JPS5976419A - Manufacture of p type silicon film - Google Patents

Manufacture of p type silicon film

Info

Publication number
JPS5976419A
JPS5976419A JP57186754A JP18675482A JPS5976419A JP S5976419 A JPS5976419 A JP S5976419A JP 57186754 A JP57186754 A JP 57186754A JP 18675482 A JP18675482 A JP 18675482A JP S5976419 A JPS5976419 A JP S5976419A
Authority
JP
Japan
Prior art keywords
silicon film
type silicon
vacuum chamber
doping
doped
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
Application number
JP57186754A
Other languages
Japanese (ja)
Other versions
JPS6361768B2 (en
Inventor
Sunao Matsubara
松原　直
Juichi Shimada
嶋田　寿一
Masatoshi Utaka
正俊 右高
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
National Institute of Advanced Industrial Science and Technology AIST
Original Assignee
Agency of Industrial Science and Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Agency of Industrial Science and Technology filed Critical Agency of Industrial Science and Technology
Priority to JP57186754A priority Critical patent/JPS5976419A/en
Publication of JPS5976419A publication Critical patent/JPS5976419A/en
Publication of JPS6361768B2 publication Critical patent/JPS6361768B2/ja
Granted legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02524—Group 14 semiconducting materials
    • H01L21/02532—Silicon, silicon germanium, germanium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/0257—Doping during depositing
    • H01L21/02573—Conductivity type
    • H01L21/02576—N-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/0257—Doping during depositing
    • H01L21/02573—Conductivity type
    • H01L21/02579—P-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Photovoltaic Devices (AREA)

Abstract

PURPOSE:To improve doping efficiency by a method wherein a metal Ga as a source for doping material is vaporized with resistance heating to be doped into an Si film. CONSTITUTION:A vacuum chamber 1 enclosed by a bell jar 2 is exhausted through an exhaustion system 3. Then, a crucible 5 including therein a metal Ga is heated and a substrate holder 7 heating a substrate 6 is also heated simultaneously. When the temperature reaches a given level, silane gas is introdueced into the vacuum chamber 1 through a gas introduction system 8. Subsequently, high frequency voltage 9 is applied and a shutter 10 for the Ga 4 is opened. The interior of the vacuum chamber 1 is brought into the plasma state and Ga vapor is ismultaneously diffused into the plasma, so that, when silane gas is decomposed and separated, Ga mixes into Si and a P type Si film is deposited on the substrate. Ga has a larger ion radius than B and is hard to move and come loose with respect to the surrounding Si group in point of crystal structure, whereby doping efficiency is improved using the Ga dope.

Description

【発明の詳細な説明】 本発明は、プラズマグロー放電法でｐ型シリコン膜を製
造する際にドープ剤に金属ガリウムを用いたｐ型シリコ
ン膜の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a p-type silicon film using metal gallium as a dopant when manufacturing the p-type silicon film by a plasma glow discharge method.

従来は、ｐ型シリコン膜の形成はプラズマグロー放電法
やスパッタ法を用いて、シラン（ＳｉＨ４）や四フッ化
シリコン（ＳｉＦ４）を分解させ、ドープ剤としてジボ
ラン（Ｂ２Ｈ６）を添加して行なわれていた。この従来
法は、Ｂ２Ｈ６がガス状態であり、）’−７’剤（７）
ボロン（Ｂ）の添加が簡単にできる特徴がある。しかし
ながら、得られたｐ型シリコン膜に対するＢのドーピン
グ効率が低いという欠点があった。さらに、Ｂドープの
ｐ型シリコン膜の光の透過率は可視光領域においてその
透過率が小さく光の吸収係数が太きいという欠点もあっ
た。Conventionally, a p-type silicon film was formed by decomposing silane (SiH4) or silicon tetrafluoride (SiF4) using a plasma glow discharge method or sputtering method, and adding diborane (B2H6) as a dopant. was. In this conventional method, B2H6 is in a gaseous state, and the )'-7' agent (7)
It has the feature that boron (B) can be easily added. However, there was a drawback that the doping efficiency of B into the obtained p-type silicon film was low. Furthermore, the B-doped p-type silicon film has a drawback in that its light transmittance is low in the visible light region and its light absorption coefficient is large.

プラズマグロー放電法で作製したＢドープｐ型シリコン
膜は光起電力効果を応用した太陽電池に利用されており
、この太陽電池においては、該ｐ型シリコン膜は、（太
陽光の入射する側の）窓側材料として使用される。Ｂド
ープｐ型シリコン膜は、Ｂのドーピング効率が低いこと
から多量のＢがドーピングされ、その結果、光の吸収係
数が大きくなる欠点があった。太陽電池の光電変換効率
の向上のためには、窓側材料として光吸収係数の小さい
ｐ型シリコン膜の形成が望ましく、必然的にｐ型シリコ
ン膜を薄くして、光吸収係数の大きいことを補う施策が
された。しかしながら、膜を薄くすると太陽電池として
の直列抵抗成分が増加することになり、光電変換効率の
低下の要因となる。A B-doped p-type silicon film produced by the plasma glow discharge method is used in a solar cell that applies the photovoltaic effect, and in this solar cell, the p-type silicon film is ) Used as window side material. The B-doped p-type silicon film has a drawback that a large amount of B is doped because the B doping efficiency is low, and as a result, the light absorption coefficient becomes large. In order to improve the photoelectric conversion efficiency of solar cells, it is desirable to form a p-type silicon film with a small light absorption coefficient as the window side material, and it is necessary to make the p-type silicon film thinner to compensate for the large light absorption coefficient. Measures were taken. However, when the film is made thinner, the series resistance component of the solar cell increases, which causes a decrease in photoelectric conversion efficiency.

本発明の目的は、ｐ型シリコン膜の太陽電池への適用を
考慮し、ｐ型シリコン膜へのドープ剤のドーピング効率
の向上および該ｐ型シリコン膜の光吸収係数の低減を重
視する視点に立って、新規・なｐ型シリコン膜の製造方
法を提供することにある。The purpose of the present invention is to take into consideration the application of p-type silicon films to solar cells, and to focus on improving the doping efficiency of dopants into p-type silicon films and reducing the light absorption coefficient of the p-type silicon films. The purpose of this invention is to provide a novel method for manufacturing p-type silicon films.

上記目的を達成するだめの本発明の構成は、ドープ剤の
ソースとしての金属ガリウムを抵抗加熱によシ蒸気化し
、シリコン膜中にガリウムをドーピングさせることにあ
る。The structure of the present invention to achieve the above object is to vaporize metallic gallium as a source of a dopant by resistance heating, thereby doping gallium into a silicon film.

すなわち、ｐ型シリコン膜のドープ剤としての１・、 Ｂ　２　Ｈａにｆわり、新たに金属ガリウムを抵抗加勢
方式によシ蒸発させ、該膜中にガリウムをドーピングす
るｐ型シリコン膜の製造方法である。That is, a method for producing a p-type silicon film, in which metal gallium is newly evaporated by a resistive addition method in place of 1., B 2 Ha as a dopant for the p-type silicon film, and the film is doped with gallium. It is.

第１図は本発明に使用した装置の概略図でちる。FIG. 1 is a schematic diagram of the apparatus used in the present invention.

以下、図を用いて具体的に説明する。ペルジャー２によ
って囲まれた真空室１内を排気系３により１０−ＩＩＴ
Ｏｒｒ程度以下の真空度に排気する。金属ガリウム４の
入ったルツボ５を加熱し、同時に基板６を加熱する基板
ホルダー７も加熱する。所定の温度になったら、ガス導
入系８によシンラン（ｓｅＨｔ）ガスを真空室内へ導入
し、プラズマグロー放電が可能な圧力（０，１Ｔｏｒｒ
程度）にする。This will be explained in detail below using figures. The inside of the vacuum chamber 1 surrounded by the Pelger 2 is evacuated by the exhaust system 3 to 10-IIT.
Evacuate to a degree of vacuum of about Orr or less. The crucible 5 containing the metal gallium 4 is heated, and at the same time, the substrate holder 7 that heats the substrate 6 is also heated. When the temperature reaches a predetermined temperature, synlan (seHt) gas is introduced into the vacuum chamber by the gas introduction system 8, and the pressure (0.1 Torr) is set at which plasma glow discharge is possible.
degree).

高周波電源９によシプラズマグロー放電を開始すると同
時に金属ガリウム４のシャッター１０を開放し、プラズ
マ中にＱａ蒸気を導入しｐ型シリコン膜の形成を行なう
。At the same time as plasma glow discharge is started by the high frequency power source 9, the shutter 10 of the metal gallium 4 is opened, Qa vapor is introduced into the plasma, and a p-type silicon film is formed.

本発明の製造方法は、上記のような装置によって行なわ
れているが、これは−例であり、装置自体としては上記
のものに限らず種々の変形や改良が可能である。Although the manufacturing method of the present invention is carried out using the above-mentioned apparatus, this is just an example, and the apparatus itself is not limited to the above-mentioned one, and various modifications and improvements can be made.

尚、本発明の製造方法によシ得られたｐ型シリコン膜の
室温暗室導度δＤ１および光吸収係数αを測定すること
により、Ｇａのドーピング量との間の関係を第２図およ
び第３図に示す。第２図および第３図において、実線で
示しだ曲線ａおよびＣはＧａをドーピングした場合で、
破線で示した曲線すおよびｄは比較のだめ従来法による
Ｂ　２　ＨｅをドーピングガスとしてＢをドープした場
合である。第２図の曲線ａのＧａをドープしたｐ型シリ
コン膜の室温暗室導度δＤは、Ｂをドープしたｐ型シリ
コン膜の曲線すよりも、少ないドーピング量で同程度の
電導度が得られている。この結果より、従来法のＢドー
ピングよυも本発明によるＱａミド−ピング方がよりド
ーピング効率が高ぐＶｌｆＦ／、を本発明によってドー
ピングされたＧｌの活性化率がＢよりも高いことが判明
した。By measuring the room temperature dark room conductivity δD1 and the light absorption coefficient α of the p-type silicon film obtained by the manufacturing method of the present invention, the relationship between the amount of Ga doping and the amount of Ga doping is shown in FIGS. 2 and 3. As shown in the figure. In FIGS. 2 and 3, curves a and C shown by solid lines are for the case where Ga is doped,
For comparison, the curves d and d shown by broken lines are the case where B is doped using B 2 He as the doping gas according to the conventional method. The room temperature dark room conductivity δD of the Ga-doped p-type silicon film shown by curve a in FIG. 2 is similar to that of the B-doped p-type silicon film with a smaller doping amount. There is. From this result, it is clear that the doping efficiency of Qa mid-doping according to the present invention is higher than that of B doping using the conventional method. did.

第３図は、室温暗室導度δＤがＩ　Ｘ　１Ｏ−４（Ω・
ｃｍ）−’であるＧ′ａドープ及びＢドープの、それぞ
れのシリコン膜の光吸収係数αについて示したものであ
り、Ｇａドープしたシリコン膜の曲線ＣがＢドープのシ
リコン膜の曲線ｄよシも吸収係数が小さくなっている。Figure 3 shows that the room temperature dark room conductivity δD is I x 1O-4 (Ω・
cm)-' for each G'a-doped and B-doped silicon film, and the curve C for the Ga-doped silicon film is different from the curve d for the B-doped silicon film. The absorption coefficient is also small.

この結果は、ｐ型シリコン膜を太陽電池の窓側材料とし
て使用する場合は、従来法のＢドープしたシリコン膜よ
りもＧａドープしたシリコ／膜の方が適していることを
示唆する。This result suggests that Ga-doped silico/film is more suitable than conventional B-doped silicon film when p-type silicon film is used as a window material for solar cells.

Ｇａドープによりドーピング効率が向上した要因として
は、ＢよりもＧａがイオン半径が大きく、結晶構造的に
周辺のシリコン群に対して動きにくくかつ、ぬけにくく
なっているためである。また、Ｂドーピングの場合は、
ドーピングするＢの量が少量であるとシリコン群に対し
Ｂが三配位に位置し、多量のドーピングで四配位に位置
することによりアクセプターとして挙動するが、Ｇａの
場合は、少量のドーピングでもシリコン群に対し四配位
に位置することによシト−ピング効率が向上したもので
ある。The reason why the doping efficiency is improved by Ga doping is that Ga has a larger ionic radius than B, and its crystal structure makes it difficult to move and escape from the surrounding silicon group. In addition, in the case of B doping,
If the amount of B doped is small, B will be located in the tri-coordination with respect to the silicon group, and if it is doped in a large amount, it will be located in the tetra-coordination, thereby acting as an acceptor. However, in the case of Ga, even a small amount of doping The cytoping efficiency is improved by being located in a four-coordinate position with respect to the silicon group.

以下に本発明の実施例を具体的に述べる。Examples of the present invention will be specifically described below.

実施例 前記第１図を使用して説明すると、ペルジャー２によっ
て囲まれた真空室１を排気系３によって一旦１０−５Ｔ
Ｏｒｒ以下の真空度に排気する。次に、金属ガリウム４
が２ｇ入ったルツボ５を９１０Ｃに加熱し、同時に基板
６を加熱する基板ホルダー７を２２０Ｃに加熱保持し、
真空室１内を１×１０−’　ＴＯｒｒとする。所定の温
度になったら、ガス導入系８によりシラン（ＳｉＨ４）
ガスを真空室１内に導入し、真空室内圧力が０．１Ｔｏ
ｒｒになるようにする。引き続き、周波数１３．５６Ｍ
Ｈｚの高周波電圧９を印加し、さらに、金属ガリウム４
のシャッター１０を開放する。真空室１内をプラズマ状
態にすると同時にそのプラズマ中にＱａ蒸気を拡散させ
、シラン（ＳｉＨ４）ガスが分解し析出する際にシリコ
ン中にＱａが混入し、ｐ型シリコン膜が基板上に析出す
る。Embodiment To explain using FIG.
Evacuate to a vacuum level of Orr or less. Next, metal gallium 4
The crucible 5 containing 2 g of
The inside of the vacuum chamber 1 is set to 1×10 −' TOrr. When the predetermined temperature is reached, silane (SiH4) is introduced by the gas introduction system 8.
Gas is introduced into the vacuum chamber 1, and the pressure in the vacuum chamber is 0.1To.
Make it rr. Continued frequency 13.56M
A high frequency voltage 9 of Hz is applied, and metal gallium 4
The shutter 10 of is opened. At the same time as the inside of the vacuum chamber 1 is brought into a plasma state, Qa vapor is diffused into the plasma, and when silane (SiH4) gas decomposes and precipitates, Qa is mixed into the silicon, and a p-type silicon film is precipitated on the substrate. .

得られたｐ型シリコン膜の室温暗室導度は、第２図に示
したごとく、Ｇａのドーピング量と密接な関係にある。The room temperature dark room conductivity of the obtained p-type silicon film is closely related to the amount of Ga doping, as shown in FIG.

そのＧａのドーピング量の制御は金属ガリウム４の蒸気
圧のコントロールで行なわれ、金属ガリウム４のチャー
ジ量と加熱温度で制御する。The amount of Ga doping is controlled by controlling the vapor pressure of the metal gallium 4, and is controlled by the amount of charge of the metal gallium 4 and the heating temperature.

【図面の簡単な説明】[Brief explanation of the drawing]

第１図は本発明に使用したｐ型シリコン膜の製造装置の
概略図、第２図はドーピング量に対するｐ型シリコン膜
の室温暗室導度との関係を示す特性図、第３図はホトン
エネルギーに対する光の吸収係数との関係を示す特性図
でおる。 １・・・真空室、４・・・金属ガリウム、５・・・ルツ
ボ、６・・・基板、７・・・基板ホルダー、８・・・ガ
ス導入系、１０・・・シャック−０Figure 1 is a schematic diagram of the p-type silicon film manufacturing apparatus used in the present invention, Figure 2 is a characteristic diagram showing the relationship between the doping amount and the room temperature dark room conductivity of the p-type silicon film, and Figure 3 is the photon energy. This is a characteristic diagram showing the relationship between the light absorption coefficient and the light absorption coefficient. DESCRIPTION OF SYMBOLS 1... Vacuum chamber, 4... Metal gallium, 5... Crucible, 6... Substrate, 7... Substrate holder, 8... Gas introduction system, 10... Shack-0

Claims (1)

【特許請求の範囲】[Claims] １、プラズマグロー放電法を用いたｐ型シリコン膜の製
造方法において、ドープ剤のソースに金属ガリウムを用
い、該金属ガリウムを抵抗加熱によシ蒸気化し、シリコ
ン膜中にガリウムをドーピングすることを特徴としたｐ
型シリコン膜の製造方法。1. In a method for manufacturing a p-type silicon film using a plasma glow discharge method, metal gallium is used as a dopant source, and the metal gallium is vaporized by resistance heating to dope the silicon film with gallium. Featured p
Method for manufacturing mold silicon film.
JP57186754A 1982-10-26 1982-10-26 Manufacture of p type silicon film Granted JPS5976419A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP57186754A JPS5976419A (en) 1982-10-26 1982-10-26 Manufacture of p type silicon film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP57186754A JPS5976419A (en) 1982-10-26 1982-10-26 Manufacture of p type silicon film

Publications (2)

Publication Number Publication Date
JPS5976419A true JPS5976419A (en) 1984-05-01
JPS6361768B2 JPS6361768B2 (en) 1988-11-30

Family

ID=16194051

Family Applications (1)

Application Number Title Priority Date Filing Date
JP57186754A Granted JPS5976419A (en) 1982-10-26 1982-10-26 Manufacture of p type silicon film

Country Status (1)

Country Link
JP (1) JPS5976419A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62214179A (en) * 1986-03-17 1987-09-19 Nec Corp Thin film forming device
EP0735597A3 (en) * 1995-03-30 1997-06-04 Sharp Kk Silicon solar cell and fabrication method thereof
JP2004297008A (en) * 2003-03-28 2004-10-21 National Institute Of Advanced Industrial & Technology P-type semiconductor material, its manufacturing method, its manufacturing device, photoelectric conversion element, light emitting device, and thin film transistor
JP2005268481A (en) * 2004-03-18 2005-09-29 Toppan Printing Co Ltd Non-single crystal solar cell and apparatus for manufacturing p type semiconductor material

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62214179A (en) * 1986-03-17 1987-09-19 Nec Corp Thin film forming device
EP0735597A3 (en) * 1995-03-30 1997-06-04 Sharp Kk Silicon solar cell and fabrication method thereof
JP2004297008A (en) * 2003-03-28 2004-10-21 National Institute Of Advanced Industrial & Technology P-type semiconductor material, its manufacturing method, its manufacturing device, photoelectric conversion element, light emitting device, and thin film transistor
JP2005268481A (en) * 2004-03-18 2005-09-29 Toppan Printing Co Ltd Non-single crystal solar cell and apparatus for manufacturing p type semiconductor material

Also Published As

Publication number Publication date
JPS6361768B2 (en) 1988-11-30

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