JP2010159471A - FILM DEPOSITION METHOD OF Ge-Sb-Te-BASED FILM AND RECORDING MEDIUM - Google Patents

FILM DEPOSITION METHOD OF Ge-Sb-Te-BASED FILM AND RECORDING MEDIUM Download PDF

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JP2010159471A
JP2010159471A JP2009003570A JP2009003570A JP2010159471A JP 2010159471 A JP2010159471 A JP 2010159471A JP 2009003570 A JP2009003570 A JP 2009003570A JP 2009003570 A JP2009003570 A JP 2009003570A JP 2010159471 A JP2010159471 A JP 2010159471A
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JP5411512B2 (en
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Yumiko Kono
有美子 河野
Susumu Arima
進 有馬
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Tokyo Electron Ltd
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    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/26—Apparatus or processes specially adapted for the manufacture of record carriers
    • G11B7/266—Sputtering or spin-coating layers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
    • G11B7/2433—Metals or elements of Groups 13, 14, 15 or 16 of the Periodic Table, e.g. B, Si, Ge, As, Sb, Bi, Se or Te
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
    • G11B2007/24302—Metals or metalloids
    • G11B2007/24312—Metals or metalloids group 14 elements (e.g. Si, Ge, Sn)
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
    • G11B2007/24302—Metals or metalloids
    • G11B2007/24314—Metals or metalloids group 15 elements (e.g. Sb, Bi)
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
    • G11B2007/24302—Metals or metalloids
    • G11B2007/24316—Metals or metalloids group 16 elements (i.e. chalcogenides, Se, Te)

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a film deposition method of a Ge-Sb-Te-based film, by which the Ge-Sb-Te-based film having a target composition can be obtained by CVD. <P>SOLUTION: A substrate is arranged in a treatment container and then a Ge-Sb-Te-based film is deposited on the substrate by CVD while introducing a gaseous Ge raw material, a gaseous Sb raw material and a gaseous Te raw material into the treatment container. At this time, a Te-containing material is formed in gas flow passages and a reaction space before film deposition, and thereafter, a Ge-Sb-Te-based film having a predetermined composition is deposited by introducing the gaseous Ge raw material, the gaseous Sb raw material and the gaseous Te raw material or the gaseous Ge raw material and the gaseous Sb raw material into the treatment container, at respective predetermined flow rates. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は、ＣＶＤによりＧｅ−Ｓｂ−Ｔｅ系膜を成膜するＧｅ−Ｓｂ−Ｔｅ系膜の成膜方法および記憶媒体に関する。   The present invention relates to a Ge—Sb—Te film forming method and a storage medium for forming a Ge—Sb—Te film by CVD.

近時、情報記録媒体として、相変化型光記録媒体が注目されている。相変化型光記録媒体は、レーザー光の照射によって記録層に非晶質状態と結晶状態とを可逆的に生じさせ、その相変化を利用して情報を記録する。このような相変化型光記憶媒体は、情報の高速処理が可能であり、しかも記録容量が大きいという利点がある。   Recently, phase change optical recording media have attracted attention as information recording media. A phase change optical recording medium reversibly generates an amorphous state and a crystalline state in a recording layer by irradiation with laser light, and records information using the phase change. Such a phase change type optical storage medium is advantageous in that it can process information at high speed and has a large recording capacity.

このような相変化型光記録媒体に用いる記録層の材料としてＧｅ−Ｓｂ−Ｔｅ系膜が多用されている（特許文献１等）。このＧｅ−Ｓｂ−Ｔｅ系膜は、特許文献１に記載されているようにスパッタリングにより形成されるのが一般的であったが、スパッタリングではステップカバレッジが十分でないことから、Ｇｅ−Ｓｂ−Ｔｅ系膜をステップカバレッジの良好なＣＶＤにより成膜することが試みられている。   A Ge—Sb—Te-based film is frequently used as a material for a recording layer used in such a phase change type optical recording medium (Patent Document 1, etc.). This Ge—Sb—Te-based film is generally formed by sputtering as described in Patent Document 1, but since the step coverage is not sufficient in sputtering, the Ge—Sb—Te-based film is used. Attempts have been made to form a film by CVD with good step coverage.

特開２００６−２５６１４３号公報JP 2006-256143 A

このようなＧｅ−Ｓｂ−Ｔｅ系膜としては、現在、Ｇｅ２Ｓｂ２Ｔｅ５の組成のものが使われており、これを一般的な金属有機化合物であるアルキル基を含むＧｅ化合物、Ｓｂ化合物、Ｔｅ化合物でＣＶＤを行った場合、膜中Ｇｅが目標組成に比べて少なくなり、目標組成であるＧｅ２Ｓｂ２Ｔｅ５を得難いという問題が生じることが判明した。 As such a Ge—Sb—Te film, a composition of Ge 2 Sb 2 Te 5 is currently used, and this is a Ge compound containing an alkyl group which is a general metal organic compound, and an Sb compound. It has been found that when CVD is performed with a Te compound, the Ge in the film is smaller than the target composition, and it is difficult to obtain Ge 2 Sb 2 Te 5 which is the target composition.

本発明はかかる事情に鑑みてなされたものであって、ＣＶＤにより目標の組成のＧｅ−Ｓｂ−Ｔｅ系膜を得ることができるＧｅ−Ｓｂ−Ｔｅ系膜の成膜方法を提供することを目的とする。
また、上記目的を達成するための方法を実行させるプログラムが記憶された記憶媒体を提供することを目的とする。 The present invention has been made in view of such circumstances, and an object thereof is to provide a method for forming a Ge—Sb—Te film that can obtain a Ge—Sb—Te film having a target composition by CVD. And
It is another object of the present invention to provide a storage medium storing a program for executing a method for achieving the above object.

本発明者らは、上記課題を解決するため検討を重ねた結果、Ｔｅ化合物ガスは、流量構成として、他のＧｅ化合物ガスおよびＳｂ化合物ガスよりも少ない流量にしても、反応空間に供給すると、膜へのＧｅの取り込みを阻害し、それが目標組成のＧｅ−Ｓｂ−Ｔｅ系膜を得難い原因であることを見出した。そこで、さらに検討した結果、予めガスの通流経路壁や反応空間壁にＴｅ含有材料を形成しておくことにより、Ｔｅ化合物ガスを供給しなくても通流経路壁や反応空間壁からのＴｅを膜中に含ませることができ、これにより膜へのＧｅの取り込み阻害を抑制して所望の組成のＧｅ−Ｓｂ−Ｔｅ系膜が得られることを見出した。   As a result of repeated studies to solve the above problems, the present inventors have supplied the Te compound gas to the reaction space even when the flow rate configuration is smaller than other Ge compound gas and Sb compound gas. It was found that Ge incorporation into the film was inhibited, and that it was difficult to obtain a Ge—Sb—Te-based film having a target composition. Therefore, as a result of further investigation, by forming a Te-containing material on the gas flow path wall and the reaction space wall in advance, the Te from the flow path wall and the reaction space wall can be supplied without supplying the Te compound gas. It was found that a Ge—Sb—Te-based film having a desired composition can be obtained by suppressing the inhibition of Ge incorporation into the film.

本発明はそのような知見に基づいて完成されたものであり、処理容器内に基板を配置し、気体状のＧｅ原料と、気体状のＳｂ原料と、気体状のＴｅ原料とを前記処理容器内に導入してＣＶＤにより基板上にＧｅ−Ｓｂ−Ｔｅ系膜を成膜するに際し、成膜に先立ってガスの通流経路および／または反応空間にＴｅ含有材料を形成し、その後前記処理容器内に所定流量の気体状のＧｅ原料、気体状のＳｂ原料および気体状のＴｅ原料、または気体状のＧｅ原料および気体状のＳｂ原料を導入して所定の組成のＧｅ−Ｓｂ−Ｔｅ系膜を成膜するＧｅ−Ｓｂ−Ｔｅ系膜の成膜方法を提供する。   The present invention has been completed based on such knowledge. A substrate is disposed in a processing container, and a gaseous Ge raw material, a gaseous Sb raw material, and a gaseous Te raw material are disposed in the processing container. When a Ge—Sb—Te-based film is introduced into the substrate by CVD and formed, a Te-containing material is formed in the gas flow path and / or reaction space prior to film formation, and then the processing vessel A Ge-Sb-Te-based film having a predetermined composition by introducing a gaseous Ge raw material, a gaseous Sb raw material and a gaseous Te raw material, or a gaseous Ge raw material and a gaseous Sb raw material in a predetermined flow rate A method for forming a Ge—Sb—Te-based film is provided.

上記構成において、成膜に先立って前記処理容器内にＴｅ原料を導入して、ガスの通流経路壁および／または反応空間壁にＴｅを含有する膜を形成することにより、ガスの通流経路および／または反応空間にＴｅ含有材料を形成することができる。また、成膜に先立ってガスの通流経路および／または反応空間にＴｅを含有する部材を設けることによっても、ガスの通流経路および／または反応空間にＴｅ含有材料を形成することができる。   In the above-described configuration, a gas flow path is formed by introducing a Te raw material into the processing container prior to film formation to form a film containing Te on the gas flow path wall and / or the reaction space wall. And / or a Te-containing material can be formed in the reaction space. Further, by providing a member containing Te in the gas flow path and / or reaction space prior to the film formation, the Te-containing material can be formed in the gas flow path and / or reaction space.

また、気体状のＧｅ原料、気体状のＳｂ原料および気体状のＴｅ原料を用いて行う第１の成膜と、気体状のＧｅ原料および気体状のＳｂ原料を用いＴｅ原料を用いない第２の成膜を交互に行うことによって成膜を行うことができる。   In addition, the first film formation using the gaseous Ge raw material, the gaseous Sb raw material, and the gaseous Te raw material, and the second film using the gaseous Ge raw material and the gaseous Sb raw material and not using the Te raw material. The film formation can be performed by alternately performing the film formation.

さらに、成膜の際に、ガスの通流経路および／または反応空間に形成されたＴｅ含有材料から膜中に取り込まれるＴｅの量に基づいて、膜が所定の組成になるように、流量を制御して、気体状のＧｅ原料、気体状のＳｂ原料および気体状のＴｅ原料、または気体状のＧｅ原料および気体状のＳｂ原料を導入するようにすることができる。   Furthermore, the flow rate is adjusted so that the film has a predetermined composition based on the amount of Te taken into the film from the Te-containing material formed in the gas flow path and / or reaction space during film formation. It can be controlled to introduce a gaseous Ge source, a gaseous Sb source and a gaseous Te source, or a gaseous Ge source and a gaseous Sb source.

本発明が適用されるＧｅ−Ｓｂ−Ｔｅ系膜の組成としては、Ｇｅ２Ｓｂ２Ｔｅ５を挙げることができる。また、Ｇｅ原料、Ｓｂ原料およびＴｅ原料としては、アルキル基を含む化合物よりなるものであることが好ましい。 Examples of the composition of the Ge—Sb—Te based film to which the present invention is applied include Ge 2 Sb 2 Te 5 . Further, the Ge raw material, the Sb raw material and the Te raw material are preferably made of a compound containing an alkyl group.

本発明は、また、コンピュータ上で動作し、成膜装置を制御するプログラムが記憶された記憶媒体であって、前記制御プログラムは、実行時に、上記成膜方法が行われるように、コンピュータに前記成膜装置を制御させることを特徴とする記憶媒体を提供する。 The present invention is also a storage medium that operates on a computer and stores a program for controlling the film forming apparatus, and the control program stores the program in the computer so that the film forming method is performed at the time of execution. A storage medium characterized by controlling a film formation apparatus is provided.

本発明によれば、ＣＶＤによりＧｅ−Ｓｂ−Ｔｅ系膜を成膜する際に、成膜に先立ってガスの通流経路および／または反応空間にＴｅ含有材料を形成するので、Ｔｅ原料によるＧｅの取り込み阻害を軽減しつつ必要なＴｅ量を確保することができ、所望の組成のＧｅ−Ｓｂ−Ｔｅ系膜を得ることができる。   According to the present invention, when a Ge—Sb—Te-based film is formed by CVD, a Te-containing material is formed in the gas flow path and / or reaction space prior to film formation. The necessary amount of Te can be ensured while reducing the uptake inhibition of Ge, and a Ge—Sb—Te-based film having a desired composition can be obtained.

本発明に係るＧｅ−Ｓｂ−Ｔｅ系膜の成膜方法の実施に用いることができる成膜装置の概略構成を示す断面図。Sectional drawing which shows schematic structure of the film-forming apparatus which can be used for implementation of the film-forming method of the Ge-Sb-Te type film | membrane which concerns on this invention. 本発明の成膜方法を説明するためのフローチャート。3 is a flowchart for explaining a film forming method of the present invention.

以下、添付図面を参照して本発明の実施形態について説明する。
図１は、本発明に係るＧｅ−Ｓｂ−Ｔｅ系膜の成膜方法の実施に用いることができる成膜装置の概略構成を示す断面図である。図１に示す成膜装置１００は、例えばアルミニウムなどにより円筒状あるいは箱状に成形された処理容器１を有しており、処理容器１内には、基板Ｓが載置される載置台３が設けられている。載置台３は厚さ１ｍｍ程度の例えばグラファイト板あるいはＳｉＣで覆われたグラファイト板などのカーボン素材、窒化アルミニウムなどの熱伝導性の良いセラッミクス等により構成される。 Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings.
FIG. 1 is a cross-sectional view showing a schematic configuration of a film forming apparatus that can be used for carrying out a method for forming a Ge—Sb—Te-based film according to the present invention. A film forming apparatus 100 shown in FIG. 1 has a processing container 1 formed into a cylindrical shape or a box shape by using aluminum or the like, for example, and a mounting table 3 on which a substrate S is placed is placed in the processing container 1. Is provided. The mounting table 3 is composed of a carbon material such as a graphite plate or a graphite plate covered with SiC having a thickness of about 1 mm, ceramics having good thermal conductivity such as aluminum nitride, and the like.

載置台３の外周側には、処理容器１底部より起立させた円筒体状の例えばアルミニウムよりなる区画壁１３が形成されており、その上端を例えばＬ字状に水平方向へ屈曲させて屈曲部１４を形成している。このように、円筒体状の区画壁１３を設けることにより、載置台３の裏面側に不活性ガスパージ室１５が形成される。屈曲部１４の上面は、載置台３の上面と実質的に同一の平面上にあり、載置台３の外周から離間しており、この間隙に連結棒１２が挿通されている。載置台３は、区画壁１３の上部内壁より延びる３本（図示例では２本のみ記す）の支持アーム４により支持されている。   A cylindrical partition wall 13 made of, for example, aluminum, which is erected from the bottom of the processing container 1 is formed on the outer peripheral side of the mounting table 3, and its bent upper portion is bent in the horizontal direction, for example, in an L shape. 14 is formed. Thus, by providing the cylindrical partition wall 13, the inert gas purge chamber 15 is formed on the back surface side of the mounting table 3. The upper surface of the bent portion 14 is substantially on the same plane as the upper surface of the mounting table 3, is separated from the outer periphery of the mounting table 3, and the connecting rod 12 is inserted through this gap. The mounting table 3 is supported by three (only two in the illustrated example) support arms 4 extending from the upper inner wall of the partition wall 13.

載置台３の下方には、複数本、例えば３本のＬ字状のリフタピン５（図示例では２本のみ記す）がリング状の支持部材６から上方に突出するように設けられている。支持部材６は、処理容器１の底部から貫通して設けられた昇降ロッド７により昇降可能となっており、昇降ロッド７は処理容器１の下方に位置するアクチュエータ１０により上下動される。載置台３のリフタピン５に対応する部分には載置台３を貫通して挿通穴８が設けられており、アクチュエータ１０により昇降ロッド７および支持部材６を介してリフタピン５を上昇させることにより、リフタピン５をこの挿通穴８に挿通させて基板Ｓを持ち上げることが可能となっている。昇降ロッド７の処理容器１への挿入部分はベローズ９で覆われており、その挿入部分から処理容器１内に外気が侵入することを防止している。   Below the mounting table 3, a plurality of, for example, three L-shaped lifter pins 5 (only two in the illustrated example) are provided so as to protrude upward from the ring-shaped support member 6. The support member 6 can be moved up and down by a lifting rod 7 penetrating from the bottom of the processing container 1, and the lifting rod 7 is moved up and down by an actuator 10 located below the processing container 1. A portion of the mounting table 3 corresponding to the lifter pin 5 is provided with an insertion hole 8 penetrating the mounting table 3. The lifter pin 5 is lifted by the actuator 10 via the lifting rod 7 and the support member 6. 5 can be inserted into the insertion hole 8 to lift the substrate S. The insertion portion of the elevating rod 7 into the processing container 1 is covered with a bellows 9 to prevent outside air from entering the processing container 1 from the insertion portion.

載置台３の周縁部には、基板Ｓの周縁部を保持してこれを載置台３側へ固定するため、例えば円板状の基板Ｓの輪郭形状に沿った略リング状の例えば窒化アルミニウムなどのセラミック製のクランプリング部材１１が設けられている。クランプリング部材１１は、連結棒１２を介して上記支持部材６に連結されており、リフタピン５と一体的に昇降するようになっている。リフタピン５や連結棒１２等はアルミナなどのセラミックスにより形成される。   In order to hold the peripheral portion of the substrate S on the peripheral portion of the mounting table 3 and fix it to the mounting table 3 side, for example, a substantially ring shape such as aluminum nitride along the contour shape of the disk-shaped substrate S, etc. A ceramic clamp ring member 11 is provided. The clamp ring member 11 is connected to the support member 6 via a connecting rod 12 and is moved up and down integrally with the lifter pin 5. The lifter pins 5 and the connecting rods 12 are formed of ceramics such as alumina.

リング状のクランプリング部材１１の内周側の下面には、周方向に沿って略等間隔で配置された複数の接触突起１６が形成されており、クランプ時には、接触突起１６の下端面が、基板Ｓの周縁部の上面と当接してこれを押圧するようになっている。なお、接触突起１６の直径は１ｍｍ程度であり、高さは略５０μｍ程度であり、クランプ時にはこの部分にリング状の第１ガスパージ用間隙１７を形成する。なお、クランプ時の基板Ｓの周縁部とクランプリング部材１１の内周側とのオーバラップ量（第１ガスパージ用間隙１７の流路長さ）Ｌ１は数ｍｍ程度である。   A plurality of contact protrusions 16 arranged at substantially equal intervals along the circumferential direction are formed on the lower surface on the inner peripheral side of the ring-shaped clamp ring member 11, and at the time of clamping, the lower end surface of the contact protrusion 16 is The upper surface of the peripheral part of the board | substrate S is contact | abutted and this is pressed. The diameter of the contact protrusion 16 is about 1 mm and the height is about 50 μm, and a ring-shaped first gas purge gap 17 is formed in this portion during clamping. It should be noted that an overlap amount (flow path length of the first gas purge gap 17) L1 between the peripheral edge of the substrate S and the inner peripheral side of the clamp ring member 11 during clamping is about several millimeters.

クランプリング部材１１の外周縁部は、区画壁１３の上端屈曲部１４の上方に位置され、ここにリング状の第２ガスパージ用間隙１８が形成される。第２ガスパージ用間隙１８の幅（高さ）は、例えば５００μｍ程度であり、第１ガスパージ用間隙１７の幅よりも１０倍程大きい幅とされる。クランプリング部材１１の外周縁部と屈曲部１４とのオーバラップ量（第２ガスパージ用間隙１８の流路長さ）は、例えば略１０ｍｍ程度である。これにより、不活性ガスパージ室１５内の不活性ガスは、両間隙１７、１８から処理空間側へ流出できるようになっている。   The outer peripheral edge portion of the clamp ring member 11 is positioned above the upper end bent portion 14 of the partition wall 13, and a ring-shaped second gas purge gap 18 is formed therein. The width (height) of the second gas purge gap 18 is, for example, about 500 μm, and is about 10 times larger than the width of the first gas purge gap 17. The overlap amount between the outer peripheral edge portion of the clamp ring member 11 and the bent portion 14 (the flow path length of the second gas purge gap 18) is, for example, about 10 mm. As a result, the inert gas in the inert gas purge chamber 15 can flow out from the gaps 17 and 18 to the processing space side.

処理容器１の底部には、上記不活性ガスパージ室１５に不活性ガスを供給する不活性ガス供給機構１９が設けられている。このガス供給機構１９は、不活性ガス例えばＡｒガス（バックサイドＡｒ）を不活性ガスパージ室１５に導入するためのガスノズル２０と、不活性ガスとしてのＡｒガスを供給するためのＡｒガス供給源２１と、Ａｒガス供給源２１からガスノズル２０にＡｒガスを導くガス配管２２とを有している。また、ガス配管２２には、流量制御器としてのマスフローコントローラ２３および開閉バルブ２４，２５が設けられている。不活性ガスとしてＡｒガスに替えてＨｅガス等の他の希ガスを用いてもよい。   An inert gas supply mechanism 19 that supplies an inert gas to the inert gas purge chamber 15 is provided at the bottom of the processing container 1. The gas supply mechanism 19 includes a gas nozzle 20 for introducing an inert gas such as Ar gas (backside Ar) into the inert gas purge chamber 15, and an Ar gas supply source 21 for supplying Ar gas as an inert gas. And a gas pipe 22 for guiding Ar gas from the Ar gas supply source 21 to the gas nozzle 20. Further, the gas pipe 22 is provided with a mass flow controller 23 as a flow rate controller and open / close valves 24 and 25. Other inert gases such as He gas may be used as the inert gas instead of Ar gas.

処理容器１の底部の載置台３の直下位置には、石英等の熱線透過材料よりなる透過窓３０が気密に設けられており、この下方には、透過窓３０を囲むように箱状の加熱室３１が設けられている。この加熱室３１内には、加熱手段として複数個の加熱ランプ３２が、反射鏡も兼ねる回転台３３に取り付けられている。回転台３３は、回転軸を介して加熱室３１の底部に設けられた回転モータ３４により回転される。したがって、加熱ランプ３２より放出された熱線が透過窓３０を透過して載置台３の下面を照射してこれを加熱する。   A transmission window 30 made of a heat ray transmission material such as quartz is airtightly provided immediately below the mounting table 3 at the bottom of the processing container 1, and a box-like heating is provided below this to surround the transmission window 30. A chamber 31 is provided. In the heating chamber 31, a plurality of heating lamps 32 are attached as a heating means to a turntable 33 that also serves as a reflecting mirror. The turntable 33 is rotated by a rotation motor 34 provided at the bottom of the heating chamber 31 via a rotation shaft. Therefore, the heat rays emitted from the heating lamp 32 pass through the transmission window 30 and irradiate the lower surface of the mounting table 3 to heat it.

また、処理容器１底部の周縁部には、排気口３６が設けられ、排気口３６には図示しない真空ポンプに接続された排気管３７が接続されている。そして、この排気口３６および排気管３７を介して排気することにより処理容器１内を所定の真空度に維持し得るようになっている。また、処理容器１の側壁には、基板Ｓを搬入出する搬入出口３９と、搬入出口３９を開閉するゲートバルブ３８が設けられる。   Further, an exhaust port 36 is provided at the peripheral edge of the bottom of the processing container 1, and an exhaust pipe 37 connected to a vacuum pump (not shown) is connected to the exhaust port 36. The inside of the processing container 1 can be maintained at a predetermined degree of vacuum by exhausting through the exhaust port 36 and the exhaust pipe 37. Further, a loading / unloading port 39 for loading / unloading the substrate S and a gate valve 38 for opening / closing the loading / unloading port 39 are provided on the side wall of the processing container 1.

一方、載置台３と対向する処理容器１の天井部には、ソースガスなどを処理容器１内へ導入するためシャワーヘッド４０が設けられている。シャワーヘッド４０は、例えばアルミニウム等により構成され、内部に空間４１ａを有する円盤状をなすヘッド本体４１を有している。ヘッド本体４１の天井部にはガス導入口４２が設けられている。ガス導入口４２には、Ｇｅ−Ｓｂ−Ｔｅ系膜の成膜に必要な処理ガスを供給する処理ガス供給機構５０がその配管５１によって接続されている。ヘッド本体４１の底部には、ヘッド本体４１内へ供給されたガスを処理容器１内の処理空間へ放出するための多数のガス噴射孔４３が全面に亘って配置されており、基板Ｓの全面にガスを放出するようになっている。また、ヘッド本体４１内の空間４１ａには、多数のガス分散孔４５を有する拡散板４４が配設されており、基板Ｓの表面に、より均等にガスを供給可能となっている。さらに、処理容器１の側壁内およびシャワーヘッド４０の側壁内およびガス噴射孔４３の配置されたウエハ対向面内には、それぞれ温度調整のためのカートリッジヒータ４６，４７が設けられており、ガスとも接触する側壁やシャワーヘッド部を所定の温度に保持できるようになっている。   On the other hand, a shower head 40 is provided on the ceiling of the processing container 1 facing the mounting table 3 in order to introduce source gas or the like into the processing container 1. The shower head 40 is made of, for example, aluminum and has a head body 41 having a disk shape having a space 41a therein. A gas inlet 42 is provided in the ceiling of the head body 41. A processing gas supply mechanism 50 that supplies a processing gas necessary for forming a Ge—Sb—Te-based film is connected to the gas inlet 42 by a pipe 51. A large number of gas injection holes 43 for discharging the gas supplied into the head main body 41 to the processing space in the processing container 1 are arranged on the entire bottom surface of the head main body 41. It is designed to release gas. A diffusion plate 44 having a large number of gas dispersion holes 45 is disposed in the space 41a in the head main body 41 so that gas can be supplied more evenly to the surface of the substrate S. Further, cartridge heaters 46 and 47 for temperature adjustment are provided in the side wall of the processing vessel 1, the side wall of the shower head 40, and the wafer facing surface where the gas injection holes 43 are arranged, respectively. The side wall and shower head part which contacts can be hold | maintained at predetermined temperature.

処理ガス供給機構５０は、Ｔｅ原料を貯留するＴｅ原料貯留部５２と、Ｓｂ原料を貯留するＳｂ原料貯留部５３と、Ｇｅ原料を貯留するＧｅ原料貯留部５４と、処理容器１内のガスを希釈するためのアルゴンガス等の希釈ガスを供給する希釈ガス供給源５５とを有している。   The processing gas supply mechanism 50 includes a Te raw material storage unit 52 that stores Te raw material, an Sb raw material storage unit 53 that stores Sb raw material, a Ge raw material storage unit 54 that stores Ge raw material, and a gas in the processing container 1. A dilution gas supply source 55 for supplying a dilution gas such as argon gas for dilution.

シャワーヘッド４０に接続されている配管５１には、Ｔｅ原料貯留部５２から延びる配管５６、Ｓｂ原料貯留部５３から延びる配管５７、Ｇｅ原料貯留部５４から延びる配管５８が接続されており、配管５１には上記希釈ガス供給源５５が接続されている。配管５１には、流量制御器としてのマスフローコントローラ（ＭＦＣ）６０とその前後の開閉バルブ６１，６２が設けられている。また、配管５８には、流量制御器としてのマスフローコントローラ（ＭＦＣ）６３とその前後の開閉バルブ６４，６５が設けられている。   The pipe 51 connected to the shower head 40 is connected to a pipe 56 extending from the Te raw material storage 52, a pipe 57 extending from the Sb raw material storage 53, and a pipe 58 extending from the Ge raw material storage 54. Is connected to the dilution gas supply source 55. The pipe 51 is provided with a mass flow controller (MFC) 60 as a flow rate controller and front and rear opening / closing valves 61 and 62. Further, the pipe 58 is provided with a mass flow controller (MFC) 63 as a flow rate controller and front and rear opening / closing valves 64 and 65.

Ｔｅ原料貯留部５２には、Ａｒ等のバブリングのためのキャリアガスを供給するキャリアガス供給源６６が配管６７を介して接続されている。配管６７には、流量制御器としてのマスフローコントローラ（ＭＦＣ）６８とその前後の開閉バルブ６９，７０が設けられている。また、Ｓｂ原料貯留部５３にも、Ａｒ等のキャリアガスを供給するキャリアガス供給源７１が配管７２を介して接続されている。配管７２には、流量制御器としてのマスフローコントローラ（ＭＦＣ）７３とその前後の開閉バルブ７４，７５が設けられている。Ｔｅ原料貯留部５２、Ｓｂ原料貯留部５３には、それぞれヒータ７６、７７が設けられている。そして、Ｔｅ原料貯留部５２に貯留されたＴｅ原料およびＳｂ原料貯留部５３に貯留されたＳｂ原料は、これらヒータ７６、７７で加熱された状態で、バブリングにより処理容器１に供給されるようになっている。また、Ｇｅ原料貯留部５４に貯留されたＧｅ原料はマスフローコントローラ（ＭＦＣ）６３により流量制御しつつ処理容器１に供給されるようになっている。図示してはいないが、Ｇｅ原料、Ｓｒ原料およびＴｉ原料を気化した状態で供給する処理容器１までの配管やマスフローコントローラにもヒータが設けられている。   A carrier gas supply source 66 for supplying a carrier gas for bubbling Ar or the like is connected to the Te raw material reservoir 52 via a pipe 67. The pipe 67 is provided with a mass flow controller (MFC) 68 as a flow rate controller and front and rear opening / closing valves 69 and 70. Further, a carrier gas supply source 71 for supplying a carrier gas such as Ar is also connected to the Sb raw material reservoir 53 via a pipe 72. The pipe 72 is provided with a mass flow controller (MFC) 73 as a flow rate controller and open / close valves 74 and 75 before and after the mass flow controller (MFC) 73. The Te raw material reservoir 52 and the Sb raw material reservoir 53 are provided with heaters 76 and 77, respectively. The Te raw material stored in the Te raw material storage unit 52 and the Sb raw material stored in the Sb raw material storage unit 53 are supplied to the processing container 1 by bubbling while being heated by the heaters 76 and 77. It has become. Further, the Ge raw material stored in the Ge raw material storage unit 54 is supplied to the processing vessel 1 while the flow rate is controlled by a mass flow controller (MFC) 63. Although not shown, a heater is also provided in the piping and the mass flow controller to the processing container 1 that supplies the Ge raw material, the Sr raw material, and the Ti raw material in a vaporized state.

なお、本実施形態では、Ｇｅ原料をマスフローコントローラ供給とし、Ｓｂ原料およびＴｅ原料をバブリング供給した例を示したが、Ｇｅ原料をバブリング供給してもよいし、Ｓｂ原料、Ｔｅ原料をマスフローコントローラ供給してもよい。また、液体の状態の原料を液体マスフローコントローラで流量制御して気化器により気化して供給するようにしてもよい。   In the present embodiment, the Ge raw material is supplied by the mass flow controller, and the Sb raw material and the Te raw material are supplied by bubbling. However, the Ge raw material may be supplied by bubbling, and the Sb raw material and Te raw material are supplied by the mass flow controller. May be. Further, the raw material in a liquid state may be supplied by being controlled by a liquid mass flow controller and vaporized by a vaporizer.

Ｇｅ原料、Ｓｂ原料、Ｔｅ原料としては、気体供給が可能な化合物であれば用いることができる。蒸気圧が高い化合物であれば気化しやすく有利である。アルキル基を含む化合物は、蒸気圧が高く安価であるため、好適に用いることができる。ただし、アルキル基を含むものに限定されない。   As the Ge raw material, the Sb raw material, and the Te raw material, any compound that can supply gas can be used. A compound having a high vapor pressure is advantageous because it is easily vaporized. A compound containing an alkyl group can be suitably used because it has a high vapor pressure and is inexpensive. However, it is not limited to the thing containing an alkyl group.

アルキル基を含むものとして具体的には、Ｇｅ原料としては、メチルゲルマニウムＧｅ（ＣＨ３）Ｈ３、ターシャリブチルゲルマニウム［Ｇｅ（（ＣＨ３）３Ｃ）Ｈ３］、テトラメチルゲルマニウム［Ｇｅ（ＣＨ３）４］、テトラエチルゲルマニウム［Ｇｅ（Ｃ２Ｈ５）４］、テトラジメチルアミノゲルマニウム［Ｇｅ（（ＣＨ３）２Ｎ）４］等を挙げることができ、Ｓｂ原料としては、トリイソプロピルアンチモン［Ｓｂ（ｉ−Ｃ３Ｈ７）３］、トリメチルアンチモン［Ｓｂ（ＣＨ３）３］、トリスジメチルアミノアンチモン［Ｓｂ（（ＣＨ３）２Ｎ）３］等を挙げることができ、Ｔｅ原料としては、ジイソプロピルテルル［Ｔｅ（ｉ−Ｃ３Ｈ７）２］、ジターシャリブチルテルル［Ｔｅ（ｔ−Ｃ４Ｈ９）２］、ジエチルテルル［Ｔｅ（Ｃ２Ｈ５）２］等を挙げることができる。 Specifically, as the Ge raw material containing an alkyl group, methyl germanium Ge (CH 3 ) H 3 , tertiary butyl germanium [Ge ((CH 3 ) 3 C) H 3 ], tetramethyl germanium [Ge ( CH 3 ) 4 ], tetraethylgermanium [Ge (C 2 H 5 ) 4 ], tetradimethylaminogermanium [Ge ((CH 3 ) 2 N) 4 ] and the like. Examples of the Sb raw material include triisopropylantimony [Sb (i-C 3 H 7 ) 3 ], trimethylantimony [Sb (CH 3 ) 3 ], trisdimethylaminoantimony [Sb ((CH 3 ) 2 N) 3 ] and the like can be mentioned as Te raw materials. is diisopropyl tellurium [Te (i-C 3 H 7) 2], di-tert-butyl tellurium [Te (t-C 4 H ) 2], diethyl tellurium [Te (C 2 H 5) 2] , and the like.

処理容器１の側壁上部には、クリーニングガスであるＮＦ３ガスを導入するクリーニングガス導入部８１が設けられている。このクリーニングガス導入部８１にはＮＦ３ガスを供給する配管８２が接続されており、この配管８２にはリモートプラズマ発生部８３が設けられている。そして、このリモートプラズマ発生部８３において配管８２を介して供給されたＮＦ３ガスがプラズマ化され、これが処理容器１内に供給されることにより処理容器１内がクリーニングされる。なお、リモートプラズマ発生部をシャワーヘッド４０の直上に設け、クリーニングガスをシャワーヘッド４０を介して供給するようにしてもよい。また、ＮＦ３の代わりにＦ２を用いてもよいし、リモートプラズマを使用せず、ＣｌＦ３等によるプラズマレスの熱クリーニングを行うようにしてもよい。 A cleaning gas introduction part 81 for introducing NF 3 gas, which is a cleaning gas, is provided on the upper side wall of the processing container 1. A pipe 82 for supplying NF 3 gas is connected to the cleaning gas introduction part 81, and a remote plasma generation part 83 is provided in the pipe 82. Then, the NF 3 gas supplied through the pipe 82 is converted into plasma in the remote plasma generation unit 83 and supplied into the processing container 1, thereby cleaning the inside of the processing container 1. Note that a remote plasma generation unit may be provided immediately above the shower head 40 and the cleaning gas may be supplied via the shower head 40. Further, F 2 may be used instead of NF 3 , and plasmaless thermal cleaning with ClF 3 or the like may be performed without using remote plasma.

成膜装置１００はマイクロプロセッサ（コンピュータ）からなるプロセスコントローラ９０を有しており、成膜装置１００の各構成部がこのプロセスコントローラ９０に接続されて制御される構成となっている。また、プロセスコントローラ９０には、オペレータが成膜装置１００の各構成部を管理するためにコマンドの入力操作などを行うキーボードや、成膜装置１００の各構成部の稼働状況を可視化して表示するディスプレイ等からなるユーザーインターフェース９１が接続されている。さらに、プロセスコントローラ９０には、成膜装置１００で実行される各種処理をプロセスコントローラ９０の制御にて実現するための制御プログラムや、処理条件に応じて成膜装置１００の各構成部に所定の処理を実行させるための制御プログラムすなわち処理レシピや、各種データベース等が格納された記憶部９２が接続されている。処理レシピは記憶部９２の中の記憶媒体（図示せず）に記憶されている。記憶媒体は、ハードディスク等の固定的に設けられているものであってもよいし、ＣＤＲＯＭ、ＤＶＤ、フラッシュメモリ等の可搬性のものであってもよい。また、他の装置から、例えば専用回線を介してレシピを適宜伝送させるようにしてもよい。   The film forming apparatus 100 includes a process controller 90 including a microprocessor (computer), and each component of the film forming apparatus 100 is connected to the process controller 90 and controlled. In addition, the process controller 90 visualizes and displays the operation status of each component of the film forming apparatus 100 and a keyboard on which an operator inputs commands to manage each component of the film forming apparatus 100. A user interface 91 including a display is connected. Further, the process controller 90 has a control program for realizing various processes executed by the film forming apparatus 100 under the control of the process controller 90, and predetermined components are assigned to respective components of the film forming apparatus 100 according to processing conditions. A storage unit 92 that stores a control program for executing the process, that is, a process recipe, various databases, and the like is connected. The processing recipe is stored in a storage medium (not shown) in the storage unit 92. The storage medium may be a fixed medium such as a hard disk or a portable medium such as a CDROM, DVD, or flash memory. Moreover, you may make it transmit a recipe suitably from another apparatus via a dedicated line, for example.

そして、必要に応じて、ユーザーインターフェース９１からの指示等にて所定の処理レシピを記憶部９２から呼び出してプロセスコントローラ９０に実行させることで、プロセスコントローラ９０の制御下で、成膜装置１００での所望の処理が行われる。   Then, if necessary, a predetermined processing recipe is called from the storage unit 92 by an instruction from the user interface 91 and is executed by the process controller 90, so that the film forming apparatus 100 can control the process controller 90. Desired processing is performed.

次に、以上のように構成された成膜装置を用いて行われる成膜処理方法の実施形態について図２のフローチャートを参照しつつ説明する。   Next, an embodiment of a film forming method performed using the film forming apparatus configured as described above will be described with reference to the flowchart of FIG.

まず、処理容器１内に基板Ｓは搬入せずに、予めガスの通流経路および／または反応空間にＴｅ含有材料を形成する（工程１）。この処理は、成膜の際にＴｅ原料ガスを供給しないとき、あるいはＴｅ原料ガスを少なくしたときのＴｅ供給源を確保するための処理である。   First, the Te-containing material is formed in advance in the gas flow path and / or the reaction space without carrying the substrate S into the processing container 1 (step 1). This process is a process for securing a Te supply source when the Te source gas is not supplied during film formation or when the Te source gas is reduced.

この工程１は、成膜に先立って、Ｔｅ原料ガスを所定の真空雰囲気に保持された処理容器１内に予め流し、ガス通流経路壁、すなわち配管５１の内壁やシャワーヘッド４０の内壁、および／または反応空間壁、すなわち処理容器１の内壁にＴｅ含有膜を形成することによって行うことができる。あるいは処理容器１の側壁に設けたノズル（図示せず）から液状のＴｅ原料を噴霧して、Ｔｅ含有膜を形成してもよい。また、ガス通流経路および／または反応空間にＴｅを含有する部材を設けることによっても行うことができる。このＴｅを含有する部材を設けることは、ガス通流経路壁および／または反応空間壁にＴｅを含有する箔やＴｅを含有する部材を貼り付けてもよいし、ガス通流経路および／または反応空間に単にＴｅを含有する部材を置くだけでもよい。   In this step 1, prior to film formation, Te source gas is pre-flowed into the processing container 1 held in a predetermined vacuum atmosphere, and the gas flow path wall, that is, the inner wall of the pipe 51 and the inner wall of the shower head 40, and It can be carried out by forming a Te-containing film on the reaction space wall, that is, the inner wall of the processing vessel 1. Alternatively, a Te-containing film may be formed by spraying a liquid Te raw material from a nozzle (not shown) provided on the side wall of the processing container 1. Moreover, it can also carry out by providing the member containing Te in a gas flow path and / or reaction space. Providing this Te-containing member may be achieved by attaching a Te-containing foil or a Te-containing member to the gas flow path wall and / or the reaction space wall, or the gas flow path and / or reaction. A member containing Te may be simply placed in the space.

次に、ゲートバルブ３８を開けて、搬入出口３９から処理容器１内に基板Ｓを搬入する（工程２）。そして、基板Ｓを載置台３の上に載置し、処理容器１内を排気して所定の真空度に調整する。載置台３はあらかじめ加熱ランプ３２により放出され透過窓３０を透過した熱線により加熱されており、その熱により基板Ｓを加熱する。   Next, the gate valve 38 is opened, and the substrate S is loaded into the processing container 1 from the loading / unloading port 39 (step 2). Then, the substrate S is mounted on the mounting table 3, the inside of the processing container 1 is evacuated, and the degree of vacuum is adjusted. The mounting table 3 is heated in advance by heat rays emitted from the heating lamp 32 and transmitted through the transmission window 30, and the substrate S is heated by the heat.

次に、Ｇｅ原料ガス、Ｓｂ原料ガス、Ｔｅ原料ガスを所定流量で流し、基板Ｓ上にＧｅ−Ｓｂ−Ｔｅ系膜を成膜する（工程３）。この工程３においては、まず希釈ガス供給源５５から希釈ガスとして例えばＡｒガスを１００〜１０００ｍＬ／ｓｅｃ（ｓｃｃｍ）の流量で供給しつつ、図示しない真空ポンプにより排気口３６および排気管３７を介して処理容器１内を排気することにより処理容器１内の圧力を６０〜１３３０Ｐａ程度に真空排気する。この際の基板Ｓの加熱温度は、例えば２００〜６００℃に、好ましくは３００〜４００℃に設定される。   Next, Ge source gas, Sb source gas, and Te source gas are flowed at a predetermined flow rate to form a Ge—Sb—Te-based film on the substrate S (step 3). In this step 3, first, for example, Ar gas is supplied as a dilution gas from the dilution gas supply source 55 at a flow rate of 100 to 1000 mL / sec (sccm), and a vacuum pump (not shown) is connected through the exhaust port 36 and the exhaust pipe 37. By evacuating the inside of the processing container 1, the pressure in the processing container 1 is evacuated to about 60 to 1330 Pa. The heating temperature of the board | substrate S in this case is set to 200-600 degreeC, for example, Preferably it is set to 300-400 degreeC.

そして、希釈用ガス、例えばＡｒガスの流量を１００〜５００ｍＬ／ｓｅｃ（ｓｃｃｍ）としつつ、処理容器１内の圧力を成膜圧力である６０〜６６５０Ｐａに制御し、実際の成膜を開始する。なお、処理容器１内の圧力調整は、排気管３７に設けられた自動圧力制御器（ＡＰＣ）によりなされる。   Then, while the flow rate of the dilution gas, for example, Ar gas is set to 100 to 500 mL / sec (sccm), the pressure in the processing container 1 is controlled to 60 to 6650 Pa, which is the film formation pressure, and actual film formation is started. The pressure in the processing vessel 1 is adjusted by an automatic pressure controller (APC) provided in the exhaust pipe 37.

この状態で、例えば所定流量のキャリアガスを流してバブリングにより、Ｔｅ原料貯留部５２からのＴｅ原料ガスおよびＳｂ原料貯留部５３からのＳｂ原料ガスを処理容器１内に導入し、さらに、マスフローコントローラ（ＭＦＣ）６３によりＧｅ原料貯留部５４から所定流量のＧｅ原料ガスを処理容器１内に導入する。   In this state, for example, a Te source gas from the Te source reservoir 52 and an Sb source gas from the Sb source reservoir 53 are introduced into the processing vessel 1 by bubbling with a predetermined flow rate of carrier gas, and further, a mass flow controller (MFC) 63 introduces a Ge raw material gas having a predetermined flow rate into the processing container 1 from the Ge raw material reservoir 54.

このとき、ガスの通流経路壁および／または反応空間壁に予めＴｅ系材料が形成されているので、これらから昇華してきたＴｅが膜中に入る。このため、Ｇｅの膜中への取り込みを阻害するＴｅ原料を少なくすることができる。すなわち、Ｔｅ原料によるＧｅの膜中への取り込み阻害が生じると、Ｇｅ原料ガスの流量を多くしても、所望の組成、典型的にはＧｅ２Ｓｂ２Ｔｅ５の組成の膜よりもＧｅ量が少なくなってしまい、逆に、それを防止するためにＴｅ原料ガスの流量を少なくすると、Ｇｅの取り込み阻害は軽減されるがＴｅ量が所望の組成よりも少なくなってしまう。このように、ガスの通流経路壁および／または反応空間壁に予めＴｅ系材料を形成しておくことにより、Ｇｅの取り込み阻害を軽減すべくＴｅ原料ガスの流量を少なくしても、所望のＴｅ量を確保することができる。 At this time, since a Te-based material is formed in advance on the gas flow path wall and / or the reaction space wall, Te sublimated from these enters the film. For this reason, it is possible to reduce the Te raw material that inhibits the incorporation of Ge into the film. That is, when the incorporation of Ge into the film by the Te material occurs, the amount of Ge is higher than that of the film having a desired composition, typically Ge 2 Sb 2 Te 5 , even if the flow rate of the Ge material gas is increased. Conversely, if the flow rate of the Te raw material gas is reduced to prevent this, inhibition of Ge uptake is reduced, but the amount of Te becomes smaller than the desired composition. Thus, by forming a Te-based material in advance on the gas flow path wall and / or the reaction space wall, even if the flow rate of the Te source gas is reduced to reduce the inhibition of Ge uptake, a desired material can be obtained. Te amount can be secured.

この際の成膜は、ガスの通流経路壁および／または反応空間壁に予め形成したＴｅ系材料からのＴｅの取り込み量を見込んでＴｅ原料ガスの流量を少なくし、Ｇｅ原料ガスの流量を取り込み阻害を見込んで多くして、Ｇｅ原料ガス、Ｓｂ原料ガスおよびＴｅ原料ガスを同時に供給してＧｅ−Ｓｂ−Ｔｅ系膜を成膜してもよいし、Ｇｅ原料ガス、Ｓｂ原料ガスおよびＴｅ原料ガスをすべて導入する成膜と、Ｔｅ原料ガスを除いたＧｅ原料ガスとＳｂ原料ガスのみによる成膜を交互に行ってＧｅ−Ｓｂ−Ｔｅ系膜を成膜してもよい。   In this film formation, the flow rate of the Te raw material gas is reduced in view of the amount of Te incorporation from the Te-based material previously formed on the gas flow path wall and / or the reaction space wall, and the flow rate of the Ge raw material gas is reduced. A Ge-Sb-Te-based film may be formed by simultaneously supplying Ge source gas, Sb source gas, and Te source gas in anticipation of uptake inhibition, or Ge source gas, Sb source gas, and Te The Ge—Sb—Te-based film may be formed by alternately performing film formation in which all of the source gas is introduced and film formation using only the Ge source gas and the Sb source gas excluding the Te source gas.

この工程３の成膜が終了したら、原料の供給を停止し、処理容器１内を希釈ガスによりパージした後、ゲートバルブ３８を開け、成膜後の基板Ｓを処理容器から搬出する（工程４）。   When the film formation in this step 3 is completed, the supply of raw materials is stopped, the inside of the processing container 1 is purged with a dilution gas, the gate valve 38 is opened, and the substrate S after film formation is unloaded from the processing container (step 4). ).

次に、実際にＧｅ−Ｓｂ−Ｔｅ膜を成膜した実験結果について示す。
＜実験１＞
上記図１の成膜装置において、カートリッジヒータにより処理容器壁の温度を１６０℃に設定し、ランプパワーを調節して、載置台の温度を３５０℃に設定し、搬送ロボットのアームを用いて処理容器内に直径２００ｍｍの円板状をなす基板を搬入し、Ｇｅ−Ｓｂ−Ｔｅ膜を成膜した。なお、Ｇｅ原料、Ｓｂ原料、Ｔｅ原料として、ターシャリブチルゲルマニウム、トリイソプロピルアンチモン、ジイソプロピルテルルを用いた。ターシャリブチルゲルマニウムは、常温の原料容器の後段に設置したマスフローコントローラにて蒸気流量を直接制御して処理容器に供給し、トリイソプロピルアンチモンは、５０℃に温度コントロールした原料容器にキャリアガスとして流量制御されたＡｒガスを容器内に通じたバブリング法にて処理容器に供給し、ジイソプロピルテルルは、３５℃に温度コントロールした原料容器にキャリアガスとして流量制御されたＡｒガスを容器内に通じたバブリング法にて処理容器に供給した。マスフローコントローラおよび原料容器から処理容器までの配管は、マントルータにより１６０℃に保持した。 Next, experimental results of actually forming a Ge—Sb—Te film will be described.
<Experiment 1>
In the film forming apparatus of FIG. 1, the temperature of the processing vessel wall is set to 160 ° C. by the cartridge heater, the lamp power is adjusted, the temperature of the mounting table is set to 350 ° C., and processing is performed using the arm of the transfer robot. A disc-shaped substrate having a diameter of 200 mm was carried into the container, and a Ge—Sb—Te film was formed. Note that tertiary butyl germanium, triisopropylantimony, and diisopropyl tellurium were used as the Ge raw material, Sb raw material, and Te raw material. Tertiary butyl germanium is supplied to the processing vessel by directly controlling the vapor flow rate with a mass flow controller installed at the latter stage of the normal temperature raw material vessel, and triisopropylantimony is supplied as a carrier gas to the raw material vessel controlled at 50 ° C. The controlled Ar gas was supplied to the processing vessel by a bubbling method that passed through the vessel, and diisopropyl tellurium was bubbled through the vessel with Ar gas that was flow controlled as a carrier gas in a raw material vessel controlled at 35 ° C. To the processing vessel by the method. The mass flow controller and the piping from the raw material container to the processing container were maintained at 160 ° C. by a mantle router.

そして、以下の条件でＧｅ−Ｓｂ−Ｔｅ系膜を成膜した（第１の成膜）。
載置台温度：３５０℃
処理容器内圧力：６６５Ｐａ
Ｇｅ原料ガス流量：１５０ｍＬ／ｍｉｎ（ｓｃｃｍ）：ただしＮ２換算にて
ＴｅキャリアＡｒガス流量：５０ｍＬ／ｍｉｎ（ｓｃｃｍ）
ＳｂキャリアＡｒガス流量：５０ｍＬ／ｍｉｎ（ｓｃｃｍ）
希釈Ａｒガス流量：１００ｍＬ／ｍｉｎ（ｓｃｃｍ）
バックサイドＡｒガス流量：２００ｍＬ／ｍｉｎ（ｓｃｃｍ）
成膜時間：１２０ｓｅｃ Then, a Ge—Sb—Te-based film was formed under the following conditions (first film formation).
Mounting table temperature: 350 ° C
Processing container pressure: 665 Pa
Ge source gas flow rate: 150 mL / min (sccm): However, Te carrier Ar gas flow rate in terms of N 2 : 50 mL / min (sccm)
Sb carrier Ar gas flow rate: 50 mL / min (sccm)
Diluted Ar gas flow rate: 100 mL / min (sccm)
Backside Ar gas flow rate: 200 mL / min (sccm)
Deposition time: 120 sec

蛍光Ｘ線分析法にて第１の成膜により得られた膜の組成を測定した結果、Ｇｅ／Ｓｂ／Ｔｅ＝９／３３／５８（ａｔ％）となり、Ｔｅ原料ガスの導入により、膜中へのＧｅの取り込みが阻害されていることがわかる。   As a result of measuring the composition of the film obtained by the first film formation by the fluorescent X-ray analysis method, Ge / Sb / Te = 9/33/58 (at%) was obtained. It can be seen that the incorporation of Ge into the is inhibited.

次に、成膜に先立ってＴｅ原料を流して予め処理容器壁等にＴｅ含有膜を形成しておき、以下の条件でＧｅ−Ｓｂ−Ｔｅ系膜を成膜した（第２の成膜）。
載置台温度：３５０℃
処理容器内圧力：６６５Ｐａ
Ｇｅ原料ガス流量：１５０ｍＬ／ｍｉｎ（ｓｃｃｍ）
ＴｅキャリアＡｒガス流量：０ｍＬ／ｍｉｎ（ｓｃｃｍ）
ＳｂキャリアＡｒガス流量：２０ｍＬ／ｍｉｎ（ｓｃｃｍ）
希釈Ａｒガス流量：１００ｍＬ／ｍｉｎ（ｓｃｃｍ）
バックサイドＡｒガス流量：２００ｍＬ／ｍｉｎ（ｓｃｃｍ）
成膜時間：１２０ｓｅｃ Next, prior to film formation, a Te raw material was flowed to form a Te-containing film on the processing vessel wall or the like in advance, and a Ge—Sb—Te-based film was formed under the following conditions (second film formation). .
Mounting table temperature: 350 ° C
Processing container pressure: 665 Pa
Ge source gas flow rate: 150 mL / min (sccm)
Te carrier Ar gas flow rate: 0 mL / min (sccm)
Sb carrier Ar gas flow rate: 20 mL / min (sccm)
Diluted Ar gas flow rate: 100 mL / min (sccm)
Backside Ar gas flow rate: 200 mL / min (sccm)
Deposition time: 120 sec

蛍光Ｘ線分析法にて第２の成膜により得られた膜の組成を測定した結果、Ｇｅ／Ｓｂ／Ｔｅ＝３７／５５／８（ａｔ％）となり、Ｔｅ原料ガスを導入しないためＧｅの取り込み阻害が生じておらず、また、Ｔｅ原料を導入しないのにもかかわらず、処理容器壁に成膜されたＴｅ含有膜からのＴｅの昇華により、膜中にＴｅが取り込まれたことが確認された。   As a result of measuring the composition of the film obtained by the second film formation by X-ray fluorescence analysis, Ge / Sb / Te = 37/55/8 (at%) was obtained, and since Te source gas was not introduced, Ge It was confirmed that Te was taken into the film by sublimation of Te from the Te-containing film formed on the processing vessel wall even though no uptake inhibition occurred and no Te raw material was introduced. It was done.

次に、成膜時間を２０ｓｅｃにした他は上記第１の成膜条件と同じ条件によるステップＡと、成膜時間を４０ｓｅｃにした他は上記第２の成膜条件と同じ条件によるステップＢとを交互に２回ずつ繰り返してＧｅ−Ｓｂ−Ｔｅ系膜を成膜した（第３の成膜）。   Next, Step A under the same conditions as the first film forming conditions except that the film forming time is set to 20 sec, and Step B under the same conditions as the second film forming conditions except that the film forming time is set to 40 sec. Were alternately repeated twice to form a Ge—Sb—Te-based film (third film formation).

蛍光Ｘ線分析法にて第３の成膜により得られた膜の組成を測定した結果、Ｇｅ／Ｓｂ／Ｔｅ＝１５／３７／４８（ａｔ％）となり、第１の成膜であるステップＡと第２の成膜であるステップＣとを組み合わせることにより、Ｇｅ−Ｓｂ−Ｔｅ系膜の組成を制御することができ、目標組成であるＧｅ２Ｓｂ２Ｔｅ５により近い組成が得られることが確認された As a result of measuring the composition of the film obtained by the third film formation by X-ray fluorescence analysis, Ge / Sb / Te = 15/37/48 (at%), which is the first film formation step A And Step C, which is the second film formation, can control the composition of the Ge—Sb—Te-based film, and a composition closer to the target composition Ge 2 Sb 2 Te 5 can be obtained. confirmed

＜実験２＞
ここでは、実験１と同様の装置を用い、成膜に先立ってＴｅ原料を流して予め処理容器壁等にＴｅ含有膜を形成しておき、以下の条件でＧｅ−Ｓｂ−Ｔｅ系膜を成膜した。Ｇｅ原料、Ｓｂ原料、Ｔｅ原料として、トリメチルゲルマニウム、トリイソプロピルアンチモン、ジイソプロピルテルルを用いた。トリメチルゲルマニウムは、マスフローコントローラにより処理容器に供給した。 <Experiment 2>
Here, using the same apparatus as in Experiment 1, a Te-containing film was formed in advance on the processing vessel wall by flowing a Te raw material prior to film formation, and a Ge—Sb—Te-based film was formed under the following conditions. Filmed. Trimethylgermanium, triisopropylantimony, and diisopropyltellurium were used as the Ge raw material, Sb raw material, and Te raw material. Trimethyl germanium was supplied to the processing vessel by a mass flow controller.

成膜条件は以下の通りとした。
載置台温度：３５０℃
処理容器内圧力：６６５Ｐａ
Ｇｅ原料ガス流量：５５０ｍＬ／ｍｉｎ（ｓｃｃｍ）：ただしＮ２換算にて
ＴｅキャリアＡｒガス流量：５０ｍＬ／ｍｉｎ（ｓｃｃｍ）
ＳｂキャリアＡｒガス流量：２０ｍＬ／ｍｉｎ（ｓｃｃｍ）
希釈Ａｒガス流量：３００ｍＬ／ｍｉｎ（ｓｃｃｍ）
バックサイドＡｒガス流量：２００ｍＬ／ｍｉｎ（ｓｃｃｍ）
成膜時間：１８０ｓｅｃ The film forming conditions were as follows.
Mounting table temperature: 350 ° C
Processing container pressure: 665 Pa
Ge source gas flow rate: 550 mL / min (sccm): However, Te carrier Ar gas flow rate in terms of N 2 : 50 mL / min (sccm)
Sb carrier Ar gas flow rate: 20 mL / min (sccm)
Diluted Ar gas flow rate: 300 mL / min (sccm)
Backside Ar gas flow rate: 200 mL / min (sccm)
Deposition time: 180 sec

蛍光Ｘ線分析法にて得られた膜の組成を測定した結果、Ｇｅ／Ｓｂ／Ｔｅ＝２２．２／２２．２／５５．６（ａｔ％）となり、Ｇｅ２Ｓｂ２Ｔｅ５膜が得られたことが確認された。 As a result of measuring the composition of the film obtained by X-ray fluorescence analysis, Ge / Sb / Te = 22.2 / 22.2 / 55.6 (at%) was obtained, and a Ge 2 Sb 2 Te 5 film was obtained. It was confirmed that

なお、本発明は上記実施形態に限定されず種々限定可能である。
成膜装置としてランプ加熱で被処理基板を加熱するものを示したが、抵抗加熱ヒータで加熱するものであってもよい。 In addition, this invention is not limited to the said embodiment, A various limitation is possible.
Although the apparatus for heating the substrate to be processed by lamp heating is shown as the film forming apparatus, it may be heated by a resistance heater.

また、上記実施形態では、Ｇｅ２Ｓｂ２Ｔｅ５組成の膜を形成する場合について示したが、これに限らず種々の組成の膜に対応することができる。Ｔｅの割合が低い膜を成膜する場合には、Ｔｅ原料を全く導入せずに成膜を行うこともできる。 Further, in the above embodiment has been described for the case of forming a film of Ge 2 Sb 2 Te 5 composition may correspond to the film having various compositions is not limited thereto. When a film having a low Te ratio is formed, the film formation can be performed without introducing any Te raw material.

本発明に係るＧｅ−Ｓｂ−Ｔｅ系膜は、相変化型光記録媒体に用いる記録層の材料として有効である。   The Ge—Sb—Te film according to the present invention is effective as a material for a recording layer used in a phase change type optical recording medium.

１；処理容器
３；載置台
３２；加熱ランプ
４０；シャワーヘッド
５０；処理ガス供給機構
５２；Ｔｅ原料貯留部
５３；Ｓｂ原料貯留部
５４；Ｇｅ原料貯留部
９０；プロセスコントローラ
９２；記憶部
１００；成膜装置
Ｓ；基板
DESCRIPTION OF SYMBOLS 1; Processing container 3; Mounting base 32; Heating lamp 40; Shower head 50; Processing gas supply mechanism 52; Te raw material storage part 53; Sb raw material storage part 54; Ge raw material storage part 90; Process controller 92; Deposition system S: Substrate

Claims (8)

処理容器内に基板を配置し、気体状のＧｅ原料と、気体状のＳｂ原料と、気体状のＴｅ原料とを前記処理容器内に導入してＣＶＤにより基板上にＧｅ−Ｓｂ−Ｔｅ系膜を成膜するに際し、
成膜に先立ってガスの通流経路および／または反応空間にＴｅ含有材料を形成し、その後前記処理容器内に所定流量の気体状のＧｅ原料、気体状のＳｂ原料および気体状のＴｅ原料、または気体状のＧｅ原料および気体状のＳｂ原料を導入して所定の組成のＧｅ−Ｓｂ−Ｔｅ系膜を成膜するＧｅ−Ｓｂ−Ｔｅ系膜の成膜方法。 A substrate is placed in a processing vessel, a gaseous Ge raw material, a gaseous Sb raw material, and a gaseous Te raw material are introduced into the processing vessel, and a Ge—Sb—Te-based film is formed on the substrate by CVD. When forming the film,
Prior to film formation, a Te-containing material is formed in a gas flow path and / or reaction space, and then a gaseous Ge raw material, a gaseous Sb raw material, and a gaseous Te raw material at a predetermined flow rate in the processing vessel, Alternatively, a Ge—Sb—Te based film forming method in which a gaseous Ge raw material and a gaseous Sb raw material are introduced to form a Ge—Sb—Te based film having a predetermined composition. 成膜に先立って前記処理容器内にＴｅ原料を導入して、ガスの通流経路壁および／または反応空間壁にＴｅを含有する膜を形成することにより、ガスの通流経路および／または反応空間にＴｅ含有材料を形成することを特徴とする請求項１に記載のＧｅ−Ｓｂ−Ｔｅ系膜の成膜方法。   Prior to film formation, a Te raw material is introduced into the processing vessel to form a film containing Te on the gas flow path wall and / or the reaction space wall, thereby allowing the gas flow path and / or reaction. The method for forming a Ge—Sb—Te film according to claim 1, wherein a Te-containing material is formed in the space. 成膜に先立ってガスの通流経路および／または反応空間にＴｅを含有する部材を設けることにより、ガスの通流経路および／または反応空間にＴｅ含有材料を形成することを特徴とする請求項１に記載のＧｅ−Ｓｂ−Ｔｅ系膜の成膜方法。   The Te-containing material is formed in the gas flow path and / or the reaction space by providing a member containing Te in the gas flow path and / or the reaction space prior to film formation. 2. A method for forming a Ge—Sb—Te-based film according to 1. 気体状のＧｅ原料、気体状のＳｂ原料および気体状のＴｅ原料を用いて行う第１の成膜と、気体状のＧｅ原料および気体状のＳｂ原料を用いＴｅ原料を用いない第２の成膜を交互に行うことを特徴とする請求項１から請求項３のいずれか１項に記載のＧｅ−Ｓｂ−Ｔｅ系膜の成膜方法。   A first film formation using a gaseous Ge raw material, a gaseous Sb raw material and a gaseous Te raw material, and a second film formation using a gaseous Ge raw material and a gaseous Sb raw material without using a Te raw material. 4. The method for forming a Ge—Sb—Te-based film according to claim 1, wherein the films are alternately formed. 5. 成膜の際に、ガスの通流経路および／または反応空間に形成されたＴｅ含有材料から膜中に取り込まれるＴｅの量に基づいて、膜が所定の組成になるように、流量を制御して、気体状のＧｅ原料、気体状のＳｂ原料および気体状のＴｅ原料、または気体状のＧｅ原料および気体状のＳｂ原料を導入することを特徴とする請求項１から請求項３のいずれか１項に記載のＧｅ−Ｓｂ−Ｔｅ系膜の成膜方法。   During film formation, the flow rate is controlled so that the film has a predetermined composition based on the amount of Te taken into the film from the Te-containing material formed in the gas flow path and / or reaction space. 4. A gaseous Ge raw material, a gaseous Sb raw material and a gaseous Te raw material, or a gaseous Ge raw material and a gaseous Sb raw material are introduced. 2. A method for forming a Ge—Sb—Te-based film according to item 1. Ｇｅ−Ｓｂ−Ｔｅ系膜の組成がＧｅ２Ｓｂ２Ｔｅ５であることを特徴とする請求項１から請求項５のいずれか１項に記載のＧｅ−Ｓｂ−Ｔｅ系膜の成膜方法。 6. The method for forming a Ge—Sb—Te film according to claim 1, wherein the composition of the Ge—Sb—Te film is Ge 2 Sb 2 Te 5 . Ｇｅ原料、Ｓｂ原料およびＴｅ原料は、アルキル基を含む化合物よりなることを特徴とする請求項１から請求項６のいずれか１項に記載のＧｅ−Ｓｂ−Ｔｅ系膜の成膜方法。   7. The method for forming a Ge—Sb—Te-based film according to claim 1, wherein the Ge raw material, the Sb raw material, and the Te raw material are made of a compound containing an alkyl group. コンピュータ上で動作し、成膜装置を制御するプログラムが記憶された記憶媒体であって、前記制御プログラムは、実行時に、請求項１から請求項７のいずれかの成膜方法が行われるように、コンピュータに前記成膜装置を制御させることを特徴とする記憶媒体。   A storage medium that operates on a computer and stores a program for controlling a film forming apparatus, wherein the control program performs the film forming method according to any one of claims 1 to 7 at the time of execution. A storage medium that causes a computer to control the film forming apparatus.
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