional view showing an RF glow discharge apparatus for forming an a-3iC film of the present invention.
【図２】
本発明及び従来例のａ−３ｉＣ膜の光吸収特性を示す特
性図である。FIG. 2 is a characteristic diagram showing the light absorption characteristics of a-3iC films of the present invention and a conventional example.
【図３】
本発明及び従来例のａ−３ｉＣ膜のＸＰＳスペクトル特
性を示す特性図であるFIG. 3 is a characteristic diagram showing the XPS spectral characteristics of a-3iC films of the present invention and conventional examples.
【図４】
本発明のａ−３ｉＣ膜の赤外線吸収特性を示す特性図で
ある。FIG. 4 is a characteristic diagram showing the infrared absorption characteristics of the a-3iC film of the present invention.
【図５】
（Ａ）は、本発明方法によりａ−３ｉＣ膜中にＢをドー
プした場合のプラズマ処理時間とａ−３ｉＣ膜の暗導電
率との関係を示す特性図であり、（Ｂ）は、ａ−３ｉＣ
膜の形成時に、Ｂ２Ｈ６ガスを用いてａ−３ｉＣ膜中に
Ｂをドープした場合のＢＨガスのＳ Ｉ Ｈｚ、ガスに
対する比率と暗導電率との関係を示す特性図である。FIG. 5 (A) is a characteristic diagram showing the relationship between the plasma treatment time and the dark conductivity of the a-3iC film when B is doped into the a-3iC film by the method of the present invention, and (B) is a-3iC
FIG. 3 is a characteristic diagram showing the relationship between the S I Hz of BH gas, the ratio to the gas, and the dark conductivity when B is doped into the a-3iC film using B2H6 gas during film formation.
【図６】
本発明の光起電力装置の一実施例を示す模式的断面図で
ある。FIG. 6 is a schematic cross-sectional view showing an embodiment of the photovoltaic device of the present invention.
【図７】
本発明の光起電力装置の他の実施例を示す模式的断面図
である。FIG. 7 is a schematic cross-sectional view showing another embodiment of the photovoltaic device of the present invention.
【図８】
本発明及び従来例の光起電力装置の光収集効率を示す特
性図である。FIG. 8 is a characteristic diagram showing the light collection efficiency of the photovoltaic devices of the present invention and the conventional example.
【図９】
本発明の光起電力装置の更に他の実施例を示す断面図で
ある。FIG. 9 is a sectional view showing still another embodiment of the photovoltaic device of the present invention.
【図１０】
本発明の光起電力装置における変換効率のｉ型ａ−３ｉ
膜膜形湿温依存性を示す特性図である。FIG. 10: Conversion efficiency of type i a-3i in the photovoltaic device of the present invention
FIG. 3 is a characteristic diagram showing the dependence of membrane shape on humidity and temperature.
【図１１】
本発明の光起電力装置のｎ型ａ−３ｉＣ膜中のＣ原子と
結合するＳｉ原子の比率と光電変換効率との関係を示す
特性図である。FIG. 11 is a characteristic diagram showing the relationship between the ratio of Si atoms bonded to C atoms in the n-type a-3iC film of the photovoltaic device of the present invention and photoelectric conversion efficiency.
【図１２】
本発明の光起電力装置のｎ型ａ−３ｉＣ膜中の水素量と
光電変換効率との関係を示す特性図である。FIG. 12 is a characteristic diagram showing the relationship between the amount of hydrogen in the n-type a-3iC film and the photoelectric conversion efficiency of the photovoltaic device of the present invention.
図面 drawing
【図１】[Figure 1]
【図２】[Figure 2]
【図３】[Figure 3]
【図４】[Figure 4]
【図５】[Figure 5]
【図６】 （Ａン[Figure 6] (A
【図７】[Figure 7]
【図８】[Figure 8]
【図９】[Figure 9]
【図１０１ 【図１１】[Figure 101 [Figure 11]
【図１２】 ○[Figure 12] ○
Claims (7)
リコン原子が結合したことを特徴とする非晶質シリコン
カーバイド膜。1. An amorphous silicon carbide film characterized in that an average of two or more silicon atoms are bonded to one carbon atom.
磁界により特定の領域に閉じ込めた反応室内において、
上記プラズマ放電領域から離れた位置に膜形成用基板を
配置する工程と、上記反応室内にシリコン化合物ガス及
びこのガス量より多い炭素化合物ガスを導入し、上記プ
ラズマ放電によって分解する工程と、分解されたガスに
より上記基板上に膜を形成する工程と、を備えたことを
特徴とする非晶質シリコンカーバイド膜の形成方法。Claim 2: In a reaction chamber in which plasma discharge generated by a discharge electrode is confined in a specific area by a magnetic field,
a step of arranging a film-forming substrate at a position away from the plasma discharge region; a step of introducing a silicon compound gas and a carbon compound gas in an amount greater than the amount of this gas into the reaction chamber and decomposing it by the plasma discharge; A method for forming an amorphous silicon carbide film, comprising the step of: forming a film on the substrate using a gas containing an amorphous silicon carbide film.
ド膜が形成された後、この非晶質シリコンカーバイド膜
中にｐ型不純物を添加することを特徴とする請求項２記
載の非晶質シリコンカーバイド膜の形成方法。3. The amorphous silicon carbide film according to claim 2, wherein p-type impurities are added to the amorphous silicon carbide film after the amorphous silicon carbide film is formed on the substrate. Method of forming silicon carbide film.
た非晶質シリコンカーバイド膜をｐ型層として備えるこ
とを特徴とする光起電力装置。4. A photovoltaic device comprising an amorphous silicon carbide film formed according to claim 3 as a p-type layer on a light-receiving surface electrode.
バイド膜との間に、均等濃度でｐ型不純物が添加された
非晶質シリコンカーバイド膜を備えたことを特徴とする
請求項４記載の光起電力装置。5. An amorphous silicon carbide film doped with p-type impurities at a uniform concentration is provided between the light-receiving surface electrode and the amorphous silicon carbide film. photovoltaic device.
びｉ型層をこの順に形成してなる光起電力装置において
、上記ｎ型層は、膜中のシリコン原子の２０〜５０％が
炭素原子と結合した非晶質シリコンカーバイド膜からな
ることを特徴とする光起電力装置。6. A photovoltaic device comprising at least an n-type layer and an i-type layer formed in this order on a conductive surface of a substrate, wherein the n-type layer contains 20 to 50% of the silicon atoms in the film. A photovoltaic device comprising an amorphous silicon carbide film bonded to carbon atoms.
の水素量が１０％以下であることを特徴とする請求項６
記載の光起電力装置。7. Claim 6, wherein the amorphous silicon carbide film has a hydrogen content of 10% or less.
The photovoltaic device described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP40432590A JP3238929B2 (en) | 1990-03-27 | 1990-12-20 | Method of forming amorphous silicon carbide film and photovoltaic device |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2-77941 | 1990-03-27 | ||
| JP7794190 | 1990-03-27 | ||
| JP40432590A JP3238929B2 (en) | 1990-03-27 | 1990-12-20 | Method of forming amorphous silicon carbide film and photovoltaic device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH046880A true JPH046880A (en) | 1992-01-10 |
| JP3238929B2 JP3238929B2 (en) | 2001-12-17 |
Family
ID=26418999
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP40432590A Expired - Fee Related JP3238929B2 (en) | 1990-03-27 | 1990-12-20 | Method of forming amorphous silicon carbide film and photovoltaic device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3238929B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06185245A (en) * | 1992-10-21 | 1994-07-05 | Mitsubishi Electric Corp | Melting treatment device |
| US6198507B1 (en) | 1995-12-21 | 2001-03-06 | Sony Corporation | Solid-state imaging device, method of driving solid-state imaging device, camera device, and camera system |
| JP2014195101A (en) * | 2009-02-17 | 2014-10-09 | Korea Inst Of Industrial Technology | Method of manufacturing solar cell utilizing induction coupled plasma chemical vapor deposition |
| KR20180082324A (en) * | 2017-01-09 | 2018-07-18 | 주식회사 테스 | Process for forming amorphous silicon layer including carbon and/or boron and amorphous silicon formed by the same |
-
1990
- 1990-12-20 JP JP40432590A patent/JP3238929B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06185245A (en) * | 1992-10-21 | 1994-07-05 | Mitsubishi Electric Corp | Melting treatment device |
| US6198507B1 (en) | 1995-12-21 | 2001-03-06 | Sony Corporation | Solid-state imaging device, method of driving solid-state imaging device, camera device, and camera system |
| JP2014195101A (en) * | 2009-02-17 | 2014-10-09 | Korea Inst Of Industrial Technology | Method of manufacturing solar cell utilizing induction coupled plasma chemical vapor deposition |
| KR20180082324A (en) * | 2017-01-09 | 2018-07-18 | 주식회사 테스 | Process for forming amorphous silicon layer including carbon and/or boron and amorphous silicon formed by the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3238929B2 (en) | 2001-12-17 |
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