JP2010153757A - Atomic layer growth apparatus - Google Patents

Atomic layer growth apparatus Download PDF

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JP2010153757A
JP2010153757A JP2008333151A JP2008333151A JP2010153757A JP 2010153757 A JP2010153757 A JP 2010153757A JP 2008333151 A JP2008333151 A JP 2008333151A JP 2008333151 A JP2008333151 A JP 2008333151A JP 2010153757 A JP2010153757 A JP 2010153757A
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raw material
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Nozomi Hattori
望 服部
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Mitsui Engineering and Shipbuilding Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To supply a plurality of raw material gases at a desired supply ratio for atomic layer growth. <P>SOLUTION: A raw material gas A supply unit 105 includes a raw material A vaporizer 151, a buffer tank A152, a charge valve A153, a supply valve A154, and a manometer A155. Further, a raw material gas B supply unit 106 includes a raw material B vaporizer 161, a buffer tank B162, a charge valve B163, a supply valve B164, and a manometer B165. A control unit 109 controls the opening extent of the charge valve A153 based upon a value of the pressure in the buffer tank A152 measured by the manometer A155. Further, the control unit 109 controls the opening extent of the charge valve B163 based upon a value of the pressure in the buffer tank B162 measured by the manometer B165. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

本発明は、原子層および分子層単位で薄膜の形成が可能な原子層成長装置に関し、特に、２種類以上の原料ガスを制御性よく安定して供給することができる原子層成長装置に関する。   The present invention relates to an atomic layer growth apparatus capable of forming a thin film in units of atomic layers and molecular layers, and more particularly to an atomic layer growth apparatus capable of stably supplying two or more kinds of source gases with good controllability.

近年、３００℃以下の低温で良質な薄膜がより均質な状態で形成可能であるなどの種々の特徴を備える技術として、原子層および分子層単位で薄膜の形成が可能な原子層成長（Atomic Layer Deposition：ＡＬＤ）法が、注目されている（特許文献１参照）。原子層成長法は、形成しようとする膜を構成する各元素の原料を基板に交互に供給することにより、原子層単位で薄膜を形成する技術である。原子層成長法では、各元素の原料を供給している間に１層あるいはｎ層（ｎは２以上の整数）だけを表面に吸着させ、余分な原料は成長に寄与させないようにしている。これを、成長の自己停止作用という。   In recent years, atomic layer growth (atomic layer capable of forming thin films in atomic layer and molecular layer units) is a technology with various features such as the ability to form high-quality thin films in a more homogeneous state at low temperatures of 300 ° C or lower. The Deposition (ALD) method has attracted attention (see Patent Document 1). The atomic layer growth method is a technique for forming a thin film in units of atomic layers by alternately supplying a raw material of each element constituting a film to be formed to a substrate. In the atomic layer growth method, only one layer or n layer (n is an integer of 2 or more) is adsorbed on the surface while the raw materials for each element are supplied, and excess raw materials are prevented from contributing to growth. This is called self-stopping action of growth.

原子層成長法によれば、一般的なＣＶＤに比較して極めて優れた形状適応性と膜厚制御性を併せ持っており、より低温でより広い面積に対して均一な薄膜を再現性よく形成できる技術として、大画面のフラットパネルディスプレイ製造への適用が検討されている。例えば、フラットパネルディスプレイの透明電極に用いられるＺｎＯなどの透明導電体膜の形成に、原子層成長法が検討されている。   The atomic layer growth method has extremely excellent shape adaptability and film thickness controllability compared to general CVD, and can form a uniform thin film with a high reproducibility over a wider area at a lower temperature. As a technology, application to the production of large-screen flat panel displays is being studied. For example, an atomic layer growth method has been studied for forming a transparent conductor film such as ZnO used for a transparent electrode of a flat panel display.

また、上述したような透明導電体膜を用いる場合、導電性を向上させるために、主材料に微量の元素を添加するようにしている。例えば、ＺｎＯ膜においては、ＡｌやＧａなどが添加されている（非特許文献１参照）。これらの２元系の酸化物からなる膜を原子層成長法で形成する場合、原料ガスを供給する工程において、各金属元素の原料ガスの流量を制御し、所定の比率で同時に供給することになる（非特許文献２参照）。このような供給量の制御においては、よく知られているように、ガスの通路の開度を変化させることで、ガスの流量を可変する流量制御装置が用いられている。   Further, when using the transparent conductor film as described above, a trace amount of element is added to the main material in order to improve conductivity. For example, Al, Ga, or the like is added to the ZnO film (see Non-Patent Document 1). When forming a film made of these binary oxides by atomic layer growth, in the step of supplying the source gas, the flow rate of the source gas of each metal element is controlled and simultaneously supplied at a predetermined ratio. (See Non-Patent Document 2). In the control of the supply amount, as is well known, a flow rate control device is used that varies the flow rate of gas by changing the opening of the gas passage.

特開２００６−０５２４２４号公報JP 2006-052424 A I. Volintiru, at al., "Evolution of the electrical and structural properties during the growth of Al doped ZnO films by remote plasma-enhanced metalorganic chemical vapor deposition", JOURNAL OF APPLIED PHYSICS, vol.102, No.043709, pp.1-9, 2007.I. Volintiru, at al., "Evolution of the electrical and structural properties during the growth of Al doped ZnO films by remote plasma-enhanced metalorganic chemical vapor deposition", JOURNAL OF APPLIED PHYSICS, vol.102, No.043709, pp. 1-9, 2007. B. Sang, et al., "Highly Stable ZnO Thin Films by Atomic Layer Deposition", Jpn.J.Appl.Phys., vol.37, pp.L1125-L1128, 1998.B. Sang, et al., "Highly Stable ZnO Thin Films by Atomic Layer Deposition", Jpn.J.Appl.Phys., Vol.37, pp.L1125-L1128, 1998. 後藤 勝彦著、「ＡＳＭ●枚葉式を製品化 １反応サイクル０．６秒を達成」、日経マイクロデバイス、５月号、５２−５３頁、２００４年。Goto Katsuhiko, “ASM ● Single-wafer type commercialized, achieving one reaction cycle of 0.6 seconds”, Nikkei Microdevices, May, 52-53, 2004.

しかしながら、工程の短時間化の要求による原料供給時間の短縮化に伴い、流量制御装置の応答が間に合わず、２種類の原料ガスの供給比の制御が不安定になるという問題が発生する。例えば、成膜を行う反応室の容積や、反応室内への原料ガスの供給を複数の方向から行うなどの工夫により、原子層成長の１反応の周期を１秒以下にまで短縮する技術が提案されている（非特許文献３参照）。このような短周期で原料ガスの供給と停止とを繰り返そうとする場合、上述したような流量制御装置では、供給する原料ガスの流量が設定値に到達せずに、１サイクルが終了してしまう。このため、２つのガスの供給比を、設定した値にすることができない。   However, with the shortening of the raw material supply time due to the demand for shortening the process, there is a problem that the response of the flow rate control device is not in time and the control of the supply ratio of the two types of raw material gases becomes unstable. For example, a technique to shorten the cycle of one reaction of atomic layer growth to 1 second or less by devising the volume of the reaction chamber for film formation and supplying the source gas into the reaction chamber from multiple directions is proposed. (See Non-Patent Document 3). When the supply and stop of the source gas are repeated in such a short cycle, the flow rate control device as described above ends one cycle without the flow rate of the supplied source gas reaching the set value. . For this reason, the supply ratio of the two gases cannot be set to a set value.

本発明は、以上のような問題点を解消するためになされたものであり、原子層成長において、所望とする供給比で複数の原料ガスが供給できるようにすることを目的とする。   The present invention has been made to solve the above-described problems, and an object thereof is to allow a plurality of source gases to be supplied at a desired supply ratio in atomic layer growth.

本発明に係る原子層成長装置は、密閉可能な内部空間を備えた反応容器と、第１金属を含む第１原料を気化することで第１原料ガスを生成する第１原料気化手段と、第２金属を含む第２原料を気化することで第２原料ガスを生成する第２原料気化手段と、第１原料気化手段が生成した第１原料ガスが充填される第１バッファタンクと、第２原料気化手段が生成した第２原料ガスが充填される第２バッファタンクと、第１バッファタンク内の圧力を測定する第１圧力計と、第２バッファタンク内の圧力を測定する第２圧力計と、第１バッファタンクの入力側に設けられて第１原料気化手段が生成した第１原料ガスの充填を制御する第１充填弁と、第２バッファタンクの入力側に設けられて第２原料気化手段が生成した第２原料ガスの充填を制御する第２充填弁と、第１バッファタンクからの第１原料ガスの反応容器に対する供給を制御する第１供給弁と、第２バッファタンクからの第２原料ガスの反応容器に対する供給を制御する第２供給弁と、第１圧力計の圧力計測値により第１充填弁の開度を制御し、第２圧力計の圧力計測値により第２充填弁の開度を制御する制御手段と、反応容器に酸化ガスを供給する酸化ガス供給手段と、反応容器にパージガスを供給するパージガス供給手段とを少なくとも備えるものである。   An atomic layer growth apparatus according to the present invention includes a reaction vessel having a sealable internal space, a first raw material vaporization unit that generates a first raw material gas by vaporizing a first raw material containing a first metal, A second raw material vaporization means for producing a second raw material gas by vaporizing a second raw material containing two metals, a first buffer tank filled with the first raw material gas produced by the first raw material vaporization means, A second buffer tank filled with the second raw material gas generated by the raw material vaporization means, a first pressure gauge for measuring the pressure in the first buffer tank, and a second pressure gauge for measuring the pressure in the second buffer tank; A first filling valve that is provided on the input side of the first buffer tank and controls the filling of the first raw material gas generated by the first raw material vaporization means, and a second raw material that is provided on the input side of the second buffer tank Control filling of second source gas generated by vaporization means A second filling valve, a first supply valve for controlling the supply of the first source gas from the first buffer tank to the reaction vessel, and a second for controlling the supply of the second source gas from the second buffer tank to the reaction vessel. 2 control valve for controlling the opening degree of the first filling valve by the pressure measurement value of the first pressure gauge and the opening degree of the second filling valve by the pressure measurement value of the second pressure gauge; The apparatus includes at least an oxidizing gas supply means for supplying an oxidizing gas and a purge gas supplying means for supplying a purge gas to the reaction vessel.

上記原子層成長装置において、第１バッファタンクからの第１原料ガスを第１供給弁を介して収容し、かつ、第２バッファタンクからの第２原料ガスを第２供給弁を介して収容するガス混合タンクを備え、第１原料ガスおよび第２原料ガスを、ガス混合タンクで混合して反応容器に導入するようにしてもよい。   In the atomic layer growth apparatus, the first source gas from the first buffer tank is accommodated via the first supply valve, and the second source gas from the second buffer tank is accommodated via the second supply valve. A gas mixing tank may be provided, and the first source gas and the second source gas may be mixed in the gas mixing tank and introduced into the reaction vessel.

以上説明したように、本発明によれば、第１圧力計による第１バッファタンクの圧力計測値により第１原料気化手段側の第１充填弁の開度を制御し、第２圧力計による第２バッファタンクの圧力計測値により第２原料気化手段側の第２充填弁の開度を制御し、第１バッファタンクより第１原料ガスを供給し、第２バッファタンクより第２原料ガスを供給するので、原子層成長において、所望とする供給比で複数の原料ガスが供給できるようになるという優れた効果が得られる。   As described above, according to the present invention, the opening degree of the first filling valve on the first raw material vaporization means side is controlled by the pressure measurement value of the first buffer tank by the first pressure gauge, and the second pressure gauge by the second pressure gauge. 2 The opening of the second filling valve on the second raw material vaporization means side is controlled by the measured pressure value of the second buffer tank, the first raw material gas is supplied from the first buffer tank, and the second raw material gas is supplied from the second buffer tank. Therefore, in the atomic layer growth, an excellent effect is obtained that a plurality of source gases can be supplied at a desired supply ratio.

以下、本発明の実施の形態について図を参照して説明する。図１は、本発明の実施の形態における原子層成長装置の構成を示す構成図である。本実施の形態における原子層成長装置は、まず、気相による膜の成長が行われる反応容器１０１と、反応容器１０１の内部に配置された加熱機構を備えた基板台１０２と、排気機構１０４とを備える。基板台１０２の上には、処理対象の基板１０３が載置される。また、この原子層成長装置は、原料ガスＡ（第１原料ガス）を供給する原料ガスＡ供給部１０５，原料ガスＢ（第２原料ガス）を供給する原料ガスＢ供給部１０６，酸素プラズマやオゾンガスなどの酸化ガスを供給する酸化ガス供給部１０７，および窒素ガスアルゴンガスなどのパージガスを供給するパージガス供給部１０８を備える。   Hereinafter, embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a configuration diagram showing a configuration of an atomic layer growth apparatus according to an embodiment of the present invention. The atomic layer growth apparatus in the present embodiment first includes a reaction vessel 101 in which a film is grown in a gas phase, a substrate stage 102 provided with a heating mechanism arranged inside the reaction vessel 101, an exhaust mechanism 104, Is provided. A substrate 103 to be processed is placed on the substrate table 102. Further, this atomic layer growth apparatus includes a source gas A supply unit 105 that supplies source gas A (first source gas), a source gas B supply unit 106 that supplies source gas B (second source gas), oxygen plasma, An oxidant gas supply unit 107 that supplies an oxidant gas such as ozone gas and a purge gas supply unit 108 that supplies a purge gas such as nitrogen gas and argon gas are provided.

また、本実施の形態における原子層成長装置は、酸化ガス供給部１０７からの酸化ガスの反応容器１０１に対する導入を制御する酸化ガス供給弁１１１、およびパージガス供給部１０８からのパージガスの反応容器１０１に対する導入を制御するパージガス供給弁１１２を備える。また、この原子層成長装置は、原料ガスＡ供給部１０５および原料ガスＢ供給部１０６の動作を制御する制御部１０９を備える。   In addition, the atomic layer growth apparatus in the present embodiment has an oxidizing gas supply valve 111 that controls introduction of oxidizing gas from the oxidizing gas supply unit 107 into the reaction vessel 101 and purge gas from the purge gas supply unit 108 to the reaction vessel 101. A purge gas supply valve 112 for controlling the introduction is provided. In addition, the atomic layer growth apparatus includes a control unit 109 that controls operations of the source gas A supply unit 105 and the source gas B supply unit 106.

原料ガスＡ供給部１０５は、原料Ａ気化器（第１原料気化手段）１５１，バッファタンクＡ（第１バッファタンク）１５２，充填弁Ａ（第１充填弁）１５３，供給弁Ａ（第１供給弁）１５４，および圧力計Ａ（第１圧力計）１５５を備える。また、原料ガスＢ供給部１０６は、原料Ｂ気化器（第２原料気化手段）１６１，バッファタンクＢ（第２バッファタンク）１６２，充填弁Ｂ（第２充填弁）１６３，供給弁Ｂ（第２供給弁）１６４，および圧力計Ｂ（第２圧力計）１６５を備える。   The raw material gas A supply unit 105 includes a raw material A vaporizer (first raw material vaporization means) 151, a buffer tank A (first buffer tank) 152, a filling valve A (first filling valve) 153, a supply valve A (first supply). Valve) 154, and a pressure gauge A (first pressure gauge) 155. The source gas B supply unit 106 includes a source B vaporizer (second source vaporization means) 161, a buffer tank B (second buffer tank) 162, a filling valve B (second filling valve) 163, and a supply valve B (first 2 supply valve) 164, and pressure gauge B (second pressure gauge) 165.

原料Ａ気化器１５１は、成膜しようとする金属酸化物の金属（第１金属）を含む原料（第１原料）として、例えば、ジエチル亜鉛（Ｚｎ（Ｃ2Ｈ5）2；ＤＥＺ）などの有機金属Ａ材料を収容し、収容しているＤＥＺを、例えば３０℃に加熱することで気化し、原料ガスＡを生成する。また、原料Ｂ気化器１６１は、添加しようとする金属（第２金属）を含む原料（第２原料）として、例えば、トリメチルガリウム（Ｇａ（ＣＨ3）3；ＴＭＧ）などの有機金属Ｂ材料を収容し、収容しているＴＭＧを、例えば３０℃に加熱することで気化し、原料ガスＢを生成する。 The raw material A vaporizer 151 is, for example, diethyl zinc (Zn (C 2 H 5 ) 2 ; DEZ) as a raw material (first raw material) containing a metal oxide metal (first metal) to be formed. The organometallic A material is accommodated, and the accommodated DEZ is vaporized, for example, by heating to 30 ° C. to generate the raw material gas A. Moreover, the raw material B vaporizer 161 uses, for example, an organic metal B material such as trimethylgallium (Ga (CH 3 ) 3 ; TMG) as a raw material (second raw material) containing a metal (second metal) to be added. The TMG accommodated and vaporized by heating the accommodated TMG to, for example, 30 ° C. to generate the raw material gas B.

制御部１０９は、圧力計Ａ１５５により計測されたバッファタンクＡ１５２内の圧力値をもとに、充填弁Ａ１５３の開度を制御する。また、制御部１０９は、圧力計Ｂ１６５により計測されたバッファタンクＢ１６２内の圧力値をもとに、充填弁Ｂ１６３の開度を制御する。例えば、制御部１０９は、圧力計Ａ１５５による計測圧力値が１．５ｋＰａとなるように充填弁Ａ１５３の開度を制御し、圧力計Ｂ１６５による計測圧力値が１ｋＰａとなるように充填弁Ｂ１６３の開度を制御する。   The control unit 109 controls the opening degree of the filling valve A153 based on the pressure value in the buffer tank A152 measured by the pressure gauge A155. Further, the control unit 109 controls the opening degree of the filling valve B163 based on the pressure value in the buffer tank B162 measured by the pressure gauge B165. For example, the control unit 109 controls the opening of the filling valve A153 so that the measured pressure value by the pressure gauge A155 becomes 1.5 kPa, and opens the filling valve B163 so that the measured pressure value by the pressure gauge B165 becomes 1 kPa. Control the degree.

従って、原料Ａ気化器１５１で生成された原料ガスＡは、バッファタンクＡ１５２内の圧力が１．５ｋＰａとなるようにバッファタンクＡ１５２に充填される。また、原料Ｂ気化器１６１で生成された原料ガスＢは、バッファタンクＢ１６２内の圧力が１ｋＰａとなるようにバッファタンクＢ１６２に充填される。これらの結果、供給弁Ａ１５４および供給弁Ｂ１６４を開放することで、ＤＥＺガスおよびＴＭＧガスは、供給量の比がおおよそ３：２の割合で混合されて、反応容器１０１に供給されることになる。   Therefore, the raw material gas A generated by the raw material A vaporizer 151 is filled into the buffer tank A152 so that the pressure in the buffer tank A152 becomes 1.5 kPa. Further, the raw material gas B generated by the raw material B vaporizer 161 is filled into the buffer tank B162 so that the pressure in the buffer tank B162 becomes 1 kPa. As a result, by opening the supply valve A154 and the supply valve B164, the DEZ gas and the TMG gas are mixed at a ratio of supply ratio of approximately 3: 2, and supplied to the reaction vessel 101. .

上述したように、本実施の形態における原子層成長装置によれば、２つの原料ガスを、流量制御装置を用いることなく、所望の混合比で反応容器１０１に供給することができる。また、本実施の形態における原子層成長装置では、各バッファタンク内の圧力値により各原料ガスの供給比を制御しているため、常に設定した比率で各原料ガスが供給できる。この結果、本実施の形態によれば、例えば１秒程度の短周期で原料ガスの供給と停止とを繰り返しても、２つの原料ガスを設定した比率で安定して供給できるようになる。   As described above, according to the atomic layer growth apparatus in the present embodiment, two source gases can be supplied to the reaction vessel 101 at a desired mixing ratio without using a flow rate control apparatus. Further, in the atomic layer growth apparatus in the present embodiment, since the supply ratio of each source gas is controlled by the pressure value in each buffer tank, each source gas can be always supplied at a set ratio. As a result, according to the present embodiment, for example, even if the supply and stop of the source gas are repeated in a short cycle of about 1 second, the two source gases can be stably supplied at a set ratio.

次に、本実施の形態における原子層成長装置を用いた原子層成長法によるＧａドープＺｎＯ膜の製造方法例について説明する。なお、以降では、原料Ａ気化器１５１からはＤＥＺガスが常に生成され、原料Ｂ気化器１６１からはＴＭＧガスが常に生成され、前述したように、各原料ガスが常に供給可能な状態とされている。また、酸化ガス供給部１０７からは、例えば、酸素プラズマよりなる酸化ガスが常に供給可能な状態とされ、パージガス供給部１０８からは、例えば、窒素ガスが常に供給可能な状態とされている。   Next, an example of a method for producing a Ga-doped ZnO film by an atomic layer growth method using the atomic layer growth apparatus in the present embodiment will be described. In the following, DEZ gas is always generated from the raw material A vaporizer 151, and TMG gas is always generated from the raw material B vaporizer 161, and as described above, each raw material gas is always supplied. Yes. Further, the oxidizing gas supply unit 107 is in a state in which, for example, an oxidizing gas made of oxygen plasma can be always supplied, and the purge gas supply unit 108 is in a state in which, for example, nitrogen gas can be always supplied.

まず、初期段階では、供給弁Ａ１５４，供給弁Ｂ１６４，酸化ガス供給弁１１１，およびパージガス供給弁１１２を閉じ、排気機構１０４を動作させ、反応容器１０１の内部を１Ｐａ程度に排気された状態とする。また、基板台１０２の上に載置されている処理対象の基板１０３を、１００〜３００℃に加熱する。例えば、３００℃に基板１０３を加熱しておく。   First, in the initial stage, the supply valve A154, the supply valve B164, the oxidizing gas supply valve 111, and the purge gas supply valve 112 are closed, the exhaust mechanism 104 is operated, and the inside of the reaction vessel 101 is exhausted to about 1 Pa. . The substrate 103 to be processed placed on the substrate table 102 is heated to 100 to 300 ° C. For example, the substrate 103 is heated to 300 ° C.

このような初期段階に次いで、原料吸着の過程が開始されると、まず、パージガス供給弁１１２および酸化ガス供給弁１１１は閉じた状態を継続し、供給弁Ａ１５４および供給弁Ｂ１６４を開ける。このことにより、反応容器１０１の内部に各原料ガスが導入され、導入された各原料ガスが、基板台１０２の上に載置されている基板１０３の上に供給される。この原料吸着の過程では、反応容器１０１の内部が例えば３０〜１００Ｐａとなる範囲で各原料ガスが供給され、基板１０３の表面に、例えば１分子層分の吸着層が形成される。   When the raw material adsorption process is started after such an initial stage, first, the purge gas supply valve 112 and the oxidizing gas supply valve 111 are kept closed, and the supply valve A154 and the supply valve B164 are opened. As a result, each source gas is introduced into the reaction vessel 101, and each introduced source gas is supplied onto the substrate 103 placed on the substrate table 102. In this raw material adsorption process, each raw material gas is supplied within a range of, for example, 30 to 100 Pa inside the reaction vessel 101, and an adsorption layer for one molecular layer, for example, is formed on the surface of the substrate 103.

次に、約０．１〜０．２秒間の原料吸着の過程が終了してパージの過程が開始されると、まず、供給弁Ａ１５４および供給弁Ｂ１６４を閉じた状態とし、酸化ガス供給弁１１１は閉じた状態を継続する。また、パージガス供給弁１１２を開ける。これらのことにより、反応容器１０１に導入されていた各原料ガスが、迅速にパージされる。   Next, when the raw material adsorption process for about 0.1 to 0.2 seconds is completed and the purge process is started, first, the supply valve A154 and the supply valve B164 are closed, and the oxidizing gas supply valve 111 is closed. Keeps closed. Further, the purge gas supply valve 112 is opened. By these things, each source gas introduced into the reaction vessel 101 is quickly purged.

次に、パージの過程が終了して酸化の過程が開始されると、まず、パージガス供給弁１１２，供給弁Ａ１５４，および供給弁Ｂ１６４を閉じた状態に継続し、酸化ガス供給弁１１１を開ける。このことにより、反応容器１０１の内部に酸化ガスが導入され、導入された酸化ガスが、基板１０３の上に供給される。例えば、反応容器１０１の内部が３０〜１００Ｐａ程度となるように、酸化ガスを供給すればよい。この結果、供給した酸化ガスにより基板１０３の表面に形成されている吸着層が酸化され、基板１０３の表面に、１分子層分のＧａドープＺｎＯ層が形成された状態となる。   Next, when the purge process is completed and the oxidation process is started, first, the purge gas supply valve 112, the supply valve A154, and the supply valve B164 are kept closed, and the oxidizing gas supply valve 111 is opened. As a result, an oxidizing gas is introduced into the reaction vessel 101, and the introduced oxidizing gas is supplied onto the substrate 103. For example, the oxidizing gas may be supplied so that the inside of the reaction vessel 101 is about 30 to 100 Pa. As a result, the adsorption layer formed on the surface of the substrate 103 is oxidized by the supplied oxidizing gas, and a Ga-doped ZnO layer for one molecular layer is formed on the surface of the substrate 103.

次に、酸化の過程が終了してパージの過程が開始されると、まず、酸化ガス供給弁１１１を閉じ、供給弁Ａ１５４および供給弁Ｂ１６４は閉じた状態を継続する。また、パージガス供給弁１１２を開ける。これらのことにより、反応容器１０１に導入された酸化ガスが、迅速にパージされる。   Next, when the oxidation process is completed and the purge process is started, first, the oxidizing gas supply valve 111 is closed, and the supply valve A154 and the supply valve B164 are kept closed. Further, the purge gas supply valve 112 is opened. As a result, the oxidizing gas introduced into the reaction vessel 101 is quickly purged.

以上の「原料吸着→パージ→酸化→パージ」を１サイクルとし、これを２００サイクル繰り返すことで、基板１０３の上に膜厚２０ｎｍ程度のＧａドープＺｎＯ膜を形成することができる。   The above-mentioned “raw material adsorption → purging → oxidation → purging” is one cycle, and by repeating this 200 cycles, a Ga-doped ZnO film having a thickness of about 20 nm can be formed on the substrate 103.

次に、本実施の形態における原子層成長装置を用いて形成したＧａドープＺｎＯ膜について説明する。バッファタンクＡ１５２の内部圧力を１．５ｋＰａ（圧力計Ａ１５５の計測値）とし、バッファタンクＢ１６２の内部圧力を０．２〜１．５ｋＰａ（圧力計Ｂ１６５の計測値）の範囲で可変させて形成したＧａドープＺｎＯ膜の特性を調査する。図２の白四角（◇）に示すように、バッファタンクＢ１６２の圧力を増加させ、ＴＭＧガス圧／ＤＥＺガス圧を大きくすると、形成したＧａドープＺｎＯ膜の比抵抗が小さくなる。また、図２の黒四角（■）に示すように、バッファタンクＢ１６２の圧力を増加させ、ＴＭＧガス圧／ＤＥＺガス圧を大きくすると、形成したＧａドープＺｎＯ膜におけるＧａ／Ｚｎ比が大きくなり、ＧａドープＺｎＯ膜中にドープされるＧａが増加していることがわかる。  Next, a Ga-doped ZnO film formed using the atomic layer growth apparatus in this embodiment will be described. The internal pressure of the buffer tank A152 was set to 1.5 kPa (measured value of the pressure gauge A155), and the internal pressure of the buffer tank B162 was varied within the range of 0.2 to 1.5 kPa (measured value of the pressure gauge B165). The characteristics of the Ga-doped ZnO film will be investigated. As shown by white squares (◇) in FIG. 2, when the pressure in the buffer tank B162 is increased and the TMG gas pressure / DEZ gas pressure is increased, the specific resistance of the formed Ga-doped ZnO film is decreased. Further, as shown by the black square (■) in FIG. 2, when the pressure of the buffer tank B162 is increased and the TMG gas pressure / DEZ gas pressure is increased, the Ga / Zn ratio in the formed Ga-doped ZnO film is increased, It can be seen that Ga doped in the Ga-doped ZnO film increases.

このように、本実施の形態によれば、バッファタンクＡ１５２およびバッファタンクＢ１６２の内部圧力を制御することで、ＧａドープＺｎＯ膜における組成の制御および抵抗率の制御ができることがわかる。   As described above, according to the present embodiment, it is understood that the composition and the resistivity of the Ga-doped ZnO film can be controlled by controlling the internal pressures of the buffer tank A152 and the buffer tank B162.

ところで、図３に示すように、原料ガスＡ供給部１０５より供給する原料ガスＡと原料ガスＢ供給部１０６より供給する原料ガスＢとを、ガス混合タンク３０１に混合してから反応容器１０１に導入してもよい。この場合、ガス混合タンク３０１内の圧力を圧力計３０２により測定し、この測定結果が設定値となるように、原料ガスＡ供給部１０５より供給する原料ガスＡおよび原料ガスＢ供給部１０６より供給する原料ガスＢの供給量を、供給弁Ａ１５４および供給弁Ｂ１６４により制御してもよい。ガス混合タンク３０１に供給された混合ガスの反応容器１０１に対する供給は、混合ガス供給弁３０３の開閉により制御される。   By the way, as shown in FIG. 3, the raw material gas A supplied from the raw material gas A supply unit 105 and the raw material gas B supplied from the raw material gas B supply unit 106 are mixed into the gas mixing tank 301 and then into the reaction vessel 101. It may be introduced. In this case, the pressure in the gas mixing tank 301 is measured by the pressure gauge 302, and supplied from the source gas A and source gas B supply unit 106 supplied from the source gas A supply unit 105 so that the measurement result becomes a set value. The supply amount of the raw material gas B may be controlled by the supply valve A154 and the supply valve B164. The supply of the mixed gas supplied to the gas mixing tank 301 to the reaction vessel 101 is controlled by opening and closing the mixed gas supply valve 303.

本発明の実施の形態における原子層成長装置の構成を示す構成図である。It is a block diagram which shows the structure of the atomic layer growth apparatus in embodiment of this invention. バッファタンクＡ１５２の内部圧力に対してバッファタンクＢ１６２の内部圧力を可変させて形成したＧａドープＺｎＯ膜の特性変化を示す特性図である。It is a characteristic view showing a characteristic change of a Ga-doped ZnO film formed by varying the internal pressure of the buffer tank B162 with respect to the internal pressure of the buffer tank A152. 本発明の実施の形態における他の原子層成長装置の構成を示す構成図である。It is a block diagram which shows the structure of the other atomic layer growth apparatus in embodiment of this invention.

符号の説明Explanation of symbols

１０１…反応容器、１０２…基板台、１０３…基板、１０４…排気機構、１０５…原料ガスＡ供給部、１０６…原料ガスＢ供給部、１０７…酸化ガス供給部、１０８…酸化ガス供給部、１０９…制御部、１１１…酸化ガス供給弁、１１２…パージガス供給弁、１５１…原料Ａ気化器（第１原料気化手段）、１５２…バッファタンクＡ（第１バッファタンク）、１５３…充填弁Ａ（第１充填弁）、１５４…供給弁Ａ（第１供給弁）、１５５…圧力計Ａ（第１圧力計）、１６１…原料Ｂ気化器（第２原料気化手段）、１６２…バッファタンクＢ（第２バッファタンク）、１６３…充填弁Ｂ（第２充填弁）、１６４…供給弁Ｂ（第２供給弁）、１６５…圧力計Ｂ（第２圧力計）。   DESCRIPTION OF SYMBOLS 101 ... Reaction container, 102 ... Substrate stand, 103 ... Substrate, 104 ... Exhaust mechanism, 105 ... Source gas A supply part, 106 ... Source gas B supply part, 107 ... Oxidation gas supply part, 108 ... Oxidation gas supply part, 109 DESCRIPTION OF SYMBOLS ... Control part 111 ... Oxidizing gas supply valve, 112 ... Purge gas supply valve, 151 ... Raw material A vaporizer (first raw material vaporization means), 152 ... Buffer tank A (first buffer tank), 153 ... Filling valve A (first 1 filling valve), 154 ... supply valve A (first supply valve), 155 ... pressure gauge A (first pressure gauge), 161 ... raw material B vaporizer (second raw material vaporization means), 162 ... buffer tank B (first 2 buffer tanks), 163 ... filling valve B (second filling valve), 164 ... supply valve B (second supply valve), 165 ... pressure gauge B (second pressure gauge).

Claims (2)

密閉可能な内部空間を備えた反応容器と、
第１金属を含む第１原料を気化することで第１原料ガスを生成する第１原料気化手段と、
第２金属を含む第２原料を気化することで第２原料ガスを生成する第２原料気化手段と、
前記第１原料気化手段が生成した前記第１原料ガスが充填される第１バッファタンクと、
前記第２原料気化手段が生成した前記第２原料ガスが充填される第２バッファタンクと、
前記第１バッファタンク内の圧力を測定する第１圧力計と、
前記第２バッファタンク内の圧力を測定する第２圧力計と、
前記第１バッファタンクの入力側に設けられて前記第１原料気化手段が生成した前記第１原料ガスの充填を制御する第１充填弁と、
前記第２バッファタンクの入力側に設けられて前記第２原料気化手段が生成した前記第２原料ガスの充填を制御する第２充填弁と、
前記第１バッファタンクからの前記第１原料ガスの前記反応容器に対する供給を制御する第１供給弁と、
前記第２バッファタンクからの前記第２原料ガスの前記反応容器に対する供給を制御する第２供給弁と、
前記第１圧力計の圧力計測値により前記第１充填弁の開度を制御し、前記第２圧力計の圧力計測値により前記第２充填弁の開度を制御する制御手段と、
前記反応容器に酸化ガスを供給する酸化ガス供給手段と、
前記反応容器にパージガスを供給するパージガス供給手段と
を少なくとも備えることを特徴とする原子層成長装置。 A reaction vessel with a sealable interior space;
First raw material vaporization means for generating a first raw material gas by vaporizing a first raw material containing a first metal;
A second raw material vaporization means for generating a second raw material gas by vaporizing a second raw material containing the second metal;
A first buffer tank filled with the first source gas generated by the first source vaporization means;
A second buffer tank filled with the second raw material gas generated by the second raw material vaporization means;
A first pressure gauge for measuring the pressure in the first buffer tank;
A second pressure gauge for measuring the pressure in the second buffer tank;
A first filling valve that is provided on the input side of the first buffer tank and controls filling of the first raw material gas generated by the first raw material vaporization means;
A second filling valve provided on the input side of the second buffer tank for controlling the filling of the second raw material gas generated by the second raw material vaporization means;
A first supply valve that controls the supply of the first source gas from the first buffer tank to the reaction vessel;
A second supply valve for controlling the supply of the second source gas from the second buffer tank to the reaction vessel;
Control means for controlling the opening of the first filling valve by the pressure measurement value of the first pressure gauge, and for controlling the opening of the second filling valve by the pressure measurement value of the second pressure gauge;
An oxidizing gas supply means for supplying an oxidizing gas to the reaction vessel;
At least a purge gas supply means for supplying a purge gas to the reaction vessel. 請求項１記載の原子層成長装置において、
前記第１バッファタンクからの前記第１原料ガスを前記第１供給弁を介して収容し、かつ、前記第２バッファタンクからの前記第２原料ガスを前記第２供給弁を介して収容するガス混合タンクを備え、
前記第１原料ガスおよび前記第２原料ガスを、前記ガス混合タンクで混合して前記反応容器に導入する
ことを特徴とする原子層成長装置。 The atomic layer growth apparatus according to claim 1,
Gas that contains the first source gas from the first buffer tank via the first supply valve, and that contains the second source gas from the second buffer tank via the second supply valve Equipped with a mixing tank,
The atomic layer growth apparatus, wherein the first source gas and the second source gas are mixed in the gas mixing tank and introduced into the reaction vessel.
JP2008333151A 2008-12-26 2008-12-26 Atomic layer growth apparatus Pending JP2010153757A (en)

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JP2013163863A (en) * 2012-02-10 2013-08-22 National Synchrotron Radiation Research Center Doping method of atomic layer deposition
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