JPS63262837A - Manufacture of p-type amorphous silicon - Google Patents
Manufacture of p-type amorphous siliconInfo
- Publication number
- JPS63262837A JPS63262837A JP62097836A JP9783687A JPS63262837A JP S63262837 A JPS63262837 A JP S63262837A JP 62097836 A JP62097836 A JP 62097836A JP 9783687 A JP9783687 A JP 9783687A JP S63262837 A JPS63262837 A JP S63262837A
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- type amorphous
- amorphous silicon
- temperature
- plasma
- 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
- 229910021417 amorphous silicon Inorganic materials 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 230000008021 deposition Effects 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 15
- 239000007789 gas Substances 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000010494 dissociation reaction Methods 0.000 abstract description 2
- 230000005593 dissociations Effects 0.000 abstract description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon 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
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明はｐ型非晶質シリコンの製造方法、特に広い光学
的バンドギャップを有するｐ型非晶質シリコンの製造方
法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for producing p-type amorphous silicon, and more particularly to a method for producing p-type amorphous silicon having a wide optical bandgap.
従来の技術
従来、ｐ型非晶質シリコン（ｐ−ａ−ｓｉ）はガラス／
透明電極／Ｐｉｎ／金属電極型の太陽電池の入射側導電
性非晶質シリコン層として利用されて来た。しかしなが
ら従来のｐ型非晶質シリコンの製造方法では、例えばＢ
＝）ｆａ （モノシラン）とＢ２Ｈ６（ジボラン）の混
合ガスを原料ガスとしたプラズマｃｖｎ法で行なってお
り、低抵抗のｐ型層を得るために基板温度を２００″Ｃ
以上に加熱していた。Conventional technology Conventionally, p-type amorphous silicon (p-a-si) is made of glass/
It has been used as a conductive amorphous silicon layer on the incident side of transparent electrode/Pin/metal electrode type solar cells. However, in the conventional manufacturing method of p-type amorphous silicon, for example, B
=) The plasma CVN method uses a mixed gas of fa (monosilane) and B2H6 (diborane) as the raw material gas, and the substrate temperature is set to 200"C in order to obtain a low resistance p-type layer.
It was heating up even more.
この場合、光学的バンドギャップが１．６〜１．７６Ｖ
と真性型もしくはｎ型非晶質シリコンの１．７〜１．８
ｅＶと比べ狭いため高い光の利用率が得られにくかった
。そのため原料ガスとしてさらにＣＨ４やＣ２Ｈ４を混
合し、ｐ型非晶質シリコンカーバイド（ｐ−ａ−５ｉＣ
）とし、光学的バンドギャップを１，９〜２．ＯｅＹに
広げてやるという手法を取っていた。In this case, the optical bandgap is 1.6-1.76V
and 1.7 to 1.8 for intrinsic or n-type amorphous silicon.
Since it is narrower than eV, it is difficult to obtain a high light utilization rate. Therefore, CH4 and C2H4 are further mixed as raw material gas, and p-type amorphous silicon carbide (p-a-5iC
), and the optical band gap is 1,9 to 2. The method was to expand it to OeY.
発明が解決しようとする問題点
しかしながら、この方法では光の利用効率は向上するが
、このｐ型層上に堆積する真性（１）型非晶質シリコン
に炭素元素が汚染不純物元素として混入し、真性層の光
活性層としての性能を低下させたり、ｐ−１接合界面特
性が悪化したシし、光利用効率の割には太陽電池として
の変換効率の向上が実現出来なかった。Problems to be Solved by the Invention However, although this method improves the efficiency of light utilization, carbon element is mixed as a contaminating impurity element into the intrinsic (1) type amorphous silicon deposited on the p-type layer. The performance of the intrinsic layer as a photoactive layer was degraded, the p-1 junction interface properties were deteriorated, and the conversion efficiency as a solar cell could not be improved considering the light utilization efficiency.
本発明は、このような従来技術における問題点を解決す
ることを目的とする。The present invention aims to solve these problems in the prior art.
問題点を解決するための手段
上記の問題点を解決するため、本発明では、ｐ型非晶質
シリコンをマイクロ波、電子サイクロトロン共鳴吸収を
用いたＫＣＲプラズマＣＶＤ法（以下μ波ＥＯＲプラズ
マｃｖｎ法を用いて基板を６０’Ｃ以下にして堆積し、
しかるのちこの堆積温度以上で熱、処理するものである
。Means for Solving the Problems In order to solve the above problems, in the present invention, p-type amorphous silicon is processed by KCR plasma CVD method (hereinafter referred to as μ-wave EOR plasma CVD method) using microwave and electron cyclotron resonance absorption. deposit the substrate at 60'C or less using
Afterwards, it is heated and processed at a temperature higher than this deposition temperature.
作用
この方法を用いれば、６０’Ｃ以下の基板温度で５ｉＨ
ａとＢ２Ｈ６の混合ガスを原料とし堆積した後、たとえ
ば２００〜３００’Ｃの熱処理を行なうことによって、
低抵抗で広い光学バンドギャップを有するｐ型非晶質シ
リコンが実現出来る事が見い出された。Operation Using this method, 5iH can be achieved at a substrate temperature of 60'C or less.
After depositing using a mixed gas of a and B2H6 as raw materials, for example, by performing heat treatment at 200 to 300'C,
It has been discovered that p-type amorphous silicon with low resistance and a wide optical bandgap can be realized.
この方法を用いれば、６０”Ｃ以下で堆積されたｐ型非
晶質シリコンはもともと１．９０Ｖ程度の光学ギャップ
を持つが抵抗が１０７０傭程度と大きい。If this method is used, p-type amorphous silicon deposited at 60"C or less originally has an optical gap of about 1.90V, but has a large resistance of about 1070V.
しかしながらこのｐ型非晶質シリコンを２００″Ｃ〜３
００°Ｃ程度の温度で熱処理を行なうと構造緩和によっ
て２．□ｅＶ程度まで増大しさらに膜中の不純物元素が
活性化し〜１０４Ω硼程度まで抵抗が減少するのである
。However, this p-type amorphous silicon is
When heat treatment is performed at a temperature of about 00°C, structural relaxation causes 2. The resistance increases to about □eV, and the impurity elements in the film are further activated, and the resistance decreases to about 104Ω.
実施例
以下図面に基づき、本発明の代表的な実施例を示す。第
１図は本実施例で使用するμ波１１ＲプラズマＣｖＤ装
置の概略図である。１１が真空チャンバーで排気孔１２
より真空に排気される。導波管１３を通してマイクロ波
発振器１４からマイクロ波がプラズマ発生室１６へ導入
される。電磁石１６によりプラズマ発生室１６に磁界が
印部される。１７はガス導入口でＳｉＨ４やＢ２Ｈ６な
どの原料ガスが導入される。磁界の強さを、電子サイク
ロトロン共鳴条件を満すように設定することにより解離
度の高いプラズマが発生する。発生したプラズマは、プ
ラズマ引出し窓１８を通過し基板ホルダ１９に達し、ホ
ルダ１９上の基板にｐ型非晶質シリコンが形成される。EXAMPLES Below, typical examples of the present invention will be shown based on the drawings. FIG. 1 is a schematic diagram of a μ-wave 11R plasma CvD apparatus used in this example. 11 is a vacuum chamber and exhaust hole 12
It is evacuated to a more vacuum. Microwaves are introduced from a microwave oscillator 14 into a plasma generation chamber 16 through a waveguide 13 . A magnetic field is applied to the plasma generation chamber 16 by the electromagnet 16 . Reference numeral 17 denotes a gas introduction port through which source gases such as SiH4 and B2H6 are introduced. Plasma with a high degree of dissociation is generated by setting the strength of the magnetic field to satisfy electron cyclotron resonance conditions. The generated plasma passes through the plasma extraction window 18 and reaches the substrate holder 19, and p-type amorphous silicon is formed on the substrate on the holder 19.
第２図は第１図で示した装置で、６０’Ｃ以下の基板温
度で形成した非晶質シリコンを３００ ’Ｃまで熱処理
した場合の電気伝導度の変化と光学的バンドギャップの
変化を示している。熱処理によって光学的バンドギャッ
プが１，９６Ｖからさらに２−ＯｅＶまで増大すると同
時に電気伝導度の変化を示している。この値は従来の技
術において、ｐ型非晶質シリコンカーバイトで得られた
光学的バンドギャップ２．ｏｅｖの時の電気伝導度〜１
ｏ−６〜１ｏ−５（Ω儂）−１よシ優れている。Figure 2 shows the changes in electrical conductivity and optical bandgap when amorphous silicon formed at a substrate temperature of 60'C or less is heat-treated to 300'C using the apparatus shown in Figure 1. ing. The optical bandgap increases from 1,96 V to 2-OeV through heat treatment, and at the same time, the electrical conductivity changes. This value corresponds to the optical band gap of 2.5% obtained with p-type amorphous silicon carbide in the prior art. Electrical conductivity at oev ~1
o-6 to 1 o-5 (Ω儂)-1 is better.
従来のプラズマＣｖＤ法で作られるｐ型非晶質シリコン
はＳｉＨ４とＢ２Ｈ６の混合ガスを原料ガスとシフ’う
ＸマＣｖＤ法で作製されるが８２Ｈ６ガスの混合比を増
重させてゆくとｐ型非晶質シリコン中に入りシリコン原
子と結合する水素量が急激に減少し、結果として光学ギ
ャップが狭くなってしまう。P-type amorphous silicon, which is produced by the conventional plasma CVD method, is produced by the X-mass CVD method in which a mixed gas of SiH4 and B2H6 is used as the raw material gas, but as the mixing ratio of 82H6 gas is increased, The amount of hydrogen that enters the amorphous silicon and bonds with silicon atoms rapidly decreases, resulting in a narrowing of the optical gap.
このことは、μ波ＩＣ（ｊＲプラズマＣＶＤ法で基板温
度２００″Ｃ〜３００ ”Ｃで作製しても同様である。This is the same even if the μ-wave IC (JR plasma CVD method is used to manufacture the substrate at a temperature of 200''C to 300''C).
しかし前記した本発明の方法によると、６０℃以下の室
温に近い温度で作られたｐ型非晶質シリコン中には充分
Ｓ１と結合した水素が存在する。したがって未処理の状
態では構造的ストレスにより光学ギャップは小さくなっ
ているが堆積温度以上の熱処理によって緩和され本発明
によれば〜２．ＯｅＶ以上の光学ギャップが得られ、か
つ電気伝導度も向上するのである。なお、従来のプラズ
マＣｖＤ法において室温で形成すると確かに広い光学ギ
ャップの膜が得られるが、熱処理を行っても充分な電気
伝導を持つｐ型非晶質シリコンは得られなかった。また
、本発明においては、基板は通常加熱しないのが望まし
いが、基板ｍ熱は行なわなくても一般的に堆積によって
基板は〜６０°Ｃ程寂に上昇するが、この程度であれば
特に問題はなかった。これ以上上昇してしまうと前記し
た効果が消失してしまうので冷却する等を行なって基板
を６０°Ｃ程度にする必要がある。However, according to the method of the present invention described above, there is sufficient hydrogen bonded to S1 in the p-type amorphous silicon produced at a temperature of 60° C. or lower, close to room temperature. Therefore, in the untreated state, the optical gap is small due to structural stress, but it is alleviated by heat treatment above the deposition temperature, and according to the present invention ~2. An optical gap of OeV or more can be obtained, and electrical conductivity can also be improved. Note that, although it is true that a film with a wide optical gap can be obtained when formed at room temperature in the conventional plasma CVD method, p-type amorphous silicon with sufficient electrical conductivity cannot be obtained even after heat treatment. In addition, in the present invention, it is preferable that the substrate is not normally heated, but even if the substrate is not heated, the temperature of the substrate will generally rise by about 60°C due to deposition, but this is a particular problem. There was no. If the temperature rises any higher than this, the above-mentioned effect will disappear, so it is necessary to cool the substrate to about 60°C.
発明の効果 本発明の効果は次のようなものである。Effect of the invention The effects of the present invention are as follows.
従来技術で得られた非晶質シリコン、非晶質シリコンカ
ーバイドのｐ型層に比べ充分広い光学的バンドギャップ
を持ち充分高い電気伝導度を示すｐ型層が実現出来た。A p-type layer having a sufficiently wide optical bandgap and sufficiently high electrical conductivity compared to p-type layers of amorphous silicon and amorphous silicon carbide obtained by conventional techniques was realized.
特に基板／透明電極／ Ｐｉｎ、／金属電極構成の非晶
質シリコン太陽電池を製造する場合ｐ型層からの１型層
への炭素元素の汚染拡散が無く好都合である。また熱処
理が必要ではあるが、その後の１型層、ｎ型層の堆積時
に通常２００〜３００’Ｃ基板ｗ熱を行なうのでこの加
熱を利用することができ、実際に熱処理を施す必要はな
く製造工程上も好都合である。Particularly when manufacturing an amorphous silicon solar cell having a substrate/transparent electrode/Pin/metal electrode configuration, it is advantageous because there is no contamination diffusion of carbon elements from the p-type layer to the 1-type layer. Although heat treatment is required, the substrate is usually heated to 200-300'C during the subsequent deposition of the 1-type layer and the n-type layer, so this heating can be used, and there is no need to actually perform heat treatment during manufacturing. It is also convenient in terms of process.
第１図は本発明で使用したμ波ＨＯＲプラズマｃｖｎ装
置の概略図、第２図は本発明の実施例としてＳｉＨ４と
Ｂ２Ｈ６を原料ガスとして第１図で示した装置によって
形成したｐ型非晶質シリコンの電気伝導度および光学的
バンドギャップの熱処理による変化を示す図である。
１１・・・・・・真空チャンバー、１２・・・・・・排
気孔、１３・・・・・・導波管、１４・・・・・・マイ
クロ波発振器、１５・・・・・・プラズマ発生室、１６
・・・・・・電磁石、１７・・・・・・ガス導入口、１
８・・・・・・プラズマ引き出し窓。
代理人の氏名 弁理士 中 尾 敏 男 ほか１名駅か
Ｃ“く）−シト°）生
Ｗ’ｘぜと１畔曇FIG. 1 is a schematic diagram of the μ-wave HOR plasma CVN device used in the present invention, and FIG. 2 is a p-type amorphous crystal formed by the device shown in FIG. 1 using SiH4 and B2H6 as raw material gases as an example of the present invention. FIG. 3 is a diagram showing changes in electrical conductivity and optical bandgap of pure silicon due to heat treatment. 11... Vacuum chamber, 12... Exhaust hole, 13... Waveguide, 14... Microwave oscillator, 15... Plasma Occurrence room, 16
...Electromagnet, 17...Gas inlet, 1
8...Plasma drawer window. Name of agent: Patent attorney Toshio Nakao and 1 other person
Claims (1)
ラズマ分解によるｐ型非晶質シリコンの形成方法におい
て、基板を６０℃以下の温度に保ち、前記基板上に前記
ｐ型非晶質シリコンを堆積した後、この堆積温度より高
い温度で加熱することを特徴とするｐ型非晶質シリコン
の製造方法。In a method for forming p-type amorphous silicon by plasma decomposition using microwaves and electron cyclotron resonance absorption, after depositing the p-type amorphous silicon on the substrate while keeping the substrate at a temperature of 60° C. or less, A method for producing p-type amorphous silicon, characterized by heating at a temperature higher than this deposition temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62097836A JPH0760802B2 (en) | 1987-04-21 | 1987-04-21 | Method for producing p-type amorphous silicon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62097836A JPH0760802B2 (en) | 1987-04-21 | 1987-04-21 | Method for producing p-type amorphous silicon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63262837A true JPS63262837A (en) | 1988-10-31 |
| JPH0760802B2 JPH0760802B2 (en) | 1995-06-28 |
Family
ID=14202802
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62097836A Expired - Fee Related JPH0760802B2 (en) | 1987-04-21 | 1987-04-21 | Method for producing p-type amorphous silicon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0760802B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002083984A (en) * | 2000-09-08 | 2002-03-22 | National Institute Of Advanced Industrial & Technology | Solar battery and its manufacturing method |
| JP2020537359A (en) * | 2017-10-09 | 2020-12-17 | アプライド マテリアルズ インコーポレイテッドＡｐｐｌｉｅｄ Ｍａｔｅｒｉａｌｓ，Ｉｎｃｏｒｐｏｒａｔｅｄ | Conformal-doped amorphous silicon as a nucleation layer for metal deposition |
-
1987
- 1987-04-21 JP JP62097836A patent/JPH0760802B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002083984A (en) * | 2000-09-08 | 2002-03-22 | National Institute Of Advanced Industrial & Technology | Solar battery and its manufacturing method |
| JP2020537359A (en) * | 2017-10-09 | 2020-12-17 | アプライド マテリアルズ インコーポレイテッドＡｐｐｌｉｅｄ Ｍａｔｅｒｉａｌｓ，Ｉｎｃｏｒｐｏｒａｔｅｄ | Conformal-doped amorphous silicon as a nucleation layer for metal deposition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0760802B2 (en) | 1995-06-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |