JPS6361768B2 - - Google Patents
Info
- Publication number
- JPS6361768B2 JPS6361768B2 JP57186754A JP18675482A JPS6361768B2 JP S6361768 B2 JPS6361768 B2 JP S6361768B2 JP 57186754 A JP57186754 A JP 57186754A JP 18675482 A JP18675482 A JP 18675482A JP S6361768 B2 JPS6361768 B2 JP S6361768B2
- Authority
- JP
- Japan
- Prior art keywords
- silicon film
- type silicon
- doping
- doped
- gallium
- 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
Links
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 38
- 229910052710 silicon Inorganic materials 0.000 claims description 35
- 239000010703 silicon Substances 0.000 claims description 35
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 15
- 229910052733 gallium Inorganic materials 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000002019 doping agent Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000031700 light absorption Effects 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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)
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
ー放電法やスパツタ法を用いて、シラン（SiH4）
や四フツ化シリコン（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、
ドープ剤のボロン(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
つた。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
光の吸収係数が大きいという欠点もあつた。 Conventionally, p-type silicon films were formed using silane (SiH 4 ) using plasma glow discharge method or sputtering method.
This was done by decomposing silicon tetrafluoride (SiF 4 ) and adding diborane (B 2 H 6 ) as a doping agent. In this conventional method, B 2 H 6 is in a gaseous state;
One of its features is that boron (B) doping agent 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 disadvantage in that the light transmittance is low in the visible light region and the 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
きくなる欠点があつた。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。 B-doped p-type silicon films produced by the plasma glow discharge method are used in solar cells that apply the photovoltaic effect.
The type silicon film is used as the window side material (on the side where sunlight enters). B-doped p-type silicon film contains a large amount of B due to low B doping efficiency.
is doped, resulting in a disadvantage that 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つて、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 the present invention is to provide a novel method for manufacturing a p-type silicon film.
上記の目的を達成するため本発明の構成は、ド
ープ剤のソースとしての金属ガリウムを抵抗加熱
により蒸気化し、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。 In order to achieve the above object, the present invention consists in vaporizing metallic gallium as a source of a dopant by resistance heating and 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
B2H6にかわり、新たに金属ガリウムを抵抗加熱
方式により蒸発させ、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, as a dopant for p-type silicon film.
This is a method for producing a p-type silicon film in which metal gallium is newly evaporated using a resistance heating method instead of B 2 H 6 and gallium is doped into the film.
第１図は本発明に使用した装置の概略図であ
る。以下、図を用いて具体的に説明する。ベルジ
ヤー２によつて囲まれた真空室１内を排気系３に
より10-5Torr程度以下の真空度に排気する。金
属ガリウム４の入つたルツボ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
定の温度になつたら、ガス導入系８によりシラン
（SiH4）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。高
周波電源９により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のシヤツター１０を開放
し、プラズマ中にGa蒸気を導入しｐ型シリコン
膜の形成を行なう。 FIG. 1 is a schematic diagram of the apparatus used in the present invention. This will be explained in detail below using figures. The inside of the vacuum chamber 1 surrounded by the bell gear 2 is evacuated to a degree of vacuum of about 10 -5 Torr or less by the exhaust system 3. 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 value, silane (SiH 4 ) gas is introduced into the vacuum chamber by the gas introduction system 8 to raise the pressure (approximately 0.1 Torr) at which plasma glow discharge is possible. 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, Ga 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つ
て行なわれているが、これは一例であり、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 only 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り得られたｐ型シリ
コン膜の室温暗電導度δD、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、実線で示した曲線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ｂおよびｄは比較のため従来法によるB2H6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
コン膜の室温暗電導度δDは、Ｂをドープしたｐ型
シリコン膜の曲線ｂ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ドーピングよりも本発明による
Gaドーピングの方がよりドーピング効率が高く、
本発明によつてドーピングされたGa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 conductivity δ D 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 Figures 2 and 3, curves a and c shown as solid lines
curves b and d shown by broken lines are for comparison when doping with B using B 2 H 6 as a doping gas according to the conventional method. The room-temperature dark conductivity δ D of the Ga-doped p-type silicon film shown by curve a in Figure 2 is similar to that of curve b of the B-doped p-type silicon film with a smaller doping amount. ing. From this result, it is clear that the method of the present invention is better than the conventional method of B doping.
Ga doping has higher doping efficiency,
It has been found that the activation rate of Ga doped according to the invention is higher than that of B.
第３図は、室温暗電導度δDが１×10-4（Ω・cm）
-1であるGa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よりも吸収係数が小さ
くなつている。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
シリコン膜の方が適していることを示唆する。 Figure 3 shows that the room temperature dark conductivity δ D is 1×10 -4 (Ω・cm)
It shows the light absorption coefficient α of Ga-doped and B-doped silicon films, which is -1 , and curve c for Ga-doped silicon film has a smaller absorption coefficient than curve d for B-doped silicon film. It's summery. This result suggests that when a p-type silicon film is used as a window material for a solar cell, a Ga-doped silicon film is more suitable than a conventional B-doped silicon film.
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、ぬけにくくなつているためである。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りドーピング効率が向
上したものである。 The reason why the doping efficiency was improved by Ga doping is that Ga has a larger ionic radius than B.
This is because the crystal structure makes it difficult to move and escape from surrounding silicon groups. In addition, in the case of B doping, when the amount of B doped is small, B is located in the tri-coordination with respect to the silicon group, and when doped in a large amount, B is located in the tetra-coordination and behaves as an acceptor. In the case of , the doping efficiency is improved even with a small amount of doping due to the four-coordination 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、ベルジヤー
２によつて囲まれた真空室１を排気系３によつて
一旦10-5Torr以下の真空度に排気する。次に、
金属ガリウム４が２ｇ入つたルツボ５を910℃に
加熱し、同時に基板６を加熱する基板ホルダー７
を220℃に加熱保持し、真空室１内を１×
10-6Torrとする。所定の温度になつたら、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0.1Torrになるよう
にする。引き続き、周波数13.56MHzの高周波電
圧９を印加し、さらに、金属ガリウム４のシヤツ
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Ga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Ga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. 1, a vacuum chamber 1 surrounded by a bell jar 2 is once evacuated to a vacuum level of 10 -5 Torr or less by an exhaust system 3. next,
A substrate holder 7 that heats a crucible 5 containing 2g of metal gallium 4 to 910°C and simultaneously heats a substrate 6.
is heated to 220℃, and the inside of vacuum chamber 1 is heated to 1×
10 -6 Torr. When the specified temperature is reached, silane (SiH 4 ) gas is introduced into the vacuum chamber 1 using the gas introduction system 8.
the pressure inside the vacuum chamber is 0.1 Torr. Subsequently, a high frequency voltage 9 with a frequency of 13.56 MHz is applied, and the shutter 10 of metal gallium 4 is opened. At the same time that the inside of the vacuum chamber 1 is brought into a plasma state, Ga vapor is diffused into the plasma, and when silane (SiH 4 ) gas decomposes and precipitates, Ga gets mixed into the silicon, and a p-type silicon film is deposited on the substrate. do.
得られたｐ型シリコン膜の室温暗電導度は、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。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のチヤージ量と加熱温度で制
御する。 The room temperature dark conductivity of the obtained p-type silicon film is closely related to the amount of Ga doping, as shown in FIG. The amount of Ga doping is controlled by controlling the vapor pressure of the metal gallium 4, and is controlled by the charge amount of the metal gallium 4 and the heating temperature.
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電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ある。
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……シヤツター。
Figure 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 conductivity of the p-type silicon film, and Figure 3 is the photon energy. FIG. 3 is a characteristic diagram showing the relationship between the light absorption coefficient and the light absorption coefficient. 1... Vacuum chamber, 4... Metal gallium, 5... Crucible, 6... Substrate, 7... Substrate holder, 8...
Gas introduction system, 10... shutter.
Claims (1)
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
り蒸気化し、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. A method for producing a p-type silicon film using a plasma glow discharge method, characterized in that metallic gallium is used as a source of a dopant, the metallic gallium is vaporized by resistance heating, and the silicon film is doped with gallium. A method for manufacturing a p-type silicon film.
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 JPS5976419A (en) | 1984-05-01 |
| JPS6361768B2 true 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) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62214179A (en) * | 1986-03-17 | 1987-09-19 | Nec Corp | Thin film forming device |
| JPH08330611A (en) * | 1995-03-30 | 1996-12-13 | Sharp Corp | Si solar cell and manufacture 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 |
| JP4691888B2 (en) * | 2004-03-18 | 2011-06-01 | 凸版印刷株式会社 | Non-single crystal solar cell and method of manufacturing non-single crystal solar cell |
-
1982
- 1982-10-26 JP JP57186754A patent/JPS5976419A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5976419A (en) | 1984-05-01 |
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