JPH0496216A - Manufacture of polycrystalline film - Google Patents
Manufacture of polycrystalline filmInfo
- Publication number
- JPH0496216A JPH0496216A JP2205955A JP20595590A JPH0496216A JP H0496216 A JPH0496216 A JP H0496216A JP 2205955 A JP2205955 A JP 2205955A JP 20595590 A JP20595590 A JP 20595590A JP H0496216 A JPH0496216 A JP H0496216A
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- polycrystalline
- film
- polycrystalline silicon
- plasma cvd
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title description 4
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 238000005268 plasma chemical vapour deposition Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 4
- 239000010408 film Substances 0.000 abstract description 23
- 229910021420 polycrystalline silicon Inorganic materials 0.000 abstract description 18
- 239000010409 thin film Substances 0.000 abstract description 15
- 229910052710 silicon Inorganic materials 0.000 abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000010703 silicon Substances 0.000 abstract description 8
- 239000013078 crystal Substances 0.000 abstract description 7
- 239000007788 liquid Substances 0.000 abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 17
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229910052732 germanium Inorganic materials 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-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
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer 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
- Y02E10/546—Polycrystalline silicon PV cells
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野］ 本発明は多結晶膜の作製法に係わる。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for manufacturing a polycrystalline film.
多結晶シリコン薄膜を用いた太陽電池は発電効率が比較
的高く、また、多結晶シリコン薄膜の製膜も比較的低コ
ストであることから、有望視され、開発が進められてい
る。Solar cells using polycrystalline silicon thin films have relatively high power generation efficiency, and the production cost of polycrystalline silicon thin films is also relatively low, so they are viewed as promising and are being developed.
多結晶シリコン薄膜の製膜法として、本発明者らはプラ
ズマＣＶＤ法の開発を進めている。プラズマＣＶＤ法は
低温で良質の結晶薄膜を製膜できる利点がある。The present inventors are currently developing a plasma CVD method as a method for forming polycrystalline silicon thin films. The plasma CVD method has the advantage of being able to form a high-quality crystalline thin film at low temperatures.
また、熔融析出法は、化合物半導体の成長や、Ｓｉ と
Ｓｎとの合金から３１を析出させてシリコン膜を形成す
ることなどに利用されている。ＳｉとＳｎとの合金を用
いる理由は析出したＳｉ膜の電気的特性が乱されないか
らである。Further, the melt precipitation method is used for growing compound semiconductors and for forming silicon films by depositing 31 from an alloy of Si and Sn. The reason for using an alloy of Si and Sn is that the electrical characteristics of the deposited Si film are not disturbed.
多結晶シリコン薄膜を用いた太陽電池を実用化するため
には、安価な基板上に良質で結晶粒径の大きい多結晶シ
リコン薄膜を製膜する必要がある。In order to put a solar cell using a polycrystalline silicon thin film into practical use, it is necessary to form a high-quality polycrystalline silicon thin film with a large crystal grain size on an inexpensive substrate.
しかしながら、プラズマＣＶＤ法は低温で製膜できる点
で基板に耐熱性を要求しない点で有利であるが、実際に
、プラズマＣＶＤ法で結晶粒径の大きい多結晶シリコン
薄膜を製膜できる基板は限られている。例えば、ステン
レス鋼は安価な耐久性の基板であるが、ステンレス鋼の
ような異質基板上に結晶粒径の大きい多結晶シリコン薄
膜を製膜することは実際上極めて困難である。However, although the plasma CVD method is advantageous in that it can form films at low temperatures and does not require heat resistance on the substrate, there are actually a limited number of substrates on which polycrystalline silicon thin films with large crystal grain sizes can be formed using the plasma CVD method. It is being For example, although stainless steel is an inexpensive and durable substrate, it is actually extremely difficult to form a polycrystalline silicon thin film with a large crystal grain size on a foreign substrate such as stainless steel.
そこで、本発明は、異質な基板上に多結晶シリコン１ｌ
ｌｌを製膜するヘテロ成長方法を提供し、多結晶シリコ
ン薄膜を用いた太陽電池の実用化に寄与することを目的
とする。Therefore, the present invention provides 1l of polycrystalline silicon on a heterogeneous substrate.
The purpose of this study is to provide a heterogeneous growth method for forming ll, and to contribute to the practical application of solar cells using polycrystalline silicon thin films.
本発明は、上記目的を達成するために、基板上に溶融析
出法で下地多結晶層を形成し、その上にプラズマＣＶＤ
法で上層多結晶膜を成長することを特徴とする多結晶膜
のヘテロ成長方法を提供する。In order to achieve the above object, the present invention forms a base polycrystalline layer on a substrate by a melt deposition method, and then deposits a base polycrystalline layer on the base polycrystalline layer by plasma CVD.
The present invention provides a method for heterogeneous growth of a polycrystalline film, which is characterized by growing an upper polycrystalline film by a method.
すなわち、本発明は、太陽電池の所望性能を実現できる
品質の多結晶膜を異質な基板上にプラズマＣＶＤ法で成
長できるようにするために、基板上に先ず下地多結晶層
即ちバッファー層を形成し、このバッファー層の形成を
溶融析出法で行うものである。That is, the present invention first forms a base polycrystalline layer, that is, a buffer layer, on a substrate in order to grow a polycrystalline film of a quality that can realize the desired performance of a solar cell on a heterogeneous substrate by plasma CVD. However, this buffer layer is formed by a melt precipitation method.
本発明でプラズマＣＶＤ法で成長する多結晶膜の典型例
は、シリコン、ゲルマニウム、シリコン・ゲルマニウム
などである。Typical examples of polycrystalline films grown by the plasma CVD method in the present invention include silicon, germanium, and silicon-germanium.
下地多結晶膜は上層多結晶膜と格子定数が同じか近い必
要がある。すなわち、上層多結晶膜と同一材料の他、こ
れと格子定数の近い材料でも良い。The underlying polycrystalline film must have the same or similar lattice constant as the upper polycrystalline film. That is, in addition to the same material as the upper polycrystalline film, it may be made of a material with a lattice constant similar to that of the upper polycrystalline film.
例えば、上層多結晶膜としてシリコンを成長する場合、
下地層はシリコンの他、ゲルマニウム、シリコン・ゲル
マニウム、フン化カルシウムなどで形成することができ
る。格子定数が近いとは格子定数の差が５％以内をいう
。For example, when growing silicon as the upper polycrystalline film,
The base layer can be formed of germanium, silicon/germanium, calcium fluoride, etc. in addition to silicon. Close lattice constants mean that the difference in lattice constants is within 5%.
本発明において基板の種類は限定されないが、太陽電池
用基板としては、例えばアルミナのようなセラミックス
基板あるいはステンレス綱のような金属基板への適用が
望まれる。Although the type of substrate is not limited in the present invention, it is desirable to apply the present invention to a ceramic substrate such as alumina or a metal substrate such as stainless steel as a solar cell substrate.
バッファー層を形成する溶融析出法は析出させるべき元
素（化合物）とその元素（化合物）よりも低い融点をも
つ元素（化合物）との合金融液を冷却することにより、
基板表面に目的の元素（化合物）を析出させる方法であ
る。これにより、目的の元素（化合物）をその融点より
低い温度で析出させることができる。バ・７フア一層を
形成する目的は上層多結晶膜の結晶性を高めることにあ
るので、下地層の多結晶は王として結晶性（粒径）だけ
に着目すればよく、上層の結晶品質（電気的特性など）
は２次的に考慮すれば足りる。そこで、例えば、シリコ
ンを成長する場合、太陽電池に使用するためには、電気
的特性の考慮からＳｉ とＳｎの合金から析出させられ
てきたが、バッファー層にする場合には、結晶性を第一
とし、低コスト、太陽電池のＢＳＦ効果が期待できる、
Ａｆｆｉとの合金を好ましく用いることができる。また
、バッファー層上に形成する活性層を成す上層多結晶膜
はプラズマＣＶＤ法によって低温で成長するので、バッ
ファー層の純度は低くてもよい。The melt precipitation method for forming a buffer layer involves cooling a liquid mixture of an element (compound) to be precipitated and an element (compound) that has a lower melting point than that element (compound).
This is a method in which a target element (compound) is deposited on the surface of a substrate. Thereby, the target element (compound) can be precipitated at a temperature lower than its melting point. Since the purpose of forming a single layer of B.7 is to improve the crystallinity of the upper polycrystalline film, it is only necessary to focus on the crystallinity (grain size) of the polycrystalline layer of the underlayer, and the crystal quality of the upper layer ( electrical characteristics, etc.)
It is sufficient to consider it secondarily. For example, when growing silicon, it has been deposited from an alloy of Si and Sn for use in solar cells due to electrical characteristics. It is possible to expect low cost and BSF effect of solar cells.
An alloy with Affi can be preferably used. Furthermore, since the upper polycrystalline film constituting the active layer formed on the buffer layer is grown at low temperature by plasma CVD, the purity of the buffer layer may be low.
第１図に水平スライド式溶融析出装置を示す。Figure 1 shows a horizontal slide type melting and precipitation apparatus.
同図中、１は成長基板、２は融液のスライダー、３は熱
転対、４は電気炉、５はヒーター、６は真空ポンプ、７
はガス入口である。例えば、第２図を参照すると、Ｓｉ
とＡ１の合金融液は９００°Ｃから７００°Ｃまで冷
却するとき、液相線に沿ってＳｉが析出する。そこで、
７００℃の５ｉ−Ａ／！合金組成よりも多くの５ｉ−ｔ
−溶かした５ｉ−Ａ１合金融液をスライダー２に入れ、
冷却しながら基板１上をスライドさせると、基板１上に
Ｓｉが析出し、膜が形成される。In the figure, 1 is a growth substrate, 2 is a melt slider, 3 is a heat converter, 4 is an electric furnace, 5 is a heater, 6 is a vacuum pump, and 7
is the gas inlet. For example, referring to FIG.
When the alloy liquid of A1 and A1 is cooled from 900°C to 700°C, Si precipitates along the liquidus line. Therefore,
5i-A/! at 700℃! More 5i-t than alloy composition
-Pour the melted 5i-A1 alloy liquid into slider 2,
When the substrate 1 is slid while being cooled, Si is deposited on the substrate 1 to form a film.
溶融析出法で結晶性のバッファー層を形成したことによ
り、異質基板上に高品質の多結晶薄膜を成長することが
できるようになる。By forming a crystalline buffer layer using a melt deposition method, it becomes possible to grow high-quality polycrystalline thin films on heterogeneous substrates.
実施■１
基板として、シリコンウェーハ、石英ガラスを用い、バ
ッファー層として第１図の装置で多結晶シリコン膜を形
成した。Implementation 1 A silicon wafer and quartz glass were used as the substrate, and a polycrystalline silicon film was formed as a buffer layer using the apparatus shown in FIG.
融液濃度 Ｓｊ：Ａｆｆｉ＝２：８融液塩度
８００°Ｃ
基板上の温度勾配 ０．５〜２０°Ｃ／ｍｉｎこ
の実施例では、槽全体を上記の鋒温速度で析出させてい
るが、炉に温度勾配を設け、スライドボートをスライド
させ、上記の陵温速度にすることにより同様の結果が期
待できる。Melt concentration Sj:Affi=2:8 Melt salinity
800°C Temperature gradient on the substrate 0.5 to 20°C/min In this example, the entire tank was deposited at the above temperature rate, but a temperature gradient was provided in the furnace and the slide boat was slid. Similar results can be expected by using the above-mentioned temperature rate.
得られたバッファー層の多結晶シリコン膜は、ＴＥＭ観
察によると、１００，１ｕｌｌ程度の粒径であることが
認められた。基板の種類のよる差は認められなかった。According to TEM observation, the obtained polycrystalline silicon film of the buffer layer had a grain size of about 100.1 μll. No difference was observed depending on the type of substrate.
次いで、この多結晶シリコン股上にプラズマＣＶＤ法で
多結晶シリコン薄膜を成長した。その条件は下記の通り
とした。Next, a polycrystalline silicon thin film was grown on this polycrystalline silicon layer by plasma CVD. The conditions were as follows.
供給ガス
ＳｉＨ４０，５〜２０ ｓｃｃ＋ｗ
Ｈｚ Ｏ〜１００ｓｃｃｍ１００５
ｃ 〜５０ ｓｅｃｍ
圧力 ０．１〜Ｉ Ｔｏｒｎ電力密度
１０〜５００ｗ１Ｗ／ｃシこうして得られ
た多結晶シリコン薄膜は、ＴＥＭ観察によると１００庫
程度の粒径であり、また結晶の品質は良好であることが
認、められた。Supply gas SiH40,5~20scc+w Hz O~100sccm1005
c ~ 50 sec Pressure 0.1 ~ I Torn Power Density 10 ~ 500 W/c According to TEM observation, the polycrystalline silicon thin film thus obtained has a grain size of about 100 cm, and the crystal quality is good. This was recognized.
ことができ、多結晶薄膜を用いた太陽電池の実用化に寄
与する。This will contribute to the practical application of solar cells using polycrystalline thin films.
第１図は溶融析出装置の模式図、第２図はＡ１−３ｉ合
金の状態図
である。
１・・・基板、 ２・・・スライダー３・・
・熱転対、 ４・・・電気炉、５・・・ヒーター
６・・・真空ポンプ、７・・・ガス入口。
〔発明の効果］
以上の如く、本発明によれば、良質でかつ結晶粒径の大
きい多結晶薄膜を異質基板上に成長するＳ＋＊千％
第１図
Ａｆ −５ｌ系平衡状態図
隼２図FIG. 1 is a schematic diagram of a melting precipitation apparatus, and FIG. 2 is a state diagram of the A1-3i alloy. 1... Board, 2... Slider 3...
- Heat converter, 4... Electric furnace, 5... Heater, 6... Vacuum pump, 7... Gas inlet. [Effects of the Invention] As described above, according to the present invention, a polycrystalline thin film of good quality and large crystal grain size can be grown on a heterogeneous substrate.
Claims (1)
上にプラズマＣＶＤ法で上層多結晶膜を成長することを
特徴とする多結晶膜のヘテロ成長方法。1. A method for heterogeneous growth of a polycrystalline film, which is characterized in that a base polycrystalline layer is formed on a substrate by a melt deposition method, and an upper polycrystalline film is grown thereon by a plasma CVD method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2205955A JPH0496216A (en) | 1990-08-04 | 1990-08-04 | Manufacture of polycrystalline film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2205955A JPH0496216A (en) | 1990-08-04 | 1990-08-04 | Manufacture of polycrystalline film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0496216A true JPH0496216A (en) | 1992-03-27 |
Family
ID=16515471
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2205955A Pending JPH0496216A (en) | 1990-08-04 | 1990-08-04 | Manufacture of polycrystalline film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0496216A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5212119A (en) * | 1990-11-28 | 1993-05-18 | Hyundai Electronics Industries Co., Ltd. | Method for maintaining the resistance of a high resistive polysilicon layer for a semiconductor device |
-
1990
- 1990-08-04 JP JP2205955A patent/JPH0496216A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5212119A (en) * | 1990-11-28 | 1993-05-18 | Hyundai Electronics Industries Co., Ltd. | Method for maintaining the resistance of a high resistive polysilicon layer for a semiconductor device |
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