JPH0611645B2 - Method for forming amorphous thin film - Google Patents
Method for forming amorphous thin filmInfo
- Publication number
- JPH0611645B2 JPH0611645B2 JP61179149A JP17914986A JPH0611645B2 JP H0611645 B2 JPH0611645 B2 JP H0611645B2 JP 61179149 A JP61179149 A JP 61179149A JP 17914986 A JP17914986 A JP 17914986A JP H0611645 B2 JPH0611645 B2 JP H0611645B2
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- layer
- thin film
- amorphous thin
- forming
- 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
- 239000010409 thin film Substances 0.000 title claims description 16
- 238000000034 method Methods 0.000 title claims description 11
- 239000000758 substrate Substances 0.000 claims description 28
- 208000028659 discharge Diseases 0.000 description 17
- 239000010408 film Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 150000001768 cations Chemical class 0.000 description 8
- 229910021417 amorphous silicon Inorganic materials 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 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
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 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
- 230000001052 transient effect Effects 0.000 description 1
- 238000007740 vapor deposition Methods 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
Landscapes
- Silicon Compounds (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Chemical Vapour Deposition (AREA)
- Photovoltaic Devices (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、非晶質薄膜の形成方法に関し、特に太陽電
池、薄膜半導体、電子感光体や光センサ等の各種電子デ
バイスに使用される非晶質薄膜の形成方法に係わる。Description: TECHNICAL FIELD The present invention relates to a method for forming an amorphous thin film, and in particular, it is used for various electronic devices such as solar cells, thin film semiconductors, electrophotosensitive members, and optical sensors. The present invention relates to a method for forming a crystalline thin film.
［従来の技術］ アモルファスシリコンに代表される非晶質薄膜の形成に
は、グロー放電プラズマを用いる、いわゆるプラズマＣ
ＶＤによる方法が数多く提案されている。[Prior Art] A glow discharge plasma is used to form an amorphous thin film typified by amorphous silicon, so-called plasma C
Many methods based on VD have been proposed.
例えば、アモルファス太陽電池は通常、第２図に示す構
造になっている。即ち、図中の１はガラス等からなる基
板であり、この基板１上には透明な伝導膜２が被覆され
ている。この伝導膜２は、酸化インジウムと酸化スズの
混合物からなるＩＴＯと呼ばれる層とＳｎＯ２とで構成
され、スパッタリングや熱ＣＶＤ等により堆積される。
前記伝導膜２上には、ｐ層３、ｉ層４、ｎ層５の３つの
層からなるアモルファスシリコンが後述するプラズマＣ
ＶＤ装置等により夫々堆積されている。前記ｎ層５上に
は、アルミニウムや銀等からなる薄膜電極６が真空蒸着
等により堆積されている。For example, an amorphous solar cell usually has the structure shown in FIG. That is, reference numeral 1 in the drawing is a substrate made of glass or the like, and a transparent conductive film 2 is coated on the substrate 1. The conductive film 2 is composed of a layer called ITO made of a mixture of indium oxide and tin oxide and SnO 2, and is deposited by sputtering, thermal CVD or the like.
Amorphous silicon composed of three layers of a p-layer 3, an i-layer 4 and an n-layer 5 is formed on the conductive film 2 by plasma C described later.
Each is deposited by a VD device or the like. A thin film electrode 6 made of aluminum, silver or the like is deposited on the n layer 5 by vacuum vapor deposition or the like.
前記アモルファスシリコンを堆積するためのプラズマＣ
ＶＤ装置は、第３図に示す構造になっている。図中の１
１は、反応容器であり、この容器１１には一対の電極１
２、１３が対向して取付けられている。前記一方の電極
１２は、高周波電源１４に接続されている。また、図中
の１５は前記反応容器１１内を排気する真空ポンプ、１
６は前記基板１を載せる支持台、１７は基板１を加熱す
るヒータ、１８は層形成用の原料ガスの導入管である。
このようなＣＶＤ装置により前記ｐ層３を形成するに
は、まず、支持台１６上に基板１を載置し、真空ポンプ
１５を作動して反応容器１１内を排気しながらシランガ
ス（ＳｉＨ４）と不純物とてのジボラン（Ｂ２Ｈ６）や
カーバイトとするためのメタン（ＣＨ４）等を導入管１
８を通して反応容器１１に導入した後、ヒータ１７によ
り基板１を加熱しながら高周波電源１４により電極１
２、１３間に例えば１３．５ＭHzの高周波電圧を印加
し、グロー放電プラズマを発生させる。この時、シラン
ガス等は電極１２、１３間のグロー放電空間で分解され
中性ラジカルが発生して基板１上のｐ層３が形成され
る。また、ｉ層４を形成するにはシランガスのみを導入
し、ｎ層５を形成するにはシランガスとフォスフィン
（ＰＨ３）を導入する。なお、ｐ層の形成にはガス濃度
によるが大体１分間程度必要とし、ｉ層の形成には１時
間程度、ｎ層の形成には３分間程度必要である。Plasma C for depositing the amorphous silicon
The VD device has the structure shown in FIG. 1 in the figure
Reference numeral 1 denotes a reaction container, and a container 11 has a pair of electrodes 1
2 and 13 are attached to face each other. The one electrode 12 is connected to a high frequency power supply 14. Reference numeral 15 in the figure is a vacuum pump for exhausting the inside of the reaction vessel 11,
Reference numeral 6 is a support table on which the substrate 1 is placed, 17 is a heater for heating the substrate 1, and 18 is an introduction pipe of a raw material gas for forming a layer.
In order to form the p-layer 3 using such a CVD apparatus, first, the substrate 1 is placed on the support 16 and the vacuum pump 15 is operated to exhaust the inside of the reaction vessel 11 and silane gas (SiH 4 ). And diborane (B 2 H 6 ) as an impurity, methane (CH 4 ) for forming a carbide, etc.
After being introduced into the reaction vessel 11 through 8, the substrate 1 is heated by the heater 17 and the electrode 1 is fed by the high frequency power source 14.
A high-frequency voltage of, for example, 13.5 MHz is applied between 2 and 13 to generate glow discharge plasma. At this time, the silane gas or the like is decomposed in the glow discharge space between the electrodes 12 and 13 to generate neutral radicals, and the p-layer 3 on the substrate 1 is formed. Further, only silane gas is introduced to form the i layer 4, and silane gas and phosphine (PH 3 ) are introduced to form the n layer 5. It should be noted that it takes about 1 minute to form the p layer, depending on the gas concentration, about 1 hour to form the i layer, and about 3 minutes to form the n layer.
［発明が解決しようとする問題点］ 上述した従来の装置では、グロー放電プラズマにより中
性ラジカルの他に、Ｈ＋やＳｉＨ＋の陽イオンが発生す
る。これらの陽イオンは、高周波電界によって加速さ
れ、膜表面を直撃する。その結果、膜内の欠陥準位が増
加する。[Problems to be Solved by the Invention] In the conventional device described above, H + and SiH + cations are generated in addition to neutral radicals by glow discharge plasma. These cations are accelerated by the high frequency electric field and hit the film surface directly. As a result, the defect level in the film increases.
また、グロー放電により発生するプラズマは、過渡状態
を経た後に定常状態に移行する。即ち、放電開始直後に
ＳｉＨラジカル濃度に急激な立ち上がりが生じた後に定
常状態になるので、形成され膜にゆらぎが生じることに
なる。Further, the plasma generated by glow discharge transits to a steady state after passing through a transient state. That is, since the SiH radical concentration rises sharply immediately after the start of discharge and then enters a steady state, fluctuations occur in the formed film.
このような現象は、非晶質薄膜をプラズマＣＶＤにより
形成する時の大きな問題になるが、特にアモルファスシ
リコン太陽電池においては伝導膜とｐ層又はｐ層とｉ層
の界面付近の欠陥が素子特性の劣化につながる。Such a phenomenon becomes a big problem when an amorphous thin film is formed by plasma CVD. In particular, in an amorphous silicon solar cell, a defect near the interface between the conductive film and the p layer or the p layer and the i layer is a device characteristic. Will lead to deterioration.
本発明は、上記従来の問題点を解決するためになされた
もので、膜形成時の陽イオンの衝撃を緩和すると共にＳ
ｉＨラジカル等の濃度の急激な立上がりを防止し得る非
晶質薄膜の形成方法を提供しようとするものである。The present invention has been made in order to solve the above-mentioned conventional problems, and alleviates the impact of cations at the time of film formation and S
An object of the present invention is to provide a method for forming an amorphous thin film capable of preventing a sharp rise in the concentration of iH radicals and the like.
［問題点を解決するための手段］ 本発明は、グロー放電プラズマを用いて基板上へ非晶質
薄膜を形成する方法において、グロー放電開始時から少
なくとも３０秒間前記基板を正の電荷に帯電させること
を特徴とする非晶質薄膜の形成方法である。[Means for Solving the Problems] The present invention relates to a method of forming an amorphous thin film on a substrate by using glow discharge plasma, wherein the substrate is charged with a positive charge for at least 30 seconds after the start of glow discharge. And a method for forming an amorphous thin film.
［作用］ 本発明では、非晶質薄膜の形成に際してグロー放電開始
時から少なくとも３０秒間基板を正の電荷に帯電させる
ので、膜形成初期の段階において陽イオンが基板の電界
により押し戻される形となり、非晶質薄膜形成界面での
陽イオンの衝撃が緩和される。また、基板側を正に帯電
させることによりＳｉＨラジカル濃度が下がり、代わっ
てＳｉＨ２濃度が上昇するので、放電初期のＳｉＨラジ
カル濃度の急激な立ち上がりが防止される。[Operation] In the present invention, since the substrate is charged with a positive charge for at least 30 seconds from the start of glow discharge in forming the amorphous thin film, cations are pushed back by the electric field of the substrate in the initial stage of film formation, The impact of cations at the amorphous thin film forming interface is relaxed. In addition, since the SiH radical concentration is decreased by positively charging the substrate side and the SiH 2 concentration is increased instead, the abrupt rise of the SiH radical concentration at the initial stage of discharge is prevented.
［発明の実施例］ 以下、本発明の実施例を第１図のプラズマＣＶＤ装置を
参照して説明する。なお、第１図において前述した第３
図と同様な部材は同符号を付して説明を省略する。[Embodiment of the Invention] An embodiment of the present invention will be described below with reference to the plasma CVD apparatus shown in FIG. In addition, the above-mentioned third in FIG.
The same members as those shown in the figure are designated by the same reference numerals and the description thereof will be omitted.
図中の１９は、支持台１６上に載置される基板１に正の
電荷を帯電させるための直流電源であり、この電源１９
のプラス側は金属製の支持台１６に接続され、マイナス
側はガス入口付近の所定の箇所に接続されている。Reference numeral 19 in the figure denotes a DC power supply for charging the substrate 1 mounted on the support 16 with positive charges.
The plus side is connected to the metal support 16 and the minus side is connected to a predetermined location near the gas inlet.
次に、基板上にｉ層を形成する方法を同第１図図示の装
置を参照して説明する。Next, a method of forming the i layer on the substrate will be described with reference to the apparatus shown in FIG.
まず、基板１を支柱台１６上に載置し、真空ポンプ１５
を作動して反応容器１１内を排気しながらシランガス
（ＳｉＨ４）を導入管１８を通して反応容器１１に導入
した後、ヒータ１７により基板１を加熱しながら高周波
電源１４により電極１２、１３間に例えば１３．５ＭHz
の高周波電圧を印加し、グロー放電プラズマを発生させ
た。この放電開始と同時に直流電源１９により基板１に
＋１５０Ｖの電圧を加え、１０秒後、又は２０秒後と１
０秒間きざみで電源１９からの電圧供給を停止して基板
上にｉ層を形成した。First, the substrate 1 is placed on the support stand 16, and the vacuum pump 15
Silane gas (SiH 4 ) is introduced into the reaction vessel 11 through the introduction pipe 18 while activating the inside of the reaction vessel 11 while evacuating the inside of the reaction vessel 11, and then the substrate 1 is heated by the heater 17 while the substrate 1 is heated by the high frequency power source 14 between the electrodes 12 and 13. 13.5 MHz
Was applied to generate glow discharge plasma. Simultaneously with the start of this discharge, a voltage of +150 V is applied to the substrate 1 by the DC power supply 19 and after 10 seconds or 20 seconds, 1
The voltage supply from the power supply 19 was stopped at intervals of 0 second to form an i-layer on the substrate.
しかして、堆積されたｉ層における基板への正の電荷を
帯電する時間とダメージ発生等の関係を調べたところ、
放電開始時から３０秒間より早い時期に基板への正の帯
電を停止した場合には陽イオンの直撃によるｉ層のダメ
ージ及びＳｉＨラジカル濃度の急激な立ち上がりの影響
を防止することができなかった。これに対し、放電開始
時から３０秒間以上の間基板に正の電荷を帯電させた場
合には、陽イオンの直撃によるｉ層のダメージ及びＳｉ
Ｈラジカル濃度の急激な立ち上がりの影響を防止するこ
とができた。但し、基板への正の電荷の帯電が放電開始
時から３分間を越えると、性能の向上はない。このた
め、生産性の問題又は不純物の熱拡散による素子劣化を
考慮すると、放電開始時から３分間が経過する前に基板
への正の帯電を停止し、ＳｉＨラジカル濃度を上昇させ
て膜形成スピードを早めた方がよいと思われる。Then, when the relationship between the time for charging positive charges to the substrate in the deposited i layer and the occurrence of damage, etc. was investigated,
When the positive charging of the substrate was stopped earlier than 30 seconds after the start of discharge, it was not possible to prevent the damage of the i layer and the rapid rise of the SiH radical concentration due to the direct impact of cations. On the other hand, when the substrate is charged with a positive charge for 30 seconds or more after the start of discharge, damage to the i layer due to direct impact of cations and Si
It was possible to prevent the effect of a sharp rise in the H radical concentration. However, if the positive charge on the substrate exceeds 3 minutes after the start of discharge, there is no improvement in performance. Therefore, considering the problem of productivity or element deterioration due to thermal diffusion of impurities, positive charging of the substrate is stopped before 3 minutes have elapsed from the start of discharge, the SiH radical concentration is increased, and the film formation speed is increased. I think it is better to speed up.
また、放電開始時から３０秒間以上の間基板に正の電荷
を帯電させる条件にてガラス基板の伝導膜上にｐ層、ｉ
層、ｎ層を形成することにより得たアモルファスシリコ
ン太陽電池では、従来法で形成した同太陽電池に比べて
短絡電流及び曲線因子を増大でき、光電変換効率が３乃
至４％改善された。Further, under the condition that the substrate is positively charged for 30 seconds or more after the start of discharge, the p layer, i
In the amorphous silicon solar cell obtained by forming the layer and the n-layer, the short-circuit current and the fill factor can be increased, and the photoelectric conversion efficiency is improved by 3 to 4%, as compared with the solar cell formed by the conventional method.
［発明の効果］ 以上詳述した如く、本発明によれば膜形成時の陽イオン
の衝撃を緩和すると共にＳｉＨラジカル等の濃度の急激
な立上がりを防止でき、ひいては太陽電池、薄膜半導
体、電子写真感光体や光センサ等の各種の電子デバイス
に好適な非晶質薄膜の形成方法を提供できる。[Effects of the Invention] As described in detail above, according to the present invention, it is possible to mitigate the impact of cations during film formation and prevent a sharp rise in the concentration of SiH radicals, etc., and thus a solar cell, a thin film semiconductor, and an electrophotography. A method for forming an amorphous thin film suitable for various electronic devices such as a photoconductor and an optical sensor can be provided.
【図面の簡単な説明】 第１図は本発明の実施例に使用されるプラズマＣＶＤ装
置の一形態を示す概略図、第２図は一般的なアモルファ
スシリコン太陽電池を示す概略図、第３図は従来のプラ
ズマＣＶＤ装置を示す概略図である。 １……基板、３……ｐ層、４……ｉ層、５……ｎ層、１
１……反応容器、１２、１３……電極、１４……高周波
電源、１６……支持台、１９……直流電源。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing one form of a plasma CVD apparatus used in an embodiment of the present invention, FIG. 2 is a schematic view showing a general amorphous silicon solar cell, and FIG. FIG. 3 is a schematic diagram showing a conventional plasma CVD apparatus. 1 ... Substrate, 3 ... p layer, 4 ... i layer, 5 ... n layer, 1
1 ... Reaction vessel, 12, 13 ... Electrode, 14 ... High frequency power source, 16 ... Supporting base, 19 ... DC power source.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭62−81021（ＪＰ，Ａ) 特開 昭59−39713（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP 62-81021 (JP, A) JP 59-39713 (JP, A)
Claims (1)
質薄膜を形成する方法において、グロー放電開始時から
３０秒間以上、３分間以内の間、前記基板を正の電荷に
帯電させることを特徴とする非晶質薄膜の形成方法。1. A method of forming an amorphous thin film on a substrate using glow discharge plasma, comprising charging the substrate to a positive charge for 30 seconds or more and 3 minutes or less from the start of glow discharge. A method for forming a characteristic amorphous thin film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61179149A JPH0611645B2 (en) | 1986-07-30 | 1986-07-30 | Method for forming amorphous thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61179149A JPH0611645B2 (en) | 1986-07-30 | 1986-07-30 | Method for forming amorphous thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6336522A JPS6336522A (en) | 1988-02-17 |
| JPH0611645B2 true JPH0611645B2 (en) | 1994-02-16 |
Family
ID=16060820
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61179149A Expired - Lifetime JPH0611645B2 (en) | 1986-07-30 | 1986-07-30 | Method for forming amorphous thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0611645B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63312852A (en) * | 1987-06-16 | 1988-12-21 | Brother Ind Ltd | Piezoelectric element drive type impact print head |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5939713A (en) * | 1982-08-29 | 1984-03-05 | Agency Of Ind Science & Technol | Thin silicon film containing crystallite and its manufacture |
| JPS6281021A (en) * | 1985-10-04 | 1987-04-14 | Fuji Electric Co Ltd | Apparatus for manufacturing thin film semiconductor |
-
1986
- 1986-07-30 JP JP61179149A patent/JPH0611645B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63312852A (en) * | 1987-06-16 | 1988-12-21 | Brother Ind Ltd | Piezoelectric element drive type impact print head |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6336522A (en) | 1988-02-17 |
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