JPH02225674A - Production of thin unsingle crystal film - Google Patents
Production of thin unsingle crystal filmInfo
- Publication number
- JPH02225674A JPH02225674A JP1092420A JP9242089A JPH02225674A JP H02225674 A JPH02225674 A JP H02225674A JP 1092420 A JP1092420 A JP 1092420A JP 9242089 A JP9242089 A JP 9242089A JP H02225674 A JPH02225674 A JP H02225674A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- film
- thin film
- single crystal
- raw material
- 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
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000007789 gas Substances 0.000 claims abstract description 66
- 239000002994 raw material Substances 0.000 claims abstract description 28
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052734 helium Inorganic materials 0.000 claims abstract description 13
- 239000001307 helium Substances 0.000 claims abstract description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- 230000005684 electric field Effects 0.000 claims abstract description 5
- 239000010409 thin film Substances 0.000 claims description 27
- 239000000758 substrate Substances 0.000 claims description 9
- 229910021480 group 4 element Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- 238000005268 plasma chemical vapour deposition Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 2
- 239000008246 gaseous mixture Substances 0.000 abstract 2
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 48
- 125000004429 atom Chemical group 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 108091008695 photoreceptors Proteins 0.000 description 2
- 230000036211 photosensitivity Effects 0.000 description 2
- 238000005546 reactive sputtering Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- -1 Fn (n = 1.2.3) Substances 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910006990 Si1-xGex Inorganic materials 0.000 description 1
- 229910007020 Si1−xGex Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000003852 thin film production method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、非単結晶薄膜の作製方法に関するものである
。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing a non-single crystal thin film.
従来の技術 水素化非晶質シリコン（以下ａ＝ｓｉ：Ｈと略記する。Conventional technology Hydrogenated amorphous silicon (hereinafter abbreviated as a=si:H).
）薄膜は光導電性に優れ、一般にプラズマＣＶＤ法によ
り作製されている。) The thin film has excellent photoconductivity and is generally produced by plasma CVD.
一方、ａ−８＋：Ｈに対して、禁止帯幅の広いおよび狭
い光導電材料として水素化非晶質シリコンカーバイド（
以下ａ −Ｓ ｉ ＋−ｔ ＣＫ ： Ｈと略記する。On the other hand, for a-8+:H, hydrogenated amorphous silicon carbide (
Hereinafter, it will be abbreviated as a-S i +-t CK:H.
但し、０＜ｘ＜１゜）や水素化非晶質シリコンゲルマニ
ウム（以下ａ−Ｓｉ＋−１Ｇｅｔ：Ｈと略記する。但し
、Ｏ＜ｘ＜’１．。）薄膜などのように異種の第■族元
素からなる非晶質合金も、ａ−８ｉ：Ｈの光感度の低い
波長領域を補うために注目されている。However, different type Amorphous alloys made of group elements are also attracting attention in order to compensate for the wavelength range in which a-8i:H has low photosensitivity.
ａ−８ｉＩ−ｘｃｘ： Ｈの場合Ｎ ａ Ｓ ＆
＋−ｘｃ＊：Ｈ薄膜は表面硬度が大きく、シかも禁止
帯幅が水素化非晶質シリコン薄膜（以下ａ−８ｉ：Ｈと
略記する。）に比べて大きいことから太陽電池の窓層、
さらに暗抵抗が高いことから電子写真感光体の表面層ま
たは光導電層として用いられている。a-8iI-xcx: For H, N a S &
+-xc*:H thin film has a large surface hardness and a larger forbidden band width than a hydrogenated amorphous silicon thin film (hereinafter abbreviated as a-8i:H), so it is used as a window layer for solar cells.
Furthermore, because of its high dark resistance, it is used as a surface layer or photoconductive layer of electrophotographic photoreceptors.
また、これらの受光素子に対して膜中のＣ含仔量を操作
することにより禁止帯幅を制御することができるため、
可視光の広範囲に渡る発光波長の発光ダイオードも試作
されている。In addition, the bandgap width can be controlled by controlling the C content in the film of these photodetectors.
Light-emitting diodes that emit light over a wide range of visible light wavelengths have also been prototyped.
しかし、グロー放電分解法あるいは反応性スパッタ法に
より作製したａ −Ｓ ＋ Ｉ−ｘ Ｃｘ ： Ｈ薄
膜の光導電性は、キャリヤのトラップまたは再結合中心
として働くダングリングボンドがａ−８ｔ：Ｈ薄膜に比
べて非常に多く存在する、あるいはＣＨｉ、ＣＨｉなど
の膜の密度を低下させる水素の高次結合が発生し易いな
どの理由から、ａ−３ｉ：Ｈに比べてよくなかった。However, the photoconductivity of a-S + I-x Cx:H thin films prepared by glow discharge decomposition or reactive sputtering is due to the fact that dangling bonds, which act as carrier traps or recombination centers, form a-8t:H thin films. It was not as good as a-3i:H because it was present in a much larger amount than a-3i:H, or because higher-order bonds of hydrogen, which reduce the density of CHi, CHi, etc., were likely to occur.
最近、モノ′７ランガス（以下ＳｉＨイと記す）七ＣＨ
Ｊの混合ガスを大量の水素で希釈したプラズマＣＶＤ法
により、膜中にＣＨ２，ＣＨ＊結合が少なく膜の密度が
高く、シかも光導電性の優れたａ−５１＋−ｘｃｘ：
Ｈ薄膜が得られることが報告されている（検出ほか、
ジャーナル オブ アプライドフィジックス（Ｊｏｕｒ
ｎａｌ ｏｆ Ａｐｐｔｌｅｄ Ｐｈｙｓｉｃｓ） Ｕ
ＳＡ［ｉ０巻 ４０２５頁 （１９Ｈ））。この大量の
水素希釈は、反応性の乏しい、言い替えれば寿命の長い
、水素の多く付いたラジカル（例えばＳ ＋ Ｈ２ＩＣ
Ｈｓなど）による成膜と、膜成長表面を水素で覆うこと
により、膜成長表面でのラジカルの寿命を長くして充分
マイグレーシロンさせることにより、膜を構成する５ｉ
−Ｃネットワークの高密度化を図っている。Recently, mono'7 run gas (hereinafter referred to as SiH) 7CH
A-51+-xcx, which has a high film density with few CH2 and CH* bonds in the film and has excellent photoconductivity, is produced by plasma CVD method in which a mixed gas of J is diluted with a large amount of hydrogen:
It has been reported that H thin film can be obtained (detection etc.
Journal of Applied Physics
nal of Applet Physics) U
SA [Volume i0, page 4025 (19H)). This large amount of hydrogen dilution creates hydrogen-rich radicals (e.g. S + H2IC) with poor reactivity, in other words, long life.
By coating the film growth surface with hydrogen, the lifetime of the radicals on the film growth surface is extended and sufficient migration is achieved, and the 5i forming the film is
-C We are trying to increase the density of the network.
ａ −８ｒ ＋−ｘＧ ｅｘ： Ｈの場合、ａ −３
１ｌ−ｘ Ｇ ｅ ｘ：Ｈ薄膜は近赤外領域に光感度を
持つため、太陽Ｎ油においては太陽光の長波長域の光吸
収量の増加、電子写真感光体においては半導体レーザの
発振波長域での増感にを効な材料として注目されている
。a −8r +−xG ex: For H, a −3
1l-x G e x:H thin film has photosensitivity in the near-infrared region, so in solar N oil it increases the amount of light absorbed in the long wavelength region of sunlight, and in electrophotographic photoreceptors it increases the oscillation wavelength of the semiconductor laser. It is attracting attention as an effective material for sensitization in the region.
しかし、ａ −Ｓ １ ＋−ｘ Ｃｍ ： Ｈと同様
にグロー放電分解法や反応性スパッタ法により作製した
ａ−３１１−Ｘ Ｇ ｅｘ ： Ｈａｍも膜中にダン
グリングボンドが多く含まれており、光導電率はａ−８
ｉ：Ｈ薄膜に比べてよくなかった。However, like a-S1+-xCm:H, a-311-XGex:Ham, which was prepared by glow discharge decomposition method or reactive sputtering method, also contains many dangling bonds in the film. Photoconductivity is a-8
It was not as good as the i:H thin film.
この場合も光導電性を向上させるために水素希釈あるい
は三電極方式などが提案されている。In this case as well, hydrogen dilution or a three-electrode system have been proposed to improve photoconductivity.
発明が解決しようとする課題
ａ −Ｓ ｒ ｌ−ｘ Ｃ−： Ｈおよびａ −Ｓ
ｉ ＋−ｘＧ ｅｘ：Ｈの膜質を向上させるために用い
られている水素希釈法は、長寿命ラジカルを生成するた
めにラジカルの濃度を減少させてしまっているため、成
膜速度は小さく、原料ガスの利用効率も悪い。また、三
電極法も、プラズマ中に存在する短寿命のラジカルは用
いずに長寿命ラジカルだけを分離して成膜しているため
、原料ガスの利用効率が悪く、成膜速度も小さい。Problem to be solved by the invention a -S r l-x C-: H and a -S
The hydrogen dilution method used to improve the film quality of i + - Gas usage efficiency is also poor. Furthermore, in the three-electrode method, only long-lived radicals are separated to form a film without using short-lived radicals present in the plasma, so the raw material gas utilization efficiency is poor and the film-forming rate is low.
従って、ａ −Ｓ ｉ＋−ｘＣｘ： Ｈおよびａ −Ｓ
＋、 Ｉ−ＸＧｅｘ：Ｈのようにネットワークを構成
しない水素原子を除く２種類以上の元素で構成される膜
を作製する場合、１種類の元素でネットワークを構成し
ているａ−８ｉ：Ｈのような場合に比べて膜中に多くの
欠陥が発生し易く、光導電性の高い良質の膜を高速で成
膜することは非常に困難であった。Therefore, a −S i+−xCx: H and a −S
+, When producing a film composed of two or more types of elements excluding hydrogen atoms that do not constitute a network, such as I-XGex:H, a-8i:H, which constitutes a network with one type of element, Compared to such cases, many defects are more likely to occur in the film, and it has been extremely difficult to form a high-quality film with high photoconductivity at high speed.
本発明は、以上のような従来の問題点を解決するもので
、２Ｎ類以上の元素で構成されるキャリヤ輸送特性の優
れた非単結晶薄膜を、原料ガスの利用効率を上げ、成膜
速度を減少させることなく作製する方法を提供するもの
である。The present invention solves the above-mentioned conventional problems, and aims to improve the utilization efficiency of raw material gas and increase the deposition rate of a non-single-crystal thin film with excellent carrier transport properties composed of 2N or higher elements. The present invention provides a method for manufacturing without reducing the
課題を解決するための手段
ガス分子内に少なくとも水素原子を含む原料ガスを少な
くとも１種類以上とヘリウムガスとを真空容器内に導入
し、原料ガスとヘリウムガスに減圧下で電界を印加して
放電を発生させ、真空容器内に配置した基体上に非単結
晶薄膜を作製する。Means for Solving the Problem At least one type of raw material gas containing at least hydrogen atoms in the gas molecules and helium gas are introduced into a vacuum container, and an electric field is applied to the raw material gas and helium gas under reduced pressure to discharge the gas. A non-single crystal thin film is produced on a substrate placed in a vacuum container.
作用
原料ガスを希釈せずに放電により分解あるいは重合させ
ると、急激に圧力は変化し、さらに圧力の変化に対して
ガスの分解、重合の反応速度は変化するため、プラズマ
が安定せず膜特性の制御が困難になる。それを防ぐため
に原料ガスを希釈して使用することが望ましく、希釈ガ
スとしては、水素原子がａ −Ｓ ｉｔ−ｔ Ｃｍ ：
Ｈやａ−ｓｔ：Ｈ膜中でダングリングボンドを終端さ
せる働きを持つことから水素ガスがよく用いられる。し
かし従来例のように長寿命ラジカルを得るがために大量
の水素を希釈ガスに使用すると、膜成長に寄与する５ｉ
Ｈｆｉｌ ｅ）Ｉｎ＋ ＧｅＨａ（ｎ＝ｏ＋ Ｌ
２＋ ３）などの活性種にＮ原子、Ｈｚ分子が衝
突する確率が高くなり、これらの衝突によりこれらの活
性種が膜成長に寄与しない分子の状態に戻され、プラズ
マ中の活性種の濃度が激減してしまい成膜速度が小さく
なる問題がある。If the raw material gas is decomposed or polymerized by electric discharge without being diluted, the pressure will change rapidly, and the reaction rate of gas decomposition and polymerization will change in response to the change in pressure, resulting in unstable plasma and poor film properties. becomes difficult to control. In order to prevent this, it is desirable to dilute the raw material gas before use, and as the diluent gas, hydrogen atoms are a-S it-t Cm:
Hydrogen gas is often used because it has the function of terminating dangling bonds in H or a-st:H films. However, if a large amount of hydrogen is used as a diluent gas to obtain long-lived radicals as in the conventional example, 5i, which contributes to film growth,
Hfil e)In+GeHa(n=o+L
The probability of N atoms and Hz molecules colliding with active species such as 2+3) increases, and these collisions return these active species to a molecular state that does not contribute to film growth, increasing the concentration of active species in the plasma. There is a problem in that the amount decreases drastically and the film formation rate decreases.
希釈ガスに不活性ガスであるヘリウムを用いた場合は、
プラズマ中に存在するＮ原子、Ｈ２分子の濃度は非常に
小さくなるため膜成長に寄与する活性種のＮ原子、Ｈ２
分子との衝突はほとんどなく、成膜速度が大きく減少す
ることがない。求たＨｅには２つの準安定状態２’Ｓ＋
＋ １ ’Ｓ＠（１Ｂ、８ｅＶ）。When using helium, an inert gas, as the diluent gas,
Since the concentration of N atoms and H2 molecules existing in the plasma becomes very small, the active species N atoms and H2 molecules that contribute to film growth
There are almost no collisions with molecules, and the film formation rate does not decrease significantly. The obtained He has two metastable states 2'S+
+ 1'S@(1B, 8eV).
２’Ｓｓ→１ ’ Ｓ 魯（２０、ＨｅＶ）を持ち、こ
れう＋７）寿命モ１０−’秒〜数秒にわたる非常に長い
ものであることが知られている。It is known that it has an extremely long life span of 10-' seconds to several seconds.
従って、原料ガスを大量のＨｅで希釈し、これらの励起
状態にあるＨｅ原子の濃度を大きくしてやると、寿命の
長いことから励起状態にあるＨｅ原子と膜成長表面と衝
突する回数を増やすことができる。衝突の時、Ｈｅ原子
は基底状態に戻るときに放出されるエネルギーを膜成長
表面に与えるので、膜成長表面に存在するラジカルのマ
イグレーシーンを活発にすることができ、５ｉ−Ｃある
いはＳ １−Ｇｅなどの結合のネットワークを高密度に
形成することができる。Therefore, if the raw material gas is diluted with a large amount of He and the concentration of these excited He atoms is increased, the number of collisions between the excited He atoms and the film growth surface can be increased due to their long lifetime. can. At the time of collision, He atoms give energy released when returning to the ground state to the film growth surface, which can activate the migration scene of radicals existing on the film growth surface, and 5i-C or S1 A network of bonds such as -Ge can be formed with high density.
さらに、準安定状態２’Ｓ＋、２’Ｓ＠よりもエネルギ
的に高い準位からの遷移では、原料ガスに原料ガスを分
解するのに必要なエネルギを与えて、原料ガスの分解を
さらに促進させるため、原料ガスの利用効率が高くなり
、成膜速度を速めることが出来る。しかも原料ガスの分
解の促進は、高励起ラジカルによる成膜が行われ、膜質
も同時に向上する。Furthermore, in the transition from a level higher in energy than the metastable states 2'S+ and 2'S@, the energy necessary to decompose the source gas is given to the source gas, further promoting the decomposition of the source gas. Therefore, the utilization efficiency of the raw material gas is increased, and the film formation rate can be increased. Moreover, the decomposition of the raw material gas is promoted by highly excited radicals, and the film quality is improved at the same time.
また、Ｈｅ原子は、Ｎ ８１ Ａ ｒｌ Ｋ Ｌ
Ｘ ｅなどの他の不活性ガスよりも質量が小さいため
、プラズマ中でイオン化して電界で加速されて膜表面と
衝突しても膜にほとんどダメージを与えることがない長
所も持っている。Moreover, the He atom is N 81 A rl K L
Since it has a smaller mass than other inert gases such as Xe, it also has the advantage of causing almost no damage to the film even if it is ionized in the plasma, accelerated by the electric field, and collides with the film surface.
実施例
本発明における薄膜の作製方法により作製される非単結
晶薄膜は、非晶質薄膜としてａ−８ｉ＋−８Ｑ、：
Ｈｌ ａ−８ｉｔ−ｍＮｘ： Ｈｌ ａ−Ｇｅｔ
−ｗｏｗ：Ｈｌ ａ −Ｇ （１１−ＸＮＩＩ：
Ｈ９ａ −Ｓ ｉ １−ｘＧ ｅｘ ： Ｈｌａ−５
Ｉ ＋−ｘｃｘ： Ｈｚ ａ−８１ｒ−ｘｓｎｘ：
Ｈｅ ａ−Ｇ ｅ ｔ−ｘｃｘ： Ｈｒ ａ
−Ｇ ｅ ｔ−ｘｓ ｎｘ： Ｈ（但し、０ ＜Ｘ
＜ １ ）’＋ ａ−８ｔ ＋−＊−ｖＧ ｅｘｃ
ｙ： Ｈ（但し、０＜ｘ、ｙ＜１）などのように周期表
第■族元素を含むもの、ａ−ＧａＮ： Ｈｌ ａ−Ｇ
ａＡｓ： Ｈｌａ−ＩｎＰ：Ｈなどの■−■族化合物半
導体を用いる。またこれらの非晶質層は微結晶を含んで
もよいし、すべて微結晶であってもよい。Examples A non-single crystal thin film produced by the thin film production method of the present invention is a-8i+-8Q, as an amorphous thin film:
Hla-8it-mNx: Hla-Get
-wow: Hl a -G (11-XNII:
H9a-Si1-xGex: Hla-5
I+-xcx: Hz a-81r-xsnx:
He a-G e t-xcx: Hra
-G e t-xs nx: H (however, 0 <
<1)'+ a-8t +-*-vG exc
y: H (however, 0<x, y<1), etc., containing elements of group Ⅰ of the periodic table, a-GaN: Hl a-G
aAs: A ■-■ group compound semiconductor such as Hla-InP:H is used. Further, these amorphous layers may contain microcrystals or may be entirely microcrystals.
またこれらの非単結晶薄膜は、膜中のダングリングボン
ドを終端し電子や正孔などのキャリヤの輸送能力を高め
るために、弗素や塩素などのハロゲンを含んでもよい。Further, these non-single crystal thin films may contain halogens such as fluorine and chlorine in order to terminate dangling bonds in the film and increase the transport ability of carriers such as electrons and holes.
上記の非結晶薄膜の作製に使用される原料ガスは、ガス
分子内にダングリングボンドを終端する働きを持つ水素
原子を含んでいることが必要であり、具体的には、Ｓｉ
原子を膜内に与える原料ガスとしてＳ Ｉ ＨＪＩ
Ｓ Ｉ ２Ｈｓ＋ Ｓ Ｉ Ｈａ−、ｌＦ、ｌ、Ｓ
ＩＨ４−ＡＣＩＡＩ Ｓ ｉ Ｈａ−ｎ （
ＣＨｌ）ｎ（但し、 ｎ＝ｌ。The raw material gas used for producing the above-mentioned amorphous thin film must contain hydrogen atoms that act to terminate dangling bonds in the gas molecules.
S I HJI as a raw material gas that provides atoms into the film
S I 2Hs+ S I Ha-, IF, l, S
IH4-ACIAI S i Han (
CHl)n (however, n=l.
２．３）などのシリコン化合物ガス、Ｃ原子の原料ガス
としてはＣＨＪ、 Ｃ５Ｈａ、 Ｃ３Ｈ＠、 Ｃ
２Ｈｔ、 Ｃ２Ｈｚ、 ＣｅＨｅ、 ＣＨ４−、
Ｆｎ（但し、ｎ ＝ １．２．３）などの炭素化合物ガ
ス、Ｇｅ原子の原料ガスとしてはＧ ｅ ＨＪＩ Ｇ
ｅ ＊Ｈｓ＋ Ｇ ｅ Ｈｓ−＊Ｆｓ （但し、
ｎ：Ｉ、２．３）、ＯｙＸ子の原料ガスとしては０２．
Ｏｘ、 Ｇｏ。2.3) and other silicon compound gases, raw material gases for C atoms include CHJ, C5Ha, C3H@, C
2Ht, C2Hz, CeHe, CH4-,
Carbon compound gas such as Fn (n = 1.2.3), and raw material gas for Ge atoms include G e HJI G
e *Hs+ G e Hs-*Fs (However,
n: I, 2.3), 02.0 as the raw material gas for OyX particles.
Ox, Go.
Ｃ０ｔｌ ＮＯ，Ｎｅｏ、Ｎｏｔ、Ｎ原子の原料ガスと
してはＮｓ、 ＮＨｓ、Ｇａ原子の原料ガスとしては
（ＣＨｎ）ｔＧａ＋ （ＣａＨｓ）ｓＧａｔ Ｉｎ
原子の原料ガスとしては（ＣａＨｓ）Ｉ ｎｌ Ｐ原子
の原料ガスとしてはＰ ＨＪ、Ａ ｓ原子の原料ガスと
してはＡｓＨａを使用し、これらのガスをヘリウムで希
釈する。ヘリウムガスの希釈の割合は、上述のヘリウム
原子の効果を引き出し、高めるために、放電を発生させ
成膜を行うための真空容器内において、ヘリウム原子の
数に対し原料ガス分子の数が２５％以下になるように設
定するのが望ましい。また、膜中のダングリングボンド
を効率よく終端させるためにヘリウムガスだけでなく水
素ガスまたは弗素ガスを添加してもよく、放電を安定に
保つためにアルゴンガスを添加してもよい。但し、これ
らのガスの添加量は、ヘリウムガスの体積に対し５０％
を越えてはならない。C0tl NO, Neo, Not, Ns as a raw material gas for N atoms, (CHn)tGa+ (CaHs)sGat In as a raw material gas for NHs, Ga atoms
As the raw material gas for atoms, (CaHs)I nl P HJ is used as the raw material gas for P atoms, and AsHa is used as the raw material gas for As atoms, and these gases are diluted with helium. In order to bring out and enhance the effect of the helium atoms mentioned above, the dilution ratio of helium gas is such that the number of source gas molecules is 25% of the number of helium atoms in the vacuum chamber for generating discharge and forming a film. It is desirable to set it as follows. Furthermore, in order to efficiently terminate dangling bonds in the film, not only helium gas but also hydrogen gas or fluorine gas may be added, and argon gas may be added to keep the discharge stable. However, the amount of these gases added is 50% of the volume of helium gas.
Must not exceed.
膜の作製方法は、上記のガスを用いた直流または高周波
（１ｋＨｚ −１００ＭＨｚ）またはマイクロ波（ｌＧ
Ｈｚ以上）グロー放電分解法、あるいは電子サイクロト
ロン共鳴（ＥＣＲ）プラズマＣＶＤ法が望ましい。また
、特に容量結合方式の高周波グロー放電分解法では、ヘ
リウム原子の励起を充分行い膜質の向上並びにガスの分
解効率を高めるために、高周波電源を接続した電極に投
入する電力密度は、単位電極面積当りＱ、０３〜１．５
１／ｃＩ”であることが望ましい。何故なら、電力密度
を０．０１Ｗ／ａｍ”より小さくするとヘリウム原子に
励起が充分に行われず、１．５Ｗ／ｃｍ”より大きくす
るとプラズマから受ける膜のダメージが大きくなり膜質
が低下するからである。また、電力密度０．０３〜Ｉ
、５Ｗ／ａｍ２の状態で、１分間当り導入される原料ガ
スの分子１個当りに投入する電力を５ｘｉＯ”Ｗ／個以
上を滴定させるようにすると原料ガスの分解が充分行わ
れ、真空容器内にポリマー状の粉体が付着し難くなる。The film can be produced using direct current, high frequency (1kHz - 100MHz) or microwave (lG) using the above gases.
Hz or higher) glow discharge decomposition method or electron cyclotron resonance (ECR) plasma CVD method is preferable. In addition, especially in the capacitively coupled high-frequency glow discharge decomposition method, in order to sufficiently excite helium atoms to improve film quality and gas decomposition efficiency, the power density applied to the electrode connected to the high-frequency power source is determined by the unit electrode area. Hit Q, 03-1.5
1/cI" is desirable. This is because if the power density is lower than 0.01 W/am", the helium atoms will not be sufficiently excited, and if it is higher than 1.5 W/cm", the film will be damaged by the plasma. This is because the power density increases and the film quality deteriorates.Also, when the power density is 0.03 to I
, 5W/am2, if the power input per molecule of raw material gas introduced per minute is titrated to 5xiO"W/molecule or more, the raw material gas will be sufficiently decomposed and polymer powder becomes difficult to adhere to.
実施例１
容量結合方式プラズマＣＶＤ装置内に石英基板を配置し
、５ｘｌＯ−’Ｔｏ ｒ ｒ以下に排気した後、石英基
板を２８０〜３８０″Ｃに加熱した。次にＳｉＨ４：０
．５〜Ｂ３ｓａｃｍ＋ ＣａＨｓ： ０．１７〜２１
ｓｃｃｍ、 Ｈｅ： ２０〜１７０ｓｃｃｍを装置内
に導入し、ガス圧力を０．２〜！、０Ｔｏｒｒの範囲に
設定し、０．２〜１．３Ｗ／ ｃ 〜２の高周波電力（
１３，５８ＭＨ２）を平板電極に印加して、石英基板上
に、０．７〜１．５μｍの膜厚を存するａ−８ｉ＋−ｘ
Ｃ，：Ｈ薄膜を作製した。この時の成膜速度は０．８〜
１０μｍ／ｈであった。この時のガスの分解効率（但し
、使用した全原料ガス流量に対する成膜に使用された原
料ガス流量の割合で定義する）は１１〜２１％であり、
非常に高かった。Example 1 A quartz substrate was placed in a capacitively coupled plasma CVD apparatus, and after exhausting to below 5xlO-'Torr, the quartz substrate was heated to 280 to 380''C. Next, SiH4:0
．． 5~B3sacm+CaHs: 0.17~21
sccm, He: 20 to 170 sccm is introduced into the device, and the gas pressure is 0.2 to ! , set in the range of 0 Torr, and set the high frequency power of 0.2 to 1.3 W/c to 2 (
A-8i+-x with a film thickness of 0.7 to 1.5 μm was deposited on the quartz substrate by applying 13,58MH2
A C,:H thin film was prepared. The film formation rate at this time is 0.8~
It was 10 μm/h. The gas decomposition efficiency at this time (defined as the ratio of the raw material gas flow rate used for film formation to the total raw material gas flow rate used) is 11 to 21%,
It was very expensive.
次に、このａ−８ｉ＋−０Ｃ，：Ｈ薄膜上にアルミニウ
ムの平行電極を蒸着し、室温（２５℃）において暗導電
率を測定したところ３ｘｌＯ”〜４．５ｘｌＯ−”（Ω
ｃｒｒ＋）−’であった。また、室温において波長５５
０１１１、 強度５０μＷ／ｃｍ”の光を照射して光
導電率を測定したところ、７ｘｌＯ−’ 〜８ｘｌＯ−
” （Ωｃｍ）−’であった。この光導電率よりημτ
（但し、η：量子効率、μ： キャリヤ移動度、τニキ
ャリャ寿命）を算出したところ１．０ｘｌＯ−７〜５．
１ｘｌＯ−” （Ωｃｍ）”１であり、ａ−８ｌ： Ｈ
薄膜とほぼ同等の値であることを確認できた。Next, aluminum parallel electrodes were deposited on this a-8i+-0C,:H thin film, and the dark conductivity was measured at room temperature (25°C).
crr+)-'. Also, at room temperature, the wavelength is 55
0111, when the photoconductivity was measured by irradiating light with an intensity of 50 μW/cm, it was 7xlO-' to 8xlO-
” (Ωcm)-'. From this photoconductivity, ημτ
(However, η: quantum efficiency, μ: carrier mobility, τ n-carrier lifetime) was calculated to be 1.0xlO-7 to 5.
1xlO-"(Ωcm)"1, a-8l: H
It was confirmed that the value was almost the same as that of the thin film.
上記のａ −Ｓ ｌ ｌ−Ｘ ＣＸ ： Ｈ薄膜の作
製において、Ｈｅの代わりにＨｚ： ２０２０−１７０
ｓｅを用いて同等の条件で膜成長を試みたところ、成膜
速度は０．１〜３μｍ／ｈとＨｅの場合に比べて小さか
った。In the production of the above a-S l l-X CX:H thin film, Hz: 2020-170 was used instead of He.
When film growth was attempted using SE under the same conditions, the film formation rate was 0.1 to 3 μm/h, which was lower than in the case of He.
また、Ｓ ｉ Ｈａｓ Ｃ２Ｈ２の代わりにＳｉａ−
＋（ＣＨ３） ａ （ｎ＝ ＋ １２＋３）、５ｆＨｊ
の代わりにＳｉ＊Ｈａ１Ｃ２Ｈ２の代わりにＣＨｎ、Ｃ
ａＨ２またはＣ３Ｈ＠を用いても上記の結果とほぼ同等
の値を得、ヘリウム希釈の効果を確認することが出来た
。Also, Sia− instead of S i Has C2H2
+(CH3) a (n= + 12+3), 5fHj
Si*Ha1C2H2 instead of CHn, C
Even when aH2 or C3H@ was used, values almost equivalent to the above results were obtained, confirming the effect of helium dilution.
実施例２
容量結合方式プラズマＣＶＤ装置内にアルミニウム基板
を配置し、５ｘｌＯ”Ｔ Ｏｒ ｒ以下に排気した後、
アルミニウム基板を２５０〜３５０℃に加熱した。Example 2 After placing an aluminum substrate in a capacitively coupled plasma CVD apparatus and evacuating to below 5xlO"T Or r,
The aluminum substrate was heated to 250-350°C.
次にＳ ｆ Ｈａ： ２〜５８ｓｃｃ１．Ｇ ｅ ＨＪ
： ４〜８８ｓｃｃ＋ａ。Next, S f Ha: 2-58scc1. G e HJ
: 4-88scc+a.
Ｈｅ：Ｉ２−４５０ｓｃｃ■を装置内に導入し、ガス圧
力を０．２〜！、ＯＴ ｏ ｒ ｒの範囲に設定し、０
．０３〜０．９８Ｗ／ｃｍ２の高周波電力を平板電極に
印加してアルミニウム基板上に０゜５〜１１μｍ／ｈの
成膜速度でａ −８ｉｔ−ｘＧｅｘ： Ｈ膜Ａを８．
５〜１２μｍ形成した。Introduce He:I2-450scc■ into the device and increase the gas pressure to 0.2~! , OT o r r range, 0
．． High-frequency power of 0.3 to 0.98 W/cm2 was applied to a flat plate electrode to form a-8it-xGex:H film A on an aluminum substrate at a film-forming rate of 0.5 to 11 μm/h.
A thickness of 5 to 12 μm was formed.
これとは別にＨｅの代わりにアルゴンガスを用いて、上
記と同じ条件でａ−８ｉｔ−８Ｇｅｍ：Ｈ膜Ｂを作製し
た。Separately, a-8it-8Gem:H film B was produced under the same conditions as above using argon gas instead of He.
この時の成膜速度は、０．４〜１０μｌハであった。The film forming rate at this time was 0.4 to 10 μl.
これらのａ−８１ｔ−ｘＧｅｘ： ＨＩＩＡ＋ Ｂの
上に０．５μｍのポリバラキシレン膜および半透明金電
極５００Ａを順次積層して、波長５００ｎｍのダイレー
ザを光源とする時間走行法によりａ−３＋ ＋−ｘＧ
ｅｘ：Ｈ膜の電子のドリフト移動度を測定したところ、
Ａ膜は８ｘｌＯ−” 〜５ｘｌＯ−”ｃｇ”／Ｖ、
Ｂ膜は１．５〜ＥｉｘｌＯ−”ｃｍ２／Ｖであり、Ｈｅ
希釈による膜の方がキャリヤ輸送特性に優れ、成膜速度
も大きいことが確認された。A 0.5 μm polyvaraxylene film and a semi-transparent gold electrode 500A were sequentially laminated on these a-81t-xGex: HIIA+ B, and a-3+ +- was produced using a time travel method using a dye laser with a wavelength of 500 nm as a light source. xG
When the electron drift mobility of the ex:H film was measured,
A film is 8xlO-" ~ 5xlO-"cg"/V,
The B film is 1.5~EixlO-”cm2/V, and He
It was confirmed that the diluted film has better carrier transport properties and faster film formation rate.
発明の効果
本発明によれば、高い光導電率を有する、あるいはキャ
リヤ輸送特性の優れた非単結晶薄膜を高い成膜速度で得
ることができる。Effects of the Invention According to the present invention, a non-single crystal thin film having high photoconductivity or excellent carrier transport properties can be obtained at a high deposition rate.
Claims (5)
を少なくとも１種類以上とヘリウムガスとを真空容器内
に導入し、前記原料ガスとヘリウムガスに減圧下で電界
を印加して放電を発生させ、前記真空容器内に配置した
基体上に非単結晶、薄膜を作製することを特徴とする非
単結晶薄膜の作製方法。(1) At least one type of raw material gas containing at least hydrogen atoms in the gas molecules and helium gas are introduced into a vacuum container, and an electric field is applied to the raw material gas and helium gas under reduced pressure to generate a discharge. . A method for producing a non-single crystal thin film, comprising producing a non-single crystal thin film on a substrate placed in the vacuum vessel.
周波電源を接続した電極を配置し、前記電極に単位電極
面積あたり０．０３〜１．５Ｗ／ｃｍ＾２の高周波電力
を印加して放電を発生させ、基体上に非単結晶薄膜を作
製することを特徴とする請求項１に記載の非単結晶薄膜
の作製方法。(2) An electrode connected to a high-frequency power source with a frequency of 1 kHz to 100 MHz is placed in a vacuum container, and a high-frequency power of 0.03 to 1.5 W/cm^2 per unit electrode area is applied to the electrode to generate discharge. 2. The method for producing a non-single crystal thin film according to claim 1, wherein the non-single crystal thin film is produced on the substrate.
含有することを特徴とする請求項１に記載の非単結晶薄
膜の作製方法。(3) The method for producing a non-single crystal thin film according to claim 1, wherein the source gas contains at least a Group IV element in the gas molecules.
原料ガス分子の数が２５％以下であることを特徴とする
請求項１に記載の非単結晶薄膜の作製方法。(4) The method for producing a non-single crystal thin film according to claim 1, wherein the number of source gas molecules is 25% or less of the number of helium atoms present in the vacuum vessel.
に投入される高周波電力が５×１０＾−＾２＾９Ｗ／個
以上であることを特徴とする請求項２に記載の非単結晶
薄膜の作製方法。(5) The high-frequency power input per one molecule of the raw material gas introduced per minute is 5×10^-^2^9 W/molecule or more. Method for producing single crystal thin films.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9375388 | 1988-04-15 | ||
| JP63-93753 | 1988-04-15 | ||
| JP63-284511 | 1988-11-10 | ||
| JP28451188 | 1988-11-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02225674A true JPH02225674A (en) | 1990-09-07 |
| JP3061811B2 JP3061811B2 (en) | 2000-07-10 |
Family
ID=26435047
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP01092420A Expired - Fee Related JP3061811B2 (en) | 1988-04-15 | 1989-04-12 | Fabrication method of non-single crystal thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3061811B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5582880A (en) * | 1992-03-27 | 1996-12-10 | Canon Kabushiki Kaisha | Method of manufacturing non-single crystal film and non-single crystal semiconductor device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101566781B (en) * | 2008-04-25 | 2012-03-28 | 鸿富锦精密工业（深圳）有限公司 | Distance-measurement tool |
| KR102275938B1 (en) * | 2019-12-10 | 2021-07-12 | 장성원 | Folding method for toilet sanitary sheet |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59224119A (en) * | 1984-01-16 | 1984-12-17 | Semiconductor Energy Lab Co Ltd | Preparation of coating |
| JPS6316616A (en) * | 1986-04-17 | 1988-01-23 | Agency Of Ind Science & Technol | Silicon thin film and manufacture of the same |
-
1989
- 1989-04-12 JP JP01092420A patent/JP3061811B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59224119A (en) * | 1984-01-16 | 1984-12-17 | Semiconductor Energy Lab Co Ltd | Preparation of coating |
| JPS6316616A (en) * | 1986-04-17 | 1988-01-23 | Agency Of Ind Science & Technol | Silicon thin film and manufacture of the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5582880A (en) * | 1992-03-27 | 1996-12-10 | Canon Kabushiki Kaisha | Method of manufacturing non-single crystal film and non-single crystal semiconductor device |
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| Publication number | Publication date |
|---|---|
| JP3061811B2 (en) | 2000-07-10 |
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