JP5593320B2 - Method for forming Co film - Google Patents

Method for forming Co film Download PDF

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JP5593320B2
JP5593320B2 JP2011529945A JP2011529945A JP5593320B2 JP 5593320 B2 JP5593320 B2 JP 5593320B2 JP 2011529945 A JP2011529945 A JP 2011529945A JP 2011529945 A JP2011529945 A JP 2011529945A JP 5593320 B2 JP5593320 B2 JP 5593320B2
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JPWO2011027835A1 (en
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正一郎 熊本
聡 豊田
治憲 牛川
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Ulvac Inc
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    • 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
    • C23C16/06—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 deposition of metallic material
    • C23C16/18—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 deposition of metallic material from metallo-organic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
    • H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
    • H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic System
    • H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic System by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
    • H01L21/28562—Selective deposition

Description

本発明は、Ｃｏ膜の形成方法に関する。   The present invention relates to a method for forming a Co film.

現行のＣｕ配線膜形成プロセスでは、ＰＶＤ−バリア膜（例えば、ＰＶＤ−Ｔｉ膜やＴａ膜）とＰＶＤ−シード膜（ＰＶＤ−Ｃｕ膜）とを真空一貫（in-situ）で形成し、その後、Ｃｕメッキ工程、ＣＭＰ工程を行っている。しかし、近年の配線の微細化によって、デバイスノード３２ｎｍ世代以降では、ＰＶＤ膜のウェハーエッジの非対称性やオーバーハングが顕著になってきており、メッキ工程でボイドが発生するという問題がある。   In the current Cu wiring film formation process, a PVD-barrier film (for example, PVD-Ti film or Ta film) and a PVD-seed film (PVD-Cu film) are formed in-situ, and then A Cu plating process and a CMP process are performed. However, due to the recent miniaturization of wiring, the asymmetry and overhang of the wafer edge of the PVD film have become prominent after the device node 32 nm generation, and there is a problem that voids are generated in the plating process.

ここで、ＰＶＤ−バリア膜とは、ＰＶＤ法により形成されたバリア膜を意味し、ＰＶＤ−シード膜とは、ＰＶＤ法により形成されたシード膜を意味する。以下に記載するＰＶＤ（ＣＶＤ）−Ｃｕ膜、ＡＬＤ−バリア膜、（ＣＶＤ、ＡＬＤ）−Ｃｏ膜は、それぞれ、ＰＶＤ、ＣＶＤ、ＡＬＤにより形成された各膜を意味するものとする。   Here, the PVD-barrier film means a barrier film formed by the PVD method, and the PVD-seed film means a seed film formed by the PVD method. The PVD (CVD) -Cu film, ALD-barrier film, and (CVD, ALD) -Co film described below mean films formed by PVD, CVD, and ALD, respectively.

例えば、図１（ａ）及び（ｂ）に示すように、Φ３２ｎｍのホールやトレンチが設けられている基板１０１上に形成されているバリア膜１０２上にＰＶＤ−シード膜１０３（ＰＶＤ−Ｃｕ膜）を形成すると、ホールやトレンチの上部がオーバーハング（Ａ部分）してホール等の開口部が狭まり、次いでメッキ工程によりホール等の内部をＣｕ膜１０４で埋め込む際に、メッキ液が内部に入り難くなると共に、Ｃｕ膜とバリア膜との密着性が良くないために、Ｃｕ膜が埋め込まれるにつれてＣｕ膜が吸いあがって、Ｃｕ膜中にボイド（Ｂ部分）が発生するという問題がある。また、図１（ｃ）及び（ｄ）に示すように、ホール等の側面にＰＶＤ−シード膜１０３が均一に対称的に形成できず（Ｃ部分）、このバリア膜の非対称性のために、次のメッキ工程において埋め込まれるＣｕ膜１０４中にボイド（Ｄ部分）が発生するという問題もある。   For example, as shown in FIGS. 1A and 1B, a PVD-seed film 103 (PVD-Cu film) is formed on a barrier film 102 formed on a substrate 101 provided with holes and trenches of Φ32 nm. When the hole is formed, the upper part of the hole or trench is overhanged (part A) and the opening of the hole or the like is narrowed. Then, when the inside of the hole or the like is filled with the Cu film 104 by the plating process, the plating solution is difficult to enter. In addition, since the adhesion between the Cu film and the barrier film is not good, there is a problem that the Cu film is sucked up as the Cu film is buried, and voids (B portion) are generated in the Cu film. Further, as shown in FIGS. 1C and 1D, the PVD-seed film 103 cannot be uniformly and symmetrically formed on the side surface of the hole or the like (C portion). Due to the asymmetry of this barrier film, There is also a problem that voids (D portion) are generated in the Cu film 104 to be embedded in the next plating step.

ＡＬＤ法やＣＶＤ法で形成したバリア膜及びＣＶＤ−Ｃｕ膜は非対称性やオーバーハングがないので、この２つのプロセスを用いてＣｕ配線膜を形成する方法が試みられている（例えば、特許文献１参照）。しかし、この場合の問題点は、ＣＶＤ−Ｃｕ膜とその下地膜のＡＬＤ−バリア膜との密着性が悪いために、Ｃｕ膜中にボイドが発生することである。そのため、いまだ実用化には至っていない。   Since the barrier film and the CVD-Cu film formed by the ALD method or the CVD method do not have asymmetry or overhang, a method of forming a Cu wiring film using these two processes has been attempted (for example, Patent Document 1). reference). However, the problem in this case is that voids are generated in the Cu film because the adhesion between the CVD-Cu film and the ALD-barrier film of the underlying film is poor. Therefore, it has not yet reached practical use.

例えば、図２（ａ）及び（ｂ）に示すように、基板２０１に設けられたホールやトレンチ内にＡＬＤ法によりＴｉＮバリア膜（ＡＬＤ−ＴｉＮバリア膜）２０２を形成した後、ホール等の内部をＣＶＤ−Ｃｕ膜２０３で埋め込んだ場合、Ｃｕ膜内部にボイド（Ａ部分）が発生する。図２（ａ）は、ＣＶＤ−Ｃｕ膜２０３で埋め込んだ状態の基板断面のＳＥＭ写真であり、図２（ｂ）はその模式図である。   For example, as shown in FIGS. 2A and 2B, after a TiN barrier film (ALD-TiN barrier film) 202 is formed by ALD in holes or trenches provided in the substrate 201, the inside of the holes or the like is formed. Is embedded in the CVD-Cu film 203, voids (A portion) are generated inside the Cu film. FIG. 2A is a SEM photograph of a cross section of the substrate in a state where it is embedded with the CVD-Cu film 203, and FIG. 2B is a schematic diagram thereof.

上記したようなＣＶＤ−Ｃｕ膜とその下地膜のＡＬＤ−バリア膜との密着性が悪いために発生するＣｕ膜中のボイドをなくし、バリア性／密着性を改善するために、カバレッジ性がよく、薄膜で低抵抗なＣｏ膜を利用しようとする試みが始まり、ＣＶＤ法やＡＬＤ法によるＣｏ膜の成膜技術の開発が急務となっている。Ｃｏ膜については、Ｃｕ配線膜の分野のみならず、シリサイド層やキャップ層の分野においても、同様にカバレッジ性の高いＣｏ膜への要求が高まりつつある。   In order to eliminate voids in the Cu film due to poor adhesion between the CVD-Cu film as described above and the ALD-barrier film of the underlying film, and to improve the barrier property / adhesion, the coverage property is good. Attempts to use a thin, low-resistance Co film have begun, and development of a film forming technique for a Co film by CVD or ALD has become an urgent task. Regarding the Co film, not only in the field of the Cu wiring film but also in the field of the silicide layer and the cap layer, there is a growing demand for a Co film having a high coverage property.

これに対し、従来技術によるＣｏとアミンとを含む有機金属材料を用いたＣＶＤ法により得られたＣｏ膜の場合（例えば、特許文献２参照）、Ｃｏ核の成長時間が２０分と長く、Ｃｏ核の成長速度も１ｎｍ／分と遅く、また、Ｃの不純物濃度が３０％と多いなどの問題を有していた。   In contrast, in the case of a Co film obtained by a CVD method using an organic metal material containing Co and amine according to the prior art (see, for example, Patent Document 2), the growth time of Co nuclei is as long as 20 minutes. The growth rate of nuclei was as low as 1 nm / min, and the impurity concentration of C was as high as 30%.

特開２００３−０５５７６９号公報JP 2003-055569 A 特開２００６−２９９４０７号公報JP 2006-299407 A

本発明の課題は、上述の従来技術の問題点を解決することにあり、特定の還元ガスを用い、ＣＶＤ法等によりＣｏ膜を形成する方法を提供することにある。   An object of the present invention is to solve the above-described problems of the prior art, and to provide a method of forming a Co film by a CVD method or the like using a specific reducing gas.

本発明のＣｏ膜の形成方法は、下地としてのＳｉ基材表面にＣｏ膜を形成する方法において、前記Ｓｉ基材表面をＮＨ３で前処理してＳｉ基材表面をＮＨでターミネートし、コバルトアルキルアミジネイトと、ＮＨ３、Ｎ２Ｈ４、ＮＨ（ＣＨ３）２、Ｎ２Ｈ３ＣＨ、及びＮ２から選ばれた還元ガスのラジカル、又はＨ２及び前記還元ガスのラジカルの組み合わせガスとを用いてＣｏ膜を形成することを特徴とする。 Method of forming a Co film of the present invention is a method of forming a Co film on the Si substrate surface as a base, and terminated with NH the Si substrate surface pretreated said Si substrate table surface with NH 3, Cobalt alkyl amidinate and a radical of a reducing gas selected from NH 3 , N 2 H 4 , NH (CH 3 ) 2 , N 2 H 3 CH, and N 2 , or a radical of H 2 and the reducing gas A Co film is formed using a combination gas.

このように、還元ガスとして、従来のＨ ２ ガスの代わりに又はＨ ２ ガスに加えて、ＮＨ ３ ガス等を用いることにより、また、Ｓｉ基材のような基材の表面をＮＨ３で前処理してＳｉ基材表面をＮＨでターミネートし、さらに還元ガスのラジカルを用いることにより、Ｃｏの核生成時間の抑制や、Ｃｏ膜の成長速度の制御、表面モフォロジーの改善、不純物濃度の抑制、低抵抗化を可能にし、半導体デバイスの微細パターンにおけるＣｏ膜の利用が可能になる。 Thus, as a reducing gas, instead of or in addition to H 2 gas of the conventional H 2 gas, by use of the NH 3 gas or the like, also, before the surface of substrates such as a Si substrate with NH 3 By treating the surface of the Si substrate with NH and further using a reducing gas radical, the Co nucleation time is suppressed, the Co film growth rate is controlled, the surface morphology is improved, the impurity concentration is suppressed, The resistance can be reduced, and the Co film can be used in a fine pattern of a semiconductor device .

上記コバルトアルキルアミジネイトが、Ｃｏ（ｔＢｕ−Ｅｔ−Ｅｔ−ａｍｄ）２であることを特徴とする。The cobalt alkyl amidinate is Co (tBu-Et-Et-amd) 2 .

本発明によれば、従来のＨ２のみを還元ガスに使って形成したＣｏ膜に比べ、Ｓｉ基材表面をＮＨ３で前処理した後、Ｈ２及び／又はＮＨ３等を還元ガスとして用いて形成したＣｏ膜は、Ｃｏの核生成時間の短縮や、Ｃｏ膜の低抵抗化、表面モフォロジーの改善、低温成膜が可能となり、半導体デバイス作製工程においてスループットの向上をもたらし、Ｃｏ膜の使用温度領域を広げることで微細加工へのＣｏ膜の使用を可能にするという効果を達成できる。 According to the present invention, compared with the Co film formed by using only conventional H 2 in the reducing gas, was pretreated with S i substrate surface with NH 3, H 2 and / or NH 3 or the like as a reducing gas The Co film formed using this method shortens the Co nucleation time, lowers the Co film resistance, improves the surface morphology, and enables low-temperature film formation, resulting in increased throughput in the semiconductor device manufacturing process. The effect of enabling the use of the Co film for microfabrication can be achieved by widening the operating temperature range.

さらに本発明によれば、Ｃｏ膜をＣＶＤ法、ＡＬＤ法で形成することができると共に、薄膜化することができ、半導体デバイスにおいてＣｏ膜をより多くの工程で利用できるようになる。   Furthermore, according to the present invention, the Co film can be formed by the CVD method or the ALD method, and can be thinned, so that the Co film can be used in more steps in the semiconductor device.

従来技術の場合のボイド発生を示す模式図であり、（ａ）及び（ｂ）は、ホール上部のオーバーハングによるボイドの発生、また、（ｃ）及び（ｄ）は、ホール側面におけるバリア膜の非対称性によるボイドの発生を示す図である。FIG. 4 is a schematic diagram showing the generation of voids in the case of the prior art, in which (a) and (b) show the generation of voids due to an overhang at the top of the hole, and (c) and (d) show the barrier film on the side of the hole. It is a figure which shows generation | occurrence | production of the void by asymmetry. 従来技術によるボイドの発生を示すＳＥＭ写真（ａ）及びその模式図（ｂ）である。It is the SEM photograph (a) which shows generation | occurrence | production of the void by a prior art, and its schematic diagram (b). 実施例１で得られたＨ２−ＮＨ３還元Ｃｏ膜及びＨ２還元Ｃｏ膜の成膜時間（分）と単位時間当たりの成膜レート（１ｎｍ／分）に相当する膜厚（ｎｍ）との関係を示すグラフである。The film formation time (min) of the H 2 —NH 3 reduced Co film and the H 2 reduced Co film obtained in Example 1 and the film thickness (nm) corresponding to the film formation rate (1 nm / min) per unit time, It is a graph which shows the relationship. 実施例３で得られたＣｏ膜についてのＡＥＳ分析結果を示すグラフであり、（ａ）はＨ２還元Ｃｏ膜の場合、（ｂ）はＨ２−ＮＨ３還元Ｃｏ膜の場合のＡＥＳ分析結果を示すグラフである。Is a graph showing the AES analysis results for the Co film obtained in Example 3, (a) in the case of H 2 reduction Co film, (b) the AES analysis results for H 2 -NH 3 reduction Co film It is a graph which shows. 実施例５で得られたＳｉ基板表面のＳＥＭ写真であり、（ａ）はＮＨ３を吸着させない場合の基板表面のＳＥＭ写真、（ｂ）はＮＨ３を吸着させた場合の基板表面のＳＥＭ写真である。It is a SEM photograph of the Si substrate surface obtained in Example 5, (a) is a SEM photograph of the substrate surface when NH 3 is not adsorbed, and (b) is a SEM photograph of the substrate surface when NH 3 is adsorbed. It is. 実施例５で得られたＳｉ基板表面上のイメージ図であり、（ａ）はＮＨ３を表面吸着させない場合、（ｂ）はＮＨ３を表面吸着させた場合である。Is an image diagram on the Si substrate surface obtained in Example. 5, (a) shows the case of not surface adsorption NH 3, and a case where (b) is allowed to surface adsorption of NH 3. 実施例７で得られたＨ２還元Ｃｏ膜とＨ２−ＮＨ３還元Ｃｏ膜についての基板温度と比抵抗値との関係を示すグラフである。10 is a graph showing the relationship between the substrate temperature and the specific resistance value for the H 2 reduced Co film and the H 2 —NH 3 reduced Co film obtained in Example 7.

本発明に係るＣｏ膜の形成方法の実施の形態によれば、下地としてのＳｉ基材のような基材の表面にＣｏ膜を形成する方法において、コバルト２−アルキルアミジネイトのようなＣｏとアルキルアミジネイト基（このアルキルは、エチル、ブチルである）とを含む有機金属材料、及びこの有機金属材料を還元してＣｏ膜を形成するための還元ガスとして、公知の還元ガスであるＮＨ３、Ｎ２Ｈ４、ＮＨ（ＣＨ３）２、Ｎ２Ｈ３ＣＨ、及びＮ２から選ばれたガス、又はＨ２及び前記還元ガス（この中でも、特にＮＨ３が好ましい）の組み合わせガスを用い、ＣＶＤ法やＡＬＤ法で、成膜圧力：１００〜１０００Ｐａ、基板温度：２００〜４００℃、還元ガス（例えば、ＮＨ３）流量：１００〜１０００ｓｃｃｍの下で、ＣＶＤ（ＡＬＤ）−Ｃｏ膜を形成することができ、このような還元ガスを用いることにより、Ｃｏの核生成時間の抑制や、Ｃｏ膜の成長速度の制御、表面モフォロジーの改善、不純物濃度の抑制、低抵抗化を可能にし、微細パターンにおけるＣｏ膜の密着層、シリサイド層、キャップ層での利用が可能になる。According to the embodiment of the method for forming a Co film according to the present invention, in a method for forming a Co film on the surface of a substrate such as a Si substrate as a base, a Co such as cobalt 2-alkyl amidinate is used. And an alkylamidinate group (this alkyl is ethyl or butyl), and a known reducing gas as a reducing gas for reducing the organometallic material to form a Co film A gas selected from NH 3 , N 2 H 4 , NH (CH 3 ) 2 , N 2 H 3 CH, and N 2 , or a combined gas of H 2 and the reducing gas (among these, NH 3 is particularly preferable). In the CVD method or the ALD method, the film forming pressure is 100 to 1000 Pa, the substrate temperature is 200 to 400 ° C., the reducing gas (for example, NH 3 ) flow rate is 100 to 1000 sccm, and the CVD (A LD) -Co film can be formed, and by using such a reducing gas, Co nucleation time is suppressed, the growth rate of Co film is controlled, surface morphology is improved, impurity concentration is suppressed, low The resistance can be achieved, and the Co film can be used in the adhesion layer, the silicide layer, and the cap layer in a fine pattern.

上記Ｃｏ膜の形成方法において、Ｓｉ基材のような基材の表面を、成膜圧力：１００〜１０００Ｐａ、基板温度：２００〜４００℃、ガス流量：１００〜１０００ｓｃｃｍのような条件下で、ＮＨ３で前処理した後に、コバルト２−アルキルアミジネイトのようなＣｏとアルキルアミジネイト基とを含む有機金属材料、及び公知の還元ガスであるＮＨ３、Ｎ２Ｈ４、ＮＨ（ＣＨ３）２、Ｎ２Ｈ３ＣＨ、及びＮ２から選ばれたガスや、Ｈ２、又はＨ２及び前記還元ガス（この中でも、特にＮＨ３が好ましい）の組み合わせガスを用い、ＣＶＤ法やＡＬＤ法で、公知のプロセス条件（例えば、成膜圧力：１００〜１０００Ｐａ、基板温度：２００〜４００℃、ガス流量：１００〜１０００ｓｃｃｍ）の下で、ＣＶＤ（ＡＬＤ）−Ｃｏ膜を形成することができ、このようにＳｉ基材表面をＮＨ３で前処理した後に、還元ガスを用いることにより、Ｃｏの核生成時間の抑制や、Ｃｏ膜の成長速度の制御、表面モフォロジーの改善、不純物濃度の抑制、低抵抗化を可能にし、微細パターンにおけるＣｏ膜の密着層、シリサイド層、キャップ層での利用が可能になる。In the above Co film formation method, the surface of a substrate such as a Si substrate is formed under conditions such as film formation pressure: 100 to 1000 Pa, substrate temperature: 200 to 400 ° C., gas flow rate: 100 to 1000 sccm. 3 is pretreated with an organometallic material containing Co and an alkylamidinate group, such as cobalt 2-alkylamidinate, and the known reducing gases NH 3 , N 2 H 4 , NH (CH 3 2 ) CVD method or ALD method using a gas selected from 2 , N 2 H 3 CH, and N 2 , a combined gas of H 2 , or H 2 and the reducing gas (among these, NH 3 is particularly preferable). Under the known process conditions (for example, film forming pressure: 100 to 1000 Pa, substrate temperature: 200 to 400 ° C., gas flow rate: 100 to 1000 sccm), CVD (ALD) -C It can form a film, after the pretreatment in this way Si substrate surface with NH 3, by using a reducing gas, suppressing or nucleation time of Co, control of the growth rate of the Co film, surface morphology Improvement, suppression of impurity concentration, and reduction in resistance, and use in the adhesion layer, silicide layer, and cap layer of the Co film in a fine pattern becomes possible.

上記したコバルトアルキルアミジネイトからなる有機金属材料としては、例えば、Ｃｏ（ｔＢｕ−Ｅｔ−Ｅｔ−ａｍｄ）２等を挙げることができる。Examples of the organometallic material composed of the above cobalt alkyl amidinate include Co (tBu-Et-Et-amd) 2 .

本実施例では、自然酸化物を除去したＳｉ基材上に、ＣＶＤ法により、成膜圧力：５００Ｐａ、基板温度：３００℃、還元ガス流量：２００ｓｃｃｍの条件下で、有機金属材料としてＣｏ（ｔＢｕ−Ｅｔ−Ｅｔ−ａｍｄ）２を用い、還元ガスとしてＮＨ３のみを用いてＣｏ膜（ＮＨ３還元Ｃｏ膜）を形成した場合と、ＣＶＤ法により、成膜圧力：５００Ｐａ、基板温度：３００℃、還元ガス流量：２００ｓｃｃｍの条件下で、有機金属材料としてＣｏ（ｔＢｕ−Ｅｔ−Ｅｔ−ａｍｄ）２を用い、還元ガスとしてＨ２を用いてＣｏ膜（Ｈ２還元Ｃｏ膜）を形成した場合との、成膜時間（分）に対する膜厚（ｎｍ）の関係を検討した。この膜厚は、単位時間当たり成膜レートに相当する。In this example, Co (tBu) is used as an organometallic material on a Si base material from which natural oxide has been removed by CVD, under conditions of film forming pressure: 500 Pa, substrate temperature: 300 ° C., reducing gas flow rate: 200 sccm. -Et-Et-amd) 2 and using only NH 3 as a reducing gas to form a Co film (NH 3 -reduced Co film) and by CVD, a film forming pressure of 500 Pa and a substrate temperature of 300 ° C. When a Co film (H 2 reduced Co film) is formed using Co (tBu-Et-Et-amd) 2 as the organometallic material and H 2 as the reducing gas under the condition of reducing gas flow rate: 200 sccm And the relationship of the film thickness (nm) to the film formation time (min). This film thickness corresponds to the film formation rate per unit time.

得られた結果を図３に示す。図３から明らかなように、Ｈ２還元Ｃｏ膜の場合は、成膜レート１ｎｍ／分、核生成時間２０分であるのに対しＮＨ３還元Ｃｏ膜の場合は、成膜レートが８ｎｍ／分で核生成時間はゼロであり、核が直ちに生成されると共に成膜が始まることが分かる。The obtained results are shown in FIG. As is apparent from FIG. 3, in the case of the H 2 reduced Co film, the film formation rate is 1 nm / min and the nucleation time is 20 minutes, whereas in the case of the NH 3 reduced Co film, the film formation rate is 8 nm / min. Thus, the nucleation time is zero, and it can be seen that the nuclei are generated immediately and the film formation starts.

これらのＮＨ３を還元ガスとして用いたことによる不純物量の低下に起因したＣｏ膜表面の平滑化、Ｃｏ膜の低抵抗化及びＣｏ成膜レートの増大、Ｃｏ核の生成時間の短縮は、ＮＨ３ラジカルが原料の分解を促進することでＣｏの分圧が増大するためだと考えられる。従って、本発明のＣｏ膜の形成には、このようなラジカルを発生する還元ガスを使用できる。Smoothing of the Co film surface due to a decrease in the amount of impurities due to the use of these NH 3 as a reducing gas, lowering the resistance of the Co film, increasing the Co film formation rate, and shortening the Co nucleus generation time are NH This is thought to be because the partial pressure of Co increases due to the 3 radicals promoting the decomposition of the raw material. Therefore, a reducing gas that generates such radicals can be used to form the Co film of the present invention.

実施例１で用いた還元ガスとしてのＮＨ３の代わりに、Ｎ２Ｈ４、ＮＨ（ＣＨ３）２、Ｎ２Ｈ３ＣＨ、及びＮ２から選ばれた還元ガスを用いた場合、また、Ｈ２とＮＨ３、ＮＨ（ＣＨ３）２、Ｎ２Ｈ３ＣＨ及びＮ２から選ばれた還元ガスとの組み合わせガスを用いた場合について、実施例１のプロセスを繰り返したところ、実施例１の場合と同様に、Ｃｏ核の生成時間は殆どゼロであり、核が直ちに生成され、成膜が始まることが分かる。When a reducing gas selected from N 2 H 4 , NH (CH 3 ) 2 , N 2 H 3 CH, and N 2 is used instead of NH 3 as the reducing gas used in Example 1, When the combined gas of H 2 and a reducing gas selected from NH 3 , NH (CH 3 ) 2 , N 2 H 3 CH and N 2 was used, the process of Example 1 was repeated. As in the case of, the generation time of Co nuclei is almost zero, and it can be seen that nuclei are immediately generated and film formation starts.

本実施例では、自然酸化物を除去したＳｉ基板上に、ＣＶＤ法により、成膜圧力：５００Ｐａ、基板温度：３００℃、還元ガス流量：５００ｓｃｃｍのプロセス条件下で、有機金属材料としてＣｏ（ｔＢｕ−Ｅｔ−Ｅｔ−ａｍｄ）２を、還元ガスとしてＨ２を用いて、Ｈ２還元Ｃｏ膜を３０ｎｍ形成した場合と、ＣＶＤ法により、成膜圧力：５００Ｐａ、基板温度：３００℃、還元ガス流量：５００ｓｃｃｍのプロセス条件下で、有機金属材料としてＣｏ（ｔＢｕ−Ｅｔ−Ｅｔ−ａｍｄ）２を用い、還元ガスとしてＨ２とＮＨ３との組み合わせガスを用いて、Ｈ２−ＮＨ３還元Ｃｏ膜を３０ｎｍ形成した場合との各試料のＡＥＳ分析を行った。In this embodiment, Co (tBu) is used as an organometallic material on a Si substrate from which a natural oxide has been removed by a CVD method under process conditions of a film forming pressure of 500 Pa, a substrate temperature of 300 ° C., and a reducing gas flow rate of 500 sccm. -Et-Et-amd) 2 using H 2 as the reducing gas and forming a 30 nm H 2 -reduced Co film and by CVD, the film forming pressure is 500 Pa, the substrate temperature is 300 ° C., and the reducing gas flow rate H 2 —NH 3 reduced Co film using Co (tBu-Et-Et-amd) 2 as the organometallic material and a combined gas of H 2 and NH 3 as the reducing gas under the process conditions of 500 sccm AES analysis was performed on each sample with a thickness of 30 nm.

得られた結果を図４（ａ）及び（ｂ）に示す。図４（ａ）に示すように、Ｈ２還元Ｃｏ膜の場合はＣの不純物量が３０％含まれているのに対し、図４（ｂ）に示すように、Ｈ２−ＮＨ３還元Ｃｏ膜の場合はＣの不純物量が５％と少ないことが分かる。The obtained results are shown in FIGS. 4 (a) and 4 (b). As shown in FIG. 4A, the H 2 -reduced Co film contains 30% of the impurity of C, whereas as shown in FIG. 4B, H 2 —NH 3 reduced Co In the case of the film, it can be seen that the impurity amount of C is as small as 5%.

実施例３で用いたＨ２−ＮＨ３還元ガスの代わりにＮＨ３還元ガスを用いて実施例３のプロセスを繰り返したところ、得られたＮＨ３還元Ｃｏ膜は実施例３の場合と同様なＡＥＳ分析結果が得られた。When the process of Example 3 was repeated using NH 3 reducing gas instead of the H 2 —NH 3 reducing gas used in Example 3, the resulting NH 3 reduced Co film was the same as in Example 3. AES analysis results were obtained.

本実施例では、Ｃｏ成膜前に、Ｓｉ基板表面をＮＨ３ガスで前処理した。In this example, the surface of the Si substrate was pretreated with NH 3 gas before the Co film formation.

Φ３００ｍｍのＳｉ基板を用意し、その表面からドライエッチングにより自然酸化膜を除去した後、５分間大気開放し、次いで有機金属材料としてコバルト２−アルキルアミジネイト（このアルキルは、エチル、ブチルである）、還元ガスとしてＨ２を用い、ＣＶＤ法により、成膜圧力：２００Ｐａ、基板温度：２００℃、還元ガス流量：３００ｓｃｃｍ、成膜時間：１０分間のプロセス条件で、Ｈ２還元Ｃｏ膜を形成した。また、自然酸化膜除去後に同様に大気開放させたＳｉ基板の表面にＮＨ３を吸着させた（成膜圧力：５００Ｐａ、基板温度：２００℃、還元ガス（ＮＨ３）流量：３００ｓｃｃｍ、処理時間：５分間）後に、同じ有機金属材料及び還元ガスを用い、同じＣＶＤプロセス条件で、Ｈ２還元Ｃｏ膜を形成した。A Si substrate having a diameter of 300 mm was prepared, the natural oxide film was removed from the surface by dry etching, and then released to the atmosphere for 5 minutes. Then, cobalt 2-alkylamidinate as the organometallic material (this alkyl is ethyl or butyl) ), Using H 2 as the reducing gas, and forming the H 2 reduced Co film under the process conditions of film forming pressure: 200 Pa, substrate temperature: 200 ° C., reducing gas flow rate: 300 sccm, film forming time: 10 minutes by CVD. did. Further, NH 3 was adsorbed on the surface of the Si substrate which was similarly opened to the atmosphere after removing the natural oxide film (film forming pressure: 500 Pa, substrate temperature: 200 ° C., reducing gas (NH 3 ) flow rate: 300 sccm, processing time: After 5 minutes, an H 2 reduced Co film was formed using the same organometallic material and reducing gas under the same CVD process conditions.

かくして得られたＳｉ基板表面のＳＥＭ写真を図５（ａ）及び（ｂ）に示す。ＮＨ３を吸着させない場合は、Ｓｉ基板表面にＣｏの核が殆ど生ぜず、Ｃｏ膜は形成されなかった（図５（ａ））が、ＮＨ３を吸着させた場合は、吸着させない場合と比べて、Ｃｏの核が成長しており、Ｃｏ膜が形成されることが分かる（図５（ｂ））。これは、ＳｉのダングリングボンドにターミネートされたＨをＮＨに置き換えることにより核成長が促進することを示しており、ＮＨ３を表面吸着させることで核生成時間の抑制が可能であることを示している。図６に、この点ついてのＳｉ基板表面上のイメージ図を示す。図６（ａ）はＮＨ３を表面吸着させない場合、図６（ｂ）はＮＨ３を表面吸着させた場合である。SEM photographs of the surface of the Si substrate thus obtained are shown in FIGS. 5 (a) and 5 (b). When NH 3 was not adsorbed, Co nuclei were hardly formed on the Si substrate surface, and no Co film was formed (FIG. 5A). However, when NH 3 was adsorbed, compared with the case where NH 3 was not adsorbed. Thus, it can be seen that Co nuclei have grown and a Co film is formed (FIG. 5B). This indicates that nucleation is promoted by replacing NH terminated with Si dangling bonds with NH, and that nucleation time can be suppressed by adsorbing NH 3 on the surface. ing. FIG. 6 shows an image diagram on the surface of the Si substrate for this point. 6A shows the case where NH 3 is not adsorbed on the surface, and FIG. 6B shows the case where NH 3 is adsorbed on the surface.

本実施例では、実施例５に従って、ＮＨ３を表面吸着させないでＨ２還元Ｃｏ成膜した場合と、ＮＨ３を表面吸着させてＨ２還元Ｃｏ成膜した場合とにおけるＣｏ成膜したＳｉ基板上の表面モフォロジーを検討した。その結果、ＮＨ３を表面吸着させた場合の表面モフォロジーは良好であった。In this embodiment, according to Example 5, Si substrate was Co deposited to the case of H 2 reduction Co deposition is not surface adsorption of NH 3, in the case where the NH 3 by surface adsorption H 2 reduction Co deposited The above surface morphology was studied. As a result, the surface morphology when NH 3 was adsorbed on the surface was good.

本実施例では、基板温度を１９０℃〜３２０℃と変動させて実施例３記載の方法に従って得られたＨ２還元Ｃｏ膜及びＨ２−ＮＨ３還元Ｃｏ膜の比抵抗に対する温度依存性を検討した。In this example, the temperature dependence on the specific resistance of the H 2 reduced Co film and the H 2 —NH 3 reduced Co film obtained according to the method described in Example 3 with the substrate temperature varied from 190 ° C. to 320 ° C. was examined. did.

すなわち、自然酸化物を除去していないＳｉ基板温度を２５０℃〜３２０℃に設定し、この基板上に、還元ガスとしてＨ２ガスを３００ｓｃｃｍ、有機金属材料としてコバルト２−アルキルアミジネイト：Ｃｏ（ｔＢｕ−Ｅｔ−Ｅｔ−ａｍｄ）２をキャニスターで６０℃〜９０℃に加温し、キャリアガスとしてＡｒガスを３００ｓｃｃｍ流し、ＣＶＤ法に従って２００Ｐａの圧力下、Ｈ２還元Ｃｏ膜を形成した。また、上記と同様な自然酸化膜を除去していないＳｉ基板温度を１９０℃〜３００℃に設定して、この基板上に、還元ガスとしてＨ２とＮＨ３との混合ガスをそれぞれ、２００ｓｃｃｍ及び４００ｓｃｃｍ用い、有機金属材料としてコバルト２−アルキルアミジネイト：Ｃｏ（ｔＢｕ−Ｅｔ−Ｅｔ−ａｍｄ）２をキャニスターで６０℃〜９０℃に加温して供給し、ＣＶＤ法に従って２００Ｐａの圧力下、Ｈ２−ＮＨ３還元Ｃｏ膜を形成した。That is, the Si substrate temperature from which the native oxide is not removed is set to 250 ° C. to 320 ° C., H 2 gas as a reducing gas is 300 sccm, and cobalt 2-alkyl amidinate as an organic metal material: Co (TBu-Et-Et-amd) 2 was heated to 60 ° C. to 90 ° C. with a canister, Ar gas was flowed at 300 sccm as a carrier gas, and an H 2 reduced Co film was formed under a pressure of 200 Pa according to the CVD method. Further, the Si substrate temperature from which the natural oxide film similar to that described above is not removed is set to 190 ° C. to 300 ° C., and a mixed gas of H 2 and NH 3 is used as a reducing gas on this substrate at 200 sccm and Using 400 sccm, cobalt 2-alkylamidinate: Co (tBu-Et-Et-amd) 2 as an organometallic material was heated to 60 ° C. to 90 ° C. with a canister and supplied under a pressure of 200 Pa according to the CVD method. A H 2 —NH 3 reduced Co film was formed.

かくして得られたＨ２−還元Ｃｏ膜とＨ２−ＮＨ３還元Ｃｏ膜とに対して、４端子法により比抵抗（μΩ・ｃｍ）を測定し、その結果を図７にプロットした。図７から明らかなように、Ｈ２還元Ｃｏ膜の場合は、比抵抗は高く、かつ基板温度による比抵抗の変動は激しいが、Ｈ２−ＮＨ３還元Ｃｏ膜との場合は、Ｈ２還元Ｃｏ膜の場合と比べて比抵抗は低く、かつ温度依存性が少ないことが分かる。Thus obtained H 2 - against the reduced Co film and H 2 -NH 3 reduction Co film, measurement of specific resistance (μΩ · cm) by 4-terminal method, and the results plotted in FIG. As apparent from FIG. 7, in the case of H 2 reduction Co film, the specific resistance is high, and although intense variation in specific resistance caused by the substrate temperature, in the case of the H 2 -NH 3 reduction Co film, H 2 reduction It can be seen that the specific resistance is lower and the temperature dependence is lower than in the case of the Co film.

本発明によれば、得られたＣｏ膜は、Ｃｏの核生成時間の短縮や、Ｃｏ膜の低抵抗化、表面モフォロジーの改善、低温成膜が可能となり、半導体デバイス作製工程においてスループットの向上をもたらし、Ｃｏ膜の使用温度領域を広げることで、微細パターン加工においてＣｏ膜を利用できるので、本発明は、半導体デバイス技術分野において利用可能である。   According to the present invention, the obtained Co film can shorten the Co nucleation time, reduce the resistance of the Co film, improve the surface morphology, and form a film at a low temperature, thereby improving the throughput in the semiconductor device manufacturing process. As a result, the Co film can be used in fine pattern processing by widening the operating temperature range of the Co film, and therefore the present invention can be used in the field of semiconductor device technology.

１０１，２０１ 基板
１０２ バリア膜
１０３ ＰＶＤ−シード膜
１０４ Ｃｕ膜
２０２ ＴｉＮバリア膜
２０３ ＣＶＤ−Ｃｕ膜101, 201 Substrate 102 Barrier film 103 PVD-seed film 104 Cu film 202 TiN barrier film 203 CVD-Cu film

Claims (4)

下地としてのＳｉ基材表面にＣｏ膜を形成する方法において、前記Ｓｉ基材表面をＮＨ ３ で前処理してＳｉ基材表面をＮＨでターミネートし、コバルトアルキルアミジネイトと、ＮＨ３、Ｎ２Ｈ４、ＮＨ（ＣＨ３）２、Ｎ２Ｈ３ＣＨ、及びＮ２から選ばれた還元ガスのラジカル、又はＨ２及び前記還元ガスのラジカルの組み合わせガスとを用いてＣｏ膜を形成することを特徴とするＣｏ膜の形成方法。 In the method of forming a Co film on the surface of a Si base material as a base, the Si base material surface is pretreated with NH 3 and the Si base material surface is terminated with NH, and a cobalt alkylamidate, NH 3 , N A Co film is formed using a radical of a reducing gas selected from 2 H 4 , NH (CH 3 ) 2 , N 2 H 3 CH, and N 2 , or a combined gas of H 2 and the radical of the reducing gas. A method for forming a Co film. 前記コバルトアルキルアミジネイトが、Ｃｏ（ｔＢｕ−Ｅｔ−Ｅｔ−ａｍｄ）２であることを特徴とする請求項１記載のＣｏ膜の形成方法。 It said cobalt alkyl amidinate Nate is, Co (tBu-Et-Et -amd) forming method of claim 1 Symbol placement of the Co film characterized in that it is a 2. 下地としての基材表面にＣｏ膜を形成する方法において、前記基材表面をＮＨ ３ で前処理して基材表面をＮＨでターミネートし、コバルトアルキルアミジネイトと、ＮＨ３、Ｎ２Ｈ４、ＮＨ（ＣＨ３）２、Ｎ２Ｈ３ＣＨ、及びＮ２から選ばれた還元ガスのラジカル、又はＨ２及び前記還元ガスのラジカルの組み合わせガスとを用いてＣｏ膜を形成することを特徴とするＣｏ膜の形成方法。 In the method of forming a Co film on the surface of a base material as a base, the base material surface is pretreated with NH 3 , the base material surface is terminated with NH, and a cobalt alkyl amidate, NH 3 , N 2 H 4 A Co film is formed using a radical of a reducing gas selected from NH (CH 3 ) 2 , N 2 H 3 CH, and N 2 , or a combination gas of radicals of H 2 and the reducing gas. A method for forming a Co film. 前記コバルトアルキルアミジネイトが、Ｃｏ（ｔＢｕ−Ｅｔ−Ｅｔ−ａｍｄ）２であることを特徴とする請求項３記載のＣｏ膜の形成方法。 4. The method of forming a Co film according to claim 3, wherein the cobalt alkyl amidinate is Co (tBu-Et-Et-amd) 2 .
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014074215A (en) * 2012-10-05 2014-04-24 Taiyo Nippon Sanso Corp Cleaning method for gas-phase growth apparatus piping, and gas-phase growth apparatus

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103874781B (en) * 2011-10-07 2016-02-10 气相成长株式会社 Cobalt-based film formation method
JP2013104100A (en) * 2011-11-14 2013-05-30 Taiyo Nippon Sanso Corp Method for depositing metallic thin film and raw material for depositing metallic thin film
JP2014045037A (en) * 2012-08-24 2014-03-13 Ulvac Japan Ltd Deposition method of metal film
JP5917351B2 (en) * 2012-09-20 2016-05-11 東京エレクトロン株式会社 Method for forming metal film
JP2014101564A (en) * 2012-11-21 2014-06-05 Ulvac Japan Ltd Formation method of cobalt film
JP6220649B2 (en) * 2013-11-25 2017-10-25 東京エレクトロン株式会社 Method for forming metal film
CN108475638B (en) 2016-05-16 2022-11-18 株式会社爱发科 Method for forming Cu film
JP6559107B2 (en) * 2016-09-09 2019-08-14 東京エレクトロン株式会社 Film forming method and film forming system

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6365502B1 (en) * 1998-12-22 2002-04-02 Cvc Products, Inc. Microelectronic interconnect material with adhesion promotion layer and fabrication method
JP2003133377A (en) * 2001-08-14 2003-05-09 Oki Electric Ind Co Ltd Inspection pattern of multilayered wring structure, semiconductor device having inspection pattern, and method and system for inspecting semiconductor device
WO2004061154A1 (en) * 2002-12-27 2004-07-22 Ulvac Inc. Method for forming tungsten nitride film
JP2005086185A (en) * 2003-09-11 2005-03-31 Tokyo Electron Ltd Deposition method
JP2006511716A (en) * 2002-11-15 2006-04-06 プレジデント・アンド・フェロウズ・オブ・ハーバード・カレッジ Atomic layer deposition using metal amidinates.
JP2006257073A (en) * 2005-02-04 2006-09-28 Air Products & Chemicals Inc Organometallic complex and method for depositing using the same
JP2009130288A (en) * 2007-11-27 2009-06-11 Ulvac Japan Ltd Thin-film forming method
WO2009088522A2 (en) * 2007-04-09 2009-07-16 President And Fellows Of Harvard College Cobalt nitride layers for copper interconnects and methods for forming them

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6365502B1 (en) * 1998-12-22 2002-04-02 Cvc Products, Inc. Microelectronic interconnect material with adhesion promotion layer and fabrication method
JP2003133377A (en) * 2001-08-14 2003-05-09 Oki Electric Ind Co Ltd Inspection pattern of multilayered wring structure, semiconductor device having inspection pattern, and method and system for inspecting semiconductor device
JP2006511716A (en) * 2002-11-15 2006-04-06 プレジデント・アンド・フェロウズ・オブ・ハーバード・カレッジ Atomic layer deposition using metal amidinates.
WO2004061154A1 (en) * 2002-12-27 2004-07-22 Ulvac Inc. Method for forming tungsten nitride film
JP2005086185A (en) * 2003-09-11 2005-03-31 Tokyo Electron Ltd Deposition method
JP2006257073A (en) * 2005-02-04 2006-09-28 Air Products & Chemicals Inc Organometallic complex and method for depositing using the same
WO2009088522A2 (en) * 2007-04-09 2009-07-16 President And Fellows Of Harvard College Cobalt nitride layers for copper interconnects and methods for forming them
JP2009130288A (en) * 2007-11-27 2009-06-11 Ulvac Japan Ltd Thin-film forming method

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014074215A (en) * 2012-10-05 2014-04-24 Taiyo Nippon Sanso Corp Cleaning method for gas-phase growth apparatus piping, and gas-phase growth apparatus

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