Film and method for producing same

Abstract

Provided is a method for producing a film containing Sn and Ge, which includes: an Sn film formation step for forming an Sn-containing film using a tin compound as a starting material gas; and a Ge film formation step for forming a Ge-containing film using a germanium 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] U.S. Patent Application Publication No. 2022 / 0230877

[0005] 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.

[0006] Therefore, it is thought that a variety of films can be created by introducing functional groups contained in a tin compound that is difficult to obtain into the elements of a second compound, and then combining this with the tin compound to form a film. In other words, it is thought that a variety of tin-containing films can be obtained by combining a tin compound with a second compound containing an element other than tin and forming a film.

[0007] The present invention aims to efficiently produce a variety of films containing Sn.

[0008] As a result of diligent research to solve the above problems, the inventors of the present invention have found that a film containing Ge and Sn can be produced by using compounds containing Ge and Sn as precursors, and have completed the present invention.

[0009] In other words, the present invention provides various specific embodiments as shown below. [1] A method for producing a film containing Sn and Ge, comprising: a Sn film formation step of forming a Sn-containing film using a tin compound as a raw material gas; and a Ge film formation step of forming a Ge-containing film using a germanium 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 according to [1], wherein the Sn film formation step and the Ge film formation step are each performed two or more times, and the Sn film formation step and the Ge film formation step are performed alternately. [3] The method according to [1] or [2], 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. [4] The manufacturing method according to any one of [1] to [3], wherein the germanium compound is at least one selected from the group consisting of germanium halide, alkylaminogermanium, alkylgermanium, alkenylgermanium, alkynylgermanium, germanium alkoxide, germanium carboxylate, arylgermanium, cyclopentadienylgermanium, and metallocenegermanium. [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 Ge film formation step. [7] The manufacturing method according to any one of [1] to [6], wherein the film has SnO and GeO structures. [8] A method for producing a film containing Sn and Ge, comprising a Sn and Ge film formation step of forming a film containing Sn and Ge using a mixture of a tin compound and a germanium 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 production method according to [8], wherein the raw material gas is a mixture consisting of only two kinds of a tin compound and a germanium compound.

[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 germanium compound is at least one selected from the group consisting of germanium halide, alkylaminogermanium, alkylgermanium, alkenylgermanium, alkynylgermanium, germanium alkoxide, germanium carboxylate, arylgermanium, cyclopentadienylgermanium, and metallocene germanium.

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

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

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

[12] , wherein the film has a SnO and GeO structure.

[14] A film containing Sn and Ge, the film having a SnO and GeO structure in the film.

[0010] According to the present invention, various films containing Sn can be efficiently produced.

[0011] 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 of the films obtained in Example 1 and Comparative Examples 1 to 2. It is a diagram showing the film forming apparatus used for the film formation of Comparative Example 1. It is a diagram showing the film forming apparatus used for the film formation of Comparative Example 2.

[0012] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, the following embodiments are examples for explaining the present invention, and the present invention is not limited thereto. That is, the present invention can be arbitrarily modified and implemented within the scope not departing from its gist. In this specification, the positional relationships such as up, down, left, and right are based on the positional relationships shown in the drawings unless otherwise specified, and the dimensional ratios in the drawings are not limited to the ratios shown. On the other hand, in this specification, when expressing before and after using "~" with numerical values or physical property values sandwiched therebetween, it is used as including the values before and after. For example, the notation of the numerical range of "1 to 100" includes both the lower limit value "1" and the upper limit value "100". The same applies to the notation of other numerical ranges.

[0013] [Method for manufacturing Sn and Ge-containing film] The present invention is a method for manufacturing a film containing Sn and Ge. One of the manufacturing methods of the present invention (also referred to as "Manufacturing Method I") includes a Sn film forming step of forming a Sn-containing film using a tin compound as a source gas, and a Ge film forming step of forming a Ge-containing film using a germanium compound as a source gas, wherein the film formation is performed by supplying the source gas into a chamber containing a workpiece having a film formation surface and by chemical vapor deposition or atomic layer deposition. One of the manufacturing methods of the present invention (also referred to as "Manufacturing Method II") includes a Sn and Ge film forming step of forming a Sn and Ge-containing film using a mixture of a tin compound and a germanium compound as a source gas, wherein the film formation is performed by supplying the source gas into a chamber containing a workpiece having a film formation surface and by chemical vapor deposition or atomic layer deposition. Manufacturing Method I and Manufacturing Method II are collectively also referred to as the manufacturing method of the present invention.

[0014] In the manufacturing method of the present invention, a tin compound and a germanium 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 Ge. The tin compound and germanium 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 Ge is obtained, and the structure of Sn and Ge in the film is not particularly limited, as long as it is a structure that forms a film.

[0015] According to the manufacturing method of the present invention, a film containing Sn and Ge can be obtained by using a combination of a tin compound and a germanium compound. This is because tin and germanium are elements of the same group and have similar periods, so their properties such as reactivity are thought to be similar, and it is presumed that a film is formed as they react with each other. However, the reason for obtaining a film is not limited to the above presumption, and the above presumption 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 created by introducing a functional group into a germanium compound and then combining it with a tin compound to form a film. In addition, by controlling the supply amount of the tin compound and the second compound containing the target functional group, it is possible to control the content ratio of tin to functional group.

[0016] In manufacturing method I, it is preferable that the Sn film deposition step and the Ge film deposition step are performed repeatedly, that is, each at least twice. It is also preferable that the Sn film deposition step and the Ge film deposition step are performed alternately. Furthermore, for example, the Sn film deposition step may be repeated at least twice, and the Ge film deposition step may be repeated at least twice, alternately. As will be described later, it is preferable to include an oxidation step after the Sn film deposition step and the Ge film deposition step. In this case, the steps are performed in the order of Sn film deposition step, first oxidation step, Ge film deposition step, second oxidation step, and if this is repeated as a series for, for example, twice, the steps are performed as follows: first Sn film deposition step, first oxidation step, first Ge film deposition step, second oxidation step, second Sn film deposition step, third oxidation step, second Ge film deposition step, and fourth oxidation step. The number of repetitions is not particularly limited, but it may be between 2 and 2000 times, between 10 and 1000 times, or between 50 and 500 times. The first film formation in manufacturing method I may be either a Sn film formation step or a Ge film formation step.

[0017] The manufacturing method of the present invention may optionally use compounds of elements other than tin and germanium as the third raw material gas, but it is preferable to use only tin compounds and germanium compounds.

[0018] (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.

[0019] 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.

[0020] Alkylaminotin is not particularly limited as long as it has at least one alkylamino group, specifically Sn(NR 1 R 2 ) n X 4-n Compounds represented by R can be preferably listed.１ and R ２ each independently represents hydrogen or an alkyl group, and at least one of R １ and R ２ 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 still 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 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 still 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.

[0021] 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 above 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.

[0022] 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.

[0023] The tin carboxylate is not particularly limited as long as it has at least one carboxylate group, specifically, Sn(OCOR 5 ) n R 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.

[0024] 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.

[0025] 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.

[0026] (Germanium Compounds) Examples of germanium compounds used in the present invention include germanium halides, alkylaminogermanium, alkylgermanium, germanium alkoxides, germanium carboxylates, and phenylgermanium.

[0027] Examples of germanium halides include germanium fluoride such as GeF2 and GeF4, germanium chloride such as GeCl2 and GeCl4, germanium bromide such as GeBr2 and GeBr4, and germanium iodide such as GeI2 and GeI4.

[0028] Alkylaminogermanium is not particularly limited as long as it has at least one alkylamino group, and specifically, Ge(NR 7 R 8 ) n X 4-n Compounds represented by R can be preferably listed. 7 and R 8 is the aforementioned R １ and R ２ The embodiment is the same as that of the alkylaminotin. n and X are the same as those of n and X in the alkylaminotin.

[0029] Alkylgermanium, alkenylgermanium, and alkynylgermanium are not particularly limited as long as they each have at least one alkyl group, alkenyl group, and alkynyl group, and specifically include Ge(R 9 ) n X 4-nCompounds represented by R can be preferably listed. ３ 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. The alkenyl group and alkynyl group are as follows: ３ 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.

[0030] Germanium alkoxides are not particularly limited as long as they have at least one alkoxy group, specifically Ge(OR 10 ) n X 4-n Compounds represented by R can be preferably listed. 10 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.

[0031] Germanium carboxylate is not particularly limited as long as it has at least one carboxylate group, specifically, Sn(OCOR 11 ) n R 12 4-n Compounds represented by R can be preferably listed. １１ and R １２ 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.

[0032] The arylgermanium is not particularly limited as long as it has at least one aryl group, and specifically, phenylgermanium can be preferably given as an example.

[0033] The germanium compound may be used alone or in combination of two or more. Among the above germanium compounds, germanium halides, alkylaminogermanium, germanium alkoxides, and germanium carboxylates are preferred, more preferably germanium chloride, tetradimethylaminogermanium, germanium acetate, and germanium alkoxides, and even more preferably tetradimethylaminogermanium.

[0034] (Film Formation) Figure 1 is a schematic diagram showing an example of a film formation apparatus 100 for forming a film containing Sn and Ge according to the present invention. This manufacturing apparatus 100 includes 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 Ge 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 making it possible to set a desired film formation temperature.

[0035] Upstream of the chamber CMB, a raw material gas supply path (indicated as Sn precursor and Ge 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 Ge precursor supply path via 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 optionally supplied oxidizer into the chamber CMB merges with the process gas supply path for introducing an 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 rate 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.

[0036] 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.

[0037] 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 raw material gases, Sn compound and Ge compound, are introduced into the chamber CMB from the raw material gas supply path. Then, in this chamber CMB, a film containing Sn and Ge 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.

[0038] 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 Ge compound, are supplied alternately into the chamber CMB. In manufacturing method II, the raw material gases, Sn compound and Ge compound, are supplied simultaneously into the chamber CMB.

[0039] The atmosphere used for film formation in the film formation process is not particularly limited, but since the above-mentioned Sn and Ge compounds are used as raw material gases, an inert gas atmosphere is preferred from the viewpoint of safety. In this specification, inert gases refer to He, Ne, Ar, Kr, and N ２ This means that, among these, He, Ne, Ar, and Kr are preferred from the viewpoint of preventing nitriding reactions.

[0040] 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.

[0041] 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 Ge film formation step (manufacturing method I), and the Sn and Ge film formation step (manufacturing method II). An oxidizing agent can be used in the oxidation step, and as an oxidizing agent, O ３ , O ２ CO, CO ２ H ２ O, H ２ O ２ , N ２ Examples include oxygen (O). These oxidizing agents may be used individually or in combination of two or more. When an oxidizing agent is used, the film containing Sn and Ge obtained by the manufacturing method of the present invention and the film containing Sn and Ge of the present invention preferably have SnO and GeO structures.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] The type of object to be processed is not particularly limited, as long as it is capable of forming a film containing Sn and Ge. In the above example, a substrate was shown as the object to be processed, but examples include semiconductor products such as silicon wafers, quartz, glass, titanium, aluminum, SUS, and steel, electrode materials, optical materials, and mechanical reinforcement materials, but are not particularly limited to these. Furthermore, the type of film deposition surface is not particularly limited, as long as it is capable of forming a film containing Sn and Ge. In the above example, the surface of the object to be processed was shown as the film deposition surface, but examples include the surface of a silicon wafer, and SiO formed on the surface of a silicon wafer. ２ Examples include, but are not limited to, films, SiN films, GaN films, polysilicon films, 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.

[0048] In the manufacturing method of the present invention, annealing may be performed after the film formation step.

[0049] [Sn and Ge-containing film] One aspect of the present invention is a film containing Sn and Ge (also referred to as "Sn and Ge-containing film"). The Sn and Ge-containing film of the present invention preferably has SnO and GeO structures within the film. The Sn and Ge-containing film of the present invention can be manufactured, for example, according to the [Method for manufacturing Sn and Ge-containing film] described above. The structure of the Sn and Ge-containing film according to the present invention can be confirmed by X-ray fluorescence analysis (XRF). Specifically, it can be confirmed, for example, according to the <Method for confirming the structure of the film> described in the examples.

[0050] The film thickness of the Sn and Ge-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.

[0051] [Applications] The Sn and Ge-containing film of the present invention and the Sn and Ge-containing film 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.

[0052] The Sn and Ge-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 effectively convert it, and by using Ge to create a difference in etching rate between the irradiated and unirradiated areas, it is suitable for forming fine patterns in semiconductor manufacturing. The Sn and Ge-containing film of the present invention can be used in dry resists.

[0053] 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.

[0054] <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.

[0055] <Method for confirming the structure of the film> The presence or absence of Sn and Ge was confirmed by measuring the obtained film using XRF under the following conditions. Specifically, the film confirmation was carried out 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 of (1) above to confirm the Sn peak), (3) Measuring the GeO2-deposited wafer (comparing with the measurement results of (1) above to confirm the Ge peak), (4) Measuring the SnO2 + GeO2-deposited wafer (confirming that there is a peak at the same fluorescent X-ray energy as the measurement results of (2) and (3) above). In Table 1, ○ indicates that Sn or Ge was confirmed, and × indicates that their presence 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

[0056] Since XRF detects Si in the substrate, the presence or absence of Si was confirmed by Fourier transform infrared spectroscopy (FT-IR). Specifically, the SiO structure in the film was confirmed by measuring the obtained film 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: 10 times. After subtracting the measurement peak of the wafer before film deposition as a blank, the peak was checked. In Table 1, ○ indicates that SiO was confirmed, and × indicates that it was not confirmed.

[0057] [Example 1] A tin compound (tetrakis(dimethylamino)tin, Sn(NMe2)4) and a germanium compound (tetrakis(dimethylamino)germanium, Ge(NMe2)4) were used as precursors, and water was used as an oxidizing agent. A film was deposited on the surface of a silicon wafer substrate using the above-described film deposition apparatus under an argon atmosphere. The bottle temperature of the tin and germanium compounds was 30°C and supplied by carrier argon gas. The bottle temperature of the water 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 total flow rate of dilution + precursor carrier argon was always 80 sccm. The chamber pressure was adjusted so that it was 1 Torr when 80 sccm of argon was flowing, and the film deposition temperature (substrate temperature) was 100°C. Film deposition sequence (1) The tin compound was supplied. (2) The valve at the rear of the chamber was fully opened and the chamber was purged. (3) The chamber was purged and stabilized in 1 torr. (4) Water was supplied. (5) The valve at the rear of the chamber was fully opened and the chamber was purged. (6) The chamber was purged and stabilized in 1 torr. (7) A germanium compound was supplied. (8) The valve at the rear of the chamber was fully opened and the chamber was purged. (9) The chamber was purged and stabilized in 1 torr. (10) Water was supplied. (11) The valve at the rear of the chamber was fully opened and the chamber was purged. (12) The chamber was purged and stabilized in 1 torr. Steps (1) to (12) were repeated a predetermined number of times. From the XRF measurement results, it was confirmed that the obtained film contained Sn and Ge.

[0058] [Reference Example 1] Film deposition was performed in accordance with Example 1, except that the sequence was changed as follows: (1) A tin compound was supplied. (2) The valve at the rear of the chamber was fully opened and the chamber was purged. (3) The chamber was purged and stabilized at 1 torr. (4) Water was supplied. (5) The valve at the rear of the chamber was fully opened and the chamber was purged. (6) The chamber was purged and stabilized at 1 torr. Steps (1) to (6) were repeated a predetermined number of times. The obtained film was confirmed to contain Sn from the XRF measurement results.

[0059] [Reference Example 2] Film deposition was performed in accordance with Example 1, except that the sequence was changed as follows: (1) A germanium compound was supplied. (2) The valve at the rear of the chamber was fully opened and the chamber was purged. (3) The chamber was purged and stabilized at 1 torr. (4) Water was supplied. (5) The valve at the rear of the chamber was fully opened and the chamber was purged. (6) The chamber was purged and stabilized at 1 torr. Steps (1) to (6) were repeated a predetermined number of times. The obtained film was confirmed to contain Ge from the XRF measurement results.

[0060] Figure 2 shows the XRF spectral data of the films obtained in Example 1 and Reference Examples 1-2.

[0061] [Comparative Example 1] Instead of a germanium compound, a silicon compound (silicon tetrachloride, SiCl4) was used, and a film was deposited on the surface of a silicon wafer substrate under an argon atmosphere using the film deposition apparatus shown in Figure 3. The bottle temperature of silicon tetrachloride was room temperature, and the supply amount was adjusted by a mass flow controller. The film deposition temperature was 200°C. The film deposition was carried out in accordance with Example 1 otherwise. Film deposition sequence (1) A tin compound was supplied. (2) The valve at the rear of the chamber was fully opened and the chamber was purged. (3) The chamber was purged and stabilized at 1 torr. (4) Water was supplied. (5) The valve at the rear of the chamber was fully opened and the chamber was purged. (6) The chamber was purged and stabilized at 1 torr. (7) A silicon compound was supplied. (8) The valve at the rear of the chamber was fully opened and the chamber was purged. (9) The chamber was purged and stabilized at 1 torr. (10) Water was supplied. (11) The valve at the rear of the chamber was fully opened and the chamber was purged. (12) The chamber was purged and stabilized at 1 torr. Steps (1) to (12) were repeated a predetermined number of times. The resulting membrane was measured by FT-IR and was 1000–1100 cm². ―１ No peaks of Si-O-Si stretching vibration were observed. XRF measurement results confirmed the presence of Sn.

[0062] [Comparative Example 2] Instead of a germanium compound, a silicon compound (dimethyl silicon dichloride, SiMe2Cl2) was used, and a film was deposited on the surface of a silicon wafer substrate under an argon atmosphere using the film deposition apparatus shown in Figure 4. 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. The film deposition temperature was 100°C. Otherwise, the film deposition was carried out in accordance with Comparative Example 1. The obtained film was measured by FT-IR and was found to have a thickness of 1000-1100 cm². ―１ No peaks of Si-O-Si stretching vibration were observed. XRF measurement results confirmed the presence of Sn.

Claims

1. A method for producing a film containing Sn and Ge, comprising: a Sn film formation step of forming a Sn-containing film using a tin compound as a raw material gas; and a Ge film formation step of forming a Ge-containing film using a germanium 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 manufacturing method according to claim 1, wherein the Sn film formation step and the Ge film formation step are each performed two or more times, and the Sn film formation step and the Ge film formation step are performed alternately.

3. 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.

4. The manufacturing method according to claim 1, wherein the germanium compound is at least one selected from the group consisting of germanium halides, alkylaminogermanium, alkylgermanium, alkenylgermanium, alkynylgermanium, germanium alkoxide, germanium carboxylate, arylgermanium, cyclopentadienylgermanium, and metallocenegermanium.

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 Ge film formation step.

7. The manufacturing method according to claim 1, wherein the film has SnO and GeO structures.

8. A method for producing a film containing Sn and Ge, comprising a Sn and Ge film formation step in which a film containing Sn and Ge is formed using a mixture of a tin compound and a germanium 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 raw material gas is a mixture consisting of only two types: a tin compound and a germanium compound.

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 germanium compound is at least one selected from the group consisting of germanium halides, alkylaminogermanium, alkylgermanium, alkenylgermanium, alkynylgermanium, germanium alkoxide, germanium carboxylate, arylgermanium, cyclopentadienylgermanium, and metallocenegermanium.

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

13. The manufacturing method according to claim 8, wherein the film has SnO and GeO structures.

14. A membrane containing Sn and Ge, wherein the membrane has SnO and GeO structures.

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