JPWO2020009048A1 - Substrate, selective film deposition method on the metal surface area of the substrate, organic deposit film and organic matter - Google Patents

Substrate, selective film deposition method on the metal surface area of the substrate, organic deposit film and organic matter Download PDF

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JPWO2020009048A1
JPWO2020009048A1 JP2020528845A JP2020528845A JPWO2020009048A1 JP WO2020009048 A1 JPWO2020009048 A1 JP WO2020009048A1 JP 2020528845 A JP2020528845 A JP 2020528845A JP 2020528845 A JP2020528845 A JP 2020528845A JP WO2020009048 A1 JPWO2020009048 A1 JP WO2020009048A1
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純基 山本
純基 山本
益隆 新免
益隆 新免
増田　隆司
隆司 増田
亮 灘野
亮 灘野
達夫 宮崎
達夫 宮崎
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    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/60—Deposition of organic layers from vapour phase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/002—Processes for applying liquids or other fluent materials the substrate being rotated
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
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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
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    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • H—ELECTRICITY
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    • 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
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02118—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating

Abstract

本開示の基板の金属表面領域への選択的な膜堆積方法は、金属を含む第一表面領域と、非金属無機材料及び／又は金属酸化物を含む第二表面領域とが両方とも露出した構造を持つ基板に対して、前記第二表面領域よりも前記第一表面領域に、下記一般式（１）で表される有機物の膜を選択的に堆積させることを特徴とする方法。（一般式（１）において、Ｎは窒素原子であり、Ｘは酸素原子又は硫黄原子である。Ｒ１は炭素数２〜１２のヘテロ原子やハロゲン原子を有していてもよい炭化水素基であり、Ｒ２、Ｒ３、Ｒ４は、それぞれ独立して、水素原子又は炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基である。但し、前記炭化水素基は、炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造の炭化水素基も含む。）［化１］（１）The selective film deposition method of the substrate of the present disclosure on the metal surface region has a structure in which both the first surface region containing a metal and the second surface region containing a non-metal inorganic material and / or a metal oxide are exposed. A method characterized by selectively depositing a film of an organic substance represented by the following general formula (1) on the first surface region rather than the second surface region. (In the general formula (1), N is a nitrogen atom, X is an oxygen atom or a sulfur atom, and R1 is a hydrocarbon group which may have a hetero atom or a halogen atom having 2 to 12 carbon atoms. , R2, R3, and R4 are hydrocarbon groups that may independently have a hydrogen atom or a ring having 1 to 10 carbon atoms, a hetero atom, or a halogen atom. However, the hydrocarbon group is a hydrocarbon group. When the number of carbon atoms is 3 or more, a branched chain or a hydrocarbon group having a cyclic structure is also included.) [Chemical formula 1] (1)

Description

本開示は、基板、基板の金属表面領域への選択的な膜堆積方法、有機物の堆積膜及び有機物である。 The present disclosure is a substrate, a method of selectively depositing a film on a metal surface region of a substrate, a deposited film of an organic substance, and an organic substance.

近年、半導体チップの構造は益々微細化しており、構造体の一部を選択的に除去することによりパターニングする従来のリソグラフィ法は、ステップ数の多さやコスト高といった問題があった。化学気相堆積（ＣＶＤ）法や原子層堆積（ＡＬＤ）法において基板上の所望の箇所に選択的に膜を形成できれば、微細構造の形成に最適なプロセスとなり、これらの問題は、解消すると考えられている。 In recent years, the structure of a semiconductor chip has become finer and finer, and the conventional lithography method for patterning by selectively removing a part of the structure has problems such as a large number of steps and high cost. If a film can be selectively formed at a desired location on a substrate by chemical vapor deposition (CVD) or atomic layer deposition (ALD), it will be the optimum process for forming fine structures, and these problems will be solved. Has been done.

しかし、電極や配線に用いられる金属や、絶縁膜に用いられる無機誘電体などの材料の異なる複数種の表面領域を持つ基板に対して、ＣＶＤ法やＡＬＤ法で膜を選択的に堆積させる場合に、堆積阻害用の膜を選択的に堆積させる必要があるが、従来の方法では選択性は十分に高くなかった。 However, when the film is selectively deposited by the CVD method or the ALD method on a substrate having a plurality of different surface regions of different materials such as a metal used for electrodes and wiring and an inorganic dielectric used for an insulating film. In addition, it is necessary to selectively deposit a film for deposition inhibition, but the selectivity was not sufficiently high by the conventional method.

選択的な膜の形成方法については、膜を形成したくない領域に、膜の堆積を阻害する材料を堆積させる方法が知られている。例えば、特許文献１には、基板上に、ＴｉＮ、ＡｌＮまたはＳｉＮ等の無機材料の薄膜のパターンを原子層堆積法（ＡＬＤ）により形成する方法であって、 基板上に、フッ素含有量が３０原子％以上であり、少なくとも１つの第３級炭素もしくは第４級炭素を有し、かつ、エステル基、ヒドロキシル基、カルボキシル基およびイミド基を有しない含フッ素樹脂から構成される原子層堆積阻害材料を用いて、スクリーン印刷等で原子層堆積阻害層のパターンを形成すること、次いで、原子層堆積法により、原子層堆積阻害層が存在しない領域に、無機材料の層を形成することを、を含む方法が開示されている。 As a selective method for forming a film, a method of depositing a material that inhibits the deposition of the film is known in a region where the film is not desired to be formed. For example, Patent Document 1 describes a method of forming a thin film pattern of an inorganic material such as TiN, AlN, or SiN on a substrate by an atomic layer deposition method (ALD), wherein the substrate has a fluorine content of 30. Atomic layer deposition inhibitory material composed of a fluorine-containing resin having at least 1% of atoms, having at least one tertiary or quaternary carbon, and having no ester group, hydroxyl group, carboxyl group or imide group. To form a pattern of the atomic layer deposition inhibitory layer by screen printing or the like, and then to form a layer of an inorganic material in a region where the atomic layer deposition inhibitory layer does not exist by the atomic layer deposition method. Methods to include are disclosed.

また、特許文献２には、露出した金属表面及び露出したケイ素含有表面を有する基板の上に層を選択的に堆積させる方法において、（ａ）前記露出した金属表面の上に第１の自己組織化単分子膜を成長させることと、（ｂ）前記露出したケイ素含有表面の上に、オルガノシラン系である第２の自己組織化単分子膜を成長させることと、（ｃ）前記基板を加熱して、前記露出した金属表面の上から前記第１の自己組織化単分子膜を除去することと、（ｄ）低誘電率誘電体層又は金属層である層を、前記露出した金属表面の上に選択的に堆積させることと、（ｅ）前記基板を加熱して、前記露出したケイ素含有表面の上から第２の自己組織化単分子膜を除去することと、を含む方法が開示されている。 Further, Patent Document 2 describes (a) a first self-assembly on the exposed metal surface in a method of selectively depositing a layer on a substrate having an exposed metal surface and an exposed silicon-containing surface. To grow a chemical monolayer, (b) to grow a second self-assembled monolayer, which is an organosilane system, on the exposed silicon-containing surface, and (c) to heat the substrate. Then, the first self-assembled monolayer is removed from the exposed metal surface, and (d) the low dielectric constant dielectric layer or the metal layer is formed on the exposed metal surface. Disclosed are methods comprising selectively depositing on top and (e) heating the substrate to remove the second self-assembled monolayer from above the exposed silicon-containing surface. ing.

上記方法によれば、異なる材料からなる第１の表面と第２の表面を有する基板に対して、両者の表面状態の相違を利用して、第１の表面に第２の表面よりも選択的に膜を堆積することができる。また、上記方法によれば、微細構造を形成するプロセスのステップ数を削減することができる。 According to the above method, for a substrate having a first surface and a second surface made of different materials, the difference in surface state between the two is utilized to select the first surface more than the second surface. Membranes can be deposited on. Further, according to the above method, the number of steps in the process of forming the fine structure can be reduced.

例えば、特許文献３には、金属性表面である第１の表面と、誘電体表面である第２の表面とを含む基板に、第１の気相前駆物質を接触させるステップと、第２の気相前駆物質を接触させるステップと、を含む堆積サイクルを行い、第２の表面よりも第１の表面上に選択的に有機薄膜を形成するプロセスが開示されている。特許文献３の実施例１では、酸化ケイ素表面と交互になったタングステン（Ｗ）フィーチャを有する２００ｍｍシリコンウェハを基板とし、１，６−ジアミノヘキサン（ＤＡＨ）と、ピロメリト酸二無水物（ＰＭＤＡ）とを用いて、２５０〜１０００堆積サイクルを行い、ポリイミド膜を形成し、ＳｉＯ２表面上のポリイミド膜の厚さより、金属タングステン表面上のポリイミド膜の厚さの方が厚かった、ことが記載されている。For example, Patent Document 3 describes a step of bringing a first gas phase precursor into contact with a substrate including a first surface which is a metallic surface and a second surface which is a dielectric surface, and a second step. Disclosed is a process of performing a deposition cycle comprising contacting a gas phase precursor and selectively forming an organic thin film on the first surface rather than on the second surface. In Example 1 of Patent Document 3, a 200 mm silicon wafer having tungsten (W) features alternating with a silicon oxide surface is used as a substrate, and 1,6-diaminohexane (DAH) and pyromeritic acid dianhydride (PMDA) are used as a substrate. It is described that the polyimide film was formed by performing 250 to 1000 deposition cycles using and, and the thickness of the polyimide film on the surface of metallic tungsten was thicker than the thickness of the polyimide film on the surface of SiO 2. ing.

特許文献４には、特許文献３に記載の有機膜の選択的堆積法を利用して、金属製の第１表面の上にパッシベーション層を選択的に形成したのち、誘電体の第２表面の上にのみ層Ｘを形成する方法、さらにはこの方法を利用して、集積回路のメタライゼーション構造を形成する方法が開示されている。 In Patent Document 4, a passivation layer is selectively formed on a first surface made of metal by utilizing the selective deposition method of an organic film described in Patent Document 3, and then a second surface of a dielectric material is formed. A method of forming layer X only on top, and a method of forming a metallization structure of an integrated circuit using this method is disclosed.

特許文献５においては、金属表面に配位結合によって単分子膜を形成する方法が開示されている。 Patent Document 5 discloses a method of forming a monolayer on a metal surface by a coordination bond.

国際公開第２０１６／１４７９４１号International Publication No. 2016/147941 特表２０１８−５１２５０４号公報Special Table 2018-521504 特開２０１７−２１６４４８号公報JP-A-2017-216448 特開２０１８−１３７４３５号公報JP-A-2018-137435 特開平１０−１８０９２９号公報Japanese Unexamined Patent Publication No. 10-180929

しかしながら、特許文献１では、単一材料の基板上に、原子層堆積阻害材料を用いて、所定のパターンを形成しており、材料の異なる複数種の表面領域を持つ基板に対して、所望の表面領域に選択的に構造を形成する方法は開示されていない。 However, in Patent Document 1, a predetermined pattern is formed on a substrate of a single material by using an atomic layer deposition inhibitory material, which is desired for a substrate having a plurality of types of surface regions of different materials. A method of selectively forming a structure in a surface region is not disclosed.

特許文献２では、金属表面上に第１のＳＡＭ膜を形成する工程は、長鎖アルキルチオール、長鎖有機ホスホン酸、長鎖スルホン酸を含む溶液に、基板を浸す方法であり、いわゆるウェットプロセスである。一方で、ＳＡＭ膜の形成の後に行われる、基板上への低誘電率誘電体層や金属層に用いられるＡＬＤやＣＶＤといったプロセスは、ドライプロセスであるため、ウェットプロセスを行った後、ドライプロセスを行う必要があり、方法が複雑となり、ドライプロセスにて、堆積阻害用の膜を形成する方法が望まれていた。 In Patent Document 2, the step of forming the first SAM film on the metal surface is a method of immersing the substrate in a solution containing a long-chain alkylthiol, a long-chain organic phosphonic acid, and a long-chain sulfonic acid, which is a so-called wet process. Is. On the other hand, since the processes such as ALD and CVD used for the low dielectric constant dielectric layer and the metal layer on the substrate, which are performed after the formation of the SAM film, are dry processes, the wet process is performed and then the dry process is performed. This has complicated the method, and a method of forming a film for deposition inhibition by a dry process has been desired.

特許文献３及び特許文献４に記載されている選択的に有機薄膜を形成する方法は、ドライプロセスではあるものの、原料と温度を切り替えての堆積サイクルを複数回繰り返す必要があり、有機薄膜の形成には大変な手間が必要であった。 Although the method of selectively forming an organic thin film described in Patent Documents 3 and 4 is a dry process, it is necessary to repeat the deposition cycle by switching the raw material and the temperature a plurality of times, and the organic thin film is formed. It took a lot of time and effort.

特許文献５では、単分子膜を形成する方法が開示されているものの、選択的な膜の形成については言及されていない。 Although Patent Document 5 discloses a method for forming a monolayer, it does not mention selective film formation.

本開示は、上記課題に鑑み、簡単な操作にて、基板上の非金属無機材料が露出した表面領域又は金属酸化物が露出した表面領域に対してよりも、金属が露出した表面領域に選択的に有機物の膜を堆積する方法、上記方法で得られた基板、有機物の堆積膜及び有機物を提供することを目的とする。 In view of the above problems, the present disclosure selects a surface region where a metal is exposed rather than a surface region where a non-metal inorganic material is exposed or a surface region where a metal oxide is exposed on a substrate by a simple operation. It is an object of the present invention to provide a method for depositing a film of an organic substance, a substrate obtained by the above method, a film for depositing an organic substance, and an organic substance.

本発明者らは、鋭意検討の結果、後述する一般式（１）で示される有機物は、基板上の非金属無機材料が露出した表面領域又は金属酸化物が露出した表面領域に対してよりも金属が露出した表面領域に選択的に有機物の膜を堆積することを見出し、本開示を完成させるに至った。 As a result of diligent studies, the present inventors have found that the organic substance represented by the general formula (1) described later is more than the surface region where the non-metal inorganic material is exposed or the surface region where the metal oxide is exposed on the substrate. We have found that a film of organic matter is selectively deposited on the exposed surface area of the metal, which completes the present disclosure.

本開示の基板の金属表面領域への選択的な膜堆積方法は、金属を含む第一表面領域と、非金属無機材料及び／又は金属酸化物を含む第二表面領域とが両方とも露出した構造を持つ基板に対して、上記第二表面領域よりも上記第一表面領域に、下記一般式（１）で表される有機物の膜を選択的に堆積させることを特徴とする。

Figure 2020009048

（１）
（一般式（１）において、Ｎは窒素原子であり、Ｘは酸素原子又は硫黄原子である。
Ｒ１は、炭素数２〜１２のヘテロ原子やハロゲン原子を有していてもよい炭化水素基であり、Ｒ２、Ｒ３、Ｒ４は、それぞれ独立して、水素原子又は炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基である。但し、この炭化水素基は、炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造の炭化水素基も含む。）The selective film deposition method of the substrate of the present disclosure on the metal surface region has a structure in which both the first surface region containing a metal and the second surface region containing a non-metal inorganic material and / or a metal oxide are exposed. It is characterized in that a film of an organic substance represented by the following general formula (1) is selectively deposited on the first surface region rather than the second surface region.
Figure 2020009048
(1)
(In the general formula (1), N is a nitrogen atom and X is an oxygen atom or a sulfur atom.
R 1 is a hydrocarbon group which may have a hetero atom or a halogen atom having 2 to 12 carbon atoms, and R 2 , R 3 and R 4 are independently hydrogen atoms or 1 to 1 hydrogen atoms. It is a hydrocarbon group that may have 10 rings, a hetero atom, or a halogen atom. However, this hydrocarbon group also includes a branched chain or a hydrocarbon group having a cyclic structure when the number of carbon atoms is 3 or more. )

上記方法によれば、一般式（１）で表される有機物を用いることにより、基板上の非金属無機材料が露出した領域及び／又は金属酸化物が露出した領域を含む第二表面領域に対してよりも、金属が露出した領域を含む第一表面領域に選択的に有機物の膜を堆積する方法を提供することができる。 According to the above method, by using the organic substance represented by the general formula (1), the second surface region including the region where the non-metal inorganic material is exposed and / or the region where the metal oxide is exposed on the substrate is covered. More than this, it is possible to provide a method for selectively depositing a film of an organic substance on a first surface region including a region where a metal is exposed.

上記第二表面領域には、非金属無機材料が露出していてもよく、金属酸化物が露出していてもよく、非金属無機材料及び金属酸化物が露出していてもよく、金属、非金属無機材料及び金属酸化物以外の物質が露出していてもよい。すなわち、上記第二表面領域は、非金属無機材料及び金属酸化物のうちの少なくとも1種が露出した領域を含む。上記第二表面領域は、非金属無機材料及び金属酸化物のうちの少なくとも1種のみが露出した領域であってもよい。上記第一表面領域は、金属のみが露出した領域であってもよい。 In the second surface region, the non-metal inorganic material may be exposed, the metal oxide may be exposed, the non-metal inorganic material and the metal oxide may be exposed, and the metal or non-metal may be exposed. Materials other than metal-inorganic materials and metal oxides may be exposed. That is, the second surface region includes a region where at least one of the non-metal inorganic material and the metal oxide is exposed. The second surface region may be a region where only at least one of the non-metal inorganic material and the metal oxide is exposed. The first surface region may be a region where only the metal is exposed.

本開示の基板は、金属を含む第一表面領域と、非金属無機材料及び／又は金属酸化物を含む第二表面領域とが両方とも露出した構造を持つ基板であって、上記第一表面領域に下記一般式（１）で表される有機物の膜を有し、上記第二表面領域に上記有機物の膜を有しないか、上記第二表面領域上の上記有機物の膜の厚さｔ２が、上記第一表面領域上の上記有機物の膜の厚さｔ１よりも薄いことを特徴とする。

Figure 2020009048

（１）
（一般式（１）においてＮは窒素原子であり、Ｘは酸素原子又は硫黄原子である。
Ｒ１は、炭素数２〜１２のヘテロ原子やハロゲン原子を有していてもよい炭化水素基であり、Ｒ２、Ｒ３、Ｒ４は水素原子又は炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基である。但し、上記炭化水素基は、炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造の炭化水素基も含む。）The substrate of the present disclosure is a substrate having a structure in which both the first surface region containing a metal and the second surface region containing a non-metallic inorganic material and / or a metal oxide are exposed, and the first surface region is described above. Has an organic film represented by the following general formula (1) and does not have the organic film in the second surface region, or the thickness t 2 of the organic film on the second surface region is It is characterized in that it is thinner than the thickness t 1 of the film of the organic substance on the first surface region.
Figure 2020009048
(1)
(In the general formula (1), N is a nitrogen atom and X is an oxygen atom or a sulfur atom.
R 1 is a hydrocarbon group which may have a hetero atom or a halogen atom having 2 to 12 carbon atoms, and R 2 , R 3 and R 4 are a hydrogen atom or a ring or a hetero atom having 1 to 10 carbon atoms. It is a hydrocarbon group which may have a halogen atom or a halogen atom. However, when the number of carbon atoms is 3 or more, the above-mentioned hydrocarbon group also includes a hydrocarbon group having a branched chain or a cyclic structure. )

上記基板によれば、一般式（１）で表される有機物を用いることにより、基板上の非金属無機材料が露出した領域及び／又は金属酸化物が露出した領域を含む第二表面領域に対してよりも、金属が露出した領域を含む第一表面領域に選択的に有機物の膜が堆積した基板を提供することができる。 According to the above-mentioned substrate, by using the organic substance represented by the general formula (1), with respect to the second surface region including the region where the non-metal inorganic material is exposed and / or the region where the metal oxide is exposed on the substrate. It is possible to provide a substrate in which a film of an organic substance is selectively deposited on a first surface region including a region where a metal is exposed.

本開示の有機物の堆積膜は、上記方法により形成された有機物の膜であって、
基板上に選択的に堆積した下記一般式（１）で表されることを特徴とする有機物の堆積膜である。

Figure 2020009048

（１）
（一般式（１）においてＮは窒素原子であり、Ｘは酸素原子又は硫黄原子である。
Ｒ１は炭素数２〜１２のヘテロ原子やハロゲン原子を有していてもよい炭化水素基であり、Ｒ２、Ｒ３、Ｒ４は水素原子又は炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基である。但し、この炭化水素基は、炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造の炭化水素基も含む。）The organic matter deposit film of the present disclosure is an organic substance film formed by the above method.
It is a deposition film of an organic substance selectively deposited on a substrate and represented by the following general formula (1).
Figure 2020009048
(1)
(In the general formula (1), N is a nitrogen atom and X is an oxygen atom or a sulfur atom.
R 1 is a hydrocarbon group which may have a hetero atom or a halogen atom having 2 to 12 carbon atoms, and R 2 , R 3 and R 4 are a hydrogen atom or a ring or a hetero atom having 1 to 10 carbon atoms. It is a hydrocarbon group that may have a halogen atom. However, this hydrocarbon group also includes a branched chain or a hydrocarbon group having a cyclic structure when the number of carbon atoms is 3 or more. )

本開示の有機物は、上記基板の金属表面領域への選択的な膜堆積方法に用いることを特徴とする下記一般式（１）で表されることを特徴とする有機物である。

Figure 2020009048

（１）
（一般式（１）においてＮは窒素原子であり、Ｘは酸素原子又は硫黄原子である。
Ｒ１は炭素数２〜１２のヘテロ原子やハロゲン原子を有していてもよい炭化水素基であり、Ｒ２、Ｒ３、Ｒ４は水素原子又は炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基である。但し、この炭化水素基は、炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造の炭化水素基も含む。）The organic substance of the present disclosure is an organic substance represented by the following general formula (1), which is used for a selective film deposition method on a metal surface region of the substrate.
Figure 2020009048
(1)
(In the general formula (1), N is a nitrogen atom and X is an oxygen atom or a sulfur atom.
R 1 is a hydrocarbon group which may have a hetero atom or a halogen atom having 2 to 12 carbon atoms, and R 2 , R 3 and R 4 are a hydrogen atom or a ring or a hetero atom having 1 to 10 carbon atoms. It is a hydrocarbon group that may have a halogen atom. However, this hydrocarbon group also includes a branched chain or a hydrocarbon group having a cyclic structure when the number of carbon atoms is 3 or more. )

本開示の有機物を用いることにより、基板上の非金属無機材料が露出した領域及び／又は金属酸化物が露出した領域を含む第二表面領域に対してよりも、金属が露出した領域を含む第一表面領域に選択的に有機物の膜を堆積することができる。 By using the organic matter of the present disclosure, the region including the exposed metal region is included rather than the second surface region including the region where the non-metal inorganic material is exposed and / or the region where the metal oxide is exposed on the substrate. A film of organic matter can be selectively deposited on one surface area.

本開示の溶液は、下記一般式（１）で表されることを特徴とする有機物と、溶媒とを含むことを特徴する溶液である。

Figure 2020009048
（１）
（一般式（１）においてＮは窒素原子であり、Ｘは酸素原子又は硫黄原子である。
Ｒ１は炭素数２〜１２のヘテロ原子やハロゲン原子を有していてもよい炭化水素基であり、Ｒ２、Ｒ３、Ｒ４は水素原子又は炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基である。但し、この炭化水素基は、炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造の炭化水素基も含む。）The solution of the present disclosure is a solution characterized by containing an organic substance represented by the following general formula (1) and a solvent.
Figure 2020009048
 (1)
(In the general formula (1), N is a nitrogen atom and X is an oxygen atom or a sulfur atom.
R 1 is a hydrocarbon group which may have a hetero atom or a halogen atom having 2 to 12 carbon atoms, and R 2 , R 3 and R 4 are a hydrogen atom or a ring or a hetero atom having 1 to 10 carbon atoms. It is a hydrocarbon group that may have a halogen atom. However, this hydrocarbon group also includes a branched chain or a hydrocarbon group having a cyclic structure when the number of carbon atoms is 3 or more. )

本開示の方法によれば、一般式（１）で表される有機物を用いることにより、基板上の非金属無機材料が露出した領域及び／又は金属酸化物が露出した領域を含む第二表面領域に対してよりも、金属が露出した領域を含む第一表面領域に選択的に有機物の膜を堆積する方法を提供することができる。 According to the method of the present disclosure, by using the organic substance represented by the general formula (1), the second surface region including the region where the non-metal inorganic material is exposed and / or the region where the metal oxide is exposed on the substrate is used. It is possible to provide a method for selectively depositing a film of an organic substance on a first surface region including a region where a metal is exposed.

また、本開示の基板によれば、一般式（１）で表される有機物を用いることにより、基板上の非金属無機材料が露出した領域及び／又は金属酸化物が露出した領域を含む第二表面領域に対してよりも、金属が露出した領域を含む第一表面領域に選択的に有機物の膜が堆積した基板を提供することができる。 Further, according to the substrate of the present disclosure, by using the organic substance represented by the general formula (1), the second region including the region where the non-metal inorganic material is exposed and / or the region where the metal oxide is exposed on the substrate is included. It is possible to provide a substrate in which a film of an organic substance is selectively deposited on a first surface region including a region where a metal is exposed, rather than on a surface region.

以下、本開示について詳細に説明するが、以下に記載する構成要件の説明は本開示の実施形態の一例であり、これらの具体的内容に限定はされない。その要旨の範囲内で種々変形して実施することができる。 Hereinafter, the present disclosure will be described in detail, but the description of the constituent requirements described below is an example of the embodiments of the present disclosure, and the specific contents thereof are not limited. It can be modified in various ways within the scope of the gist.

本開示の実施の形態に係る基板の金属表面領域への選択的な膜堆積方法は、金属を含む第一表面領域と、非金属無機材料及び／又は金属酸化物を含む第二表面領域とが両方とも露出した構造を持つ基板に対して、上記第二表面領域よりも上記第一表面領域に、一般式（１）で表される有機物の膜を選択的に堆積させることを特徴とする。 The method of selectively depositing a film on the metal surface region of the substrate according to the embodiment of the present disclosure includes a first surface region containing a metal and a second surface region containing a non-metal inorganic material and / or a metal oxide. It is characterized in that a film of an organic substance represented by the general formula (1) is selectively deposited on the first surface region rather than the second surface region on a substrate having an exposed structure.

上記方法においては、第二表面領域に対してよりも、一般式（１）で表される有機物の膜を選択的に堆積させる。この際、上記基板には、第一表面領域のみに上記有機物の膜を選択的に堆積させ、第二表面領域には、上記有機物の膜を堆積させないか、又は、第一表面領域上の有機物の膜の厚さｔ１は、第二表面領域上の有機物の膜の厚さｔ２よりも厚く、ｔ１をｔ２で除したｔ１／ｔ２の値が５以上であるように堆積させることが好ましい。ｔ１／ｔ２の値は、１０以上であることが好ましく、１００以上であることがより好ましい。なお、ｔ１は、１ｎｍ以上であることが好ましく、２ｎｍ以上であることがより好ましく、２００ｎｍ以下であることが好ましく、１００ｎｍ以下であることがより好ましい。また、ｔ２は１ｎｍ未満であることが好ましく、０ｎｍであってもよい。ｔ１及びｔ２の厚さは、原子間力顕微鏡（ＡＦＭ）により測定することができる。ｔ２が０ｎｍである場合は、上記した条件、すなわち、第一表面領域のみに上記有機物の膜を選択的に堆積させることを意味する。In the above method, the organic film represented by the general formula (1) is selectively deposited rather than on the second surface region. At this time, the film of the organic substance is selectively deposited only on the first surface region on the substrate, and the film of the organic substance is not deposited on the second surface region, or the organic substance on the first surface region is not deposited. The film thickness t 1 is thicker than the organic film thickness t 2 on the second surface region, and the value of t 1 / t 2 obtained by dividing t 1 by t 2 is 5 or more. It is preferable to let it. The value of t 1 / t 2 is preferably 10 or more, and more preferably 100 or more. In addition, t 1 is preferably 1 nm or more, more preferably 2 nm or more, preferably 200 nm or less, and more preferably 100 nm or less. Further, t 2 is preferably less than 1 nm and may be 0 nm. The thicknesses of t 1 and t 2 can be measured by an atomic force microscope (AFM). When t 2 is 0 nm, it means that the above-mentioned condition, that is, the film of the organic substance is selectively deposited only in the first surface region.

第一表面領域を構成する金属としては、Ｃｕ、Ｃｏ、Ｒｕ、Ｎｉ、Ｐｔ、Ａｌ、Ｔａ、Ｔｉ及びＨｆを使用することができ、特に、Ｃｕ、Ｃｏ及びＲｕを用いることが好ましい。なお、第一表面領域を構成する金属は、上記金属の合金であってもよい。 Cu, Co, Ru, Ni, Pt, Al, Ta, Ti and Hf can be used as the metal constituting the first surface region, and Cu, Co and Ru are particularly preferable. The metal constituting the first surface region may be an alloy of the above metals.

第二表面領域を構成する上記金属酸化物としては、前述の金属の酸化物が挙げられる。 Examples of the metal oxide constituting the second surface region include the above-mentioned metal oxide.

第二表面領域を構成する上記非金属無機材料としては、シリコン、シリコン酸化物、シリコン窒化物、シリコン酸窒化物などのシリコン系材料と、ゲルマニウム、ゲルマニウム酸化物、ゲルマニウム窒化物、ゲルマニウム酸窒化物などのゲルマニウム系材料を挙げることができ、これらの非金属無機材料のなかでは、シリコン系材料が好ましい。
上記シリコンは、多結晶シリコンと単結晶シリコンの両方を含む。シリコン酸化物はＳｉＯｘ（ｘは１以上２以下）の化学式で表され、通常はＳｉＯ２である。また、シリコン窒化物はＳｉＮｘ（ｘは０．３以上９以下）の化学式で表され、通常はＳｉ３Ｎ４である。シリコン酸窒化物はＳｉ４ＯｘＮｙ（ｘは３以上６以下、ｙは２以上４以下）で表され、例えばＳｉ４Ｏ５Ｎ３である。Examples of the non-metallic inorganic material constituting the second surface region include silicon-based materials such as silicon, silicon oxide, silicon nitride, and silicon oxynitride, and germanium, germanium oxide, germanium nitride, and germanium oxynitride. Among these non-metallic inorganic materials, silicon-based materials are preferable.
The silicon includes both polycrystalline silicon and single crystal silicon. Silicon oxide is represented by the chemical formula of SiO x (x is 1 or more and 2 or less), and is usually SiO 2. Further, the silicon nitride is represented by the chemical formula of SiN x (x is 0.3 or more and 9 or less), and is usually Si 3 N 4 . The silicon oxynitride is represented by Si 4 O x N y (x is 3 or more and 6 or less, y is 2 or more and 4 or less), for example, Si 4 O 5 N 3 .

金属を含む第一表面領域を得る方法としては、化学気相堆積（ＣＶＤ）法、物理気相堆積（ＰＶＤ）法などを用いて金属の膜を得る方法が挙げられる。例えば、上記の非金属無機材料又は金属酸化物の膜の上に、上記方法により金属膜を形成し、フォトリソグラフィー法にて金属膜を所定のパターンに形成する方法や、非金属無機材料又は金属酸化物の膜に穴や溝を形成し、その溝に金属を埋め込む方法により、金属を含む第一表面領域と、非金属無機材料及び／又は金属酸化物を含む第二表面領域とが両方とも露出した構造の基板を得ることができる。 Examples of the method for obtaining the first surface region containing a metal include a method for obtaining a metal film by using a chemical vapor deposition (CVD) method, a physical vapor deposition (PVD) method, or the like. For example, a method of forming a metal film on a film of the above-mentioned non-metal inorganic material or metal oxide by the above method and forming a metal film in a predetermined pattern by a photolithography method, or a method of forming a metal film in a predetermined pattern, or a non-metal inorganic material or metal. By forming holes or grooves in the oxide film and embedding metal in the grooves, both the first surface region containing the metal and / or the second surface region containing the non-metallic inorganic material and / or the metal oxide are formed. A substrate having an exposed structure can be obtained.

例えば、本開示の方法に使用する基板としては、構造中に金属膜を有する半導体デバイスの基板や、半導体デバイスのパターニング工程中で金属膜が形成される基板等であり、特に、半導体素子の絶縁膜に所定のパターンを持つ金属配線を形成した基板が挙げられる。即ち、第一表面領域としては、金属配線が該当し、第二表面領域としては、非金属無機材料及び／又は金属酸化物からなる絶縁膜が該当する。しかし、本開示の基板の金属表面領域への選択的な膜堆積方法に用いる基板は、これらの部材に限定されない。 For example, the substrate used in the method of the present disclosure includes a substrate of a semiconductor device having a metal film in its structure, a substrate on which a metal film is formed in a patterning process of the semiconductor device, and the like, and in particular, insulation of a semiconductor element. Examples thereof include a substrate in which a metal wiring having a predetermined pattern is formed on a film. That is, the first surface region corresponds to metal wiring, and the second surface region corresponds to an insulating film made of a non-metal inorganic material and / or a metal oxide. However, the substrate used in the selective film deposition method of the substrate of the present disclosure on the metal surface region is not limited to these members.

上記有機物としては、下記一般式（１）で表される有機物を用いる。

Figure 2020009048

（１）
（一般式（１）においてＮは窒素原子であり、Ｘは酸素原子または硫黄原子である。
Ｒ１は、炭素数２〜１２のヘテロ原子やハロゲン原子を有していてもよい炭化水素基であり、Ｒ２、Ｒ３、Ｒ４は、それぞれ独立して、水素原子又は炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基である。但し、炭化水素基は、炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造の炭化水素基も含む。）As the organic substance, an organic substance represented by the following general formula (1) is used.
Figure 2020009048
(1)
(In the general formula (1), N is a nitrogen atom and X is an oxygen atom or a sulfur atom.
R 1 is a hydrocarbon group which may have a hetero atom or a halogen atom having 2 to 12 carbon atoms, and R 2 , R 3 and R 4 are independently hydrogen atoms or 1 to 1 hydrogen atoms. It is a hydrocarbon group that may have 10 rings, a hetero atom, or a halogen atom. However, the hydrocarbon group also includes a branched-chain or cyclic hydrocarbon group when the number of carbon atoms is 3 or more. )

Ｒ１〜Ｒ４のヘテロ原子としては、窒素原子、酸素原子、硫黄原子、リン原子が挙げられる。Ｒ１としては、Ｃ２Ｈ４、Ｃ３Ｈ６、Ｃ４Ｈ８、Ｃ５Ｈ１０、Ｃ６Ｈ１２、フェニル基等が挙げられ、フェニル基の一部は、炭化水素基、ヒドロキシ基、チオール基、アミノ基、ハロゲン等で置換されていてもよい。
Ｒ２、Ｒ３、Ｒ４としては、水素基やＣＨ３、Ｃ２Ｈ５、Ｃ３Ｈ７等の炭化水素基等が挙げられる。Ｒ２、Ｒ３、Ｒ４を構成する炭化水素基の一部は、ヒドロキシ基、チオール基、アミノ基、ハロゲン等で置換されていてもよい。
更に、Ｒ３とＲ４が共に炭素数１以上の場合、Ｒ３とＲ４とが直接結合して、一般式（１）が環状構造をとっても良い。Ｒ２、Ｒ３、Ｒ４は、同じ置換基である場合もあるし、異なる置換基である場合もある。Examples of the heteroatom of R 1 to R 4 include a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Examples of R 1 include C 2 H 4 , C 3 H 6 , C 4 H 8 , C 5 H 10 , C 6 H 12 , phenyl group and the like, and some of the phenyl groups are hydrocarbon groups and hydroxy groups. , A thiol group, an amino group, a halogen or the like.
Examples of R 2 , R 3 , and R 4 include hydrogen groups and hydrocarbon groups such as CH 3 , C 2 H 5 , and C 3 H 7. Some of the hydrocarbon groups constituting R 2 , R 3 and R 4 may be substituted with a hydroxy group, a thiol group, an amino group, a halogen or the like.
Further, when both R 3 and R 4 have 1 or more carbon atoms, R 3 and R 4 may be directly bonded to each other, and the general formula (1) may have a cyclic structure. R 2, R 3, R 4 may or be the same substituent or may be different substituents.

特に、一般式（１）で表される有機物としては、Ｒ２、Ｒ３が水素原子であり、アミノ基（−ＮＨ２）を持つ化合物が好ましい。さらに、Ｒ４が水素原子であり、−ＸＲ４が、ヒドロキシ基（−ＯＨ）や、チオール基（−ＳＨ）である化合物が好ましい。In particular, as the organic substance represented by the general formula (1), a compound in which R 2 and R 3 are hydrogen atoms and have an amino group (-NH 2) is preferable. Further, a compound in which R 4 is a hydrogen atom and -XR 4 is a hydroxy group (-OH) or a thiol group (-SH) is preferable.

一般式（１）で表される具体的な化合物として、例えば、ｏ−アミノチオフェノール、２−アミノベンジルアルコール、２−アミノエタノール、２−（エチルアミノ）エタノール、２−アミノエタンチオール、３−アミノ−１−プロパノール、ｏ−アミノフェノールなどが挙げられ、これらのなかでは、ｏ−アミノチオフェノール又は２−アミノベンジルアルコールが好ましい。これらの化合物は、単独または併用して用いることができる。 Specific compounds represented by the general formula (1) include, for example, o-aminothiophenol, 2-aminobenzyl alcohol, 2-aminoethanol, 2- (ethylamino) ethanol, 2-aminoethanethiol, 3-. Examples thereof include amino-1-propanol and o-aminophenol, and among these, o-aminothiophenol or 2-aminobenzyl alcohol is preferable. These compounds can be used alone or in combination.

第二表面領域よりも第一表面領域に、一般式（１）で表される有機物の膜を選択的に堆積させる具体的な方法としては、有機物と溶媒とを含む溶液に基板を暴露する方法（湿式法）、及び、有機物の気体を含む雰囲気に前記基板を暴露する方法（乾式法）の二つの方法を採用することができる。以下、これらの方法について説明する。 As a specific method for selectively depositing a film of an organic substance represented by the general formula (1) on the first surface region rather than the second surface region, a method of exposing the substrate to a solution containing an organic substance and a solvent is used. Two methods can be adopted: (wet method) and a method of exposing the substrate to an atmosphere containing an organic gas (dry method). Hereinafter, these methods will be described.

［湿式法］
本開示の実施の形態に係る湿式法では、上記した有機物と溶媒とを含む溶液に基板を暴露するが、その一例として、有機物と溶媒とを含む溶液に、第一表面領域と第二表面領域とを有する基板を浸漬することにより、上記基板の表面と上記溶液とを接触させ、有機物の膜を、基板の第一表面領域に選択的に堆積させる膜堆積工程を行うことができる。溶液に基板を暴露する方法として、浸漬法以外に、基板に溶液を滴下した後に高速回転させるスピンコート法や、溶液を基板に噴霧するスプレーコート法を用いることもできる。[Wet method]
In the wet method according to the embodiment of the present disclosure, the substrate is exposed to the above-mentioned solution containing an organic substance and a solvent. As an example thereof, a first surface region and a second surface region are exposed to a solution containing an organic substance and a solvent. By immersing the substrate having the above, the surface of the substrate and the solution can be brought into contact with each other, and a film deposition step of selectively depositing an organic film on the first surface region of the substrate can be performed. As a method for exposing the substrate to the solution, in addition to the dipping method, a spin coating method in which the solution is dropped on the substrate and then rotated at high speed, or a spray coating method in which the solution is sprayed on the substrate can also be used.

上記溶液中の有機物の濃度は、有機物と溶媒の合計に対して０．１質量％以上１０質量％以下が好ましく、０．５質量％以上８質量％以下がより好ましく、１質量％以上５質量％以下が特に好ましい。 The concentration of the organic substance in the solution is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.5% by mass or more and 8% by mass or less, and 1% by mass or more and 5% by mass with respect to the total of the organic substance and the solvent. % Or less is particularly preferable.

溶液に使用する溶媒としては、特に限定されないが、有機物を溶解可能な有機溶媒を使用することが好ましく、例えば、エタノールやイソプロピルアルコール（ＩＰＡ）などのアルコール等が挙げられる。 The solvent used in the solution is not particularly limited, but it is preferable to use an organic solvent capable of dissolving an organic substance, and examples thereof include alcohols such as ethanol and isopropyl alcohol (IPA).

上記湿式の膜堆積工程における溶液の温度は、０〜８０℃が好ましく、上記溶液に基板を浸漬する時間は、１〜１０００秒が好ましい。上記溶液に基板を浸漬する際、攪拌羽根等により溶液を攪拌することが好ましい。 The temperature of the solution in the wet film deposition step is preferably 0 to 80 ° C., and the time for immersing the substrate in the solution is preferably 1 to 1000 seconds. When immersing the substrate in the above solution, it is preferable to stir the solution with a stirring blade or the like.

また、有機物を含む溶液に基板を浸漬させた後、基板を引き上げ、溶媒で基板を洗浄する洗浄工程を行うことが好ましい。上記洗浄工程で使用できる溶媒としては、前述の有機溶媒を挙げることができる。洗浄の方法としては、０〜８０℃の上記溶媒に１〜１０００秒浸漬することが好ましい。 Further, it is preferable to perform a cleaning step of immersing the substrate in a solution containing an organic substance, pulling up the substrate, and cleaning the substrate with a solvent. Examples of the solvent that can be used in the cleaning step include the above-mentioned organic solvent. As a washing method, it is preferable to immerse in the above solvent at 0 to 80 ° C. for 1 to 1000 seconds.

上記洗浄工程の後、窒素、アルゴン等の不活性ガスを基板に吹き付けることにより、基板を乾燥させることが好ましい。吹き付ける不活性ガスの温度は、０〜８０℃が好ましい。 After the cleaning step, it is preferable to dry the substrate by blowing an inert gas such as nitrogen or argon onto the substrate. The temperature of the inert gas to be sprayed is preferably 0 to 80 ° C.

［乾式法］
本開示の実施の形態に係る乾式法では、有機物の気体を含む雰囲気に前記基板を暴露するが、具体的には、チャンバ内に基板を載置し、有機物を含む気体をチャンバ内に導入することにより、有機物を含む気体を基板の表面と接触させ、有機物の膜を、基板の第一表面領域に選択的に堆積させる膜堆積工程を行う。[Dry method]
In the dry method according to the embodiment of the present disclosure, the substrate is exposed to an atmosphere containing an organic gas. Specifically, the substrate is placed in a chamber and a gas containing an organic substance is introduced into the chamber. As a result, a film deposition step is performed in which a gas containing an organic substance is brought into contact with the surface of the substrate, and a film of the organic substance is selectively deposited on the first surface region of the substrate.

乾式の膜堆積工程で用いる有機物としては、湿式法と同様に一般式（１）で表される有機物が好ましい。 As the organic substance used in the dry film deposition step, the organic substance represented by the general formula (1) is preferable as in the wet method.

有機物の気体を含むチャンバ内の雰囲気ガスの温度は、０℃以上２００℃以下であることが好ましく、４０℃以上２００℃以下であることがより好ましく、６０℃以上１８０℃以下であることが特に好ましい。 The temperature of the atmospheric gas in the chamber containing the organic gas is preferably 0 ° C. or higher and 200 ° C. or lower, more preferably 40 ° C. or higher and 200 ° C. or lower, and particularly preferably 60 ° C. or higher and 180 ° C. or lower. preferable.

有機物の気体を含むチャンバ内の雰囲気ガスの圧力範囲は、０．１Ｔｏｒｒ（１３Ｐａ）以上５００Ｔｏｒｒ（６７ｋＰａ）以下であることが好ましく、１Ｔｏｒｒ（０．１３ｋＰａ）以上１００Ｔｏｒｒ（１３ｋＰａ）以下であることがより好ましい。 The pressure range of the atmospheric gas in the chamber containing the organic gas is preferably 0.1 Torr (13 Pa) or more and 500 Torr (67 kPa) or less, and more preferably 1 Torr (0.13 kPa) or more and 100 Torr (13 kPa) or less. preferable.

なお、有機物を気体で基板に接触させるため、チャンバ内の温度と圧力は有機物が気体のままである条件に設定する必要がある。 Since the organic substance is brought into contact with the substrate by gas, the temperature and pressure in the chamber must be set under the condition that the organic substance remains gas.

チャンバ内の雰囲気ガス中には、有機物の気体を１体積％以上１００体積％以下含むことが好ましく、１０体積％以上１００体積％以下含むことがより好ましく、５０体積％以上１００体積％以下含むことが更に好ましい。 The atmospheric gas in the chamber preferably contains 1% by volume or more and 100% by volume or less of the organic gas, more preferably 10% by volume or more and 100% by volume or less, and 50% by volume or more and 100% by volume or less. Is more preferable.

液体の有機物を減圧及び／又は加熱することにより気体の有機物を得てもよいし、液体の有機物に不活性ガスをバブリングすることにより、不活性ガスで希釈された気体の有機物を得てもよい。不活性ガスとしては、窒素ガスやアルゴンガス、クリプトンガス、ネオンガスなどを用いることができる。 A gaseous organic substance may be obtained by reducing the pressure and / or heating the liquid organic substance, or a gaseous organic substance diluted with the inert gas may be obtained by bubbling the liquid organic substance with an inert gas. .. As the inert gas, nitrogen gas, argon gas, krypton gas, neon gas and the like can be used.

乾式の膜堆積工程を行った後に、チャンバ内を１〜１００Ｐａに減圧することにより、余分な有機物を除去することができる。乾式法においては、乾燥工程を必要としない。 Excess organic matter can be removed by reducing the pressure in the chamber to 1 to 100 Pa after performing the dry film deposition step. The dry method does not require a drying step.

本開示の上記湿式法や上記乾式法を用いることにより、簡単な操作にて、基板上の非金属無機材料が露出した表面領域又は金属酸化物が露出した表面領域に対してよりも、金属が露出した表面領域に選択的に有機物の膜を堆積させることができる。 By using the above-mentioned wet method and the above-mentioned dry method of the present disclosure, the metal can be more easily applied to the surface region where the non-metal inorganic material is exposed or the surface region where the metal oxide is exposed on the substrate by a simple operation. A film of organic material can be selectively deposited on the exposed surface area.

上記湿式法や上記乾式法を行うことにより基板上に選択的に堆積した一般式（１）で表される有機物の堆積膜も、本開示の有機物の堆積膜の一実施形態に該当する。 The organic matter deposit film represented by the general formula (1) selectively deposited on the substrate by performing the wet method or the dry method also corresponds to one embodiment of the organic matter deposit film of the present disclosure.

［選択的堆積後の基板］
本開示の基板は、金属を含む第一表面領域と、非金属無機材料及び／又は金属酸化物を含む第二表面領域とが両方とも露出した構造を持つ基板であって、上記第一表面領域に下記一般式（１）で表される有機物の膜を有し、上記第二表面領域に上記有機物の膜を有しないか、上記第二表面領域上の上記有機物の膜の厚さｔ２が、上記第一表面領域上の上記有機物の膜の厚さｔ１よりも薄いことを特徴とする。

Figure 2020009048

（１）
（一般式（１）においてＮは窒素原子であり、Ｘは酸素原子又は硫黄原子である。
Ｒ１は炭素数２〜１２のヘテロ原子やハロゲン原子を有していてもよい炭化水素基であり、Ｒ２、Ｒ３、Ｒ４は水素原子又は炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基である。但し、上記炭化水素基は、炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造の炭化水素基も含む。）[Substrate after selective deposition]
The substrate of the present disclosure is a substrate having a structure in which both the first surface region containing a metal and the second surface region containing a non-metallic inorganic material and / or a metal oxide are exposed, and the first surface region is described above. Has an organic film represented by the following general formula (1) and does not have the organic film in the second surface region, or the thickness t 2 of the organic film on the second surface region is It is characterized in that it is thinner than the thickness t 1 of the film of the organic substance on the first surface region.
Figure 2020009048
(1)
(In the general formula (1), N is a nitrogen atom and X is an oxygen atom or a sulfur atom.
R 1 is a hydrocarbon group which may have a hetero atom or a halogen atom having 2 to 12 carbon atoms, and R 2 , R 3 and R 4 are a hydrogen atom or a ring or a hetero atom having 1 to 10 carbon atoms. It is a hydrocarbon group that may have a halogen atom. However, when the number of carbon atoms is 3 or more, the above-mentioned hydrocarbon group also includes a hydrocarbon group having a branched chain or a cyclic structure. )

本開示の基板においては、上述のように、上記第一表面領域に下記一般式（１）で表される有機物の膜を有し、上記第二表面領域に上記有機物の膜を有しないか、上記第二表面領域上の上記有機物の膜の厚さｔ２が、上記第一表面領域上の上記有機物の膜の厚さｔ１よりも薄い。In the substrate of the present disclosure, as described above, the first surface region has an organic film represented by the following general formula (1), and the second surface region has no organic film. The thickness t 2 of the organic film on the second surface region is thinner than the thickness t 1 of the organic film on the first surface region.

本開示の基板において、第二表面領域上の有機物の膜の厚さｔ２が、第一表面領域上の有機物の膜の厚さｔ１よりも薄い場合、ｔ１をｔ２で除したｔ１／ｔ２の値が５以上であることが望ましい。ｔ１／ｔ２の値は、１０以上であることが好ましく、１００以上であることがより好ましい。なお、ｔ１は、１ｎｍ以上であることが好ましく、２ｎｍ以上であることがより好ましく、２００ｎｍ以下であることが好ましく、１００ｎｍ以下であることがより好ましい。また、ｔ２は１ｎｍ未満であることが好ましく、０ｎｍであってもよい。ｔ１及びｔ２の厚さは、原子間力顕微鏡（ＡＦＭ）により測定することができる。ｔ２が０ｎｍである場合は、上記した条件、すなわち、第一表面領域のみに上記有機物の膜が選択的に堆積している。In the substrate of the present disclosure, when the thickness t 2 of the organic film on the second surface region is thinner than the thickness t 1 of the organic film on the first surface region , t 1 is divided by t 2. It is desirable that the value of 1 / t 2 is 5 or more. The value of t 1 / t 2 is preferably 10 or more, and more preferably 100 or more. In addition, t 1 is preferably 1 nm or more, more preferably 2 nm or more, preferably 200 nm or less, and more preferably 100 nm or less. Further, t 2 is preferably less than 1 nm and may be 0 nm. The thicknesses of t 1 and t 2 can be measured by an atomic force microscope (AFM). When t 2 is 0 nm, the above-mentioned condition, that is, the above-mentioned organic film is selectively deposited only in the first surface region.

本開示の基板において、金属を含む第一表面領域、非金属無機材料及び／又は金属酸化物を含む第二表面領域、一般式（１）で表される有機物等については、上記した本開示の基板の金属表面領域への選択的な膜堆積方法において説明したので、ここでは、詳しい説明を省略することとする。 In the substrate of the present disclosure, the first surface region containing a metal, the second surface region containing a non-metallic inorganic material and / or a metal oxide, an organic substance represented by the general formula (1), and the like are described in the above-mentioned present disclosure. Since the method of selectively depositing a film on the metal surface region of the substrate has been described, detailed description thereof will be omitted here.

上記有機物の膜は、上記有機物の分子中の窒素原子、酸素原子または硫黄原子を有する基が、第一表面領域の金属と相互作用して形成されていると考えられる。 It is considered that the organic film is formed by a group having a nitrogen atom, an oxygen atom or a sulfur atom in the molecule of the organic substance interacting with a metal in the first surface region.

以下に、金属が露出した表面領域に有機物により選択的に膜を堆積できることを下記の実験により確認した。 Below, it was confirmed by the following experiment that a film can be selectively deposited by an organic substance on the surface region where the metal is exposed.

［実験例１−１］
イソプロピルアルコール（以下、ＩＰＡという）に１％のｏ−アミノチオフェノールを溶解させ、有機物としてｏ−アミノチオフェノールと溶媒とを含む溶液を調製した。
次に、この溶液にＣｕ表面を含有する基板を６０秒浸漬させ、有機物の膜を堆積させた。溶液の温度は２０〜２５℃であった。その後、２０〜２５℃のＩＰＡの液に６０秒、２回浸漬させて、余分な有機物の除去を行い、続いて、２０〜２５℃の窒素ガスを６０秒間吹き付けて基板を乾燥させた。
基板上に形成された有機物の膜厚を原子間力顕微鏡（ＡＦＭ）で測定したところ、４８ｎｍであった。また、Ｘ線光電子分光法（ＸＰＳ）で元素組成を解析したところ、窒素と硫黄の強いピークを確認した。[Experimental Example 1-1]
1% o-aminothiophenol was dissolved in isopropyl alcohol (hereinafter referred to as IPA) to prepare a solution containing o-aminothiophenol as an organic substance and a solvent.
Next, the substrate containing the Cu surface was immersed in this solution for 60 seconds to deposit an organic film. The temperature of the solution was 20-25 ° C. Then, the substrate was immersed in an IPA solution at 20 to 25 ° C. twice for 60 seconds to remove excess organic matter, and then nitrogen gas at 20 to 25 ° C. was sprayed for 60 seconds to dry the substrate.
The film thickness of the organic matter formed on the substrate was measured with an atomic force microscope (AFM) and found to be 48 nm. Moreover, when the elemental composition was analyzed by X-ray photoelectron spectroscopy (XPS), strong peaks of nitrogen and sulfur were confirmed.

［実験例１−２〜１−２４］
基板表面の金属、有機物の種類、溶媒の種類、溶液濃度などを、表１に示したように変更した以外は、実験例１−１と同様に実施し、評価を行った。その結果を表１に示す。[Experimental Examples 1-2 to 1-24]
The evaluation was carried out in the same manner as in Experimental Example 1-1, except that the types of metals and organic substances on the surface of the substrate, the types of solvents, the solution concentration, etc. were changed as shown in Table 1. The results are shown in Table 1.

［実験例２−１］
ＩＰＡに５％のｏ−アミノチオフェノールを溶解させ、有機物としてｏ−アミノチオフェノールと溶媒とを含む溶液を調製した。
次に、この溶液にＳｉ表面を含有する基板を６０秒浸漬させ、有機物の膜を堆積させた。溶液の温度は２０〜２５℃であった。その後、２０〜２５℃のＩＰＡの液に６０秒、２回浸漬させて、余分な有機物の除去を行い、２０〜２５℃の窒素ガスを６０秒間吹き付けて基板を乾燥させた。
基板上に形成された有機物の膜厚をＡＦＭで測定したところ、０ｎｍであった。また、ＸＰＳで元素組成を解析したところ、窒素と硫黄のピークは確認できなかった。[Experimental Example 2-1]
5% o-aminothiophenol was dissolved in IPA to prepare a solution containing o-aminothiophenol as an organic substance and a solvent.
Next, the substrate containing the Si surface was immersed in this solution for 60 seconds to deposit an organic film. The temperature of the solution was 20-25 ° C. Then, the substrate was immersed in an IPA solution at 20 to 25 ° C. twice for 60 seconds to remove excess organic matter, and nitrogen gas at 20 to 25 ° C. was sprayed for 60 seconds to dry the substrate.
When the film thickness of the organic substance formed on the substrate was measured by AFM, it was 0 nm. Moreover, when the elemental composition was analyzed by XPS, the peaks of nitrogen and sulfur could not be confirmed.

［実験例２−２〜２−１０］
基板表面の金属、有機物の種類、溶媒の種類、溶液濃度などを、表２に示したように変更した以外は、実験例２−１と同様に実施し、評価を行った。その結果を表２に示す。[Experimental Examples 2-2-2-10]
The evaluation was carried out in the same manner as in Experimental Example 2-1 except that the types of metals and organic substances on the surface of the substrate, the types of solvents, the solution concentration, etc. were changed as shown in Table 2. The results are shown in Table 2.

［実験例３−１］
真空プロセスが可能なチャンバ内にＣｕ表面を含有する基板をセットし、チャンバ圧力を１Ｔｏｒｒ（０．１３ｋＰａ、絶対圧）に設定した。次に、チャンバに接続したｏ−アミノチオフェノールのシリンダーを８０℃に加熱してバルブを解放し、ｏ−アミノチオフェノールの気体をチャンバ内に供給し、Ｃｕを含有する基板上に有機物の膜を堆積させた。なお、チャンバの温度は、シリンダーの温度と同じにし、ｏ−アミノチオフェノールの気体の温度は、基板に接触するまで、シリンダーを保温する温度と同じに保たれるようにした。有機物の膜の堆積後、チャンバ内を０．１Ｔｏｒｒ（１３Ｐａ）に減圧して余分な有機物を除去した。
基板上に形成された有機物の膜厚をＡＦＭで測定したところ、１０ｎｍであった。また、ＸＰＳで元素組成を解析したところ、窒素と硫黄の強いピークを確認した。[Experimental Example 3-1]
A substrate containing a Cu surface was set in a chamber capable of a vacuum process, and the chamber pressure was set to 1 Torr (0.13 kPa, absolute pressure). Next, the cylinder of o-aminothiophenol connected to the chamber is heated to 80 ° C. to open the valve, the gas of o-aminothiophenol is supplied into the chamber, and an organic film is formed on the substrate containing Cu. Was deposited. The temperature of the chamber was made the same as the temperature of the cylinder, and the temperature of the gas of o-aminothiophenol was kept the same as the temperature of keeping the cylinder warm until it came into contact with the substrate. After depositing the organic matter film, the pressure inside the chamber was reduced to 0.1 Torr (13 Pa) to remove excess organic matter.
The film thickness of the organic matter formed on the substrate was measured by AFM and found to be 10 nm. Moreover, when the elemental composition was analyzed by XPS, strong peaks of nitrogen and sulfur were confirmed.

［実験例３−２〜３−１２］
基板上の金属、有機物の種類、シリンダーを保温する温度（有機物加熱温度）、チャンバ圧力などを表３に示したように変更した以外は、実験例３−１と同様に実施し、評価を行った。その結果を表３に示す。[Experimental Examples 3-2-3-12]
The evaluation was carried out in the same manner as in Experimental Example 3-1 except that the metal on the substrate, the type of organic matter, the temperature at which the cylinder was kept warm (organic matter heating temperature), the chamber pressure, etc. were changed as shown in Table 3. rice field. The results are shown in Table 3.

［実験例４−１］
真空プロセスが可能なチャンバ内にＳｉ表面を含有する基板をセットし、チャンバ圧力を１０Ｔｏｒｒに設定した。次に、チャンバに接続したｏ−アミノチオフェノールのシリンダーを１２０℃に加熱してバルブを解放し、ｏ−アミノチオフェノールの気体をチャンバ内に供給し、Ｓｉ表面を含有する基板上に有機物の膜を堆積させた。有機物の膜の堆積後、チャンバ内を０．１Ｔｏｒｒに減圧して余分な有機物を除去した。
基板上に形成された有機物の膜厚をＡＦＭで測定したところ、０ｎｍであった。また、ＸＰＳで元素組成を解析したところ、窒素と硫黄のピークは確認できなかった。[Experimental Example 4-1]
A substrate containing a Si surface was set in a chamber capable of vacuum processing, and the chamber pressure was set to 10 Torr. Next, the cylinder of o-aminothiophenol connected to the chamber is heated to 120 ° C. to open the valve, the gas of o-aminothiophenol is supplied into the chamber, and the organic substance is placed on the substrate containing the Si surface. The membrane was deposited. After depositing the organic matter film, the pressure inside the chamber was reduced to 0.1 Torr to remove excess organic matter.
When the film thickness of the organic substance formed on the substrate was measured by AFM, it was 0 nm. Moreover, when the elemental composition was analyzed by XPS, the peaks of nitrogen and sulfur could not be confirmed.

［実験例４−２〜４−１０］
基板上の金属、有機物の種類、シリンダーを保温する温度、チャンバ圧力などを表４に示したように変更した以外は、実験例４−１と同様に実施し、評価を行った。その結果を表４に示す。[Experimental Examples 4-2-4-10]
The evaluation was carried out in the same manner as in Experimental Example 4-1 except that the types of metals and organic substances on the substrate, the temperature at which the cylinder was kept warm, the chamber pressure, etc. were changed as shown in Table 4. The results are shown in Table 4.

なお、上記実験例において、Ｃｕ表面を含有する基板は、蒸着によりシリコン基板上に銅の膜を厚さ約１００ｎｍで成膜した後、表面自然酸化膜を除去することにより作製した。
Ｃｏ表面を含有する基板は、蒸着によりシリコン基板上にコバルトの膜を厚さ約１００ｎｍで成膜した後、表面自然酸化膜を除去することにより作製した。
Ｒｕ表面を含有する基板は、蒸着によりシリコン基板上にルテニウムの膜を厚さ約１００ｎｍで成膜した後、表面自然酸化膜を除去することにより作製した。In the above experimental example, the substrate containing the Cu surface was prepared by forming a copper film on a silicon substrate with a thickness of about 100 nm by vapor deposition and then removing the natural oxide film on the surface.
The substrate containing the Co surface was prepared by forming a cobalt film on a silicon substrate with a thickness of about 100 nm by vapor deposition and then removing the natural oxide film on the surface.
The substrate containing the Ru surface was prepared by forming a ruthenium film on a silicon substrate with a thickness of about 100 nm by vapor deposition and then removing the natural oxide film on the surface.

また、Ｓｉ表面を含有する基板は、シリコン基板の自然酸化膜を除去することにより作製した。
ＳｉＯ２表面を含有する基板は、化学的気相堆積法によりシリコン基板上に二酸化シリコンの膜を厚さ約３０ｎｍで成膜することにより作製した。
ＳｉＮ表面を含有する基板は、化学的気相堆積法によりシリコン基板上にＳｉ３Ｎ４の化学式で表される窒化シリコン膜を厚さ約３０ｎｍで成膜することにより作製した。
ＳｉＯＮ表面を含有する基板は、化学的気相堆積法によりシリコン基板上にＳｉＮ表面を形成させた後に酸化してＳｉ４ＯｘＮｙ（ｘは３以上６以下、ｙは２以上４以下）の化学式で表される酸窒化シリコン膜を厚さ約１０ｎｍで成膜することにより作製した。
ＣｕＯ表面を含有する基板は、蒸着によりシリコン基板上に酸化銅の膜を厚さ約１００ｎｍで成膜することにより作製した。
ＣｏＯ表面を含有する基板は、蒸着によりシリコン基板上に酸化コバルトの膜を厚さ約１００ｎｍで成膜することにより作製した。Further, the substrate containing the Si surface was produced by removing the natural oxide film of the silicon substrate.
The substrate containing the SiO 2 surface was produced by forming a silicon dioxide film on a silicon substrate with a thickness of about 30 nm by a chemical vapor phase deposition method.
The substrate containing the SiN surface was prepared by forming a silicon nitride film represented by the chemical formula of Si 3 N 4 on a silicon substrate by a chemical vapor phase deposition method to a thickness of about 30 nm.
Substrate containing a SiON surface oxidizes after forming the SiN surface on a silicon substrate by chemical vapor deposition Si 4 O x N y (x is 3 to 6, y is 2 to 4) It was produced by forming a silicon oxynitride film represented by the chemical formula of No. 1 in a thickness of about 10 nm.
The substrate containing the CuO surface was produced by forming a copper oxide film on a silicon substrate with a thickness of about 100 nm by vapor deposition.
The substrate containing the CoO surface was produced by forming a cobalt oxide film on a silicon substrate with a thickness of about 100 nm by vapor deposition.

以上の結果を下記の表１〜表４にまとめた。 The above results are summarized in Tables 1 to 4 below.

Figure 2020009048
Figure 2020009048

Figure 2020009048
Figure 2020009048

Figure 2020009048
Figure 2020009048

Figure 2020009048
Figure 2020009048

表１〜表４に示す結果より明らかなように、上記実験例において、有機物はＣｕ、Ｃｏ、Ｒｕなどの金属上には膜を堆積したが、Ｓｉ、ＳｉＯ２、ＳｉＮ、ＳｉＯＮなどの非金属無機材料上またはＣｕＯ、ＣｏＯなどの金属酸化物上には膜を堆積しなかった。従って、金属が露出した表面領域と非金属無機材料が露出した表面領域又は金属酸化物が露出した表面領域を有する基板を用いる場合、表１〜表４に示す有機物を用いることにより、金属が露出した表面領域のみに選択的に膜を堆積することができる。As is clear from the results shown in Tables 1 to 4, in the above experimental example, the organic substance deposited a film on metals such as Cu, Co, and Ru, but non-metals such as Si, SiO 2 , SiN, and SiON. No film was deposited on the inorganic material or on the metal oxides such as CuO and CoO. Therefore, when a substrate having a surface region where the metal is exposed and a surface region where the non-metal inorganic material is exposed or a surface region where the metal oxide is exposed is used, the metal is exposed by using the organic substances shown in Tables 1 to 4. The film can be selectively deposited only on the surface area.

なお、一般式（１）で表される有機物は、Ｃｏ、Ｃｕ、Ｒｕ以外にも、半導体装置などの配線材料や電極材料として適する導電性材料であるＮｉ、Ｐｔ、Ａｌ、Ｔａ、Ｔｉ、Ｈｆなどの金属上にも膜を堆積させることができる。 In addition to Co, Cu, and Ru, the organic substances represented by the general formula (1) are Ni, Pt, Al, Ta, Ti, and Hf, which are conductive materials suitable as wiring materials and electrode materials for semiconductor devices and the like. A film can also be deposited on a metal such as.

Claims (18)

金属を含む第一表面領域と、非金属無機材料及び／又は金属酸化物を含む第二表面領域とが両方とも露出した構造を持つ基板に対して、
前記第二表面領域よりも前記第一表面領域に、下記一般式（１）で表される有機物の膜を選択的に堆積させることを特徴とする方法。
Figure 2020009048
 （１）
（一般式（１）において、Ｎは窒素原子であり、Ｘは酸素原子又は硫黄原子である。
Ｒ１は、炭素数２〜１２のヘテロ原子やハロゲン原子を有していてもよい炭化水素基であり、Ｒ２、Ｒ３及びＲ４は、それぞれ独立して、水素原子又は炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基である。但し、この炭化水素基は、炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造の炭化水素基も含む。）For a substrate having a structure in which both the first surface region containing a metal and the second surface region containing a non-metal inorganic material and / or a metal oxide are exposed.
A method characterized by selectively depositing a film of an organic substance represented by the following general formula (1) on the first surface region rather than the second surface region.
Figure 2020009048
 (1)
(In the general formula (1), N is a nitrogen atom and X is an oxygen atom or a sulfur atom.
R 1 is a hydrocarbon group which may have a hetero atom or a halogen atom having 2 to 12 carbon atoms, and R 2 , R 3 and R 4 are independently hydrogen atoms or 1 to 1 hydrogen atoms. It is a hydrocarbon group that may have 10 rings, a hetero atom, or a halogen atom. However, this hydrocarbon group also includes a branched chain or a hydrocarbon group having a cyclic structure when the number of carbon atoms is 3 or more. ) 前記金属は、Ｃｕ、Ｃｏ、Ｒｕ、Ｎｉ、Ｐｔ、Ａｌ、Ｔａ、Ｔｉ及びＨｆからなる群より選ばれる少なくとも一つである、請求項１に記載の方法。 The method according to claim 1, wherein the metal is at least one selected from the group consisting of Cu, Co, Ru, Ni, Pt, Al, Ta, Ti and Hf. 前記非金属無機材料は、シリコン、シリコン酸化物、シリコン窒化物及びシリコン酸窒化物からなる群から選ばれる少なくとも一つである、請求項１又は２に記載の方法。 The method according to claim 1 or 2, wherein the non-metallic inorganic material is at least one selected from the group consisting of silicon, silicon oxide, silicon nitride and silicon oxynitride. 前記金属酸化物は、Ｃｕ、Ｃｏ、Ｒｕ、Ｎｉ、Ｐｔ、Ａｌ、Ｔａ、Ｔｉ及びＨｆからなる群より選ばれる少なくとも一つの金属の酸化物である、請求項１〜３のいずれか１項に記載の方法。 The metal oxide is an oxide of at least one metal selected from the group consisting of Cu, Co, Ru, Ni, Pt, Al, Ta, Ti and Hf, according to any one of claims 1 to 3. The method described. 前記一般式（１）において、Ｒ２、Ｒ３及びＲ４は、水素原子である、請求項１〜４のいずれか１項に記載の方法。The method according to any one of claims 1 to 4, wherein in the general formula (1), R 2 , R 3 and R 4 are hydrogen atoms. 前記有機物は、ｏ−アミノチオフェノール、２−アミノベンジルアルコール、２−アミノエタノール、２−（エチルアミノ）エタノール、２−アミノエタンチオール、３−アミノ−１−プロパノール及びｏ−アミノフェノールからなる群から選ばれる少なくとも一つである、請求項１に記載の方法。 The organic matter is a group consisting of o-aminothiophenol, 2-aminobenzyl alcohol, 2-aminoethanol, 2- (ethylamino) ethanol, 2-aminoethanethiol, 3-amino-1-propanol and o-aminophenol. The method according to claim 1, which is at least one selected from. 前記第二表面領域よりも前記第一表面領域に有機物の膜を選択的に堆積させる工程は、前記有機物と溶媒とを含む溶液に前記基板を暴露する工程である、請求項１〜６のいずれか１項に記載の方法。 Any of claims 1 to 6, wherein the step of selectively depositing a film of an organic substance on the first surface region rather than the second surface region is a step of exposing the substrate to a solution containing the organic substance and a solvent. The method according to item 1. 前記溶液は、有機物と溶媒の合計に対して０．１質量％以上１０質量％以下の前記一般式（１）で表される有機物を含む、請求項７に記載の方法。 The method according to claim 7, wherein the solution contains an organic substance represented by the general formula (1) of 0.1% by mass or more and 10% by mass or less based on the total amount of the organic substance and the solvent. 前記基板に対して、前記一般式（１）で表される有機物の膜を選択的に堆積させた後、前記基板を溶媒で洗浄する、請求項７又は８に記載の方法。 The method according to claim 7 or 8, wherein a film of an organic substance represented by the general formula (1) is selectively deposited on the substrate, and then the substrate is washed with a solvent. 前記第二表面領域よりも前記第一表面領域に、前記一般式（１）で表される有機物の膜を選択的に堆積させる工程が、前記有機物の気体を含む雰囲気に前記基板を暴露する工程である、請求項１〜６のいずれか１項に記載の方法。 The step of selectively depositing the film of the organic substance represented by the general formula (1) on the first surface region rather than the second surface region is a step of exposing the substrate to an atmosphere containing the gas of the organic substance. The method according to any one of claims 1 to 6. 前記雰囲気の温度範囲は、０℃以上２００℃以下である請求項１０に記載の方法。 The method according to claim 10, wherein the temperature range of the atmosphere is 0 ° C. or higher and 200 ° C. or lower. 前記雰囲気の圧力範囲は、１３Ｐａ以上６７ｋＰａ以下である請求項１０又は１１に記載の方法。 The method according to claim 10 or 11, wherein the pressure range of the atmosphere is 13 Pa or more and 67 kPa or less. 前記第一表面領域上の有機物の膜の厚さｔ１と、前期第二表面領域上の有機物の膜の厚さｔ２との比（ｔ１／ｔ２）が５以上である、請求項１〜１２のいずれか１項に記載の方法。The claim that the ratio (t 1 / t 2 ) of the thickness t 1 of the organic substance film on the first surface region to the thickness t 2 of the organic substance film on the second surface region in the previous period is 5 or more. The method according to any one of 1 to 12. 金属を含む第一表面領域と、非金属無機材料及び／又は金属酸化物を含む第二表面領域とが両方とも露出した構造を持つ基板であって、
前記第一表面領域に下記一般式（１）で表される有機物の膜を有し、
前記第二表面領域に前記有機物の膜を有しないか、前記第二表面領域上の前記有機物の膜の厚さｔ２が、前記第一表面領域上の前記有機物の膜の厚さｔ１よりも薄いことを特徴とする基板。
Figure 2020009048
 （１）
（一般式（１）においてＮは窒素原子であり、Ｘは酸素原子又は硫黄原子である。
Ｒ１は炭素数２〜１２のヘテロ原子やハロゲン原子を有していてもよい炭化水素基であり、Ｒ２、Ｒ３、Ｒ４は水素原子又は炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基である。但し、この炭化水素基は、炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造の炭化水素基も含む。）A substrate having a structure in which both the first surface region containing a metal and the second surface region containing a non-metal inorganic material and / or a metal oxide are exposed.
The first surface region has a film of an organic substance represented by the following general formula (1).
The second surface region does not have the organic film, or the thickness t 2 of the organic film on the second surface region is higher than the thickness t 1 of the organic film on the first surface region. A substrate characterized by being thin.
Figure 2020009048
 (1)
(In the general formula (1), N is a nitrogen atom and X is an oxygen atom or a sulfur atom.
R 1 is a hydrocarbon group which may have a hetero atom or a halogen atom having 2 to 12 carbon atoms, and R 2 , R 3 and R 4 are a hydrogen atom or a ring or a hetero atom having 1 to 10 carbon atoms. It is a hydrocarbon group that may have a halogen atom. However, this hydrocarbon group also includes a branched chain or a hydrocarbon group having a cyclic structure when the number of carbon atoms is 3 or more. ) 請求項１〜１３のいずれか1項に記載された方法により形成された有機物の膜であって、
基板上に選択的に堆積した下記一般式（１）で表されることを特徴とする有機物の堆積膜。
Figure 2020009048
 （１）
（一般式（１）においてＮは窒素原子であり、Ｘは酸素原子又は硫黄原子である。
Ｒ１は炭素数２〜１２のヘテロ原子やハロゲン原子を有していてもよい炭化水素基であり、Ｒ２、Ｒ３、Ｒ４は水素原子又は炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基である。但し、この炭化水素基は、炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造の炭化水素基も含む。）A film of an organic substance formed by the method according to any one of claims 1 to 13.
A deposit film of an organic substance selectively deposited on a substrate, which is represented by the following general formula (1).
Figure 2020009048
 (1)
(In the general formula (1), N is a nitrogen atom and X is an oxygen atom or a sulfur atom.
R 1 is a hydrocarbon group which may have a hetero atom or a halogen atom having 2 to 12 carbon atoms, and R 2 , R 3 and R 4 are a hydrogen atom or a ring or a hetero atom having 1 to 10 carbon atoms. It is a hydrocarbon group that may have a halogen atom. However, this hydrocarbon group also includes a branched chain or a hydrocarbon group having a cyclic structure when the number of carbon atoms is 3 or more. ) 請求項１〜１３のいずれか1項に記載された方法に用いることを特徴とする下記一般式（１）で表されることを特徴とする有機物。
Figure 2020009048
 （１）
（一般式（１）においてＮは窒素原子であり、Ｘは酸素原子又は硫黄原子である。
Ｒ１は炭素数２〜１２のヘテロ原子やハロゲン原子を有していてもよい炭化水素基であり、Ｒ２、Ｒ３、Ｒ４は水素原子又は炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基である。但し、この炭化水素基は、炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造の炭化水素基も含む。）An organic substance represented by the following general formula (1), which is used in the method according to any one of claims 1 to 13.
Figure 2020009048
 (1)
(In the general formula (1), N is a nitrogen atom and X is an oxygen atom or a sulfur atom.
R 1 is a hydrocarbon group which may have a hetero atom or a halogen atom having 2 to 12 carbon atoms, and R 2 , R 3 and R 4 are a hydrogen atom or a ring or a hetero atom having 1 to 10 carbon atoms. It is a hydrocarbon group that may have a halogen atom. However, this hydrocarbon group also includes a branched chain or a hydrocarbon group having a cyclic structure when the number of carbon atoms is 3 or more. ) 下記一般式（１）で表されることを特徴とする有機物と、溶媒とを含むことを特徴とする溶液。
Figure 2020009048
 （１）
（一般式（１）においてＮは窒素原子であり、Ｘは酸素原子又は硫黄原子である。
Ｒ１は炭素数２〜１２のヘテロ原子やハロゲン原子を有していてもよい炭化水素基であり、Ｒ２、Ｒ３、Ｒ４は水素原子又は炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基である。但し、この炭化水素基は、炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造の炭化水素基も含む。）A solution containing an organic substance represented by the following general formula (1) and a solvent.
Figure 2020009048
 (1)
(In the general formula (1), N is a nitrogen atom and X is an oxygen atom or a sulfur atom.
R 1 is a hydrocarbon group which may have a hetero atom or a halogen atom having 2 to 12 carbon atoms, and R 2 , R 3 and R 4 are a hydrogen atom or a ring or a hetero atom having 1 to 10 carbon atoms. It is a hydrocarbon group that may have a halogen atom. However, this hydrocarbon group also includes a branched chain or a hydrocarbon group having a cyclic structure when the number of carbon atoms is 3 or more. ) 前記有機物が、ｏ−アミノチオフェノール、２−アミノベンジルアルコール、２−アミノエタノール、２−（エチルアミノ）エタノール、２−アミノエタンチオール、３−アミノ−１−プロパノール及びｏ−アミノフェノールからなる群から選ばれる少なくとも一つであり、
前記溶媒が、エタノール及びイソプロピルアルコールからなる群から選ばれる少なくとも一つであり、
前記溶液は、有機物と溶媒の合計に対して０．１質量％以上１０質量％以下の前記一般式（１）で表される有機物を含む、ことを特徴とする請求項１７に記載の溶液。The group consisting of o-aminothiophenol, 2-aminobenzyl alcohol, 2-aminoethanol, 2- (ethylamino) ethanol, 2-aminoethanethiol, 3-amino-1-propanol and o-aminophenol. At least one chosen from
The solvent is at least one selected from the group consisting of ethanol and isopropyl alcohol.
The solution according to claim 17, wherein the solution contains an organic substance represented by the general formula (1) of 0.1% by mass or more and 10% by mass or less based on the total amount of the organic substance and the solvent.
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