WO2020009048A1

WO2020009048A1 - Substrate, selective method for accumulating film on metal surface region of substrate, accumulated film of organic matter, and organic matter

Info

Publication number: WO2020009048A1
Application number: PCT/JP2019/026014
Authority: WO
Inventors: 純基山本; 益隆新免; 増田　隆司; 亮灘野; 達夫宮崎
Original assignee: セントラル硝子株式会社
Priority date: 2018-07-02
Filing date: 2019-07-01
Publication date: 2020-01-09
Also published as: TW202012680A; JPWO2020009048A1; JP7303447B2; TWI827630B; KR20210029142A

Abstract

This selective method for accumulating a film on a metal surface region of a substrate is characterized in that a film of organic matter represented by general formula (1) is selectively accumulated on a substrate having a structure in which both of a first surface region that includes metal and a second surface region that includes a non-metal inorganic material and/or a metal oxide are exposed, the film being accumulated to a greater extent in the first surface region than in the second surface region. (In general formula (1), N represents a nitrogen atom, and X represents an oxygen atom or a sulfur atom. R¹ represents a C2-12 hydrocarbon group that may have a hetero atom or a halogen atom, and R², R³, and R⁴ each independently represent a hydrogen atom or a C1-10 hydrocarbon group that may have a hetero atom or a halogen atom. In the case of a C3 or higher hydrocarbon group, a branched or cyclic hydrocarbon group is also included.)

Description

Substrate, method for selectively depositing film on metal surface area of substrate, deposited film of organic matter, and organic matter

The present disclosure is a substrate, a method for selectively depositing a film on a metal surface region of a substrate, a deposited film of an organic substance, and an organic substance.

2. Description of the Related Art In recent years, the structure of a semiconductor chip has been increasingly miniaturized, and the conventional lithography method of performing patterning by selectively removing a part of the structure has problems such as a large number of steps and a high cost. It is thought that if a film can be selectively formed at a desired position on a substrate by a chemical vapor deposition (CVD) method or an atomic layer deposition (ALD) method, an optimal process for forming a fine structure will be solved, and these problems will be solved. Have been.

However, when a film is selectively deposited by a CVD method or an ALD method on a substrate having a plurality of types of surface regions made of different materials such as a metal used for an electrode or a wiring and an inorganic dielectric used for an insulating film. First, it is necessary to selectively deposit a film for inhibiting deposition, but the selectivity is not sufficiently high in the conventional method.

As a method of forming a film selectively, a method of depositing a material that inhibits film deposition in a region where a film is not desired to be formed is known. For example, Patent Document 1 discloses a method of forming a pattern of a thin film of an inorganic material such as TiN, AlN or SiN on a substrate by atomic layer deposition (ALD). Atomic% or more, an atomic layer deposition inhibiting material composed of a fluorine-containing resin having at least one tertiary carbon or quaternary carbon and having no ester group, hydroxyl group, carboxyl group and imide group To form a pattern of the atomic layer deposition inhibiting layer by screen printing or the like, and then form an inorganic material layer in a region where the atomic layer deposition inhibiting layer does not exist by the atomic layer deposition method. A method is disclosed.

Also, Patent Document 2 discloses a method for selectively depositing a layer on a substrate having an exposed metal surface and an exposed silicon-containing surface, comprising: (a) first self-assembly on the exposed metal surface; (B) growing an organosilane-based second self-assembled monolayer on the exposed silicon-containing surface; and (c) heating the substrate. Removing the first self-assembled monolayer from above the exposed metal surface; and (d) changing a layer that is a low dielectric constant dielectric layer or a metal layer to the exposed metal surface. A method is disclosed that comprises selectively depositing on the substrate and (e) heating the substrate to remove a second self-assembled monolayer from over the exposed silicon-containing surface. ing.

According to the above method, a substrate having a first surface and a second surface made of different materials is selectively applied to the first surface over the second surface by utilizing the difference in the surface states of the two. A film can be deposited on the substrate. Further, according to the above method, the number of steps in the process of forming a fine structure can be reduced.

For example, Patent Document 3 discloses that a first gas-phase precursor is brought into contact with a substrate including a first surface that is a metallic surface and a second surface that is a dielectric surface; Contacting a gas phase precursor to form an organic thin film selectively on a first surface over a second surface. In Example 1 of Patent Document 3, a 200 mm silicon wafer having tungsten (W) features alternated with a silicon oxide surface was used as a substrate, and 1,6-diaminohexane (DAH) and pyromellitic dianhydride (PMDA) were used. And that a 250-1000 deposition cycle was performed to form a polyimide film, and the thickness of the polyimide film on the metal tungsten surface was larger than the thickness of the polyimide film on the SiO ₂ surface. ing.

In Patent Document 4, a passivation layer is selectively formed on a first metal surface by using a selective deposition method of an organic film described in Patent Document 3, and then a second surface of a dielectric is formed. A method of forming layer X only on top, and a method of using this method to form a metallization structure of an integrated circuit are disclosed.

Patent Document 5 discloses a method of forming a monomolecular film on a metal surface by coordination bonds.

WO 2016/147941 JP-T-2018-512504 JP-A-2017-216448 JP 2018-137435 A JP-A-10-180929

However, in Patent Document 1, a predetermined pattern is formed on a substrate of a single material by using an atomic layer deposition inhibiting material, and a desired pattern is formed on a substrate having a plurality of types of surface regions of different materials. No method is disclosed for selectively forming structures in the surface region.

In Patent Document 2, the step of forming a first SAM film on a metal surface is a method of immersing a substrate in a solution containing a long-chain alkyl thiol, a long-chain organic phosphonic acid, and a long-chain sulfonic acid. It is. On the other hand, 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. Therefore, the method becomes complicated, and a method of forming a film for inhibiting deposition in a dry process has been desired.

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 a deposition cycle by switching a material and a temperature a plurality of times. Required a lot of trouble.

Patent Document 5 discloses a method for forming a monomolecular film, but does not mention selective film formation.

The present disclosure has been made in view of the above problems, and selects a surface region where a metal is exposed, with a simple operation, over a surface region where a nonmetallic inorganic material is exposed or a surface region where a metal oxide is exposed on a substrate. It is an object of the present invention to provide a method for selectively depositing a film of an organic substance, a substrate obtained by the above method, a deposited film of an organic substance, and an organic substance.

The present inventors have conducted intensive studies, and as a result, the organic substance represented by the general formula (1) described later has a higher surface area than the surface area where the nonmetallic inorganic material is exposed or the surface area where the metal oxide is exposed on the substrate. The present inventors have found that an organic film is selectively deposited on a surface region where metal is exposed, and have completed the present disclosure.

The method for selectively depositing a film on a metal surface region of a substrate according to the present disclosure includes a method in which a first surface region including a metal and a second surface region including a nonmetallic inorganic material and / or a metal oxide are both exposed. Wherein a film of an organic substance represented by the following general formula (1) is selectively deposited on the first surface region rather than on the second surface region.

(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 each independently represent a hydrogen atom or a carbon atom having 1 to 12 carbon atoms. It is a hydrocarbon group which may have 10 rings, hetero atoms or halogen atoms. However, when the hydrocarbon group has 3 or more carbon atoms, the hydrocarbon group also includes a branched or cyclic hydrocarbon group. )

According to the above method, by using the organic material represented by the general formula (1), the second surface region including the region where the nonmetallic inorganic material is exposed and / or the region where the metal oxide is exposed on the substrate is used. Thus, a method of selectively depositing an organic film on a first surface region including a region where a metal is exposed can be provided.

In the second surface region, the nonmetallic inorganic material may be exposed, the metal oxide may be exposed, the nonmetallic inorganic material and the metal oxide may be exposed, Substances other than the metal inorganic material and the metal oxide may be exposed. That is, the second surface region includes a region where at least one of the nonmetallic inorganic material and the metal oxide is exposed. The second surface region may be a region where at least one of the nonmetallic inorganic material and the metal oxide is exposed. The first surface region may be a region where only the metal is exposed.

The substrate of the present disclosure is a substrate having a structure in which both a first surface region including a metal and a second surface region including a nonmetallic inorganic material and / or a metal oxide are exposed, and the first surface region includes Has a film of an organic material represented by the following general formula (1), does not have a film of the organic material in the second surface region, or has a thickness t ₂ of the film of the organic material on the second surface region. , characterized in that less than the thickness t ₁ of said organic film on said first surface region.

(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 having 2 to 12 carbon atoms and optionally having a halogen atom, and R ² , R ³ and R ⁴ are a hydrogen atom or a ring or hetero atom having 1 to 10 carbon atoms. And a hydrocarbon group which may have a halogen atom. However, when the hydrocarbon group has 3 or more carbon atoms, the hydrocarbon group also includes a branched or cyclic hydrocarbon group. )

According to the substrate, by using the organic material represented by the general formula (1), the second surface region including the region where the nonmetallic inorganic material is exposed and / or the region where the metal oxide is exposed on the substrate is used. Rather, it is possible to provide a substrate in which an organic film is selectively deposited on the first surface region including the region where the metal is exposed.

An organic deposited film of the present disclosure is an organic film formed by the above method,
An organic deposited film, which is selectively deposited on a substrate and is represented by the following general formula (1).

(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 heteroatom having 2 to 12 carbon atoms or a hydrocarbon group optionally having a halogen atom, and R ² , R ³ and R ⁴ are a hydrogen atom or a ring or heteroatom having 1 to 10 carbon atoms. It is a hydrocarbon group which may have a halogen atom. However, when the hydrocarbon group has 3 or more carbon atoms, the hydrocarbon group also includes a branched or cyclic hydrocarbon group. )

The organic substance of the present disclosure is an organic substance represented by the following general formula (1), which is used in a method for selectively depositing a film on a metal surface region of the substrate.

By using the organic substance of the present disclosure, the second region including the metal-exposed region is more than the second surface region including the region where the non-metallic inorganic material is exposed and / or the region where the metal oxide is exposed on the substrate. An organic film can be selectively deposited on one surface region.

The solution of the present disclosure is a solution containing an organic substance represented by the following general formula (1) and a solvent.

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 nonmetallic inorganic material is exposed and / or the region where the metal oxide is exposed on the substrate It is possible to provide a method of selectively depositing an organic film on the first surface region including the region where the metal is exposed, as compared with the method described above.

According to the substrate of the present disclosure, by using the organic material represented by the general formula (1), the second region including the region where the nonmetallic 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 substrate in which the organic film is selectively deposited on the first surface region including the region where the metal is exposed, as compared with the surface region.

Hereinafter, the present disclosure will be described in detail, but the description of the constituent requirements described below is an example of an embodiment of the present disclosure, and the specific contents are not limited thereto. Various modifications can be made within the scope of the gist.

In the method for selectively depositing a film on a metal surface region of a substrate according to an embodiment of the present disclosure, the first surface region including a metal and the second surface region including a nonmetallic inorganic material and / or a metal oxide may be used. An organic film represented by the general formula (1) is selectively deposited on the first surface region rather than on the second surface region on a substrate having both exposed structures.

In the above method, the organic film represented by the general formula (1) is deposited more selectively than on the second surface region. At this time, the organic substance film is selectively deposited only on the first surface area on the substrate, and the organic substance film is not deposited on the second surface area, or the organic substance film on the first surface area is not deposited. the thickness t ₁ of the film is deposited as larger than the thickness t ₂ of the organic film on the second surface region, the value of t _{1 /} t ₂ obtained by dividing the t ₁ at t ₂ is 5 or more Preferably. The value of t ₁ / t ₂ is preferably 10 or more, and more preferably 100 or more. Incidentally, _{t 1} is preferably at 1nm or more, more preferably 2nm or more, preferably 200nm or less, and more preferably 100nm or less. Further, it is preferable that _{t 2} is less than 1 nm, may be 0 nm. The thicknesses of t ₁ and t ₂ can be measured by an atomic force microscope (AFM). If t ₂ is 0nm shows the above-mentioned conditions, that is, means to selectively deposit a film of the organic substance only in the first surface region.

As a metal constituting the first surface region, Cu, Co, Ru, Ni, Pt, Al, Ta, Ti, and Hf can be used, and particularly, Cu, Co, and Ru are preferably used. The metal constituting the first surface region may be an alloy of the above metals.

Examples of the metal oxide constituting the second surface region include oxides of the above-mentioned metals.

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. And the like. Among these nonmetallic inorganic materials, a silicon-based material is preferable.
The silicon includes both polycrystalline silicon and single crystal silicon. Silicon oxide is represented by a chemical formula of SiO _x (x is 1 or more and 2 or less), and is usually SiO ₂ . Further, silicon nitride is represented by a 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), and is, for example, Si ₄ O ₅ N ₃ .

Examples of a method for obtaining the first surface region containing a metal include a method for obtaining a metal film 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 by the above method on the film of the non-metallic inorganic material or metal oxide and forming the metal film in a predetermined pattern by a photolithography method, or a method of forming a non-metallic inorganic material or metal By forming a hole or a groove in the oxide film and embedding the metal in the groove, both the first surface region containing the metal and 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.

For example, the substrate used in the method of the present disclosure includes a substrate of a semiconductor device having a metal film in a structure and a substrate on which a metal film is formed in a patterning step of the semiconductor device. A substrate in which a metal wiring having a predetermined pattern is formed on a film is exemplified. That is, the first surface region corresponds to a metal wiring, and the second surface region corresponds to an insulating film made of a nonmetallic inorganic material and / or a metal oxide. However, the substrate used in the method for selectively depositing a film on the metal surface region of the substrate of the present disclosure is not limited to these members.

As the organic substance, an organic substance represented by the following general formula (1) is used.

(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 each independently represent a hydrogen atom or a carbon atom having 1 to 12 carbon atoms. It is a hydrocarbon group which may have 10 rings, hetero atoms or halogen atoms. However, when the number of carbon atoms is 3 or more, the hydrocarbon group also includes a branched or cyclic hydrocarbon group. )

Examples of the hetero atom 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 , a phenyl group, and the like. , A thiol group, an amino group, a halogen or the like.
Examples of R ² , R ³ , and R ⁴ include a hydrogen group and a hydrocarbon group 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 form a cyclic structure in general formula (1). R ² , R ³ , and R ⁴ may be the same substituent or different substituents.

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 has 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.

Specific examples of the compound represented by the general formula (1) include, for example, o-aminothiophenol, 2-aminobenzyl alcohol, 2-aminoethanol, 2- (ethylamino) ethanol, 2-aminoethanethiol, Examples thereof include amino-1-propanol and o-aminophenol, among which o-aminothiophenol and 2-aminobenzyl alcohol are preferred. These compounds can be used alone or in combination.

As a specific method of selectively depositing the organic film 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 material and a solvent is used. Two methods can be employed: a wet method, and a method of exposing the substrate to an atmosphere containing an organic gas (a dry method). Hereinafter, these methods will be described.

[Wet method]
In the wet method according to the embodiment of the present disclosure, the substrate is exposed to a solution containing the above-described organic substance and the solvent.As one example, a solution containing the organic substance and the solvent contains a first surface region and a second surface region. By dipping the substrate having the above, the surface of the substrate is brought into contact with the solution to perform a film deposition step of selectively depositing an organic film on the first surface region of the substrate. As a method of exposing the substrate to the solution, besides the dipping method, a spin coating method in which the solution is dropped onto the substrate and then rotated at a high speed, or a spray coating method in which the solution is sprayed on the substrate can also be used.

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 more preferably 1% by mass or more and 5% by mass based on the total amount of the organic material and the solvent. % Or less is particularly preferred.

The solvent used for 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).

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 the substrate is immersed in the solution, it is preferable to stir the solution with a stirring blade or the like.

After the substrate is immersed in a solution containing an organic substance, it is preferable to perform a washing step of lifting the substrate and washing the substrate with a solvent. Examples of the solvent that can be used in the washing step include the above-mentioned organic solvents. As a washing method, it is preferable to immerse the above solvent at 0 to 80 ° C. for 1 to 1000 seconds.

After the above-described 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 blown inert gas is preferably from 0 to 80 ° C.

[Dry method]
In the dry method according to the embodiment of the present disclosure, the substrate is exposed to an atmosphere containing an organic substance gas. Specifically, the substrate is placed in a chamber, and the gas containing an organic substance is introduced into the chamber. Thus, a film deposition step of bringing a gas containing an organic substance into contact with the surface of the substrate and selectively depositing a film of the organic substance on the first surface region of the substrate is performed.

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.

The temperature of the atmosphere gas in the chamber containing the organic gas is preferably from 0 ° C to 200 ° C, more preferably from 40 ° C to 200 ° C, and particularly preferably from 60 ° C to 180 ° C. preferable.

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, more preferably 1 Torr (0.13 kPa) or more and 100 Torr (13 kPa) or less. preferable.

Note that, since the organic substance is brought into contact with the substrate with a gas, the temperature and pressure in the chamber need to be set to conditions under which the organic substance remains as a gas.

The atmosphere gas in the chamber preferably contains 1% by volume or more and 100% by volume or less, more preferably 10% by volume or more and 100% by volume or less, and more preferably 50% by volume or more and 100% by volume or less. Is more preferred.

A gaseous organic substance may be obtained by decompressing and / or heating a liquid organic substance, or a gaseous organic substance diluted with an inert gas may be obtained by bubbling an inert gas to the liquid organic substance. . As the inert gas, a nitrogen gas, an argon gas, a krypton gas, a neon gas, or the like can be used.

After performing the dry film deposition step, the pressure inside the chamber is reduced to 1 to 100 Pa, whereby excess organic substances can be removed. The dry process does not require a drying step.

By using the wet method or the dry method of the present disclosure, by a simple operation, compared to the surface region where the nonmetallic inorganic material is exposed on the substrate or the surface region where the metal oxide is exposed, the metal is An organic film can be selectively deposited on the exposed surface area.

An organic deposited film represented by the general formula (1) selectively deposited on a substrate by performing the wet method or the dry method also corresponds to an embodiment of the organic deposited film of the present disclosure.

[Substrate after selective deposition]
The substrate of the present disclosure is a substrate having a structure in which both a first surface region including a metal and a second surface region including a nonmetallic inorganic material and / or a metal oxide are exposed, and the first surface region includes Has a film of an organic material represented by the following general formula (1), does not have a film of the organic material in the second surface region, or has a thickness t ₂ of the film of the organic material on the second surface region. , characterized in that less than the thickness t ₁ of said organic film on said first surface region.

(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 heteroatom having 2 to 12 carbon atoms or a halogen atom, and R ² , R ³ and R ⁴ are a hydrogen atom or a ring or heteroatom having 1 to 10 carbon atoms. It is a hydrocarbon group which may have a halogen atom. However, when the hydrocarbon group has 3 or more carbon atoms, the hydrocarbon group also includes a branched or cyclic hydrocarbon group. )

In the substrate of the present disclosure, as described above, the first surface region includes an organic material film represented by the following general formula (1), and the second surface region does not include the organic material film. the thickness t ₂ of the organic film on the second surface region is thinner than the thickness t ₁ of said organic film on said first surface region.

T In the substrate of the present disclosure, the thickness t ₂ of the organic film on the second surface region, which when less than the thickness t ₁ of the organic film on the first surface region, a t ₁ divided by t ₂ It is desirable that the value of ₁ / t ₂ be 5 or more. The value of t ₁ / t ₂ is preferably 10 or more, and more preferably 100 or more. Incidentally, _{t 1} is preferably at 1nm or more, more preferably 2nm or more, preferably 200nm or less, and more preferably 100nm or less. Further, it is preferable that _{t 2} is less than 1 nm, may be 0 nm. The thicknesses of t ₁ and t ₂ can be measured by an atomic force microscope (AFM). If t ₂ is 0nm shows the above-mentioned conditions, namely, film of the organic substance is selectively deposited only on the first surface region.

In the substrate of the present disclosure, the first surface region containing a metal, the second surface region containing a nonmetallic inorganic material and / or a metal oxide, the organic substance represented by the general formula (1), and the like are described above. Since a method for selectively depositing a film on a metal surface region of a substrate has been described, a detailed description thereof will be omitted here.

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 material interacting with the metal in the first surface region.

In the following, it was confirmed by the following experiment that a film could be selectively deposited with an organic substance on a surface region where a metal was exposed.

[Experimental example 1-1]
1% of 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, a substrate containing a Cu surface was immersed in this solution for 60 seconds to deposit an organic film. The solution temperature was 20-25 ° C. Thereafter, the substrate was immersed twice in an IPA solution at 20 to 25 ° C. for 60 seconds to remove excess organic substances, and subsequently, nitrogen gas at 20 to 25 ° C. was blown for 60 seconds to dry the substrate.
The thickness of the organic substance formed on the substrate was measured by an atomic force microscope (AFM) and found to be 48 nm. Further, when the elemental composition was analyzed by X-ray photoelectron spectroscopy (XPS), strong peaks of nitrogen and sulfur were confirmed.

[Experimental Examples 1-2 to 1-24]
The evaluation and evaluation were performed in the same manner as in Experimental Example 1-1, except that the metal on the substrate surface, the type of organic substance, the type of solvent, and the solution concentration were changed as shown in Table 1. Table 1 shows the results.

[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 solution temperature was 20-25 ° C. Thereafter, the substrate was immersed twice in an IPA solution at 20 to 25 ° C. for 60 seconds to remove excess organic substances, and nitrogen gas at 20 to 25 ° C. was blown 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. When the elemental composition was analyzed by XPS, nitrogen and sulfur peaks could not be confirmed.

[Experimental Examples 2-2 to 2-10]
Except that the metal on the substrate surface, the type of organic substance, the type of solvent, the concentration of the solution, and the like were changed as shown in Table 2, the evaluation was performed in the same manner as in Experimental Example 2-1. Table 2 shows the results.

[Experimental example 3-1]
A substrate containing a Cu surface was set in a chamber capable of performing 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 was heated to 80 ° C. to open the valve, gas of o-aminothiophenol was supplied into the chamber, and an organic film was formed on the Cu-containing substrate. Was deposited. The temperature of the chamber was the same as the temperature of the cylinder, and the temperature of the gas of o-aminothiophenol was kept at the same temperature as that for keeping the cylinder warm until it came into contact with the substrate. After the deposition of the organic material film, the pressure inside the chamber was reduced to 0.1 Torr (13 Pa) to remove excess organic material.
The film thickness of the organic substance formed on the substrate was measured by AFM and found to be 10 nm. When the elemental composition was analyzed by XPS, strong peaks of nitrogen and sulfur were confirmed.

[Experimental Examples 3-2 to 3-12]
Except that the metal on the substrate, the type of organic substance, the temperature for keeping the cylinder warm (organic substance heating temperature), the chamber pressure, etc. were changed as shown in Table 3, the same procedure as in Experimental Example 3-1 was carried out and evaluated. Was. Table 3 shows the results.

[Experimental example 4-1]
The substrate containing the Si surface was set in a chamber capable of performing a vacuum process, and the chamber pressure was set to 10 Torr. Next, the cylinder of o-aminothiophenol connected to the chamber was heated to 120 ° C. to open the valve, gas of o-aminothiophenol was supplied into the chamber, and the organic substance was placed on the substrate containing the Si surface. The film was deposited. After deposition of the organic film, the pressure inside the chamber was reduced to 0.1 Torr to remove excess organic material.
When the film thickness of the organic substance formed on the substrate was measured by AFM, it was 0 nm. When the elemental composition was analyzed by XPS, nitrogen and sulfur peaks could not be confirmed.

[Experimental examples 4-2 to 4-10]
The evaluation was performed in the same manner as in Experimental Example 4-1 except that the types of metals and organic substances on the substrate, the temperature for keeping the cylinder warm, the chamber pressure, and the like were changed as shown in Table 4. Table 4 shows the results.

In the experimental example, the substrate containing the Cu surface was prepared by forming a copper film with a thickness of about 100 nm on a silicon substrate by vapor deposition and then removing the surface natural oxide film.
The substrate containing the Co surface was prepared by forming a cobalt film with a thickness of about 100 nm on a silicon substrate by vapor deposition and then removing the surface natural oxide film.
The substrate containing the Ru surface was prepared by forming a ruthenium film with a thickness of about 100 nm on a silicon substrate by vapor deposition and then removing the surface natural oxide film.

The substrate containing the Si surface was prepared by removing the natural oxide film of the silicon substrate.
The substrate containing the SiO ₂ surface was prepared by forming a silicon dioxide film to a thickness of about 30 nm on a silicon substrate by a chemical vapor deposition method.
The substrate containing the SiN surface was manufactured by forming a silicon nitride film represented by a chemical formula of Si ₃ N ₄ to a thickness of about 30 nm on a silicon substrate by a chemical vapor deposition method.
The substrate containing the SiON surface is oxidized after forming a SiN surface on the silicon substrate by a chemical vapor deposition method, and then Si ₄ O _x N _y (x is 3 or more and 6 or less, y is 2 or more and 4 or less) The silicon oxynitride film represented by the chemical formula was formed to a thickness of about 10 nm.
The substrate containing the CuO surface was produced by depositing a copper oxide film with a thickness of about 100 nm on a silicon substrate by vapor deposition.
The substrate containing the CoO surface was produced by depositing a cobalt oxide film with a thickness of about 100 nm on a silicon substrate by vapor deposition.

The above results are summarized in Tables 1 to 4 below.

As is clear from the results shown in Tables 1 to 4, in the above experimental example, the organic substance deposited a film on a metal such as Cu, Co, and Ru, but a nonmetal such as Si, SiO ₂ , SiN, and SiON was used. No film was deposited on inorganic materials or metal oxides such as CuO and CoO. Therefore, when a substrate having a surface region where a metal is exposed and a surface region where a non-metallic inorganic material is exposed or a surface region where a metal oxide is exposed is used, the metal is exposed by using the organic substances shown in Tables 1 to 4. It is possible to selectively deposit a film only on the surface region that has been set.

The organic material represented by the general formula (1) includes Ni, Pt, Al, Ta, Ti, and Hf, which are conductive materials suitable as wiring materials and electrode materials for semiconductor devices in addition to Co, Cu, and Ru. Films can also be deposited on metals such as.

Claims

For a substrate having a structure in which both a first surface region containing a metal and a second surface region containing a non-metallic inorganic material and / or a metal oxide are both exposed,
A method comprising selectively depositing an organic film represented by the following general formula (1) on the first surface region rather than the second surface region.

(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 each independently represent a hydrogen atom or a carbon atom having 1 to 12 carbon atoms. It is a hydrocarbon group which may have 10 rings, hetero atoms or halogen atoms. However, when the hydrocarbon group has 3 or more carbon atoms, the hydrocarbon group also includes a branched or cyclic hydrocarbon group. )
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.
The method according to claim 1, wherein the nonmetallic inorganic material is at least one selected from the group consisting of silicon, silicon oxide, silicon nitride, and silicon oxynitride.
The method according to any one of claims 1 to 3, wherein 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. The described method.
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.
The organic substance 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, wherein the method is at least one selected from the group consisting of:
7. The method according to claim 1, wherein the step of selectively depositing a film of an organic substance on the first surface area rather than the second surface area is a step of exposing the substrate to a solution containing the organic substance and a solvent. Or the method of claim 1.
The method according to claim 7, wherein the solution contains 0.1% by mass or more and 10% by mass or less of the organic substance represented by the general formula (1) based on the total of the organic substance and the solvent.
The method according to claim 7 or 8, wherein the substrate is washed with a solvent after selectively depositing the organic film represented by the general formula (1) on the substrate.
Selectively depositing the organic film represented by the general formula (1) on the first surface region rather than the second surface region, exposing the substrate to an atmosphere containing the organic gas. The method according to any one of claims 1 to 6, wherein
The method according to claim 10, wherein a temperature range of the atmosphere is 0 ° C. or more and 200 ° C. or less.
The method according to claim 10, wherein a pressure range of the atmosphere is 13 Pa or more and 67 kPa or less.
The ratio (t 1 / t 2 ) of the thickness t 1 of the organic material film on the first surface region to the thickness t 2 of the organic material film on the second surface region is 5 or more. 13. The method according to any one of 1 to 12.
A substrate having a structure in which a first surface region including a metal and a second surface region including a nonmetallic inorganic material and / or a metal oxide are both exposed,
An organic material film represented by the following general formula (1) in the first surface region;
Either having no film of the organic substance in the second surface region, the thickness t 2 of the organic material of the film on the second surface area is, than the thickness t 1 of said organic film on said first surface region A substrate characterized by being thin.

(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 heteroatom having 2 to 12 carbon atoms or a hydrocarbon group optionally having a halogen atom, and R 2 , R 3 and R 4 are a hydrogen atom or a ring or heteroatom having 1 to 10 carbon atoms. It is a hydrocarbon group which may have a halogen atom. However, when the hydrocarbon group has 3 or more carbon atoms, the hydrocarbon group also includes a branched or cyclic hydrocarbon group. )
An organic film formed by the method according to any one of claims 1 to 13,
An organic deposited film represented by the following general formula (1) selectively deposited on a substrate.

(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 heteroatom having 2 to 12 carbon atoms or a hydrocarbon group optionally having a halogen atom, and R 2 , R 3 and R 4 are a hydrogen atom or a ring or heteroatom having 1 to 10 carbon atoms. It is a hydrocarbon group which may have a halogen atom. However, when the hydrocarbon group has 3 or more carbon atoms, the hydrocarbon group also includes a branched or cyclic hydrocarbon group. )
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.

(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 heteroatom having 2 to 12 carbon atoms or a hydrocarbon group optionally having a halogen atom, and R 2 , R 3 and R 4 are a hydrogen atom or a ring or heteroatom having 1 to 10 carbon atoms. It is a hydrocarbon group which may have a halogen atom. However, when the hydrocarbon group has 3 or more carbon atoms, the hydrocarbon group also includes a branched or cyclic hydrocarbon group. )
A solution comprising an organic substance represented by the following general formula (1) and a solvent.

(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 heteroatom having 2 to 12 carbon atoms or a hydrocarbon group optionally having a halogen atom, and R 2 , R 3 and R 4 are a hydrogen atom or a ring or heteroatom having 1 to 10 carbon atoms. It is a hydrocarbon group which may have a halogen atom. However, when the hydrocarbon group has 3 or more carbon atoms, the hydrocarbon group also includes a branched or cyclic hydrocarbon group. )
The organic substance is a 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 selected 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 0.1% by mass or more and 10% by mass or less of the organic substance represented by the general formula (1) based on the total of the organic substance and the solvent.