JPH0650726B2 - Semiconductor thin film - Google Patents
Semiconductor thin filmInfo
- Publication number
- JPH0650726B2 JPH0650726B2 JP60049231A JP4923185A JPH0650726B2 JP H0650726 B2 JPH0650726 B2 JP H0650726B2 JP 60049231 A JP60049231 A JP 60049231A JP 4923185 A JP4923185 A JP 4923185A JP H0650726 B2 JPH0650726 B2 JP H0650726B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- semiconductor thin
- hydrogen
- substrate
- compound
- 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 - Fee Related
Links
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
- H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
- H10P14/24—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials using chemical vapour deposition [CVD]
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
- H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
- H10P14/34—Deposited materials, e.g. layers
- H10P14/3402—Deposited materials, e.g. layers characterised by the chemical composition
- H10P14/3404—Deposited materials, e.g. layers characterised by the chemical composition being Group IVA materials
- H10P14/3411—Silicon, silicon germanium or germanium
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Photovoltaic Devices (AREA)
Description
【発明の詳細な説明】 〔技術分野〕 本発明は半導体薄膜に関し、特に高い導電率を有する弗
素系非晶質シリコン膜に関する。TECHNICAL FIELD The present invention relates to a semiconductor thin film, and more particularly to a fluorine-based amorphous silicon film having a high conductivity.
弗素系非晶質シリコン膜はその優れた膜性能のために最
近よく研究されており、その用途は太陽電池、感光ドラ
ム、イメージセンサー等の種々の薄膜半導体装置に開け
ている。Fluorine-based amorphous silicon films have recently been well researched for their excellent film performance, and their applications are open to various thin film semiconductor devices such as solar cells, photosensitive drums and image sensors.
これらの半導体装置の性能を向上させるためには、装置
を構成する要素たる半導体薄膜の性能をまず向上させね
ばならない。この性能の一つにｐ型の導電型を付与する
不純物の導入（以下不純物ドーピングと称す）による価
電子制御がある。たとえば、ｐ型の不純物ドーピングに
よりｐ型の導電型を与え、不純物量や薄膜の作製条件等
によりこの導電度の大きさを制御するものである。In order to improve the performance of these semiconductor devices, the performance of the semiconductor thin film, which is a constituent element of the device, must first be improved. One of the performances is valence electron control by introducing impurities imparting p-type conductivity (hereinafter referred to as impurity doping). For example, a p-type conductivity is provided by p-type impurity doping, and the magnitude of this conductivity is controlled by the amount of impurities, the thin film manufacturing conditions, and the like.
従来技術においては、不純物量、作製条件、作製方法な
どをいろいろと変化させることが試みられたが、導電度
は高々数Ｓ／cmの程度であつた。すなわちこの導電度を
大きくすることが大いに要求されていたにもかかわら
ず、これを達成することはできなかつた。In the prior art, various attempts were made to change the amount of impurities, production conditions, production method, etc., but the electrical conductivity was at most about several S / cm. That is, despite the great demand for greater conductivity, this could not be achieved.
本発明の目的は新しい薄膜形成物質を用いる光分解法に
よりこの問題を解決しようとするものである。The object of the present invention is to solve this problem by a photolysis method using a new thin film forming material.
本発明はシリコン−弗素結合を有する化合物を水素の共
在下に紫外線を照射し、光分解により基体上に形成した
半導体薄膜である。また、本発明においてはシリコン−
弗素結合を有する化合物がSiHnF4-n（ｎ＝１〜３の整
数）である。また、本発明においてはシリコン−弗素結
合を有する化合物が水素で希釈されて光分解反応器に送
入されるものである。また、本発明においてはシリコン
−弗素結合を有する化合物、水素およびジボランを含む
ガスを光分解するものである。また、本発明においては
紫外線は低圧水銀ランプを光源として照射されることが
好ましい。光分解反応は水銀増感法により低圧水銀ラン
プを光源として行われることが好ましい。The present invention is a semiconductor thin film formed on a substrate by irradiating a compound having a silicon-fluorine bond with ultraviolet rays in the coexistence of hydrogen and photodecomposing it. In the present invention, silicon-
The compound having a fluorine bond is SiH n F 4-n (n = 1 to 3). Further, in the present invention, the compound having a silicon-fluorine bond is diluted with hydrogen and fed into the photolysis reactor. Further, in the present invention, a gas containing a compound having a silicon-fluorine bond, hydrogen and diborane is photolyzed. Further, in the present invention, it is preferable to irradiate the ultraviolet rays with a low pressure mercury lamp as a light source. The photolysis reaction is preferably carried out by a mercury sensitization method using a low pressure mercury lamp as a light source.
本発明に用いるシリコン−弗素結合を有する化合物は一
般式SiHnF4-n（ｎ＝１〜３の整数）で表されるものであ
る。すなわち、SiHF3、SiH2F2およびSiH3Fで表される化
合物であり、それぞれトリフロロシラン、ジフロロシラ
ンおよびモノフロロシランと称せられるものである。以
下これらを単にフロロシラン類と総称する。これらは単
独または混合状態で用いることができるが、薄膜の作製
においては単独の方が用いるに容易であり、また、得ら
れる薄膜の性能も一定する。The compound having a silicon-fluorine bond used in the present invention is represented by the general formula SiH n F 4-n (n = 1 to 3). That is, it is a compound represented by SiHF 3 , SiH 2 F 2 and SiH 3 F, and is called trifluorosilane, difluorosilane and monofluorosilane, respectively. Hereinafter, these are simply referred to as fluorosilanes. These can be used alone or in a mixed state, but when used alone in the production of a thin film, it is easier to use, and the performance of the obtained thin film is also constant.
本発明において、フロロシラン類は水素の共在下すなわ
ち水素で希釈された状態で紫外線照射し光分解される。
水素での希釈度合についてはフロロシラン類の体積の５
倍以上、好ましくは１０倍以上、特に好ましくは２０倍
以上が用いられる。フロロシラン類ははじめから水素で
希釈されていて光分解反応器に送入されてもよいし、光
分解反応器の中で前記の希釈度合を満足するように水素
を添加し容器中で混合することもできる。後者の場合に
おいては希釈度合は水素のフロロシラン類に対する光分
解反応器への供給流量比がそれぞれ５倍以上、好ましく
は１０倍以上、特に好ましくは２０倍以上となればよ
い。In the present invention, fluorosilanes are photodecomposed by irradiation with ultraviolet rays in the presence of hydrogen, that is, in the state of being diluted with hydrogen.
Regarding the degree of dilution with hydrogen, the volume of fluorosilanes should be 5
It is used at least twice, preferably at least 10 times, particularly preferably at least 20 times. Fluorosilanes may be diluted with hydrogen from the beginning and fed into the photolysis reactor, or hydrogen may be added to the photolysis reactor so as to satisfy the above-mentioned dilution degree and mixed in a container. You can also In the latter case, the degree of dilution may be such that the supply flow rate ratio of hydrogen to fluorosilanes to the photolysis reactor is 5 times or more, preferably 10 times or more, and particularly preferably 20 times or more.
本発明において、得られる膜はｐ型の不純物ドーピング
が可能である。ｐ型の不純物であるところのIII属のホ
ウ素化合物たとえばジボラン（B2H6）を光分解反応時に
フロロシラン類と共在させることによりｐ型の導電度を
与えることができる。ドーパントたるジボラン／フロロ
シラン類の容積パーセントは0.01％〜１０％で充分低抵
抗のｐ型膜を得る。実施例に示すようにｐ型の不純物の
容積パーセントが0.6％と低い場合にも充分高い導電度
のｐ型膜を得ることができることは本発明の特徴の一つ
である。In the present invention, the obtained film can be doped with p-type impurities. P-type conductivity can be provided by coexisting a group III boron compound, which is a p-type impurity, such as diborane (B 2 H 6 ) with fluorosilanes during the photolysis reaction. The volume percentage of the dopant diborane / fluorosilanes is 0.01% to 10% to obtain a p-type film having a sufficiently low resistance. As shown in the examples, it is one of the features of the present invention that a p-type film having a sufficiently high conductivity can be obtained even when the volume percentage of p-type impurities is as low as 0.6%.
光分解反応は水銀ランプ、希ガスランプ、水銀−希ガス
ランプ等が用られる。これらの内でも特に水銀ランプの
一種である低圧水銀ランプを用いることが実用上便利で
ある。A mercury lamp, a rare gas lamp, a mercury-rare gas lamp, or the like is used for the photolysis reaction. Among these, it is practically convenient to use a low-pressure mercury lamp, which is a kind of mercury lamp.
光分解反応は直接的にまたは増感剤を介して間接的に行
うことができる。これも実用的な観点から水銀を増感剤
とする水銀増感法が効果的に用いられる。The photolysis reaction can be carried out directly or indirectly via a sensitizer. Also from the practical point of view, the mercury sensitizing method using mercury as a sensitizer is effectively used.
薄膜が形成される基体の温度は400℃以下と比較的低温
でよい。基体の温度が250℃以下のさらに低温の条件に
おいて薄膜の導電度が極めて向上することは本発明のさ
らなる特徴の一つである。基体の温度の低下と共に光学
バンドギャップは大きくなり２eVを越える。これにもか
かわらず得られる膜の導電度は低下するどころか大きく
なることは本発明のさらなる優れた特徴の一つである。The temperature of the substrate on which the thin film is formed may be a relatively low temperature of 400 ° C. or lower. It is one of the further characteristics of the present invention that the conductivity of the thin film is remarkably improved under the condition that the substrate temperature is lower than 250 ° C. As the temperature of the substrate decreases, the optical bandgap increases and exceeds 2 eV. Notwithstanding this, it is one of the further excellent features of the present invention that the conductivity of the obtained film is increased rather than decreased.
光分解反応時の反応圧力、フロロシラン類およびｐ型の
不純物等の原料ガス流量、水銀溜の温度等についてはつ
ぎに示す薄膜速度以外特に限定される条件はなく従来技
術における条件を用いて行われる。これらの条件は当然
のことながら薄膜の成膜速度に影響を与えるものであ
る。本発明を有効に実施するためには成膜速度をある程
度小さくすることが好ましい。高い導電度を得るために
は成膜速度は１Å／秒、好ましくは0.1Å／秒以下にお
さえられる。この成膜速度は基体の温度にほとんど影響
されないので、その制御が容易であるということも本発
明のさらなる優れた特徴の一つである。The reaction pressure during the photolysis reaction, the flow rates of the raw material gases such as fluorosilanes and p-type impurities, and the temperature of the mercury reservoir are not particularly limited except for the thin film speed shown below, and the conditions in the prior art are used. These conditions naturally affect the film forming rate of the thin film. In order to effectively carry out the present invention, it is preferable to reduce the film formation rate to some extent. In order to obtain high conductivity, the film formation rate is kept at 1Å / sec, preferably 0.1Å / sec or less. This film forming rate is hardly influenced by the temperature of the substrate, and thus it is also one of the more excellent features of the present invention that the control is easy.
つぎに本発明の実施の態様についてしるす。光透過窓、
基体導入手段、基体保持手段、基体加熱手段、ガス導入
手段、真空排気手段を少なくとも有する光分解反応器に
基体を設置し真空排気下基体を100〜300℃に加熱する。
原料ガスの導入にあたりその一部を水銀溜を経由させて
該反応器に導入する。水素を原料ガス流量の５倍量以上
同時に導入する。真空排気手段で該反応器の圧力を１０
Torr以下として、低圧水銀ランプを点灯し反応を開始す
る。同ランプ点灯と共に薄膜の形成がはじまるので成膜
速度を考慮にいれて必要膜厚になる時間において同ラン
プを消灯する。また、膜厚モニターによつて膜厚を計測
しつつ成膜時間を決めることもできる。光分解反応器の
光透過窓に高沸点油を塗布しておくことにより、光透過
窓への膜形成を抑えることができる。Next, embodiments of the present invention will be described. Light transmission window,
The substrate is placed in a photolysis reactor having at least a substrate introducing means, a substrate holding means, a substrate heating means, a gas introducing means, and a vacuum exhaust means, and the substrate is heated to 100 to 300 ° C. under vacuum exhaust.
When introducing the raw material gas, a part thereof is introduced into the reactor via a mercury reservoir. Hydrogen is simultaneously introduced at least 5 times the flow rate of the raw material gas. The pressure in the reactor was adjusted to 10 by evacuation means.
When the pressure is below Torr, the low-pressure mercury lamp is turned on to start the reaction. Since the thin film starts to be formed when the lamp is turned on, the lamp is turned off at the time when the required film thickness is reached in consideration of the film forming speed. Further, it is possible to determine the film formation time while measuring the film thickness with a film thickness monitor. By coating the high-boiling point oil on the light-transmitting window of the photolysis reactor, it is possible to suppress film formation on the light-transmitting window.
本発明により得られる半導体薄膜は導電度が２０Ｓ／cm
を越える低抵抗膜であり、かつ、光学バンドギャップは
1.8〜2.2eVを有するところに特徴がる。これらの低抵抗
膜は基体の温度が250℃以下で形成されるものであり、
半導体薄膜や半導体装置の低温形成を目指している半導
体装置の製造分野において極めて有用な技術を提供する
ものである。The semiconductor thin film obtained by the present invention has a conductivity of 20 S / cm.
Is a low resistance film that exceeds
It is characterized by having 1.8 to 2.2 eV. These low resistance films are formed at a substrate temperature of 250 ° C or lower,
The present invention provides an extremely useful technique in the field of semiconductor device manufacturing aiming at low-temperature formation of semiconductor thin films and semiconductor devices.
以下実施例を示し本発明をさらに具体的に説明する。Hereinafter, the present invention will be described more specifically with reference to examples.
実施例 第１図に示すところの紫外光透過窓１、基体導入手段
２、基体保持手段３、基体加熱手段４、ガス導入手段
５、真空排気手段６を有す光分解反応器７を用いる。基
体導入手段２を用いて膜付のための基体８であるところ
のガラス板を基体保持手段に設置する。真空排気手段で
真空排気しつつ基体加熱手段により基体を200℃に加熱
した。ついでジフロロシラン／ジボラン／水素を100／
0.6／500−2000の流量比で導入し、真空排気手段に設備
されている調節弁９で２Torrの圧力に保持する。導管１
０により導入されるフロロシランの内の一部を約４０℃
に加熱された水銀溜１１の上を通過させて導入する。な
お、１３はジボラン、１４は水素の導入管である。基体
の温度および光分解反応器内の圧力が一定となつた時低
圧水銀ランプ１２を点灯し、膜厚が約5000Åになつた時
に消灯する。水素／ジフロロシランの流量比を５、１
０、１５および２０に変化させた時の導電度を第１図に
示した。水素／ジフロロシランの流量比が約１０を越え
るところから導電度は急激に向上し、水素／ジフロロシ
ランの流量比が２０の時には光学バンドギャップ約２eV
で導電度２０Ｓ／cmを有するｐ型の半導体薄膜を得るこ
とができた。Example A photolysis reactor 7 having an ultraviolet light transmitting window 1, a substrate introducing means 2, a substrate holding means 3, a substrate heating means 4, a gas introducing means 5 and a vacuum exhausting means 6 as shown in FIG. 1 is used. Using the substrate introducing means 2, a glass plate, which is the substrate 8 for film attachment, is set on the substrate holding means. The substrate was heated to 200 ° C. by the substrate heating means while being evacuated by the vacuum evacuation means. Then difluorosilane / diborane / hydrogen 100 /
It is introduced at a flow rate ratio of 0.6 / 500-2000, and is maintained at a pressure of 2 Torr by the control valve 9 provided in the vacuum exhaust means. Conduit 1
Some of the fluorosilane introduced by 0
It is introduced by passing it over the mercury reservoir 11 heated to. Incidentally, 13 is diborane, and 14 is a hydrogen introducing pipe. The low-pressure mercury lamp 12 is turned on when the temperature of the substrate and the pressure inside the photolysis reactor are constant, and is turned off when the film thickness reaches about 5000Å. Hydrogen / difluorosilane flow rate ratio of 5, 1
The electric conductivity when changed to 0, 15 and 20 is shown in FIG. When the flow rate ratio of hydrogen / difluorosilane exceeds about 10, the conductivity sharply improves, and when the flow rate ratio of hydrogen / difluorosilane is 20, the optical band gap is about 2 eV.
Thus, a p-type semiconductor thin film having a conductivity of 20 S / cm could be obtained.
このように、200℃と低い基体の温度において高い導電
度を達成できる本発明は半導体装置の製造の低温化に極
めて有効な発明である。As described above, the present invention, which can achieve high conductivity at a substrate temperature as low as 200 ° C., is an extremely effective invention for lowering the manufacturing temperature of semiconductor devices.
第１図は本発明を実施するための光分解反応器の模式図
である。 第２図は本発明の実施例の結果を示すグラフである。横
軸は水素／ジフロロシランの流量比を、縦軸は導電度を
しめす。FIG. 1 is a schematic diagram of a photolysis reactor for carrying out the present invention. FIG. 2 is a graph showing the results of the examples of the present invention. The horizontal axis represents the flow rate ratio of hydrogen / difluorosilane, and the vertical axis represents the conductivity.
Claims (6)
の共存下に紫外線を照射し、光分解により基体上に形成
した半導体薄膜。1. A semiconductor thin film formed on a substrate by irradiating a compound having a silicon-fluorine bond in the presence of hydrogen with ultraviolet rays and photodecomposing it.
一項記載の半導体薄膜。2. The semiconductor thin film according to claim 1, wherein the compound having a silicon-fluorine bond is SiH n F 4-n (n = 1 to 3).
で希釈されて光分解反応器に送入される特許請求の範囲
第一項記載の半導体薄膜。3. The semiconductor thin film according to claim 1, wherein the compound having a silicon-fluorine bond is diluted with hydrogen and fed into the photolysis reactor.
およびジボランを含むガスを光分解する特許請求の範囲
第一項記載の半導体薄膜。4. A semiconductor thin film according to claim 1, which photolyzes a gas containing a compound having a silicon-fluorine bond, hydrogen and diborane.
される特許請求の範囲第一項記載の半導体薄膜。5. The semiconductor thin film according to claim 1, wherein the ultraviolet rays are irradiated by using a low pressure mercury lamp as a light source.
ンプを光源として行われる特許請求の範囲第一項記載の
半導体薄膜。6. The semiconductor thin film according to claim 1, wherein the photolysis reaction is carried out by a mercury sensitization method using a low pressure mercury lamp as a light source.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60049231A JPH0650726B2 (en) | 1985-03-14 | 1985-03-14 | Semiconductor thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60049231A JPH0650726B2 (en) | 1985-03-14 | 1985-03-14 | Semiconductor thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61208825A JPS61208825A (en) | 1986-09-17 |
| JPH0650726B2 true JPH0650726B2 (en) | 1994-06-29 |
Family
ID=12825125
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60049231A Expired - Fee Related JPH0650726B2 (en) | 1985-03-14 | 1985-03-14 | Semiconductor thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0650726B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62221109A (en) * | 1986-03-24 | 1987-09-29 | Semiconductor Energy Lab Co Ltd | Film forming method |
-
1985
- 1985-03-14 JP JP60049231A patent/JPH0650726B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61208825A (en) | 1986-09-17 |
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