JP2763100B2 - Thin film formation method - Google Patents
Thin film formation methodInfo
- Publication number
- JP2763100B2 JP2763100B2 JP63023007A JP2300788A JP2763100B2 JP 2763100 B2 JP2763100 B2 JP 2763100B2 JP 63023007 A JP63023007 A JP 63023007A JP 2300788 A JP2300788 A JP 2300788A JP 2763100 B2 JP2763100 B2 JP 2763100B2
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- Japan
- Prior art keywords
- thin film
- substrate
- processed
- container
- gas
- Prior art date
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Description
【発明の詳細な説明】 ［発明の目的］ （産業上の利用分野） 本発明は、超LSIデバイス等の半導体製造に用いられ
る薄膜堆積方法に係わり、特に溝部内に薄膜を埋め込み
形成する薄膜形成方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial application field) The present invention relates to a method of depositing a thin film used for manufacturing a semiconductor such as an VLSI device, and more particularly, to a method of forming a thin film by embedding a thin film in a groove. About the method.
（従来の技術） 薄膜形成方法を大別すると、化学的気相成長法（Chem
ical Vapor Deposition;CVD）と物理的気相成長法（Phy
sical Vapor Depositon;PVD）とに分類される。CVD法は
基板表面や気相中での化学反応を利用して基板上に薄膜
を堆積する方法であり、主にシリコン酸化膜やシリコン
窒化膜等の絶縁膜の形成に用いられている。また、PVD
法は気相中で生成した堆積粒子を基板へ衝突させて薄膜
を形成するもので、主に金属膜の形成に用いられてい
る。(Prior art) A thin film forming method is roughly classified into a chemical vapor deposition method (Chem.
ical Vapor Deposition (CVD) and physical vapor deposition (Phy)
sical Vapor Depositon (PVD). The CVD method is a method of depositing a thin film on a substrate using a chemical reaction in a substrate surface or in a gas phase, and is mainly used for forming an insulating film such as a silicon oxide film or a silicon nitride film. Also, PVD
The method is to form a thin film by colliding deposited particles generated in a gas phase with a substrate, and is mainly used for forming a metal film.
一方、最近の超LSIデバイスではアスペクト比（深さ
／幅）の高い溝内への薄膜堆積技術が必須となりつつあ
る。しかし、CVD法の一つであるプラズマCVD法（例え
ば、J.L.Vossen ＆ W.Kern;Thin Film Process;Academi
c Press 1978）等を用いて、第８図（ａ）に示すように
Si基板81に形成された深い溝82内に絶縁物83を堆積する
と、気相中で生じた堆積種の角部への堆積が大きく、堆
積種が次第に溝底部に入り難くなり空洞84を生じ、段差
被覆特性が劣化する。On the other hand, in recent VLSI devices, a technique of depositing a thin film in a trench having a high aspect ratio (depth / width) is becoming essential. However, one of the CVD methods, the plasma CVD method (for example, JLVossen & W. Kern; Thin Film Process; Academi
c Press 1978) etc., as shown in FIG.
When the insulator 83 is deposited in the deep groove 82 formed in the Si substrate 81, the deposition species generated in the gas phase are greatly deposited at the corners, and the deposition species gradually become difficult to enter the bottom of the groove, thereby generating a cavity 84. As a result, the step coverage characteristics deteriorate.
この段差被覆形状を改善する方法として、PVD法の一
つであるバイアススパッタ法と称される技術が用いられ
ている（例えば、T.Mogami,Morimoto ＆ Okabayashi;Ex
tended abstracts 16th conf.Solid State Devices ＆
Materials.Kobe.1984,p43）。この方法は、Arイオンで
基板表面を物理的にスパッタリングしながら、例えばシ
リコン酸化膜を形成するため、角部での堆積は起こらず
平坦部でのみ堆積を生じる。従って、空洞発生なしに溝
内への埋め込みが可能になるが、気相中の堆積種が溝内
に斜めに入射してくるため、アスペクト比＞１ではやは
り埋め込み困難となる。さらに、物理的スパッタリング
による堆積膜の除去と堆積の競合反応を用いているの
で、正味の堆積速度が低く生産性が極めて悪い。また、
プラズマ中での照射照射も避けられない。最近、堆積種
の溝内への斜め入射の成分を少なくしたECRバイアスス
パッタ法（例えば、H.Oikawa;SEMITECNOLOGY SYM.1986
E3−１）も提案されているが、上記の問題は軽減される
ものの本質的な解決策とはならない。As a method of improving the step covering shape, a technique called a bias sputtering method, which is one of the PVD methods, is used (for example, T. Mogami, Morimoto &Okabayashi; Ex.
tended abstracts 16th conf.Solid State Devices &
Materials. Kobe. 1984, p43). In this method, for example, a silicon oxide film is formed while physically sputtering the substrate surface with Ar ions, so that deposition does not occur at corners but occurs only at flat portions. Therefore, although embedding into the groove is possible without generating cavities, embedding species in the gas phase enter the groove obliquely, so that embedding becomes difficult when the aspect ratio is> 1. Further, since a competitive reaction between the removal of the deposited film and the deposition by physical sputtering is used, the net deposition rate is low and productivity is extremely poor. Also,
Irradiation in plasma is inevitable. Recently, the ECR bias sputtering method that reduces the oblique incidence component of the deposited species into the trench (for example, H. Oikawa; SEMITECNOLOGY SYM. 1986)
E3-1) has also been proposed, but the above problems are reduced, but not an essential solution.
この他、例えばTEOSの熱分解法（例えば、R.D.Rang,
Y.Momose ＆ Y.Nagakubo;IEDM.TECH.DIG.1982,p.237）
を用いてシリコン酸化膜を形成すると、堆積種の大きな
表面移動によって第８図（ｂ）に示すように優れた段差
被覆特性を示す。しかし、この方法により溝内に埋め込
んだ酸化膜83を例えば希釈したHF溶液で洗浄処理する
と、第８図（ｃ）に示すように中央部85での酸化膜83の
除去速度が異常に速くなり、結局埋め込み平坦化が実現
できないのが現状である。この原因は、溝の壁の両側か
ら成長してきた酸化膜同士の歪みが中央部付近で残存す
るためと考えられる。このように、コンフアーマブルに
薄膜を形成する方法でも、高アスペクト比の溝内への埋
め込みは極めて困難であると考えられていた。In addition, for example, the pyrolysis method of TEOS (for example, RDRang,
Y.Momose &Y.Nagakubo; IEDM.TECH.DIG.1982, p.237)
When a silicon oxide film is formed by using GaN, excellent step coverage characteristics are exhibited as shown in FIG. 8 (b) due to large surface movement of the deposited species. However, when the oxide film 83 buried in the groove by this method is washed with, for example, a diluted HF solution, the removal rate of the oxide film 83 at the central portion 85 becomes abnormally high as shown in FIG. At the present, embedded flattening cannot be realized. It is considered that this is because the strain between the oxide films grown from both sides of the trench wall remains near the center. As described above, it has been considered that embedding in a groove having a high aspect ratio is extremely difficult even by a method of forming a thin film in a configurable manner.
上記の問題を解決するために、テトラメチルシラン
（SiCH3;TMS）ガスとマイクロ波放電によって励起した
酸素原子による反応中間生成物の沸点以下に基板を冷却
することによって、高アスペクト比の溝内にシリコン酸
化膜を堆積する方法がある。しかし、この方法によって
堆積した膜は−40℃という低温で堆積しているため、密
度が低い粗密な膜である。これは、反応中間生成物の沸
点以下に基板温度を冷却しているため、酸化され固相化
した原子が自由に動き回ることができないと言う液相酸
化法の本質的な問題のためによる。また、この方法によ
ると基板上で液化する物質、即ち原料ガスであるテトラ
メトキシシランと酸素をマイクロ波放電によって励起し
た酸素原子による反応中間生成物の供給と、この液体の
マイクロ波放電によって励起した酸素原子による酸化が
同時に進行しており、液体の供給速度と酸化速度の制御
が難しい。従って、膜の組成及び膜の緻密性の制御や改
善が困難となっている。In order to solve the above-mentioned problem, by cooling the substrate to below the boiling point of the reaction intermediate product by the tetramethylsilane (SiCH 3 ; TMS) gas and the oxygen atom excited by the microwave discharge, the groove in the high aspect ratio groove is formed. There is a method of depositing a silicon oxide film. However, since the film deposited by this method is deposited at a low temperature of -40 ° C., it is a low-density dense film. This is due to an essential problem of the liquid phase oxidation method in that the substrate temperature is cooled below the boiling point of the reaction intermediate product, so that atoms that are oxidized and solidified cannot move freely. According to this method, a substance liquefied on the substrate, that is, a raw material gas of tetramethoxysilane and oxygen, is supplied with a reaction intermediate product by oxygen atoms excited by microwave discharge, and is excited by microwave discharge of the liquid. Oxidation by oxygen atoms is proceeding simultaneously, and it is difficult to control the liquid supply rate and the oxidation rate. Therefore, it is difficult to control and improve the composition of the film and the denseness of the film.
第９図（ａ）は液体の供給が速すぎたためにSi基板81
の溝の底の部分に溜まっていた液体が十分酸化されず液
体のままであったため、空洞86が生じてしまった例であ
る。また、第９図（ｂ）は十分に酸化されず液体のまま
であった所が泡のように存在し、空洞87が生じてしまっ
た例である。また、第10図は全流量に対する堆積速度と
堆積形状の関係を示したものであるが、全流量を少なく
して堆積速度を遅くすると気相反応が進んで前記第８図
（ａ）のような堆積形状となってしまう。逆に、全流量
を多くして堆積速度を速くすると、液化反応が進んで第
９図に示すように空洞が発生するのである。FIG. 9 (a) shows that the Si substrate 81 was supplied because the liquid supply was too fast.
This is an example in which the liquid accumulated at the bottom of the groove is not sufficiently oxidized and remains liquid, so that the cavity 86 is formed. FIG. 9 (b) is an example in which a portion that has not been sufficiently oxidized and remains a liquid exists like a bubble and a cavity 87 has been formed. FIG. 10 shows the relationship between the deposition rate and the deposition shape with respect to the total flow rate. If the deposition rate is reduced by decreasing the total flow rate, the gas phase reaction proceeds, as shown in FIG. 8 (a). Resulting in a different deposition shape. Conversely, if the total flow rate is increased and the deposition rate is increased, the liquefaction reaction proceeds and cavities are generated as shown in FIG.
（発明が解決しようとする課題） このように従来、液相酸化法を用いて溝内を酸化膜等
で埋め混む方法にあっては、液体の供給量と酸化速度と
の制御が難しく、膜の組成及び膜の緻密性の制御や改良
が困難である問題があった。(Problems to be Solved by the Invention) As described above, in the conventional method of filling the groove with an oxide film or the like using the liquid phase oxidation method, it is difficult to control the supply amount of the liquid and the oxidation rate, and the film However, there is a problem that it is difficult to control and improve the composition and the denseness of the film.
本発明は上記事情を考慮してなされたもので、その目
的とするところは、液相酸化法等における液体の供給量
と酸化速度の制御を独立に行うことができ、溝内に薄膜
を良好に埋め込むことができ、且つ膜質の向上をはかり
得る薄膜形成方法を提供することにある。The present invention has been made in view of the above circumstances, and an object of the present invention is to control a liquid supply amount and an oxidation rate in a liquid phase oxidation method or the like independently and to form a thin film in a groove. An object of the present invention is to provide a method for forming a thin film that can be embedded in a thin film and can improve the film quality.
［発明の構成］ （課題を解決するための手段） 本発明の骨子は、液相酸化法等によって薄膜を形成す
る際に、基板表面で液化させる原料ガス又は原料ガスと
励起した反応ガスによって生成される反応中間生成物の
供給を行う時間と、基板表面で液化した液体を反応ガス
によって薄膜化する時間を分離し、これらを繰返して堆
積膜を形成することにより、液体の供給量とその液体の
酸化速度を独立に自由に制御することにある。また、基
板表面で液化した液体を励起した反応ガスによって酸化
膜とした後に基板温度を上昇させ、励起した反応ガスに
よって膜質を向上させる過程を行い、これらを繰返して
堆積膜を形成することによって膜質も向上させることに
ある。[Structure of the Invention] (Means for Solving the Problems) When forming a thin film by a liquid phase oxidation method or the like, the gist of the present invention is generated by a raw material gas to be liquefied on the substrate surface or a raw material gas and an excited reaction gas. The time during which the reaction intermediate product is supplied is separated from the time during which the liquid liquefied on the substrate surface is thinned by the reaction gas, and these steps are repeated to form a deposited film. To independently and independently control the oxidation rate. In addition, the process of raising the substrate temperature after forming an oxide film by the excited reaction gas from the liquid liquefied on the substrate surface and improving the film quality by the excited reaction gas is performed, and by repeating these processes to form a deposited film, Is also to improve.
即ち本発明は、表面に溝が形成された被処理基体を反
応容器内に収容し、容器内に所定のガスを供給して被処
理基体の溝部に薄膜を形成する薄膜形成方法において、 第１番目の薄膜形成過程として、前記容器内に原料ガ
スのみ又は前記容器とは別の領域で励起された第１の反
応ガスと原料ガスとの両方を供給し、前記被処理基体を
原料ガスの露点以下又は原料ガスと第１の反応ガスとの
反応中間生成物の露点以下に冷却し、前記被処理基体の
表面に原料ガス又は反応生成物を液化して付着させ、 第２番目の薄膜形成過程として、第１番目の薄膜形成
過程を終了した後、前記容器内に該容器とは別の領域で
励起した第２の反応ガスを供給し、前記被処理基体の表
面に付着した液体から薄膜を生成し、 これら２つの薄膜形成過程を時間的に分離し、且つ交
互に繰返して前記被処理基体の溝部を薄膜で埋め込むよ
うにした方法である。That is, the present invention provides a thin film forming method for accommodating a substrate having a groove formed on a surface thereof in a reaction container and supplying a predetermined gas into the container to form a thin film in the groove of the substrate. As a thin film forming process, only the raw material gas or both the first reaction gas and the raw material gas excited in a region different from the container are supplied into the container, and the substrate to be processed is subjected to the dew point of the raw material gas. Cooling below or below the dew point of the reaction intermediate product of the source gas and the first reaction gas, liquefying the source gas or the reaction product on the surface of the substrate to be processed, and attaching the same to the second thin film forming step After the first thin film forming process is completed, a second reaction gas excited in a region different from the container is supplied into the container, and the thin film is formed from the liquid attached to the surface of the substrate to be processed. Generates and separates these two thin film formation processes temporally A method in which the grooves of the substrate to be processed so as to fill a thin film and repeated alternately.
また本発明は、表面に溝が形成された被処理基体を反
応容器内に収容し、容器内に所定のガスを供給して被処
理基体の溝部に薄膜を形成する薄膜形成方法において、 第１番目の薄膜形成過程として、前記容器内に原料ガ
スのみ又は前記容器とは別の領域で励起された第１の反
応ガスと原料ガスとの両方を供給し、前記被処理基体を
原料ガスの露点以下又は原料ガスと第１の反応ガスとの
反応中間生成物の露点以下に冷却し、前記被処理基体の
表面に原料ガス又は反応生成物を液化して付着させ、 第２番目の薄膜形成過程として、第１番目の薄膜形成
過程を終了した後、前記容器内に該容器とは別の領域で
励起した第２の反応ガスを供給し、前記被処理基体の表
面に付着した液体から薄膜を生成し、 第３番目の薄膜形成過程として、第２番目の薄膜形成
過程を終了した後、前記被処理基体を原料ガス又は反応
生成物の沸点以上に加熱し、前記容器内に該容器とは別
の領域で励起した第２の反応ガスを供給し、 これら３つの薄膜形成過程を時間的に分離し、且つ順
次繰返して前記被処理基体の溝部を薄膜で埋め込むよう
にした方法である。Further, the present invention provides a thin film forming method for accommodating a substrate having a groove formed on its surface in a reaction vessel and supplying a predetermined gas into the vessel to form a thin film in the groove of the substrate to be treated. As a thin film forming process, only the raw material gas or both the first reaction gas and the raw material gas excited in a region different from the container are supplied into the container, and the substrate to be processed is subjected to the dew point of the raw material gas. Cooling below or below the dew point of the reaction intermediate product of the source gas and the first reaction gas, liquefying the source gas or the reaction product on the surface of the substrate to be processed, and attaching the same to the second thin film forming step After the first thin film forming process is completed, a second reaction gas excited in a region different from the container is supplied into the container, and the thin film is formed from the liquid attached to the surface of the substrate to be processed. The second thin film formation process After finishing the thin film formation process, the substrate to be processed is heated to a temperature equal to or higher than the boiling point of the raw material gas or the reaction product, and a second reaction gas excited in a region different from the container is supplied into the container. This is a method in which three thin film forming processes are temporally separated and sequentially repeated so as to fill the groove of the substrate to be processed with a thin film.
（作用） 本発明によれば、液相酸化法等によって薄膜を堆積す
る際に、液体の供給量と酸化の速度の制御が独立に自由
に設定できる。従って、溝内に埋め込む膜の膜質の制御
が容易となり、膜の緻密化や膜の十分な酸化が行える。
即ち、第１の薄膜形成過程により被処理基体の表面に液
体を薄く付着させた後、第２の薄膜形成過程により十分
な酸化等を行うことによって、空洞の発生を招くことな
く良質の薄膜を形成することができる。そして、この工
程を繰返すことにより、溝内部を十分に埋め込む厚さの
薄膜を形成することが可能となる。(Function) According to the present invention, when depositing a thin film by a liquid phase oxidation method or the like, the supply amount of the liquid and the control of the oxidation rate can be independently and freely set. Therefore, it is easy to control the film quality of the film embedded in the groove, and it is possible to make the film denser and sufficiently oxidize the film.
That is, after a liquid is thinly adhered to the surface of the substrate to be processed in the first thin film forming process, a sufficient oxidation or the like is performed in the second thin film forming process, so that a high quality thin film can be formed without causing voids. Can be formed. Then, by repeating this process, it is possible to form a thin film having a thickness enough to bury the inside of the groove.
また、基板表面で液化した液体を励起した反応ガス又
はイオン，光によって酸化膜とした後に基板温度を上昇
させ、励起した反応ガス又はイオン，光によって膜質を
向上させる工程（第３の薄膜形成過程）を行い、これら
（第１〜第３の薄膜形成過程）を繰返して堆積膜を形成
することにより、膜の緻密化や膜質の向上をより一層進
めることができる。A step of raising the substrate temperature after forming an oxide film with a reaction gas or ions or light excited by the liquid liquefied on the substrate surface and improving the film quality with the excited reaction gas or ions or light (third thin film forming process) ), And by repeating these (the first to third thin film forming processes) to form a deposited film, it is possible to further advance the densification of the film and the improvement of the film quality.
（実施例） 以下、本発明の詳細を図示の実施例によって説明す
る。(Examples) Hereinafter, details of the present invention will be described with reference to the illustrated examples.
第１図は本発明の請求項１記載の方法を実施するため
の手順を示す模式図である。まず、被処理基体収容した
反応容器内に原料ガスのみ又は前記容器とは別の領域で
励起された第１の反応ガスと原料ガスとの両方を供給
し、被処理基体を原料ガスの露点以下又は原料ガスと第
１の反応ガスとの反応中間生成物の露点以下に冷却す
る。これにより、被処理基体の表面に原料ガス又は反応
生成物が液化して付着する（液体の供給）。この液体は
被処理基体の溝内に溜まるが、その量は極めて少ないも
のである。FIG. 1 is a schematic diagram showing a procedure for carrying out the method according to claim 1 of the present invention. First, only the source gas or both the first reaction gas and the source gas excited in a region different from the container are supplied into the reaction vessel containing the substrate to be processed, and the substrate to be processed is kept at the dew point of the source gas or lower. Alternatively, cooling is performed to a dew point or lower of a reaction intermediate product of the raw material gas and the first reaction gas. As a result, the source gas or the reaction product is liquefied and adheres to the surface of the substrate to be processed (liquid supply). This liquid accumulates in the groove of the substrate to be processed, but its amount is extremely small.
次いで、液体の供給を停止した後、容器内に該容器と
は別の領域で励起した第２の反応ガスを供給する，基体
表面に光を照射する及び基体表面にイオンを照射するう
ちの少なくとも１つを行い、被処理基体の溝内に付着し
た液体を酸化し酸化膜を形成する（液体の酸化）。この
とき、溝内の液体の量は極めて少ないものであるから、
空洞等が発生することもなく、液体は十分に酸化されて
良質の酸化膜が形成される。Next, after the supply of the liquid is stopped, at least one of supplying the second reaction gas excited in a region different from the container to the inside of the container, irradiating the substrate surface with light, and irradiating the substrate surface with ions. One is performed to oxidize the liquid attached in the groove of the substrate to be processed to form an oxide film (oxidation of the liquid). At this time, since the amount of liquid in the groove is extremely small,
The liquid is sufficiently oxidized without forming a cavity or the like, and a high-quality oxide film is formed.
さらに、上記液体の供給及び液体の酸化を繰返すこと
により、被処理基体の溝内を薄い酸化膜の積層膜で確実
に埋め込むことができる。なお、薄膜形成に際しては酸
化膜に限らず、窒化膜その他各種の膜形成に適用するこ
とができる。Furthermore, by repeating the supply of the liquid and the oxidation of the liquid, the inside of the groove of the substrate to be processed can be reliably filled with the thin oxide film. In forming a thin film, the present invention can be applied to not only an oxide film but also a nitride film and other various films.
第２図は第１図に示す方法を実施するための薄膜形成
装置を示す概略構成図である。図中11は反応容器であ
り、この容器11内には被処理基体としてのSi基板12を載
置する試料台13が収容されている。試料台13は図示しな
い冷却機構により冷却されており、この上に載置される
基板12も冷却されるものとなっている。FIG. 2 is a schematic diagram showing a thin film forming apparatus for performing the method shown in FIG. In the figure, reference numeral 11 denotes a reaction vessel, in which a sample table 13 on which a Si substrate 12 as a substrate to be processed is placed is accommodated. The sample stage 13 is cooled by a cooling mechanism (not shown), and the substrate 12 placed thereon is also cooled.
容器11内には、ガス導入口14から原料ガスが供給さ
れ、このガスはガス排気口15から排気される。また、容
器11内には、マイクロ波放電管16により励起された反応
ガスがガス導入口17を介して供給され、このガスもガス
排気口15から排気されるものとなっている。なお、図中
18はマイクロ波電源、21,22,23はそれぞれバルブを示し
ている。A source gas is supplied into the container 11 from a gas inlet 14, and the gas is exhausted from a gas exhaust port 15. Further, the reaction gas excited by the microwave discharge tube 16 is supplied into the container 11 through the gas inlet 17, and this gas is also exhausted from the gas outlet 15. In the figure
Reference numeral 18 denotes a microwave power supply, and 21, 22, and 23 indicate valves.
次に、第２図の装置を用いた薄膜形成方法について説
明する。原料ガスとしてテトラメチルシラン（TMS）、
第１及び第２の反応ガスとして酸素をマイクロ波放電し
た酸素原子を用いた。まず、容器11内を十分に排気し、
基板12を−40℃に冷却した後、バルブ21,22を開き、TMS
を7sccm,酸素を168sccm流し、容器11内の圧力を2Torrと
する。そして、マイクロ波放電を開始し30秒間放電し、
反応中間生成物を基板12上で液化し供給した。そして、
マイクロ波放電を止め、バルブ21,22を閉じてガスの供
給を止め、排気を行った。Next, a method of forming a thin film using the apparatus shown in FIG. 2 will be described. Tetramethylsilane (TMS) as source gas,
Oxygen atoms obtained by microwave discharge of oxygen were used as the first and second reaction gases. First, exhaust the inside of the container 11 sufficiently,
After cooling the substrate 12 to −40 ° C., open the valves 21 and 22 and
Is flowed at 7 sccm and oxygen at 168 sccm, and the pressure in the container 11 is set to 2 Torr. And start microwave discharge, discharge for 30 seconds,
The reaction intermediate was liquefied on the substrate 12 and supplied. And
The microwave discharge was stopped, the valves 21 and 22 were closed, the supply of gas was stopped, and the gas was exhausted.
次いで、バルブ23を開き酸素ガスを容器11内に供給
し、圧力2Torrとして放電を開始し、基板12上に供給し
た反応生成物を５分間酸化した。そして、バルブ23を閉
じまたバルブ21,22を開き、TMSと酸素を供給し、同様の
操作を行った。Next, the valve 23 was opened, oxygen gas was supplied into the container 11, the discharge was started at a pressure of 2 Torr, and the reaction product supplied on the substrate 12 was oxidized for 5 minutes. Then, the valve 23 was closed and the valves 21 and 22 were opened to supply TMS and oxygen, and the same operation was performed.
これを16回繰返して酸化膜の堆積を行ったところ、そ
の堆積膜中にはメチル基は殆ど含まれておらず、完全な
シリコン酸化膜を堆積することができた。これは、上に
のべた手順を繰返すことにより、実質的な堆積速度を1/
11にし酸化を十分に行ったためであると考えられる。ま
た、このときの堆積形状も高アスペクト比の溝を完全に
埋め込んだものであった。このように、堆積形状に変化
を与えずに液体の供給速度と酸化の速度を制御し、堆積
速度をゆっくりにして酸化を十分に行い、膜質を改善す
ることができた。This was repeated 16 times to deposit an oxide film. As a result, the deposited film contained almost no methyl groups, and a complete silicon oxide film could be deposited. This reduces the effective deposition rate by 1 / by repeating the above procedure.
This is considered to be because oxidation was sufficiently performed to 11. Also, the deposited shape at this time was such that the grooves with a high aspect ratio were completely buried. As described above, the liquid supply rate and the oxidation rate were controlled without changing the deposition shape, and the deposition rate was reduced to sufficiently perform oxidation, thereby improving the film quality.
第３図は第２の薄膜形成過程、即ち基板上に吸着させ
た液体を酸化する工程において基板表面に光を照射し基
板上に吸着させた液体を光化学反応によって分解酸化す
るための装置である。なお、第２図と同一部分には同一
符号を付して、その詳しい説明は省略する、この装置が
第２図の装置と異なる点は、第２の反応ガスを供給する
代りに、基板表面に光を照射する機構を設けたことにあ
る。即ち、容器11の上壁には光透過窓31が設けられてお
り、光源32からの光33が窓31を介して容器11内に導入さ
れ基板12の表面に照射されるものとなっている。FIG. 3 shows an apparatus for decomposing and oxidizing the liquid adsorbed on the substrate by irradiating the substrate surface with light in the second thin film forming process, that is, the step of oxidizing the liquid adsorbed on the substrate. . The same parts as those in FIG. 2 are denoted by the same reference numerals, and detailed description thereof will be omitted. This apparatus is different from the apparatus of FIG. 2 in that instead of supplying the second reactive gas, To provide a mechanism for irradiating light. That is, a light transmission window 31 is provided on the upper wall of the container 11, and light 33 from the light source 32 is introduced into the container 11 through the window 31 and irradiates the surface of the substrate 12. .
原料ガス，第１及び第２の反応ガスとして先に示した
のと同様のものを用い、また照射する光としてArFエキ
シマレーザ（波長193nm）を用いた。堆積膜の形成は、
先に示したのと同様にし、基板を−40℃に冷却後、TMS
と第１の反応ガスとして酸素を導入し30秒間マイクロ波
放電したのち、TMSの導入を止め、ArFレーザを５分間照
射した。これを16回繰返して堆積を行ったところ、その
堆積膜中にはメチル基が殆ど含まれておらず硬質なシリ
コン酸化膜を堆積することができ。これは、TMSと酸素
の反応中間生成物で基板上で液化したヘキサメチルジシ
ロキサンが193nmの付近に吸収があるため光による化学
反応が進んだためと考えられる。As the source gas, the first and second reaction gases, the same ones as described above were used, and an ArF excimer laser (wavelength: 193 nm) was used as irradiation light. The formation of the deposited film
After cooling the substrate to −40 ° C. as described above,
Then, oxygen was introduced as a first reaction gas, and microwave discharge was performed for 30 seconds. Then, introduction of TMS was stopped, and ArF laser was irradiated for 5 minutes. When deposition was repeated 16 times, a hard silicon oxide film could be deposited because the deposited film contained almost no methyl groups. This is probably because hexamethyldisiloxane liquefied on the substrate as a reaction intermediate product of TMS and oxygen is absorbed near 193 nm, and the chemical reaction by light has progressed.
第４図は第２の薄膜形成過程、即ち基板上に吸着させ
た液体を酸化する工程において基板表面にイオンを照射
し基板上に吸着させた液体を光化学反応によって分解酸
化するための装置である。なお、第２図と同一部分には
同一符号を付して、その詳しい説明は省略する、この装
置が第２図の装置と異なる点は、第２の反応ガスを供給
する代りに、基板表面にイオンを照射する機構を設けた
ことにある。即ち、容器11の上部にはイオン源41が設け
られており、このイオン源41に導入されたガスがイオン
化されて容器11内に導入されるものとなっている。な
お、図中42はイオン加速電源、43はバルブを示してい
る。FIG. 4 shows an apparatus for decomposing and oxidizing the liquid adsorbed on the substrate by irradiating ions to the substrate surface in the second thin film forming process, that is, the step of oxidizing the liquid adsorbed on the substrate. . The same parts as those in FIG. 2 are denoted by the same reference numerals, and detailed description thereof will be omitted. This apparatus is different from the apparatus of FIG. 2 in that instead of supplying the second reactive gas, Is provided with a mechanism for irradiating ions. That is, an ion source 41 is provided on the upper part of the container 11, and the gas introduced into the ion source 41 is ionized and introduced into the container 11. In the drawing, reference numeral 42 denotes an ion accelerating power supply, and reference numeral 43 denotes a valve.
原料ガスとしてTMS,第１の反応ガスとして酸素をマイ
クロ波放電した酸素原子を用いた。また、イオンとして
は酸素をイオン源でイオン化し、加速電圧100Vにより加
速したものを用いた。堆積膜の形成は、先に示したのと
同様にし、基板を−40℃に冷却後、TMSと第１の反応ガ
スとして酸素を導入し30秒間マイクロ波放電したのち、
TMSの導入を止め、酸素イオンを５分間照射した。これ
を16回繰返して堆積を行ったところ、その堆積膜中には
メチル基が殆ど含まれておらず、また緻密でBHFに対す
るエッチング速度も1000Å/minと極めて遅いものであっ
た。これは、基板温度が低く基板上を動き回ることがで
きなかった堆積種にイオンの運動エネルギーが与えら
れ、基板上を動き回ることができるようになったためで
あると考えられる。TMS was used as a source gas, and oxygen atoms obtained by microwave discharge of oxygen were used as a first reaction gas. As the ions, those obtained by ionizing oxygen with an ion source and accelerating by an acceleration voltage of 100 V were used. The deposited film was formed in the same manner as described above. After cooling the substrate to −40 ° C., TMS and oxygen were introduced as a first reaction gas, and microwave discharge was performed for 30 seconds.
The introduction of TMS was stopped, and oxygen ions were irradiated for 5 minutes. The deposition was repeated 16 times. As a result, the deposited film contained almost no methyl group, was dense, and had an extremely low etching rate with respect to BHF of 1000 ° / min. This is presumably because the kinetic energy of the ions was given to the deposited species that could not move around on the substrate due to the low substrate temperature, and could move around on the substrate.
かくして本実施例方法によれば、基板冷却と共にTMS
及び活性化した酸素ガスの供給という液体供給工程と、
活性化した酸素ガスの供給による液体の酸化工程とを交
互に行うことにより、液体の供給量と液体の酸化時間と
を独立に且つ自由に設定することができ、膜の緻密化や
膜の十分な酸化が容易に行える。このため、基板に設け
た溝内に良質の酸化膜を埋め込むことができ、さらに空
洞等の発生を未然に防止することができる。また、バイ
アススパッタ法等とは異なり、溝の底部から薄い酸化膜
を積層していく方法であることから、アスペクト比の大
きな溝であっても確実に埋め込むことができ、超LSIの
製造に極めて有効である。Thus, according to the method of this embodiment, the TMS is
And a liquid supply step of supplying activated oxygen gas,
By alternately performing the liquid oxidizing step by supplying the activated oxygen gas, the liquid supply amount and the liquid oxidizing time can be set independently and freely. Oxidation can be easily performed. For this reason, a high-quality oxide film can be embedded in the groove provided in the substrate, and the occurrence of a cavity or the like can be prevented. Also, unlike the bias sputtering method, etc., since a thin oxide film is deposited from the bottom of the groove, it can be reliably embedded even in a groove with a large aspect ratio, making it extremely useful for the production of VLSI. It is valid.
第５図は本発明の請求項２記載の方法を実施するため
の手順を示す模式図である。この方法は、前記液体の供
給工程及び前記液体の酸化工程は第１図と同様であり、
その後、容器内に該容器とは別の領域で励起した第３の
反応ガスを供給する，基体表面に光を照射する及び基体
表面にイオンを照射するうちの少なくとも１つを行い、
前記液体の酸化工程により酸化された酸化膜を膜を更に
酸化、又は酸化されずに残った液体を酸化する。これに
より、液体は確実に酸化され、且つ膜質の改善が可能と
なる。FIG. 5 is a schematic diagram showing a procedure for carrying out the method according to claim 2 of the present invention. In this method, the liquid supply step and the liquid oxidation step are the same as those in FIG.
Thereafter, at least one of supplying a third reaction gas excited in a region different from the container, irradiating the substrate surface with light, and irradiating the substrate surface with ions is performed in the container,
The oxide film oxidized by the liquid oxidizing step is further oxidized, or the remaining liquid is oxidized. Thereby, the liquid is reliably oxidized, and the film quality can be improved.
さらに、上記液体の供給，液体の酸化及び膜質改善処
理を繰返すことにより、被処理基体の溝内を薄い酸化膜
の積層膜で確実に埋め込むことができ、且つ酸化膜の膜
質をより優れたものとすることができる。なお、薄膜形
成に際しては酸化膜に限らず、窒化膜その他各種の膜形
成に適用することができる。Further, by repeating the above-described liquid supply, liquid oxidation and film quality improvement processing, the inside of the groove of the substrate to be processed can be reliably filled with a thin oxide film laminated film, and the oxide film quality is further improved. It can be. In forming a thin film, the present invention can be applied to not only an oxide film but also a nitride film and other various films.
第６図は第５図に示す方法を実施するための薄膜形成
装置を示す概略構成図である。なお、第２図と同一部分
には同一符号を付して、その詳しい説明は省略する。こ
の装置が第２図に示す装置と異なる点は、試料台に冷却
機構と共に加熱のための加熱機構を設けたことにある。
即ち、試料台13の内部にはヒータ61が設けられており、
このヒータ61により基板12が加熱されるものとなってい
る。また、62は第３の反応ガスを供給，停止するための
バルブである。FIG. 6 is a schematic diagram showing a thin film forming apparatus for performing the method shown in FIG. The same parts as those in FIG. 2 are denoted by the same reference numerals, and detailed description thereof will be omitted. This apparatus differs from the apparatus shown in FIG. 2 in that a heating mechanism for heating together with a cooling mechanism is provided on the sample stage.
That is, a heater 61 is provided inside the sample table 13,
The substrate 12 is heated by the heater 61. Reference numeral 62 denotes a valve for supplying and stopping the third reaction gas.
次に、第６図の装置を用いた薄膜形成方法について説
明する。原料ガスとしてTMS、第１乃至第３の反応ガス
として酸素をマイクロ波放電した酸素原子を用いた。ま
ず、容器11内を十分に排気し、基板12を−40℃に冷却し
た後、バルブ21,22を開き、TMSを7sccm,酸素を168sccm
流し、容器11内の圧力を2Torrとする。そして、マイク
ロ波放電を開始し30秒間放電し、反応中間生成物を基板
12上で液化し供給した。そして、マイクロ波放電を止
め、バルブ21,22を閉じてガスの供給を止め、排気を行
った。Next, a method of forming a thin film using the apparatus shown in FIG. 6 will be described. TMS was used as a source gas, and oxygen atoms obtained by microwave discharge of oxygen were used as the first to third reaction gases. First, the inside of the container 11 was sufficiently evacuated, and after cooling the substrate 12 to −40 ° C., the valves 21 and 22 were opened, and TMS was 7 sccm and oxygen was 168 sccm.
The pressure in the vessel 11 is set to 2 Torr. Then, start microwave discharge and discharge for 30 seconds.
Liquefied on 12 and fed. Then, the microwave discharge was stopped, the valves 21 and 22 were closed, the supply of gas was stopped, and the gas was exhausted.
次いで、バルブ23を開き酸素ガスを容器11内に供給
し、圧力2Torrとして放電を開始し、基板12上に供給し
た反応生成物を５分間酸化した。次いで、バルブ23を閉
じ、ヒータ61を通電加熱し基板12の温度を300℃にし
た。さらに、バルブ62を開き第３の反応ガスとして酸素
を導入し、酸素雰囲気下で５分間アニールした。Next, the valve 23 was opened, oxygen gas was supplied into the container 11, the discharge was started at a pressure of 2 Torr, and the reaction product supplied on the substrate 12 was oxidized for 5 minutes. Next, the valve 23 was closed, the heater 61 was energized and heated, and the temperature of the substrate 12 was set to 300 ° C. Further, the valve 62 was opened, oxygen was introduced as a third reaction gas, and annealing was performed for 5 minutes in an oxygen atmosphere.
次いで、バルブ62を閉じ、再びバルブ21,22を開き、T
MSと酸素を供給し、同様の操作を行った。これを16回繰
返して酸化膜の堆積を行ったところ、その堆積膜中には
メチル基は殆ど含まれておらず、完全なシリコン酸化膜
を堆積することができた。また、この膜のBHFに対する
エッチング速度は1000Å/minとなり、熱酸化による膜と
略同様であった。Next, the valve 62 is closed, the valves 21 and 22 are opened again, and T
The same operation was performed by supplying MS and oxygen. This was repeated 16 times to deposit an oxide film. As a result, the deposited film contained almost no methyl groups, and a complete silicon oxide film could be deposited. The etching rate of this film with respect to BHF was 1000 ° / min, which was almost the same as that of the film formed by thermal oxidation.
第７図は前記ヒータの代わりにレーザによって瞬時に
アニールを行う装置を示す概略構成図である。この装置
では、容器11の上壁に光導入窓71を設け、レーザ光源72
からの光73を容器11内に導光できるようになっている。
この装置を用いることにより、第３の薄膜形成過程であ
る膜質改善処理を短時間で行うことができ、スループッ
トの向上をはかることが可能となる。FIG. 7 is a schematic configuration diagram showing an apparatus for performing instantaneous annealing by laser instead of the heater. In this apparatus, a light introducing window 71 is provided on the upper wall of the container 11 and a laser light source 72 is provided.
Light 73 can be guided into the container 11.
By using this apparatus, the film quality improvement process, which is the third thin film formation process, can be performed in a short time, and the throughput can be improved.
かくして本実施例方法によれば、先の実施例方法と同
様の効果が得られるのは勿論のこと、溝内に埋め込む酸
化膜の膜質をより改善できる利点がある。Thus, according to the method of this embodiment, the same effects as those of the above-described embodiment can be obtained, and further, there is an advantage that the film quality of the oxide film embedded in the trench can be further improved.
なお、本発明は上述した各実施例方法に限定されるも
のではない。例えば、前記原料ガスとしてテトラエトキ
シシラン，ヘキサメチルジシロキサン，トリメチルシラ
ノール，テトラメトキシシランのようなシリコン原子に
酸素原子が結合しているものを用いると、生成膜の組成
はよりSiO2に近いものとなる。この場合、原料ガス中に
酸素原子が含まれることから、第１の反応ガスの供給を
不要とすることが可能である。The present invention is not limited to the above-described embodiments. For example, when a gas in which an oxygen atom is bonded to a silicon atom such as tetraethoxysilane, hexamethyldisiloxane, trimethylsilanol, or tetramethoxysilane is used as the raw material gas, the composition of the resulting film is closer to SiO 2. Becomes In this case, since the source gas contains oxygen atoms, the supply of the first reaction gas can be made unnecessary.
また、第2,第３の反応ガスとして塩素等のハロゲンガ
スを酸素と結合して用いると、メチル基等シリコン原子
に結合している原子が還元され、CH4やCH3Cl等が形成さ
れ除去されるため、膜中の炭素濃度が減少し、生成膜の
組成はよりSiO2に近いものとなる。さらに、第３の反応
ガスとして塩素等のハロゲンガスのみを用いても同様の
効果が得られる。また、第2,第３の反応ガスとしてアル
ゴンガス等の不活性ガスを酸素と混合して用いると、高
エネルギー状態のメタスティブルな励起膜が生成され、
反応が進むため、緻密で質の良い膜が形成される。さら
に、第３の反応ガスとしてアルゴンガス等の不活性ガス
のみを用いても同様の効果が得られる。When a halogen gas such as chlorine is used as the second and third reaction gases in combination with oxygen, atoms bonded to silicon atoms such as a methyl group are reduced to form CH 4 or CH 3 Cl. Since it is removed, the carbon concentration in the film decreases, and the composition of the resulting film becomes closer to SiO 2 . Further, the same effect can be obtained by using only a halogen gas such as chlorine as the third reaction gas. When an inert gas such as an argon gas is mixed with oxygen as the second and third reaction gases, a metastable excitation film in a high energy state is generated,
As the reaction proceeds, a dense and high-quality film is formed. Further, the same effect can be obtained by using only an inert gas such as an argon gas as the third reaction gas.
また、本発明は酸化膜の形成に限るものではなく、窒
化膜，高分子膜，金属膜その他の薄膜形成に適用するこ
とができる。例えば、高分子膜の形成の場合は、原料ガ
スとしてMMA（メタクリル酸メタル）を、反応ガスとし
てH2，N2或いはSiCl4等を用い、PMMA膜を形成すること
ができる。さらに、金属膜の形成の場合、原料ガスとし
てAl(CH3)3を、反応ガスとしてH2等を用いることによ
り、Al膜を形成することができる。つまり、前記原料ガ
ス及び反応ガスの種類は形成しようとする薄膜の組成に
より適宜変更可能である。その他、本発明の要旨を逸脱
しない範囲で、種々変形して実施することができる。Further, the present invention is not limited to the formation of an oxide film, but can be applied to the formation of a nitride film, a polymer film, a metal film, and other thin films. For example, in the case of forming a polymer film, a PMMA film can be formed using MMA (metal methacrylate) as a source gas and H 2 , N 2 or SiCl 4 as a reaction gas. Further, in the case of forming a metal film, an Al film can be formed by using Al (CH 3 ) 3 as a source gas and H 2 or the like as a reaction gas. That is, the types of the source gas and the reaction gas can be appropriately changed depending on the composition of the thin film to be formed. In addition, various modifications can be made without departing from the scope of the present invention.
［発明の効果］ 以上詳述したように本発明によれば、液相酸化法等に
おける液体の供給量と酸化速度の制御を独立に行うこと
ができ、高アスペクト比の溝であっても溝内に薄膜を良
好に埋め込むことができ、且つ膜質の向上をはかり得る
薄膜形成方法を実現することができる。[Effects of the Invention] As described in detail above, according to the present invention, it is possible to independently control the amount of liquid supplied and the oxidation rate in a liquid phase oxidation method or the like, and even if the groove has a high aspect ratio, A thin film forming method capable of satisfactorily embedding a thin film therein and improving the film quality can be realized.
第１図は本発明の請求項１記載の薄膜形成方法を実施す
るための手順を示す模式図、第２図乃至第４図はそれぞ
れ第１図の方法を実施するために用いた薄膜製造装置を
示す概略構成図、第５図は本発明の請求項２記載の薄膜
形成方法を実施するための手順を示す模式図、第６図及
び第７図はそれぞれ第５図の方法を実施するために用い
た薄膜製造装置を示す概略構成図、第８図及び第９図は
それぞれ従来の問題点を説明するための断面図、第10図
は流量と堆積速度との関係を示す特性図である。 11……反応容器、12……Si基板、13……試料台、14,17
……ガス導入口、15……ガス排気口、16……マイクロ波
放電管、18……マイクロ波電源、21,22,23,43,62……バ
ルブ、32,72……光源、41……イオン源、61……ヒー
タ。FIG. 1 is a schematic diagram showing a procedure for carrying out the thin film forming method according to claim 1 of the present invention, and FIGS. 2 to 4 are thin film manufacturing apparatuses used for carrying out the method of FIG. FIG. 5 is a schematic view showing a procedure for carrying out the method for forming a thin film according to claim 2 of the present invention, and FIGS. 6 and 7 are diagrams for carrying out the method of FIG. 5, respectively. 8 and 9 are cross-sectional views for explaining a conventional problem, respectively, and FIG. 10 is a characteristic diagram showing a relationship between a flow rate and a deposition rate. . 11… Reaction vessel, 12… Si substrate, 13… Sample stand, 14,17
... gas inlet, 15 ... gas outlet, 16 ... microwave discharge tube, 18 ... microwave power supply, 21, 22, 23, 43, 62 ... bulb, 32, 72 ... light source, 41 ... ... Ion source, 61 ... Heater.
フロントページの続き (56)参考文献 特開 昭63−207121（ＪＰ，Ａ) 特開 平１−179410（ＪＰ，Ａ) Ｅｘｔｅｎｄｅｄ Ａｂｓｔｒａｃｔ ｓ ｏｆ ｔｈｅ 19ｔｈ Ｃｏｎｆｅ ｒｅｎｃｅ ｏｎ Ｓｏｌｉｄ Ｓｔａ ｔｅ Ｄｅｖｉｃｅｓ ａｎｄ Ｍａｔ ｅｒｉａｌｓ，Ｔｏｋｙｏ，1987，Ｐ. 451−454 応用物理 Ｖｏｌ．57 Ｎｏ．12 （1988) (58)調査した分野(Int.Cl.6，ＤＢ名) H01L 21/316 H01L 21/31 H01L 21/76Continuation of the front page (56) References JP-A-63-207121 (JP, A) JP-A-1-179410 (JP, A) Extended Abstracts of the 19th Conference on Solid State Devices and Materia, 1987, P. 451-454 Applied Physics Vol. 57 No. 12 (1988) (58) Fields investigated (Int. Cl. 6 , DB name) H01L 21/316 H01L 21/31 H01L 21/76
Claims (6)
器内に収容し、容器内に所定のガスを供給して被処理基
体の溝部に薄膜を形成する薄膜形成方法において、 第１番目の薄膜形成過程として、前記容器内に原料ガス
を供給し、前記被処理基体を原料ガスの露点以下に冷却
し、前記被処理基体の表面に原料ガスを液化して付着さ
せ、 第２番目の薄膜形成過程として、第１番目の薄膜形成過
程を終了した後、前記容器内に該容器とは別の領域で励
起した第２の反応ガスを供給し、前記被処理基体の表面
に付着した液体から薄膜を生成し、 これら２つの薄膜形成過程を時間的に分離し、且つ交互
に繰り返して前記被処理基体の溝部を薄膜で埋め込むこ
とを特徴とする薄膜形成方法。1. A method for forming a thin film in a groove of a substrate to be processed, wherein the substrate to be processed having a groove formed on its surface is accommodated in a reaction container and a predetermined gas is supplied into the container to form a thin film in the groove of the substrate to be processed. As a thin film forming process, a source gas is supplied into the container, the substrate to be processed is cooled to a temperature equal to or lower than the dew point of the source gas, and the source gas is liquefied and adhered to the surface of the substrate to be processed. After the first thin film forming step is completed as the thin film forming step, a second reaction gas excited in a region different from the container is supplied into the container, and adheres to the surface of the substrate to be processed. A thin film forming method comprising: forming a thin film from a liquid; separating these two thin film forming processes in time; and alternately repeating the process to fill the groove of the substrate to be processed with the thin film.
器内に収容し、容器内に所定のガスを供給して被処理基
体の溝部に薄膜を形成する薄膜形成方法において、 第１番目の薄膜形成過程として、前記容器内に該容器と
は別の領域で励起された第１の反応ガスと原料ガスとの
両方を供給し、前記被処理基体を原料ガスと第１の反応
ガスとの反応中間生成物の露点以下に冷却し、前記被処
理基体の表面に反応中間生成物を液化して付着させ、 第２番目の薄膜形成過程として、第１番目の薄膜形成過
程を終了した後、前記容器内に該容器とは別の領域で励
起した第２の反応ガスを供給し、前記被処理基体の表面
に付着した液体から薄膜を生成し、 これら２つの薄膜形成過程を時間的に分離し、且つ交互
に繰り返して前記被処理基体の溝部を薄膜で埋め込むこ
とを特徴とする薄膜形成方法。2. A method for forming a thin film in a groove of a substrate to be processed, wherein the substrate to be processed having a groove formed on its surface is accommodated in a reaction vessel and a predetermined gas is supplied into the vessel to form a thin film in the groove of the substrate to be processed. As a thin film forming step, both the first reaction gas and the source gas excited in a region different from the container are supplied into the container, and the substrate to be processed is mixed with the source gas and the first reaction gas. The reaction intermediate product is cooled below the dew point of the reaction intermediate product, and the reaction intermediate product is liquefied and adhered to the surface of the substrate to be treated. As a second thin film formation process, the first thin film formation process is completed. Thereafter, a second reaction gas excited in a region different from the container is supplied into the container, and a thin film is generated from the liquid attached to the surface of the substrate to be processed. And the grooves of the substrate to be processed are alternately and repeatedly formed in a thin film. Thin film formation method characterized by embedding.
器内に収容し、容器内に所定のガスを供給して被処理基
体の溝部に薄膜を形成する薄膜形成方法において、 第１番目の薄膜形成過程として、前記容器内に原料ガス
を供給し、前記被処理基体を原料ガスの露点以下に冷却
し、前記被処理基体の表面に原料ガスを液化して付着さ
せ、 第２番目の薄膜形成過程として、第１番目の薄膜形成過
程を終了した後、前記容器内に該容器とは別の領域で励
起した第２の反応ガスを供給し、前記被処理基体の表面
に付着した液体から薄膜を生成し、 第３番目の薄膜形成過程として、第２番目の薄膜形成過
程を終了した後、前記被処理基体を原料ガスの沸点以上
に加熱し、前記容器内に該容器とは別の領域で励起した
第３の反応ガスを供給し、 これら３つの薄膜形成過程を時間的に分離し、且つ順次
繰り返して前記被処理基体の溝部を膜で埋め込むことを
特徴とする薄膜形成方法。3. A method for forming a thin film in a groove of a substrate to be processed, wherein the substrate to be processed having a groove formed on its surface is accommodated in a reaction vessel, and a predetermined gas is supplied into the vessel to form a thin film in the groove of the substrate to be processed. As a thin film forming process, a source gas is supplied into the container, the substrate to be processed is cooled to a temperature equal to or lower than the dew point of the source gas, and the source gas is liquefied and adhered to the surface of the substrate to be processed. After the first thin film forming step is completed as the thin film forming step, a second reaction gas excited in a region different from the container is supplied into the container, and adheres to the surface of the substrate to be processed. After forming a thin film from the liquid and completing the second thin film forming process as a third thin film forming process, the substrate to be processed is heated to a temperature equal to or higher than the boiling point of the source gas, and the container is placed in the container. Supplying a third reaction gas excited in another region, A method of forming a thin film, wherein two thin film forming processes are temporally separated and sequentially repeated to fill a groove of the substrate to be processed with a film.
器内に収容し、容器内に所定のガスを供給して被処理基
体の溝部に薄膜を形成する薄膜形成方法において、 第１番目の薄膜形成過程として、前記容器内に該容器と
は別の領域で励起された第１の反応ガスと原料ガスとの
両方を供給し、前記被処理基体を原料ガスと第１の反応
ガスとの反応中間生成物の露点以下に冷却し、前記被処
理基体の表面に反応中間生成物を液化して付着させ、 第２番目の薄膜形成過程として、第１番目の薄膜形成過
程を終了した後、前記容器内に該容器とは別の領域で励
起した第２の反応ガスを供給し、前記被処理基体の表面
に付着した液体から薄膜を生成し、 第３番目の薄膜形成過程として、第２番目の薄膜形成過
程を終了した後、前記被処理基体を反応中間生成物の沸
点以上に加熱し、前記容器内に該容器とは別の領域で励
起した第３の反応ガスを供給し、 これら３つの薄膜形成過程を時間的に分離し、且つ順次
繰り返して前記被処理基体の溝部を膜で埋め込むことを
特徴とする薄膜形成方法。4. A method for forming a thin film in a groove of a substrate to be processed, wherein the substrate to be processed having a groove formed on its surface is accommodated in a reaction vessel, and a predetermined gas is supplied into the vessel to form a thin film in the groove of the substrate to be processed. As a thin film forming step, both the first reaction gas and the source gas excited in a region different from the container are supplied into the container, and the substrate to be processed is mixed with the source gas and the first reaction gas. The reaction intermediate product is cooled below the dew point of the reaction intermediate product, and the reaction intermediate product is liquefied and adhered to the surface of the substrate to be treated. As a second thin film formation process, the first thin film formation process is completed. After that, a second reaction gas excited in a region different from the container is supplied into the container, and a thin film is generated from the liquid attached to the surface of the substrate to be processed. As a third thin film forming process, After the second thin film forming step is completed, the substrate to be processed is reacted. The product is heated to a temperature higher than the boiling point of the product, and a third reaction gas excited in a region different from the container is supplied into the container. These three thin film forming processes are temporally separated and sequentially repeated. A method for forming a thin film, comprising: filling a groove of a substrate to be processed with a film.
テトラエトキシシラン，ヘキサメチルジシロキサン又は
トリメチルシラノール，テトラメトキシシランを用いた
ことを特徴とする請求項１〜４の何れかに記載の薄膜形
成方法。5. A method according to claim 1, wherein said source gas is tetramethylsilane.
5. The method according to claim 1, wherein tetraethoxysilane, hexamethyldisiloxane, trimethylsilanol, or tetramethoxysilane is used.
いは塩素や弗素等のハロゲンガスを含むガス，若しくは
アルゴン等の不活性ガス，の１つ又はこれらの混合ガス
を用いたことを特徴とする請求項２又は４に記載の薄膜
形成方法。6. A gas containing one of oxygen, hydrogen, nitrogen, a gas containing a halogen gas such as chlorine or fluorine, or an inert gas such as argon, or a mixture thereof. The method for forming a thin film according to claim 2, wherein:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63023007A JP2763100B2 (en) | 1988-02-03 | 1988-02-03 | Thin film formation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63023007A JP2763100B2 (en) | 1988-02-03 | 1988-02-03 | Thin film formation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01198033A JPH01198033A (en) | 1989-08-09 |
| JP2763100B2 true JP2763100B2 (en) | 1998-06-11 |
Family
ID=12098438
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63023007A Expired - Lifetime JP2763100B2 (en) | 1988-02-03 | 1988-02-03 | Thin film formation method |
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| Country | Link |
|---|---|
| JP (1) | JP2763100B2 (en) |
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| DE69231390D1 (en) * | 1991-06-10 | 2000-10-05 | At & T Corp | Anisotropic deposition of dielectrics |
| JPH05299412A (en) * | 1992-04-23 | 1993-11-12 | Kojundo Chem Lab Co Ltd | Manufacture of silicon oxide film in semiconductor device |
| CN101527263B (en) * | 2005-02-17 | 2013-03-20 | 株式会社日立国际电气 | Production method for semiconductor device |
| US20070277734A1 (en) * | 2006-05-30 | 2007-12-06 | Applied Materials, Inc. | Process chamber for dielectric gapfill |
| US7943531B2 (en) * | 2007-10-22 | 2011-05-17 | Applied Materials, Inc. | Methods for forming a silicon oxide layer over a substrate |
| US7803722B2 (en) * | 2007-10-22 | 2010-09-28 | Applied Materials, Inc | Methods for forming a dielectric layer within trenches |
| JP2010103495A (en) * | 2008-09-29 | 2010-05-06 | Adeka Corp | Semiconductor device, and apparatus and method for manufacturing the same |
| US8980382B2 (en) | 2009-12-02 | 2015-03-17 | Applied Materials, Inc. | Oxygen-doping for non-carbon radical-component CVD films |
| US9285168B2 (en) | 2010-10-05 | 2016-03-15 | Applied Materials, Inc. | Module for ozone cure and post-cure moisture treatment |
| US10283321B2 (en) | 2011-01-18 | 2019-05-07 | Applied Materials, Inc. | Semiconductor processing system and methods using capacitively coupled plasma |
| US9404178B2 (en) | 2011-07-15 | 2016-08-02 | Applied Materials, Inc. | Surface treatment and deposition for reduced outgassing |
| US8889566B2 (en) | 2012-09-11 | 2014-11-18 | Applied Materials, Inc. | Low cost flowable dielectric films |
| US9018108B2 (en) | 2013-01-25 | 2015-04-28 | Applied Materials, Inc. | Low shrinkage dielectric films |
| US9412581B2 (en) | 2014-07-16 | 2016-08-09 | Applied Materials, Inc. | Low-K dielectric gapfill by flowable deposition |
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| JPS63207121A (en) * | 1987-02-23 | 1988-08-26 | Nikon Corp | Method and apparatus for manufacturing thin film by photo-cvd |
| JPH01179410A (en) * | 1988-01-07 | 1989-07-17 | Nikon Corp | Method and apparatus for forming thin film by cvd |
-
1988
- 1988-02-03 JP JP63023007A patent/JP2763100B2/en not_active Expired - Lifetime
Non-Patent Citations (2)
| Title |
|---|
| Ｅｘｔｅｎｄｅｄ Ａｂｓｔｒａｃｔｓ ｏｆ ｔｈｅ １９ｔｈ Ｃｏｎｆｅｒｅｎｃｅ ｏｎ Ｓｏｌｉｄ Ｓｔａｔｅ Ｄｅｖｉｃｅｓ ａｎｄ Ｍａｔｅｒｉａｌｓ，Ｔｏｋｙｏ，１９８７，Ｐ．４５１−４５４ |
| 応用物理 Ｖｏｌ．５７ Ｎｏ．１２ （１９８８） |
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