JP7303447B2 - SUBSTRATE, METHOD FOR SELECTIVE FILM DEPOSITION ON METAL SURFACE REGION OF SUBSTRATE, ORGANIC MATERIAL DEPOSITION FILM AND ORGANIC MATERIAL - Google Patents

Description

SUMMARY OF THE DISCLOSURE The present disclosure is a substrate, a method for selectively depositing a film on a metal surface region of a substrate, an organic deposition film and an organic.

In recent years, the structure of semiconductor chips has become increasingly finer, and the conventional lithography method, in which patterning is performed by selectively removing a part of the structure, has problems such as a large number of steps and high costs. If the chemical vapor deposition (CVD) method or the atomic layer deposition (ALD) method can selectively form a film on a desired location on a substrate, it will be the most suitable process for forming a fine structure, and these problems will be solved. It is

However, when selectively depositing a film by CVD or ALD on a substrate having a plurality of surface regions made of different materials such as metals used for electrodes and wiring, inorganic dielectrics used for insulating films, etc. In addition, it is necessary to selectively deposit a film for inhibiting deposition, but the selectivity was not sufficiently high in the conventional methods.

As a selective film forming method, a method of depositing a material that inhibits film deposition in a region where the 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), wherein the substrate has a fluorine content of 30 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 or imide group to form a pattern of an atomic layer deposition inhibition 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 inhibition layer does not exist by an atomic layer deposition method. A method of including is disclosed.

Also, US Pat. No. 6,200,004 discloses a method for selectively depositing a layer on a substrate having an exposed metal surface and an exposed silicon-containing surface, comprising: (a) a first self-assembled layer on the exposed metal surface; (b) growing a second self-assembled monolayer that is organosilane-based on the exposed silicon-containing surface; and (c) heating the substrate. (d) removing a layer, which is a low-k dielectric layer or a metal layer, from the exposed metal surface; and (e) heating the substrate to remove a second self-assembled monolayer from above the exposed silicon-containing surface. ing.

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 surfaces is used to select the first surface over the second surface. The film can be deposited on Moreover, according to the above method, the number of steps in the process of forming the fine structure can be reduced.

For example, in US Pat. No. 5,200,000, a substrate comprising a first surface, which is a metallic surface, and a second surface, which is a dielectric surface, is contacted with a first gas phase precursor; and contacting a vapor phase precursor to perform a deposition cycle to selectively form an organic thin film on a first surface over a second surface. In Example 1 of US Pat. No. 5,400,000, 1,6-diaminohexane (DAH) and pyromellitic dianhydride (PMDA) were used on a 200 mm silicon wafer with tungsten (W) features alternating with a silicon oxide surface as the substrate. 250-1000 deposition cycles to form a polyimide film, and the thickness of the polyimide film on the metal tungsten surface was greater than the thickness of the polyimide film on the _SiO2 surface. ing.

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

Patent Document 5 discloses a method of forming a monomolecular film on a metal surface by coordinate bonding.

WO2016/147941 Japanese translation of PCT publication No. 2018-512504 JP 2017-216448 A JP 2018-137435 A JP-A-10-180929

However, in Patent Document 1, a predetermined pattern is formed on a substrate made of a single material using an atomic layer deposition inhibitor material, and a desired pattern is formed on a substrate having a plurality of types of surface regions made of different materials. A method for selectively forming structures on surface regions is not disclosed.

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 long-chain alkylthiol, long-chain organic phosphonic acid, and long-chain sulfonic acid, a so-called wet process. is. On the other hand, processes such as ALD and CVD used for a low-k dielectric layer and a metal layer on a substrate, which are performed after the formation of the SAM film, are dry processes. This makes the method complicated, and a method of forming a film for inhibiting deposition in a dry process has been desired.

Although the method for 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 multiple times, and the formation of the organic thin film is difficult. required a great deal of effort.

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

In view of the above problems, the present disclosure provides a surface region where a metal is exposed rather than a surface region where a non-metallic inorganic material on a substrate is exposed or a metal oxide is exposed by a simple operation. An object of the present invention is to provide a method for depositing an organic film, a substrate obtained by the above method, a deposited film of an organic substance, and an organic substance.

As a result of extensive studies, the present inventors found that the organic substance represented by the general formula (1) described later is more suitable for the surface region where the non-metallic inorganic material on the substrate is exposed or the metal oxide is exposed. The inventors have found that an organic film can be deposited selectively on surface regions where metal is exposed, and have completed the present disclosure.

（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。
Ｒ^１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、Ｒ^２、Ｒ^３、Ｒ^４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 method of selectively depositing a film on a metal surface region of a substrate of the present disclosure includes 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 exposed. 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 on a substrate having a

(1)
(In general formula (1), N is a nitrogen atom, and X is an oxygen atom or a sulfur atom.
R ¹ is a hydrocarbon group optionally having a heteroatom or halogen atom having 2 to 12 carbon atoms, and R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a It is a hydrocarbon group optionally having 10 rings, heteroatoms or halogen atoms. However, when the number of carbon atoms is 3 or more, the hydrocarbon group includes a hydrocarbon group having a branched chain or a cyclic structure. )

According to the above method, by using the organic substance represented by the general formula (1), It is possible to provide a method for selectively depositing an organic film on a first surface region, including regions where metal is exposed, rather than by depositing.

In the second surface region, a non-metallic inorganic material may be exposed, a metal oxide may be exposed, a non-metallic inorganic material and a metal oxide may be exposed, a metal, a non-metal Substances 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 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 metal is exposed.

（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。
Ｒ^１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、Ｒ^２、Ｒ^３、Ｒ^４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。）A substrate of the present disclosure is 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 exposed, wherein the first surface region has an organic film represented by the following general formula (1) in the second surface region, or the second surface region does not have the organic film, or the thickness _t2 of the organic film on the second surface region is , which is thinner than the thickness _t1 of the organic film on the first surface region.

(1)
(In general formula (1), N is a nitrogen atom, and X is an oxygen atom or a sulfur atom.
R ¹ is a hydrocarbon group optionally having a heteroatom or halogen atom having 2 to 12 carbon atoms, and R ² , R ³ , and R ⁴ are a hydrogen atom, a ring having 1 to 10 carbon atoms, or a heteroatom. or a hydrocarbon group optionally having a halogen atom. However, the above hydrocarbon group includes a hydrocarbon group having a branched chain or a cyclic structure when the number of carbon atoms is 3 or more. )

According to the substrate, by using the organic substance represented by the general formula (1), the second surface region including the region where the non-metallic inorganic material on the substrate is exposed and / or the region where the metal oxide is exposed It is possible to provide a substrate having an organic film selectively deposited on the first surface region including the region where the metal is exposed.

（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。
Ｒ^１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、Ｒ^２、Ｒ^３、Ｒ^４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 deposited organic film of the present disclosure is an organic film formed by the above method,
A deposited film of an organic substance selectively deposited on a substrate and represented by the following general formula (1).

(1)
(In 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; It is a hydrocarbon group optionally having a halogen atom. However, when the number of carbon atoms is 3 or more, the hydrocarbon group includes a hydrocarbon group having a branched chain or a cyclic structure. )

（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。
Ｒ^１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、Ｒ^２、Ｒ^３、Ｒ^４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 of the present disclosure is an organic matter represented by the following general formula (1), which is characterized by being used in a selective film deposition method on the metal surface region of the substrate.

(1)
(In 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; It is a hydrocarbon group optionally having a halogen atom. However, when the number of carbon atoms is 3 or more, the hydrocarbon group includes a hydrocarbon group having a branched chain or a cyclic structure. )

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

（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。
Ｒ^１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、Ｒ^２、Ｒ^３、Ｒ^４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.

(1)
(In 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; It is a hydrocarbon group optionally having a halogen atom. However, when the number of carbon atoms is 3 or more, the hydrocarbon group includes a hydrocarbon group having a branched chain or a cyclic structure. )

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-metallic inorganic material on the substrate is exposed and / or the region where the metal oxide is exposed A method can be provided for selectively depositing an organic film on a first surface region, including regions where metal is exposed, rather than against.

Further, according to the substrate of the present disclosure, by using the organic substance represented by the general formula (1), the second It is possible to provide a substrate having an organic film selectively deposited on a first surface region, including regions where metal is exposed, rather than on surface regions.

The present disclosure will be described in detail below, but the description of the constituent elements described below is an example of the embodiments of the present disclosure, and is not limited to these specific contents. Various modifications can be made within the scope of the gist.

A method for selective film deposition on a metal surface region of a substrate according to embodiments of the present disclosure includes a first surface region comprising a metal and a second surface region comprising a non-metallic inorganic material and/or a metal oxide. It is characterized by selectively depositing an organic film represented by the general formula (1) on the first surface region rather than the second surface region on a substrate having a structure in which both are exposed.

In the above method, the organic film represented by general formula (1) is selectively deposited over the second surface region. At this time, the organic film is selectively deposited only on the first surface region of the substrate, and the organic film is not deposited on the second surface region, or the organic film on the first surface region is not deposited on the second surface region. is thicker than the thickness _t2 of the organic film on the second surface region, and is deposited such that the value of _t1 / _t2 , which _{is t1} divided by _t2 , is greater than or equal to 5 It is preferable to let The value of t ₁ /t ₂ is preferably 10 or more, more preferably 100 or more. Note that _t1 is preferably 1 nm or more, more preferably 2 nm or more, preferably 200 nm or less, and more preferably 100 nm or less. Also, _t2 is preferably less than 1 nm, and may be 0 nm. The thickness of _t1 and _t2 can be measured by atomic force microscopy (AFM). When _t2 is 0 nm, it means the condition described above, that is, selectively depositing the organic film only on the first surface region.

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

Examples of the metal oxide forming the second surface region include oxides of the metals described above.

Examples of the nonmetallic 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 preferred.
The silicon includes both polycrystalline silicon and monocrystalline silicon. Silicon oxide is represented by a chemical formula of SiO _x (where x is 1 or more and 2 or less), and is usually SiO ₂ . Silicon nitride is represented by a chemical formula of SiN _x (where x is 0.3 or more and 9 or less), and is usually Si ₃ N ₄ . 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 .

Methods for obtaining the first surface region containing metal include methods 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 nonmetallic inorganic material or metal oxide, and forming the metal film in a predetermined pattern by a photolithography method, or 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 by forming holes or grooves in the oxide film and filling the grooves with the metal. A substrate with an exposed structure can be obtained.

For example, substrates used in the method of the present disclosure include semiconductor device substrates having metal films in their structures, substrates on which metal films are formed during the patterning process of semiconductor devices, and the like. A substrate on which a metal wiring having a predetermined pattern is formed on a film can be mentioned. That is, the first surface region corresponds to metal wiring, and the second surface region corresponds to an insulating film made of a non-metallic inorganic material and/or a metal oxide. However, the substrate used in the selective film deposition method on the metal surface region of the substrate of the present disclosure is not limited to these members.

（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。
Ｒ^１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、Ｒ^２、Ｒ^３、Ｒ^４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.

(1)
(In general formula (1), N is a nitrogen atom, and X is an oxygen atom or a sulfur atom.
R ¹ is a hydrocarbon group optionally having a heteroatom or halogen atom having 2 to 12 carbon atoms, and R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a It is a hydrocarbon group optionally having 10 rings, heteroatoms or halogen atoms. However, when the number of carbon atoms is 3 or more, the hydrocarbon group also includes a hydrocarbon group with a branched chain or cyclic structure. )

Hetero atoms of R ¹ to R ⁴ include nitrogen atom, oxygen atom, sulfur atom and 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 part of the phenyl group is a hydrocarbon group, a hydroxy 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 hydrogen groups and hydrocarbon groups such as CH ₃ , C ₂ H ₅ and C ₃ H ₇ . Part of the hydrocarbon groups constituting R ² , R ³ and R ⁴ may be substituted with hydroxy groups, thiol groups, amino groups, halogens and the like.
Furthermore, when both R ³ and R ⁴ have 1 or more carbon atoms, R ³ and R ⁴ may be directly bonded to give the general formula (1) a cyclic structure. R ² , R ³ and R ⁴ may be the same substituent or different substituents.

In particular, the organic substance represented by the general formula (1) is preferably a compound in which R ² and R ³ are hydrogen atoms and which has an amino group (--NH ₂ ). Furthermore, compounds in which R ⁴ is a hydrogen atom and —XR ⁴ is a hydroxy group (—OH) or a thiol group (—SH) are preferred.

Specific compounds represented by general formula (1) include, for example, o-aminothiophenol, 2-aminobenzyl alcohol, 2-aminoethanol, 2-(ethylamino)ethanol, 2-aminoethanethiol, 3- Amino-1-propanol, o-aminophenol, and the like, among these, o-aminothiophenol and 2-aminobenzyl alcohol are preferred. These compounds can be used alone or in combination.

A specific method for selectively depositing the organic film represented by the general formula (1) on the first surface region rather than the second surface region is a method of exposing the substrate to a solution containing an organic substance and a solvent. (wet method) and a method of exposing the substrate to an atmosphere containing an organic gas (dry method) can be employed. These methods are described below.

[Wet method]
In the wet method according to the embodiment of the present disclosure, the substrate is exposed to the solution containing the above-described organic matter and solvent. By immersing the substrate having the above, the surface of the substrate and the solution are brought into contact, and a film deposition step can be performed in which an organic film is selectively deposited on the first surface region of the substrate. As a method for 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 high speed, or a spray coating method in which the solution is sprayed onto 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 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 preferred.

The solvent used for the solution is not particularly limited, but it is preferable to use an organic solvent capable of dissolving organic matter, and examples thereof include alcohols such as ethanol and isopropyl alcohol (IPA).

The temperature of the solution in the wet film deposition process 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.

Moreover, after immersing the substrate in a solution containing an organic substance, it is preferable to perform a cleaning step of pulling up the substrate and cleaning the substrate with a solvent. Examples of the solvent that can be used in the washing step include the aforementioned organic solvents. As a washing method, immersion in the above solvent at 0 to 80° C. for 1 to 1000 seconds is preferable.

After the cleaning step, the substrate is preferably dried by blowing an inert gas such as nitrogen or argon onto the substrate. The temperature of the inert gas to be blown is preferably 0 to 80.degree.

[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. Thus, a film deposition step of selectively depositing an organic film on the first surface region of the substrate is performed by bringing the gas containing the organic substance into contact with the surface of the substrate.

The organic substance used in the dry film deposition process is preferably the organic substance represented by the general formula (1) as in the wet method.

The temperature of the atmosphere 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 60° C. or higher and 180° C. or lower. preferable.

The pressure range of the atmosphere 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.

Since the organic matter is brought into contact with the substrate as a gas, the temperature and pressure in the chamber must be set so that the organic matter remains gaseous.

The atmosphere gas in the chamber preferably contains 1% by volume or more and 100% by volume or less of 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 preferred.

A gaseous organic substance may be obtained by depressurizing 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 into a liquid organic substance. . Nitrogen gas, argon gas, krypton gas, neon gas, or the like can be used as the inert gas.

By reducing the pressure in the chamber to 1 to 100 Pa after performing the dry film deposition process, excess organic matter can be removed. The dry method does not require a drying step.

By using the wet method and the dry method of the present disclosure, the metal is more exposed than the surface area where the non-metallic inorganic material on the substrate is exposed or the metal oxide is exposed with a simple operation. An organic film can be selectively deposited on the exposed surface areas.

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

（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。
Ｒ^１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、Ｒ^２、Ｒ^３、Ｒ^４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]
A substrate of the present disclosure is 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 exposed, wherein the first surface region has an organic film represented by the following general formula (1) in the second surface region, or the second surface region does not have the organic film, or the thickness _t2 of the organic film on the second surface region is , which is thinner than the thickness _t1 of the organic film on the first surface region.

(1)
(In 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; It is a hydrocarbon group optionally having a halogen atom. However, the above hydrocarbon group includes a hydrocarbon group having a branched chain or a cyclic structure when the number of carbon atoms is 3 or more. )

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 does not have the organic film, The thickness _t2 of the organic film on the second surface region is less than the thickness _t1 of the organic film on the first surface region.

In the substrate of the present disclosure, when the thickness _t2 of the organic film on the second surface region is thinner than the thickness _t1 of the organic film on the first surface region, _t1 divided by _t2 is t It is desirable that the value of ₁ / _t2 is 5 or more. The value of t ₁ /t ₂ is preferably 10 or more, more preferably 100 or more. Note that _t1 is preferably 1 nm or more, more preferably 2 nm or more, preferably 200 nm or less, and more preferably 100 nm or less. Also, _t2 is preferably less than 1 nm, and may be 0 nm. The thickness of _t1 and _t2 can be measured by atomic force microscopy (AFM). When _t2 is 0 nm, the condition described above, that is, the organic film 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 non-metallic inorganic material and/or a metal oxide, the organic substance represented by the general formula (1), etc. are as described above in the present disclosure. Since a method for selectively depositing a film on a metal surface region of a substrate has been described, a detailed description will be omitted here.

It is considered that the organic film is formed by the interaction of groups having nitrogen atoms, oxygen atoms or sulfur atoms in the molecules of the organic substance with the metal of the first surface region.

It was confirmed by the following experiment that a film can be selectively deposited on the surface region where the metal is exposed using an organic substance.

[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, a substrate containing a Cu surface was immersed in this solution for 60 seconds to deposit an organic film. The temperature of the solution was 20-25°C. Thereafter, the substrate was immersed twice in an IPA liquid at 20 to 25° C. for 60 seconds to remove excess organic matter, and then dried by blowing nitrogen gas at 20 to 25° C. for 60 seconds.
When the film thickness of the organic material formed on the substrate was measured with an atomic force microscope (AFM), it was 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]
Except that the metal on the substrate surface, the type of organic matter, the type of solvent, the solution concentration, etc. were changed as shown in Table 1, the experiment was carried out and evaluated in the same manner as in Experimental Example 1-1. 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 temperature of the solution was 20-25°C. Thereafter, the substrate was immersed in IPA liquid at 20 to 25° C. for 60 seconds twice to remove excess organic matter, and was dried by blowing nitrogen gas at 20 to 25° C. for 60 seconds.
When the film thickness of the organic material formed on the substrate was measured by AFM, it was 0 nm. Further, when the elemental composition was analyzed by XPS, peaks of nitrogen and sulfur could not be confirmed.

[Experimental Examples 2-2 to 2-10]
Except for changing the metal on the substrate surface, the type of organic matter, the type of solvent, the concentration of the solution, etc. as shown in Table 2, the experiment was carried out and evaluated 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 vacuum processing, 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., the valve was opened, the gas of o-aminothiophenol was supplied into the chamber, and an organic film was formed on the substrate containing Cu. was deposited. The temperature of the chamber was the same as the temperature of the cylinder, and the temperature of the o-aminothiophenol gas was kept the same as the temperature at which the cylinder was kept warm until it came into contact with the substrate. After depositing the organic matter film, the chamber was evacuated to 0.1 Torr (13 Pa) to remove excess organic matter.
When the film thickness of the organic material formed on the substrate was measured by AFM, it was 10 nm. Further, when the elemental composition was analyzed by XPS, strong peaks of nitrogen and sulfur were confirmed.

[Experimental Examples 3-2 to 3-12]
Experimental Example 3-1 was conducted and evaluated 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. Table 3 shows the results.

[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., the valve is opened, the o-aminothiophenol gas is supplied into the chamber, and the organic material is deposited on the substrate containing the Si surface. A film was deposited. After depositing the organic film, the chamber was evacuated to 0.1 Torr to remove excess organic matter.
When the film thickness of the organic material formed on the substrate was measured by AFM, it was 0 nm. Further, when the elemental composition was analyzed by XPS, peaks of nitrogen and sulfur could not be confirmed.

[Experimental Examples 4-2 to 4-10]
The experiment was conducted and evaluated 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, and the like were changed as shown in Table 4. Table 4 shows the results.

In the above experimental example, the substrate containing the Cu surface was produced by forming a copper film with a thickness of about 100 nm on a silicon substrate by vapor deposition, and then removing the surface native oxide film.
A substrate containing a 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 native oxide film.
A substrate containing a Ru surface was prepared by depositing a ruthenium film with a thickness of about 100 nm on a silicon substrate by vapor deposition, and then removing the surface native oxide film.

A substrate containing a Si surface was prepared by removing the natural oxide film of the silicon substrate.
Substrates containing SiO ₂ surfaces were prepared by depositing a film of silicon dioxide with a thickness of about 30 nm on a silicon substrate by chemical vapor deposition.
A substrate containing a SiN surface was fabricated by forming a silicon nitride film represented by the chemical formula of Si ₃ N ₄ on a silicon substrate by chemical vapor deposition to a thickness of about 30 nm.
A substrate containing a SiON surface is oxidized to Si ₄ O _x N _y (x is 3 or more and 6 or less, y is 2 or more and 4 or less) after forming a SiN surface on a silicon substrate by a chemical vapor deposition method. A silicon oxynitride film having a thickness of about 10 nm was formed to have a thickness of about 10 nm.
A substrate containing a CuO surface was prepared by depositing a film of copper oxide with a thickness of about 100 nm on a silicon substrate by vapor deposition.
A substrate containing a CoO surface was prepared by depositing a film of cobalt oxide 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 examples, films of organic substances were deposited on metals such as Cu, Co, and Ru, but on non-metals such as Si, SiO ₂ , SiN, and SiON. No films were deposited on inorganic materials or on metal oxides such as CuO, CoO. Therefore, when using a substrate having a surface region in which a metal is exposed and a surface region in which a non-metallic inorganic material is exposed or a surface region in which a metal oxide is exposed, the metal is exposed by using the organic substances shown in Tables 1 to 4. A film can be selectively deposited only on the surface areas that have been exposed.

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

Claims (18)

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 exposed,
A method characterized by selectively depositing an organic film represented by the following general formula (1) on the first surface region rather than on the second surface region.

(1)
(In general formula (1), N is a nitrogen atom, and X is an oxygen atom or a sulfur atom.
R ¹ is a hydrocarbon group optionally having a heteroatom or halogen atom having 2 to 12 carbon atoms, and R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a It is a hydrocarbon group optionally having 10 rings, heteroatoms or halogen atoms. However, when the number of carbon atoms is 3 or more, the hydrocarbon group includes a hydrocarbon group having a branched chain or a cyclic structure. ) 2. The method according to claim 1, wherein said metal is at least one selected from the group consisting of Cu, Co, Ru, Ni, Pt, Al, Ta, Ti and Hf. 3. The method according to claim 1, wherein said nonmetallic inorganic material is at least one selected from the group consisting of silicon, silicon oxide, silicon nitride and silicon oxynitride. The metal oxide 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. 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. 2. The method of claim 1, wherein at least one selected from 7. The step of selectively depositing an organic film on said first surface region over said second surface region is a step of exposing said substrate to a solution containing said organic substance and a solvent. or the method according to item 1. 8. 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) with respect to the total of the organic substance and the solvent. 9. The method according to claim 7, wherein after selectively depositing the organic film represented by the general formula (1) on the substrate, the substrate is washed with a solvent. The step of selectively depositing the organic film represented by the general formula (1) on the first surface region rather than the second surface region is the step of exposing the substrate to an atmosphere containing the organic gas. The method according to any one of claims 1 to 6, wherein 11. The method according to claim 10, wherein the temperature range of said atmosphere is from 0[deg.]C to 200[deg.]C. 12. The method according to claim 10, wherein the atmosphere has a pressure range of 13 Pa or more and 67 kPa or less. The ratio ( _t1 / _t2 ) between the thickness _t1 of the organic film on the first surface region and the thickness _t2 of the organic 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 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 exposed,
Having an organic film represented by the following general formula (1) on the first surface region,
The second surface region does not have the organic film, or the thickness _t2 of the organic film on the second surface region is greater than the thickness _t1 of the organic film on the first surface region. A substrate characterized in that it is also thin.

(1)
(In 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; It is a hydrocarbon group optionally having a halogen atom. However, when the number of carbon atoms is 3 or more, the hydrocarbon group includes a hydrocarbon group having a branched chain or a cyclic structure. ) A deposited film of an organic substance, characterized by being represented by the following general formula (1).

(1)
(In 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; It is a hydrocarbon group optionally having a halogen atom. However, when the number of carbon atoms is 3 or more, the hydrocarbon group includes a hydrocarbon group having a branched chain or a cyclic structure. ) A deposited film-forming composition comprising an organic substance represented by the following general formula (1).

(1)
(In 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; It is a hydrocarbon group optionally having a halogen atom. However, when the number of carbon atoms is 3 or more, the hydrocarbon group includes a hydrocarbon group having a branched chain or a cyclic structure. ) A solution comprising an organic substance represented by the following general formula (1) and a solvent.

(1)
(In 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; It is a hydrocarbon group optionally having a halogen atom. However, when the number of carbon atoms is 3 or more, the hydrocarbon group includes a hydrocarbon group having a branched chain or a cyclic structure. ) The organic substance is the group consisting of o-aminothiophenol, 2-aminobenzyl alcohol, 2-aminoethanol, 2-(ethylamino)ethanol, 2-aminoethanethiol, 3-amino-1-propanol and o-aminophenol. is at least one selected from
The solvent is at least one selected from the group consisting of ethanol and isopropyl alcohol,
18. 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) with respect to the total of the organic substance and the solvent.