Film and method for producing same

Abstract

Provided is a method for producing a film containing Sn and Si, which includes: an Sn film formation step for forming an Sn-containing film using a tin compound as a starting material gas; and an Si film formation step for forming an Si-containing film using a silicon compound as a starting material gas. The film formation is performed by a chemical vapor deposition method or an atomic layer deposition method by supplying the starting material gas into a chamber in which an object to be processed having a film formation surface is housed.

Description

Membrane and method for manufacturing the same

[0001] This invention relates to a membrane and a method for producing the same.

[0002] Tin-containing films are used, for example, as transparent conductive films (ITO films) for electronic devices such as liquid crystal displays, solar cells, and thin-film transistors; as tin oxide thin films for solar cells, gas sensors, and anti-glare films; and as thin-film transistors for organic electronics and tin alloy thin films for semiconductor materials.

[0003] As a method for forming a tin-containing film, for example, Patent Document 1 describes a method for forming a boron-silicon-germanium-tin (SiGeSn:B) film on a substrate using a boron precursor, a silicon precursor, a germanium precursor, and a tin precursor.

[0004] Furthermore, for example, Patent Document 2 describes a method in which a hydrophobic surface treatment compound is introduced into a processing chamber, the processing chamber includes a processing substrate having an SnO2 layer, the hydrophobic surface treatment compound forms a modification on the surface of the SnO2 layer to enhance the hydrophobicity of the surface, and a photoresist layer is deposited on the surface of the SnO2 layer by spin coating, the modification of the surface of the SnO2 layer enhances the adhesion of the contact between the photoresist and the SnO2 layer during spin coating.

[0005] U.S. Patent Application Publication No. 2022 / 0230877, JP 2021-534584

[0006] To improve the functionality of tin-containing membranes and obtain a variety of membrane types, one approach is to introduce various functional groups into the tin compounds that serve as the membrane material. However, it is difficult to synthesize or obtain tin compounds with the desired functional groups, making it challenging to create diverse membranes through functional group introduction.

[0007] Therefore, for example, it is considered that various films can be created by introducing a functional group contained in a tin compound that is difficult to obtain into an element of a second compound and combining this with the tin compound to form a film. That is, it is considered that by combining a tin compound and a second compound containing another element other than tin to form a film, various films containing tin can be obtained.

[0008] An object of the present invention is to efficiently produce various films containing Sn.

[0009] As a result of intensive studies to solve the above problems, the present inventors have found that a film containing Sn and Si can be produced by using a compound containing Sn and a predetermined silicon compound as precursors, and have completed the present invention.

[0010] In other words, the present invention provides various specific embodiments as shown below. [1] A method for producing a film containing Sn and Si, comprising: an Sn film formation step of forming an Sn-containing film using a tin compound as a raw material gas; and a Si film formation step of forming a Si-containing film using a silicon compound as a raw material gas, wherein the film formation is carried out by supplying the raw material gas into a chamber containing a workpiece having a film formation surface, and by chemical vapor deposition or atomic layer deposition. [2] The method for producing the film according to [1], wherein the silicon compound is a compound represented by formula (1): X3-Si-R-Si-X3 (wherein formula (1) is a hydrocarbon group which may have substituents, and X is a halogen). [3] The method for producing the film according to [1] or [2], wherein the Sn film formation step and the Si film formation step are each performed two or more times, and the Sn film formation step and the Si film formation step are performed alternately. [4] The manufacturing method according to any one of [1] to [3], wherein the tin compound is at least one selected from the group consisting of tin halides, alkylaminotin, alkyltin, alkenyltin, alkynyltin, tin alkoxide, tin carboxylate, aryltin, cyclopentadienyltin, and metallocenstin. [5] The manufacturing method according to any one of [1] to [4], wherein the film formation is carried out by thermal atomic layer deposition or thermochemical vapor deposition. [6] The manufacturing method according to any one of [1] to [5], further comprising an oxidation step after the Sn film formation step and the Si film formation step. [7] The manufacturing method according to any one of [1] to [6], wherein the film has SnO and SiO structures. [8] A method for producing a film containing Sn and Si, comprising a Sn and Si film formation step of forming a Sn and Si-containing film using a mixture of a tin compound and a silicon compound as a raw material gas, wherein the film formation is carried out by supplying the raw material gas into a chamber containing a workpiece having a film formation surface, and by chemical vapor deposition or atomic layer deposition. [9] The method for producing a film according to [8], wherein the silicon compound is a compound represented by formula (1): X3-Si-R-Si-X3 (wherein formula (1) is a hydrocarbon group which may have substituents, and X is a halogen element).

[10] The production method according to [8] or [9], wherein the tin compound is at least one selected from the group consisting of tin halide, alkylaminotin, alkyltin, alkenyltin, alkynyltin, tin alkoxide, tin carboxylate, aryltin, cyclopentadienyltin, and metallocenes tin.

[11] The production method according to any one of [8] to

[10] , wherein the film formation is performed by a thermal atomic layer deposition method or a thermal chemical vapor deposition method.

[12] The production method according to any one of [8] to

[11] , wherein the film has a SnO and SiO structure.

[13] A film containing Sn and Si, the film having a SnO and SiO structure in the film.

[0011] According to the present invention, various films containing Sn can be efficiently produced.

[0012] It is a schematic diagram showing an example of a film forming apparatus 100 used in the production method of the present invention. It is a diagram showing the spectral data of XRF measurement of the films obtained in Example 1 and Reference Examples 1 to 2. It is a diagram showing the spectral data of FT-IR measurement of the films obtained in Example 1 and Reference Examples 1 to 2. It is a schematic diagram used for film formation in Example 2. It is a schematic diagram used for film formation in Comparative Example 1. It is a diagram showing the Si spectral data (TEY) of XAFS measurement in Example 1. It is a diagram showing the Si spectral data (AEY) of XAFS measurement in Example 1. It is a diagram showing the Sn spectral data (TEY) of XAFS measurement in Example 1. It is a diagram showing the Sn spectral data (AEY) of XAFS measurement in Example 1. It is the measurement result of the elemental composition of the film.

[0013] Embodiments of the present invention will be described in detail below with reference to the drawings. However, the following embodiments are illustrative for explaining the present invention, and the present invention is not limited thereto. That is, the present invention can be modified and implemented as appropriate without departing from its essence. In this specification, positional relationships such as up, down, left, and right shall be based on the positional relationships shown in the drawings unless otherwise specified. Also, the dimensional ratios in the drawings are not limited to the ratios shown. On the other hand, in this specification, when "~" is used to express a numerical value or physical property value before and after it, it is used to include the values ​​before and after it. For example, the notation of a numerical range "1 to 100" shall include both the lower limit value "1" and the upper limit value "100". The same applies to other numerical range notations.

[0014] [Method for Manufacturing Sn and Si-Containing Films] The present invention relates to a method for manufacturing films containing Sn and Si. One of the manufacturing methods of the present invention (also referred to as "Manufacturing Method I") includes a Sn film deposition step in which a Sn-containing film is formed using a tin compound as a raw material gas, and a Si film deposition step in which a Si-containing film is formed using a silicon compound as a raw material gas, wherein the film deposition is carried out by supplying the raw material gases into a chamber containing a workpiece having a film deposition surface, and by chemical vapor deposition or atomic layer deposition. Another manufacturing method of the present invention (also referred to as "Manufacturing Method II") includes a Sn and Si film deposition step in which a Sn and Si-containing film is formed using a mixture of a tin compound and a silicon compound as a raw material gas, wherein the film deposition is carried out by supplying the raw material gases into a chamber containing a workpiece having a film deposition surface, and by chemical vapor deposition or atomic layer deposition. Manufacturing Method I and Manufacturing Method II together are also referred to as the manufacturing method of the present invention.

[0015] In the manufacturing method of the present invention, a tin compound and a silicon compound are used as raw material gases, and these compounds react by chemical vapor deposition or atomic layer deposition to form a film containing Sn and Si. The tin compound and silicon compound used in the present invention are also called precursors, and are materials that constitute the film obtained by the manufacturing method of the present invention. According to the manufacturing method of the present invention, a film containing Sn and Si is obtained, and the structure of Sn and Si in the film is not particularly limited, as long as it is a structure that forms a film.

[0016] According to the manufacturing method of the present invention, a film containing Sn and Si can be obtained by using a combination of a tin compound and a silicon compound. This is thought to be because tin and silicon are elements of the same group and have similar properties, and tin compounds and silicon halide compounds react readily. It should be noted that the reason for obtaining a film is not limited to the above assumption, and the above assumption does not limit the scope of the present invention in any way. Furthermore, although it is difficult to synthesize or obtain a tin compound with a desired functional group introduced into it, it is thought that a variety of films can be produced by introducing a functional group into a silicon compound and then combining it with a tin compound to form a film. In addition, by controlling the supply amounts of the tin compound and the second compound containing the desired functional group, it is possible to control the content ratio of tin to functional group.

[0017] In manufacturing method I, it is preferable that the Sn film deposition step and the Si film deposition step are performed repeatedly, that is, each two or more times. It is also preferable that the Sn film deposition step and the Si film deposition step are performed alternately. Furthermore, for example, the Sn film deposition step may be repeated two or more times, and the Si film deposition step may be repeated two or more times alternately. As will be described later, it is preferable to include an oxidation step after the Sn film deposition step and the Si film deposition step. In this case, the steps are performed in the order of Sn film deposition step, first oxidation step, Si film deposition step, second oxidation step, and second oxidation step, and if this is repeated as a series for example two times, the steps are performed as follows: first Sn film deposition step, first oxidation step, first Si film deposition step, second oxidation step, second Sn film deposition step, third oxidation step, second Si film deposition step, and fourth oxidation step. The number of repetitions is not particularly limited, but it may be 2 to 2000 times, 10 to 1000 times, or 50 to 500 times. The initial film deposition in manufacturing method I may be either a Sn film deposition step or a Si film deposition step.

[0018] The manufacturing method of the present invention may optionally use compounds of elements other than tin and silicon as a third raw material gas, but it is preferable to use only tin compounds and silicon compounds.

[0019] (Tin Compounds) Examples of tin compounds used in the present invention include tin halides, alkylaminotin, alkyltin, alkenyltin, alkynyltin, tin alkoxide, tin carboxylate, aryltin, cyclopentadienyltin, and metallocensine.

[0020] Examples of tin halides include tin fluoride such as SnF2 and SnF4, tin chloride such as SnCl2 and SnCl4, tin bromide such as SnBr2 and SnBr4, and tin iodide such as SnI2 and SnI4.

[0021] Alkylaminotin is not particularly limited as long as it has at least one alkylamino group, specifically Sn(NR 1 R 2 )nX 4-n Compounds represented by R can be preferably listed. 1 and R2 each independently represents hydrogen or an alkyl group, and R 1 and R 2 at least one of which is an alkyl group. The alkyl group is an alkyl group having 1 to 20 carbon atoms, which may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 6. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, and the like. Among these, preferably, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, more preferably a methyl group and an ethyl group, and even more preferably an ethyl group. n is an integer of 1 to 4, preferably 4. X is a halogen and may be any of fluorine, chlorine, bromine, and iodine, preferably chlorine.

[0022] Alkyltin, alkenyltin, and alkynyltin are not particularly limited as long as they each have at least one alkyl group, alkenyl group, or alkynyl group. Specifically, compounds represented by Sn(R 3 ) n X 4-n can be preferably cited. R 3 is an alkyl group, an alkenyl group, or an alkynyl group. The alkyl group is the same as the aforementioned R 1 and R 2The configuration of the alkyl group is the same as in the above. The alkenyl group only needs to have at least one double bond, preferably has 1 to 20 carbon atoms, and may be linear or branched. The number of carbon atoms in the alkenyl group is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 6. Examples of alkenyl groups include ethylene, propylene, and butylene groups. The alkynyl group only needs to have at least one triple bond, preferably has 1 to 20 carbon atoms, and may be linear or branched. The number of carbon atoms in the alkenyl group is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 6. Examples of alkenyl groups include ethynyl, propynyl, and butynyl groups. n and X are the same as the configurations of n and X in the above alkylaminotin.

[0023] Tin alkoxides are not particularly limited as long as they have at least one alkoxy group, specifically, Sn(OR 4 ) n X 4-n Compounds represented by R can be preferably listed. 4 is an alkyl group. As an alkyl group, R 1 and R 2 The form of the alkyl group is the same as in the above-mentioned alkylaminotin. n and X are the same as the forms of n and X in the above-mentioned alkylaminotin.

[0024] The tin carboxylate is not particularly limited as long as it has at least one carboxylate group, specifically, Sn(OCOR 5 )nR 6 4-n Compounds represented by R can be preferably listed. 5 and R 6 is an alkyl group. As an alkyl group, R 1 and R 2 The form of the alkyl group is the same as in the above alkylaminotin. n is the same as the form of n and X in the above alkylaminotin.

[0025] The aryl tin is not particularly limited as long as it has at least one aryl group, and phenyl tin is a particularly suitable example.

[0026] The tin compound may be used alone or in combination of two or more. Among the above tin compounds, preferred are tin halides, alkylaminotin, tin alkoxides, and tin carboxylates; more preferred are tin chloride, tetradimethylaminotin, tin acetate, and tin alkoxides; and even more preferred is tetradimethylaminotin.

[0027] (Silicon Compounds) Examples of silicon compounds used in the present invention include silicon halides.

[0028] Examples of silicon halides include silicon fluoride such as SiF2 and SiF4, silicon chloride such as SiCl2 and SiCl4, silicon bromide such as SiBr2 and SiBr4, and silicon iodide such as SiI2 and SiI4.

[0029] The silicon compound may be used alone or in combination of two or more. Among the silicon compounds mentioned above, silicon tetrachloride is preferred.

[0030] Examples of silicon compounds used in the present invention include compounds represented by formula (1): X3-Si-R-Si-X3. In formula (1), R is an optionally substituted hydrocarbon group, and X is a halogen.

[0031] The hydrocarbon group in the hydrocarbon group which may have the above substituent may be linear or cyclic, may contain unsaturated bonds, and may contain heteroatoms such as oxygen and nitrogen. Examples of the above hydrocarbon group include alkylene groups and aryl groups.

[0032] X may be any of fluorine, chlorine, bromine, or iodine, and is preferably chlorine.

[0033] Examples of substituents in formula (1) include linear or branched alkyl groups, alkylene groups, and alkynyl groups, as well as silyl groups.

[0034] In formula (1), the alkylene group may be linear or branched, may contain unsaturated carbon bonds, and preferably has 1 to 20 carbon atoms. Examples of the alkylene group are formula (2): -(CR a R b ) m Suitable examples of organic groups represented by - are shown. In formula (2), R a and R b Each of these independently represents hydrogen, a linear or branched alkyl group, an alkylene group, an alkynyl group, and a silyl group. m is an integer from 1 to 10, preferably from 1 to 4, and more preferably from 1 to 3.

[0035] R a and R b Examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, etc. a and R b Examples of alkenyl groups include ethylene, propylene, and butylene groups. a and R b Examples of alkenyl groups include ethynyl, propynyl, and butynyl groups.

[0036] R a and R b Examples of the silyl group include formula (3): -SiR c R d R e Suitable examples of organic groups represented by formula (3) are: c , R d , and R e Each of these independently represents hydrogen, a linear or branched alkyl group, an alkylene group, and an alkynyl group, as well as a silyl group and a halogen. c , R d, and R e The embodiments of the alkyl group, alkylene group, and alkynyl group are R a and R b The forms of the alkyl group, alkylene group, and alkynyl group are the same as those of the above. c , R d , and R e The halogen may be any of fluorine, chlorine, bromine, or iodine.

[0037] In formula (1), a suitable example of the aryl group is a phenylene group which may have substituents.

[0038] A compound represented by formula (1) is preferably formula (1-1): X3-Si-(CR a R b ) m -Si-X 3 Compounds represented by the formula (1-1) can be listed. In formula (1-1), R a and R b It is preferable that is hydrogen, and m is preferably an integer from 1 to 10.

[0039] (Film Formation) Figure 1 is a schematic diagram showing an example of a film formation apparatus 100 for forming a film containing Sn and Si according to the present invention. This manufacturing apparatus 100 is equipped with a chamber CMB (film formation chamber, indicated as CMB in Figure 1) for housing a workpiece having a film formation surface and forming a film containing Sn and Si on that surface. Inside the chamber CMB, a substrate, which is the workpiece fixed to a susceptor, is set in the center. The chamber CMB is also equipped with a hot-wall type and / or cold-wall type heating device. The hot-wall type heating device heats the entire chamber CMB and controls it to a predetermined temperature, while the cold-wall type heating device controls the workpiece placed inside the chamber CMB to a predetermined temperature. Through these controls, the substrate can be heated from, for example, room temperature to 1200°C, thereby enabling the setting of a desired film formation temperature.

[0040] Upstream of the chamber CMB, a raw material gas supply path (indicated as Sn precursor and Si precursor in Figure 1) for introducing the raw material gas into the chamber CMB is connected via mass flow controllers MFC1 and MFC2, and valves for flow rate control. Also upstream of the chamber CMB, a process gas supply path for introducing an inert gas such as Ar gas as a process gas into the chamber CMB is connected to the Si precursor supply path via a mass flow controller MFC3, and valves for flow rate control, and is connected to the chamber CMB. Furthermore, upstream of the chamber CMB, a process gas supply path for introducing an optional oxidizer into the chamber CMB merges with the process gas supply path for introducing the inert gas into the chamber CMB (equipped with a mass flow controller MFC4, and valves for flow rate control) and is connected to the chamber CMB. The process gas supply path for introducing the oxidizer into the chamber CMB is equipped with a valve and a flow control valve. Furthermore, upstream of the chamber CMB, a process gas supply path for introducing inert gas into the chamber CMB merges with the Sn precursor supply path via a mass flow controller MFC5 and valves that control the flow rate, and is connected to the chamber CMB.

[0041] Downstream of the chamber CMB, a gas discharge path for discharging excess raw material gas and process gas is connected via a rotary pump and valve. A pressure gauge is connected to the chamber CMB to monitor the pressure inside, and the pressure can be adjusted by opening and closing an angle valve. Various gases supplied to the chamber CMB are drawn in by the rotary pump, diluted to a desired ratio with a diluent gas (not shown) as needed, and discharged to an external gas recovery mechanism (not shown). The pressure inside the chamber CMB can also be adjusted using the rotary pump and angle valve; for example, the chamber can be reduced to a low-pressure atmosphere.

[0042] In the film deposition process using this film deposition apparatus 100, first, the workpiece having a film deposition surface is placed in the chamber CMB, and if necessary, a process gas such as an inert gas is supplied to purge it. While controlling the temperature to reach a predetermined film deposition temperature, the Sn compound and Si compound, which are the raw material gases mentioned above, are introduced into the chamber CMB from the raw material gas supply path. Then, in this chamber CMB, a film containing Sn and Si is deposited on the film deposition surface by chemical vapor deposition or atomic layer deposition at the desired film deposition temperature. Any excess gases flowing into the chamber CMB are sucked out by a rotary pump or angle valve while maintaining a predetermined pressure, and discharged through the gas discharge path as described above.

[0043] Both manufacturing methods I and II of the present invention can be carried out using the film deposition apparatus 100. In manufacturing method I, the raw material gases, Sn compound and Si compound, are supplied alternately into the chamber CMB. In manufacturing method II, the raw material gases, Sn compound and Si compound, are supplied simultaneously into the chamber CMB.

[0044] The atmosphere used for film formation in the film formation process is not particularly limited, but since the above-mentioned Sn and Si compounds are used as raw material gases, an inert gas atmosphere is preferred from the viewpoint of safety. In this specification, inert gas means He, Ne, Ar, Kr, and N2. Among these, He, Ne, Ar, and Kr are preferred from the viewpoint of preventing nitriding reactions.

[0045] The film deposition temperature in the film deposition process is not particularly limited, but is preferably above room temperature. More preferably, the film deposition temperature is 40°C or higher, even more preferably 50°C or higher, and even more preferably 80°C or higher. The upper limit of the film deposition temperature is not particularly limited, but is preferably 1000°C or lower, more preferably 800°C or lower, and even more preferably 500°C or lower. In this specification, the film deposition temperature refers to the surface temperature of the film deposition surface of the workpiece, and means the value measured by a contact surface thermometer.

[0046] In the manufacturing method of the present invention, an oxidation step may be optionally performed after the Sn film formation step (manufacturing method I), the Si film formation step (manufacturing method I), and the Sn and Si film formation step (manufacturing method II). An oxidizing agent can be used in the oxidation step, and examples of oxidizing agents include O3, O2, CO, CO2, H2O, H2O2, N2O, etc. These oxidizing agents may be used individually or in combination of two or more. When an oxidizing agent is used, it is preferable that the film containing Sn and Si obtained by the manufacturing method of the present invention and the film containing Sn and Si of the present invention have SnO and SiO structures.

[0047] In the film formation process, a catalyst may be used, and film formation can be carried out by supplying a catalyst during the film formation process. Examples of catalysts used in the manufacturing method of the present invention include pyridine and ammonia.

[0048] The deposition pressure in the film formation process is not particularly limited and may be at atmospheric pressure, under pressure, or under reduced pressure. For example, as for reduced pressure conditions, from the viewpoint of film density, uniformity, conformability (uniform film adhesion to uneven surfaces), 0.05 Torr to 760 Torr is preferred, and 0.05 Torr to 10 Torr is more preferred.

[0049] The film deposition mode in the film deposition process can be any method, such as chemical vapor deposition (CVD) or atomic layer deposition (ALD), and is not particularly limited. Specifically, examples include thermal CVD, thermal ALD, plasma CVD, and plasma ALD. Among these, thermal CVD and thermal ALD are preferred from the viewpoint of productivity and economic efficiency. In thermal CVD and thermal ALD, as well as plasma CVD and plasma ALD, "thermal" or "plasma" refers to a method that accelerates the reaction by adding thermal or plasma energy.

[0050] The flow rate of the raw material gas introduced during the film formation process is not particularly limited, but is preferably 0.1 to 10 sccm, more preferably 0.5 to 5 sccm, and even more preferably 1 to 3 sccm. An introduction flow rate of 0.1 sccm or more tends to result in efficient film formation. An introduction flow rate of 10 sccm or less tends to result in excellent film density, uniformity, and conformability.

[0051] The flow rate of the inert gas introduced during the film formation process is not particularly limited, but is preferably 1 to 500 sccm, more preferably 10 to 300 sccm, and even more preferably 50 to 100 sccm.

[0052] The flow rate of the oxidizing agent introduced during the film formation process is not particularly limited, but is preferably 0.1 to 10 sccm, more preferably 0.5 to 5 sccm, and even more preferably 1 to 3 sccm.

[0053] The type of material to be processed is not particularly limited, as long as it is capable of forming a film containing Sn and Si. In the above example, a substrate was shown as the material to be processed, but examples of materials that can be processed include, but are not particularly limited to, silicon wafers, quartz, glass, titanium, aluminum, SUS, steel, semiconductor products, electrode materials, optical materials, mechanical reinforcement materials, etc. Furthermore, the type of film deposition surface is not particularly limited, as long as it is capable of forming a film containing Sn and Si. In the above example, the surface of the material to be processed was shown as the film deposition surface, but examples of materials that can be processed include, but are not particularly limited to, the surface of a silicon wafer, an SiO2 film formed on the surface of a silicon wafer, a SiN film, a GaN film, a polysilicon film, metallic materials such as SUS and copper, precious metals such as platinum, ruthenium, iridium, and silver, and transition metals such as tungsten, cobalt, nickel, and molybdenum, etc.

[0054] In the manufacturing method of the present invention, annealing may be performed after the film formation step.

[0055] [Sn and Si-containing film] One aspect of the present invention is a film containing Sn and Si (also referred to as "Sn and Si-containing film"). Preferably, the Sn and Si-containing film of the present invention has SnO and SiO structures within the film. The Sn and Si-containing film of the present invention can be manufactured, for example, according to the [Method for manufacturing Sn and Si-containing film] described above. The structure of the Sn-containing film according to the present invention can be confirmed by X-ray fluorescence analysis (XRF), and the structure of the Si-containing film can be confirmed by Fourier transform infrared spectroscopy (FT-IR). The presence of Sn in the Sn and Si-containing film according to the present invention can also be confirmed by X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure analysis (XAFS). The presence of Si in the Sn and Si-containing film according to the present invention can be confirmed by X-ray photoelectron spectroscopy (XPS), X-ray absorption fine structure analysis (XAFS), and Fourier transform infrared spectroscopy (FT-IR). Specifically, for example, it can be confirmed according to the <Method for confirming the film structure> described in the examples.

[0056] The film thickness of the Sn and Si-containing film of the present invention can be appropriately set according to the application and required performance, and is not particularly limited. For example, in the case of semiconductor and optical applications, it is generally preferable to have a thickness of more than 0 nm and less than or equal to 200 nm, and more preferably 2 nm to 50 nm. In the case of applications or when used as a structure for which mechanical strength is required, it is generally preferable to have a thickness of 100 nm to 10 μm, and more preferably 300 nm to 5 μm.

[0057] The Sn and Si-containing film of the present invention contains at least Sn and Si. It may also contain any other element, such as C. The amount of components in the film of the present invention can be controlled by selecting the type of tin and silicon compounds used as source gases, adjusting the pulse ratio [Sn / Si], the film deposition temperature, the film deposition method (sealing / flow), and the annealing temperature. These control methods are particularly suitable for controlling the Sn and C components.

[0058] [Applications] The Sn and Si-containing films of the present invention and the Sn and Si-containing films obtained by the manufacturing method of the present invention are used as transparent conductive films (ITO films) for electronic devices such as liquid crystal displays, solar cells, and thin-film transistors, as well as tin oxide thin films for solar cells, gas sensors, and anti-glare films, as well as thin-film transistors for organic electronics and films for semiconductor materials.

[0059] The Sn and Si-containing film of the present invention can be used for EUV (extreme ultraviolet) lithography. EUV light can form shorter and finer patterns than visible light or ultraviolet light. Tin can absorb EUV light with high efficiency and is suitable for effectively converting EUV light to form fine patterns in semiconductor manufacturing. The Sn and Si-containing film of the present invention can be used in dry resists and liquid resists.

[0060] The features of the present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited in any way by these. That is, the materials, amounts used, proportions, processing content, processing procedures, etc., shown in the following examples can be changed as appropriate, as long as they do not depart from the spirit of the present invention. Furthermore, the various manufacturing conditions and evaluation result values ​​in the following examples have meaning as preferred upper or lower limits in embodiments of the present invention, and the preferred range may be defined by a combination of the aforementioned upper or lower limits and the values ​​of the following examples or the values ​​of the examples themselves.

[0061] <Film Deposition Equipment> As the ALD equipment, we used an ALD equipment manufactured by Japan Advanced Chemicals Co., Ltd., which has a configuration equivalent to that shown in Figure 1. This ALD equipment is equipped with a tubular furnace with an inner diameter of 35 mm and a length of 500 mm as the film deposition chamber.

[0062] <Method for Confirming Film Structure> The presence or absence of Sn was confirmed by measuring the obtained film using XRF under the following conditions. Specifically, the film confirmation was performed in the following flow: (1) measuring the wafer before film deposition (confirming the blank peak), (2) measuring the SnO2-deposited wafer (comparing with the measurement results in (1) above to confirm the Sn peak), and (3) measuring the SnO2 + SiO(C)-deposited wafer (confirming that there is a peak at the same fluorescence X-ray energy as the measurement results in (2) above). In Table 3, ○ indicates that Sn content was confirmed, and × indicates that content was not confirmed. <XRF Conditions> Equipment: MESA-50K Tube Voltage: 50kV Filter: None Measurement Time: 30s Tube Current: 50μA Collimator: 3mm Pulse Processing Time: Process 2

[0063] The SiO and CH structures in the obtained film were confirmed by measuring them using FT-IR under the following conditions: <FT-IR conditions> Apparatus: Nicolet iS10 FT-IR Method: Transmission method Measurement range: 400-4000 cm -1 Resolution: 4cm -1 Number of cumulative measurements: After subtracting the measurement peaks of the wafer before film deposition as blanks 10 times, the peaks were checked. In Table 3, ○ indicates that SiO, CH2, or CH3 content was confirmed, and × indicates that these structures were not confirmed.

[0064] X-ray photoelectron spectroscopy (XPS) was performed, and the film was drilled in the depth direction using argon, and the elemental composition of the film was measured at depths of several nanometers. This measurement confirmed the elemental content in the film. The results are shown in Figure 10. In addition, for Example 1 and Reference Example, Table 5 indicates with ○ if content was confirmed and with × if it was not confirmed. <Conditions> Measurement conditions Instrument name: PHI5000 VersaProbe III ULVAC-PHI Output: 100u 25 W 15 kV Ion gun: 5 V Detection angle: 45 deg Irradiation method: Area (100 × 50 μm) Exposure time: Narrow: 50 ms / 1 step × 1 sweep × 1 cycle × Ratio 4 Data interval: Narrow: 0.05 eV Pass energy: Narrow: 55 eV Sputtering: Ar+ 1 kV, 7 mA, 2 × 2 mm

[0065] X-ray absorption fine structure analysis (XAFS) was performed, and the obtained films were measured under the conditions shown in Tables 1 and 2 below to confirm the SiO and Si-C structures within the films. In Table 4, for the films of Example 1 and Reference Example 2, ○ indicates that Si-O bonds and Si-C bonds were confirmed, and × indicates that they were not confirmed. In addition, the presence of Sn element in the films was confirmed by XAFS. ○ indicates that Sn presence was confirmed. <XAFS Conditions> The measurement conditions are shown in Tables 1 and 2.

[0066]

[0067]

[0068] [Example 1] A tin compound (tetrakis(dimethylamino)tin, Sn(NMe2)4) and a silicon compound (1,2-bis(trichlorosilyl)ethane, Cl3SiCH2CH2SiCl3) were used as precursors, water as an oxidizing agent, and pyridine as a catalyst. Films were deposited on the surface of a silicon wafer substrate using the above-mentioned film deposition apparatus under an argon atmosphere. The bottle temperature of the tin compound was 30°C and supplied by carrier argon gas. The bottle temperature of the silicon compound was 35°C and supplied by carrier argon gas. The bottle temperature of the water was 40°C, and the supply amount was adjusted using the scale of a Swagelok stainless steel metering bellows seal valve (SS-4BMG-VCR) located downstream of the bottle. The bottle temperature of the pyridine was 30°C, and the supply amount was adjusted using the scale of a Swagelok stainless steel metering bellows seal valve (SS-4BMG-VCR) located downstream of the bottle. The deposition temperature (substrate temperature) was set to 100°C. Deposition sequence: (1) A tin compound and argon gas were supplied. (2) The valve at the rear of the chamber was fully opened and the chamber was purged with argon gas. (3) The valve at the rear of the chamber was fully closed and water and argon gas were supplied. (4) The chamber was sealed and held. (5) The valve at the rear of the chamber was fully opened and the chamber was purged with argon gas. (6) The valve at the rear of the chamber was fully closed and silicon compound, pyridine, and argon gas were supplied. (7) The chamber was sealed and held. (8) The valve at the rear of the chamber was fully opened and the chamber was purged with argon gas. (9) The valve at the rear of the chamber was fully closed and water, pyridine, and argon gas were supplied. (10) The chamber was sealed and held. (11) The valve at the rear of the chamber was fully opened and the chamber was purged with argon gas. Steps (1) to (11) were repeated a predetermined number of times. The resulting membrane was measured by FT-IR and measured to have a thickness of 10¹⁰–10²⁰ cm⁻¹. -1 Si-O-Si stretching vibration with peaks at Si-(CH2) n - A peak where Si bending vibrations overlapped was observed. Also, 2900 cm -1 C-H nearby ２We were able to confirm the peak of the stretching vibration. XRF measurement results showed that it contained Sn. Although the presence of Cl was confirmed, a decrease in Cl content was confirmed by annealing at 400°C.

[0069] [Reference Example 1] Film deposition was performed in accordance with Example 1, except that the sequence was changed as follows: (1) A tin compound and argon gas were supplied. (2) The valve at the rear of the chamber was fully opened and the chamber was purged. (3) The valve at the rear of the chamber was fully closed and water and argon gas were supplied. (4) The chamber was sealed and held. (5) The valve at the rear of the chamber was fully opened and the chamber was purged with argon gas. Steps (1) to (5) were repeated a predetermined number of times. The obtained film contained Sn, as determined by XRF measurement results.

[0070] [Reference Example 2] Film deposition was performed in accordance with Example 1, except that the sequence was changed as follows: (1) The rear valve of the chamber was fully closed and silicon compound, pyridine, and argon gas were supplied. (2) The chamber was sealed and held. (3) The rear valve of the chamber was fully opened and the chamber was purged with argon gas. (4) The rear valve of the chamber was fully closed and water, pyridine, and argon gas were supplied. (5) The chamber was sealed and held. (6) The rear valve of the chamber was fully opened and the chamber was purged with argon gas. Steps (1) to (6) were repeated a predetermined number of times. The obtained film was measured by FT-IR and was 10¹⁰ to 10²⁰ cm⁻¹. -1 A peak was observed where the Si-O-Si stretching vibration and the Si-(CH2)n-Si bending vibration, both with peaks at 2900 cm, overlapped. -1 C-H nearby ２ We were able to confirm the peak of the stretching vibration.

[0071] Figure 2 shows the XRF spectral data of the films obtained in Example 1 and Reference Examples 1-2, and Figure 3 shows the FT-IR spectral data.

[0072] [Example 2] Silicon tetrachloride was used instead of 1,2-bis(trichlorosilyl)ethane, Cl3SiCH2CH2SiCl3, and a film was deposited on the surface of a silicon wafer substrate under an argon atmosphere using the deposition apparatus shown in Figure 4. The silicon tetrachloride bottle temperature was room temperature, and the supply amount was adjusted by a mass flow controller. The deposition temperature was 50°C. Otherwise, the deposition was carried out in accordance with Example 1. FT-IR (transmission method) measurement showed a depth of 1060 cm⁻¹. -1 A peak of Si-O-Si stretching vibration was observed in the vicinity. Furthermore, FT-IR peaks confirmed the presence of dimethylamine hydrochloride as an impurity. XRF measurements revealed the presence of Sn.

[0073] [Comparative Example 1] Dimethyl silicon dichloride (SiMe2Cl2) was used instead of 1,2-bis(trichlorosilyl)ethane (Cl3SiCH2CH2SiCl3) and a film was deposited on the surface of a silicon wafer substrate under an argon atmosphere using the deposition apparatus shown in Figure 5. The bottle temperature of dimethyl silicon dichloride was 30°C, and the supply amount was adjusted using the scale of a Swagelok stainless steel metering bellows seal valve (SS-4BMG-VCR) located downstream of the bottle. Film deposition was carried out in accordance with Example 1. The obtained film was measured by FT-IR and was found to have a thickness of 1000-1100 cm². -1 No peak of Si-O-Si stretching vibration was observed at 1260 cm. -1 A peak of Si-CH3 bending vibration is observed in the vicinity, between 2800 and 3000 cm. -1 No peak of C-H3 stretching vibration was observed. XRF measurement results indicated the presence of Sn.

[0074]

[0075]

[0076]

Claims

1. A method for producing a film containing Sn and Si, comprising: a Sn film formation step of forming a Sn-containing film using a tin compound as a raw material gas; and a Si film formation step of forming a Si-containing film using a silicon compound as a raw material gas, wherein the film formation is carried out by supplying the raw material gas into a chamber containing a workpiece having a film formation surface, and by chemical vapor deposition or atomic layer deposition.

2. The method for producing the silicon compound according to claim 1, wherein the silicon compound is a compound represented by formula (1): X3-Si-R-Si-X3 (wherein formula (1) is a hydrocarbon group which may have substituents, and X is a halogen).

3. The manufacturing method according to claim 1, wherein the Sn film formation step and the Si film formation step are each performed two or more times, and the Sn film formation step and the Si film formation step are performed alternately.

4. The production method according to claim 1, wherein the tin compound is at least one selected from the group consisting of tin halides, alkylaminotin, alkyltin, alkenyltin, alkynyltin, tin alkoxide, tin carboxylate, aryltin, cyclopentadienyltin, and metallocensinetin.

5. The manufacturing method according to claim 1, wherein the film formation is carried out by thermal atomic layer deposition or thermochemical vapor deposition.

6. The manufacturing method according to claim 1, further comprising an oxidation step after the Sn film formation step and the Si film formation step.

7. The manufacturing method according to claim 1, wherein the film has an SnO and SiO structure.

8. A method for producing a film containing Sn and Si, comprising a Sn and Si film formation step of forming a Sn and Si-containing film using a mixture of a tin compound and a silicon compound as a raw material gas, wherein the film formation is carried out by supplying the raw material gas into a chamber containing a workpiece having a film formation surface, and by chemical vapor deposition or atomic layer deposition.

9. The manufacturing method according to claim 8, wherein the silicon compound is a compound represented by formula (1): X3-Si-R-Si-X3 (wherein formula (1) is a hydrocarbon group which may have substituents, and X is a halogen element).

10. The production method according to claim 8, wherein the tin compound is at least one selected from the group consisting of tin halides, alkylaminotin, alkyltin, alkenyltin, alkynyltin, tin alkoxide, tin carboxylate, aryltin, cyclopentadienyltin, and metallocensinetin.

11. The manufacturing method according to claim 8, wherein the film formation is carried out by thermal atomic layer deposition or thermochemical vapor deposition.

12. The manufacturing method according to claim 8, wherein the film has an SnO and SiO structure.

13. A film containing Sn and Si, wherein the film has SnO and SiO structures.

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