Manufacturing method of film, and film

Abstract

To provide a film of a low dielectric constant applicable as an insulation film material by making available a material which cannot be used conventionally for an electronic device because of a temperature in deposition of the insulation film material, for example, and a manufacturing method thereof and reduce power consumption e.g., during electronic device manufacturing.SOLUTION: A manufacturing method of a film includes the steps of: heating and sublimating a raw material containing a compound expressed by a specific formula (1) within a temperature range from 150°C or higher to 250°C or lower; and depositing generated molecular beams on a substrate, thereby forming a film containing the compound expressed by the formula (1).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing a membrane, and to a membrane. [Background technology]

[0002] SiO 2 Like carbon, it exists in inexhaustible quantities on Earth and has been used to this day. 4 A group of siloxane compounds having a cage-shaped skeleton, which can be regarded as condensations of siloxanes (Si), or derivatives thereof, are promising functional silicon materials in various fields, and various investigations are being conducted into the search for new compounds and their production methods.

[0003] For example, Patent Document 1 proposes a method for producing a compound, in which a compound represented by the following general formula (2) is reacted with an alkylating agent to obtain a compound represented by the following general formula (3). [ka] (In the formula, p 1 is 0, 1 or 2.) [ka] (In the formula, Z 3 is a hydrogen atom or an alkyl group which may have a substituent, (2p 1 +6) Z's 3 may be the same or different, provided that one or more Z 3 represents the above-mentioned alkyl group which may have a substituent; 1 is the same as above.)

[0004] Furthermore, for example, Patent Document 2 proposes a method for producing a compound, in which a compound represented by the following general formula (1) is reacted with a compound represented by the following general formula (2) in the presence of a dehydrogenation catalyst to obtain a compound represented by the following general formula (3). [ka] (wherein p 1 is 0, 1 or 2; R 1 is an alkyl group which may have a substituent; i is 0 or 1.) H(Si(R 2 )) 2 O) j Si(OR 3 ) 3 ···(2) (wherein R 2 and R 3 are each independently an alkyl group which may have a substituent; j is 0, 1, 2, 3, 4 or 5.)

Chemical formula

[0005] In addition, as a method for obtaining an SiO 2 material constructed by controlling SiO 2 at the atomic level like a nanocarbon material, orthosilicic acid (Si(OH) 2 ), which is the basic unit of SiO 4) is considered to be an efficient method. For example, a given Si(OH) 4 It has been proposed that the oligomers are self-organized under control at the atomic level, and the oligomers are obtained as crystals in which they are regularly aligned. Specifically, for example, Patent Document 3 proposes a crystal that contains at least one silanol compound selected from the group consisting of a hexamer represented by the following formula (1), an octamer represented by the following formula (2), and a decamer represented by the following formula (3), and that has interaction between the silanol compounds via a hydrogen bond formed by at least one hydroxyl group. [ka] [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent Publication No. 2021-070651 [Patent Document 2] JP 2022-172690 A [Patent Document 3] International Publication No. 2020 / 085403 Summary of the Invention [Problem to be solved by the invention]

[0007] In recent years, SiO 2 films made from tetraethoxysilane (hereinafter referred to as "TEOS"), which is used in the back-end line (BEOL) process of semiconductor manufacturing, have been 2 Materials for the insulating film (interlayer insulating film) such as SiCN are being considered. SiO 2SiCN is usually deposited at high temperatures of 400°C or higher in a chemical vapor deposition (CVD) device. Low-k insulating films made of spin-on glass (SOG) made from liquid raw materials are heated after the liquid is spin-coated, so generally need to be heated to temperatures of 400°C or higher. Heating at such high temperatures limits the materials that can be used in semiconductor elements, and also tends to consume electricity for heating. SiO described in Patent Documents 1 to 3 2 The material has only been available as a powder, and no technology has been developed to form a film from it, making it difficult to apply to electronic devices, etc.

[0008] The present invention has been made in consideration of the above circumstances, and aims to provide a low dielectric constant film that can be used as an insulating film material, and a method for manufacturing the same, which makes it possible to use materials that could not be used in electronic devices due to the temperature at which the insulating film material was formed. Another aim of the present invention is to reduce power consumption during the manufacture of electronic devices. [Means for solving the problem]

[0009] As a result of extensive research, the inventors have discovered that the above-mentioned problems can be solved by forming a film from a raw material containing a compound represented by a specific formula by a specific method, and have thus completed the present invention.

[0010] That is, the present invention relates to the following. [1] A method for producing a film, comprising the steps of heating a raw material containing a compound represented by the following formula (1) in a temperature range of 150°C to 250°C to sublimate it, and depositing the generated molecular beam on a substrate to form a film containing the compound represented by the formula (1): [ka] (In formula (1), R is a methyl group, an ethyl group, a normal propyl group, an isopropyl group, or a phenyl group.) [2] The density of the film is 1 g / cm 3 More than 3g / cm 3 The method for producing the film according to [1], wherein the range is as follows: [3] The density of the film is 1 g / cm 3 More than 2g / cm 3 The method for producing the film according to [1], wherein the range is as follows: [4] The method for producing a film according to any one of [1] to [3], wherein the dielectric constant of the film is in the range of 1 F / m or more and 3 F / m or less. [5] The method for producing a film according to any one of [1] to [3], wherein the dielectric constant of the film is in the range of 1 F / m or more and 2.5 F / m or less. [6] A film comprising a compound represented by the following formula (1): [ka] (In formula (1), R is a methyl group, an ethyl group, a normal propyl group, an isopropyl group, or a phenyl group.) [7] Density is 1g / cm 3 More than 3g / cm 3 The membrane according to [6], wherein the membrane is in the following range: [8] Density is 1g / cm 3 More than 2g / cm 3 The membrane according to [6], wherein the membrane is in the following range: [9] The film according to any one of [6] to [8], having a dielectric constant in the range of 1 F / m or more and 3 F / m or less.

[10] The film according to any one of [6] to [8], having a dielectric constant in the range of 1 F / m or more and 2.5 F / m or less. Effect of the Invention

[0011] According to the present invention, for example, it is possible to use materials that could not be used in electronic devices due to the temperature at which the insulating film material was formed, and it is possible to provide a low-dielectric-constant film that can be used as an insulating film material, and a method for manufacturing the same. Furthermore, according to the present invention, it is possible to reduce power consumption during the manufacture of electronic devices, for example. [Brief description of the drawings]

[0012] [Figure 1] FIG. 1 shows an example of the results of measurement by X-ray diffraction (XRD) of the film according to the present invention. [Diagram 2] FIG. 2 shows an example of the measurement results of the film according to the present invention by X-ray photoelectron spectroscopy (XPS). [Diagram 3] FIG. 3 shows an example of the results of Raman spectroscopy of the film according to the present invention. [Figure 4] FIG. 4 shows an example of the measurement results of the terahertz electromagnetic wave transmittance of the film according to the present invention. [Diagram 5] FIG. 5 is an example of the results of observation of the film according to the present invention using a transmission electron microscope (TEM). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] Hereinafter, an embodiment of the present invention (hereinafter, also referred to as "the present embodiment") will be described in detail. Note that the present invention is not limited to the present embodiment, and various modifications can be made within the scope of the gist of the present invention.

[0014] [Membrane manufacturing method] The method for producing a film according to the present embodiment includes a step of heating a raw material containing a compound represented by the following formula (1) in a temperature range of 150° C. or more and 250° C. or less to sublimate it, and depositing the generated molecular beam on a substrate to form a film containing the compound represented by the formula (1). [ka] (In formula (1), R is a methyl group, an ethyl group, a normal propyl group, an isopropyl group, or a phenyl group.)

[0015] The film manufacturing method of the present embodiment includes such steps, and thus, for example, it is possible to form a film at a low temperature that can maintain good performance when made into an electronic device, and it is possible to obtain a film with a low dielectric constant that can be used as an insulating film material.

[0016] In formula (1), R is preferably a methyl group, an ethyl group, a normal propyl group, an isopropyl group, or a phenyl group, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. When R is such a group, for example, there is a tendency that a film can be formed at a low temperature so that the performance of an electronic device can be maintained in a better state. In addition, in the formula (1), R may be the same or different.

[0017] In the film manufacturing method of this embodiment, the temperature at which the raw material containing the compound represented by formula (1) is heated is 150°C or higher and 250°C or lower, and more preferably 175°C or higher and 200°C or lower. When the heating temperature is equal to or lower than the upper limit, for example, decomposition of the raw material during film formation of the insulating film material can be suppressed, making it possible to use materials that could not be used in electronic devices due to the temperature at which the insulating film material is formed, and there is a tendency to reduce power consumption during the manufacture of electronic devices. On the other hand, when the heating temperature is equal to or higher than the lower limit, the raw material containing the compound represented by formula (1) can be sublimated, and a film can be appropriately formed.

[0018] In the method for producing the film of the present embodiment, the pressure when heating and sublimating the raw material containing the compound represented by formula (1) is 10 2 Pa or less, and -2 It is more preferable that the pressure is in the above range. When the pressure is in the above range, the obtained film tends to be flat. The upper limit of the pressure is not particularly limited, but is, for example, 10 3 It is Pa.

[0019] The apparatus for producing the film of this embodiment is not particularly limited, but examples thereof include a vacuum chamber, a vacuum deposition apparatus, and a chemical vapor deposition apparatus.

[0020] Specific examples of the substrate on which the generated molecular beam is deposited include, but are not limited to, silicon (Si), sapphire, and SiO 2 , diamond, SiC, and GaN.

[0021] The density of the film is 1 g / cm 3 More than 3g / cm 3 The range is preferably 1 g / cm 3 More than 2g / cm 3 It is more preferable that the density is in the following range: When the density of the film is in the above range, the mechanical strength of the film tends to be excellent.

[0022] The method for controlling the density of the film within the above range is not particularly limited, but examples thereof include adjusting the film formation rate and adjusting the distance between the source material and the substrate. In this embodiment, the density of the film can be measured by the method described in the Examples below.

[0023] The dielectric constant of the film is preferably in the range of 1 F / m to 3 F / m, more preferably 1 F / m to 2.5 F / m. If the dielectric constant of the film is within the above range, for example, when the film is made into an electronic device, the electric capacitance between wirings is reduced, enabling high frequency operation.

[0024] The method for controlling the dielectric constant of the film within the above range is not particularly limited, but examples thereof include adjusting the film formation rate and adjusting the distance between the source material and the substrate. The dielectric constant of the film can be obtained by preparing a capacitor structure using metal electrodes and measuring the capacitance, and in this embodiment, it can be calculated by the method described in the Examples below.

[0025] The thickness of the film is preferably in the range of 1 nm to 100 μm, more preferably in the range of 10 nm to 1 μm, and even more preferably in the range of 10 nm to 100 nm. When the thickness of the film is within the above range, good insulating properties are obtained and flatness tends to be high.

[0026] The method for controlling the thickness of the film within the above range is not particularly limited, but may be, for example, controlling the film formation time by opening and closing a shutter mechanism provided on the heating portion of the substrate or the raw material. In this embodiment, the thickness of the film can be measured by the method described in the Examples below.

[0027] In the film manufacturing method of the present embodiment, the time for depositing the generated molecular beam on the substrate is, for example, preferably 10 seconds to 20 minutes, and more preferably 1 to 10 minutes.

[0028] The film manufacturing method of this embodiment may include a step of forming a layer other than the film containing the compound represented by formula (1). The layer other than the film containing the compound represented by formula (1) is not particularly limited, but may be, for example, a titanium layer, a tungsten layer, a Si oxide film layer, a SiN layer, a TiN layer, a copper layer, an aluminum layer, a ruthenium layer, etc. In addition, the method of forming the other layer is not particularly limited, but may be, for example, sputtering, deposition, plating, chemical vapor deposition, atomic layer deposition, etc.

[0029] [film] The film of the present embodiment contains a compound represented by the following formula (1) (hereinafter also referred to as "compound (1)"). [ka] (In formula (1), R is a methyl group, an ethyl group, a normal propyl group, an isopropyl group, or a phenyl group.)

[0030] The film of the present embodiment contains compound (1), and thus, for example, when made into an electronic device, the performance can be maintained in a good state, and, for example, excellent performance can be exhibited as an insulating film material.

[0031] The compound represented by formula (1), the density, the dielectric constant and the thickness of the film are the same as those in the above-mentioned method for producing the film.

[0032] The membrane of the present embodiment may contain other components besides the compound (1) within the range that does not impair the effects of the present invention. The types of other components are not particularly limited and can be arbitrarily selected depending on the purpose.

[0033] Specific examples of compound (1) include, but are not limited to, the following compounds: [ka] [ka] [ka]

[0034] The method for producing compound (1) is not particularly limited. For example, a compound represented by the following formula (2) (2,4,6,8,10,12,14,16,17,18,19,20-dodecaoxa-1,3,5,7,9,11,13,15-octasilapentacyclo[9.5.1.1 3,9 .1 5,15 .1 7,13 .] A method for producing it includes reacting icosane-1,3,5,7,9,11,13,15-octanol (CAS number 119558-12-2) (hereinafter also referred to as "compound (2)") with an alkylating agent. [ka]

[0035] Compound (2) can be produced, for example, by the method described in International Publication No. 2018 / 193732, although it is not particularly limited thereto. Compound (2) that does not contain water of hydration can be prepared by appropriately selecting the operations during its production (e.g., washing conditions, extraction conditions, purification conditions, etc.). By using such compound (2) (e.g., crystals) that does not contain water of hydration, it is possible to avoid using a large excess of the raw materials for producing compound (1), such as an alkylating agent, and compound (1) can be produced efficiently in a good yield.

[0036] Compound (2) may not contain any solvent component molecules, or may contain any solvent component molecules other than water. Examples of the solvent component include N,N-dimethylacetamide (DMAc). Compound (2) containing DMAc molecules is a preferred example of compound (2) that is easy to produce and does not contain water of hydration.

[0037] The number of molecules of the solvent component contained in one molecule of compound (2) can be adjusted by the operating conditions during the production of compound (2). For example, in compound (2) containing a molecule of DMAc, the number of molecules of DMAc contained in one molecule of compound (2) may be, for example, any one of 1 to 20, but this is just one example. For example, dodecane (nC 12 H 26 In compound (2) containing a molecule of dodecane (nC 12 H 26 The number of molecules of may be, for example, any one of 1 to 20, but this is just one example.

[0038] <Alkylating agents> The alkylating agent is not particularly limited, but examples thereof include alkyl triflates (methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, etc.), alkyl halides, alkyl sulfates (dimethyl sulfate, diethyl sulfate, etc.), alkyl tosylates (methyl p-toluenesulfonate, etc.), and alkyl mesylates (methyl methanesulfonate, etc.). The alkyl halide is not particularly limited, but examples thereof include methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide, propyl chloride, propyl bromide, propyl iodide, butyl chloride, butyl bromide, butyl iodide, hexyl chloride, hexyl bromide, hexyl iodide, decyl chloride, decyl bromide, decyl iodide, hexadecyl chloride, hexadecyl bromide, hexadecyl iodide, octadecyl chloride, octadecyl bromide, octadecyl iodide, cholesteryl chloride, cholesteryl bromide, cholesteryl iodide, cholestaryl chloride, cholestaryl bromide, cholestaryl iodide, 3-acetoxypropyl iodide, methyl 4-iodobutyrate, polyfluoroalkyl chloride having 1 to 50 carbon atoms, polyfluoroalkyl bromide having 1 to 50 carbon atoms, polyfluoroalkyl iodide having 1 to 50 carbon atoms, and benzyl bromide.

[0039] Next, the general method for reacting compound (2) with an alkylating agent will be described.

[0040] <Reaction conditions of compound (2) with alkylating agent> Compound (1) can be obtained by reacting compound (2) with an alkylating agent. The alkylating agent to be subjected to the reaction may be one kind or two or more kinds, which may be appropriately selected depending on the structure of the target compound (1). When two or more alkylating agents are used, their combination and ratio can be appropriately adjusted depending on the purpose.

[0041] In this specification, the descriptions regarding the number of types of compounds (1), (2) and alkylating agents do not take into consideration stereoisomers, unless otherwise specified.

[0042] The amount of the alkylating agent used can be appropriately adjusted depending on the structure of the desired compound (1) and other factors. For example, the amount of alkylating agent used can be adjusted depending on the number of alkyl groups in compound (1).

[0043] For example, when the amount of the alkylating agent used is 1 to 2 times the molar amount of the compound (2) used, the compound (1) having 1 to 2 alkyl groups in one molecule is preferably obtained. For example, when the amount of the alkylating agent used is 3 to 4 times the amount of compound (2) used, compound (1) having 3 to 4 alkyl groups in one molecule can be suitably obtained. For example, when the amount of the alkylating agent used is 5 to 6 times the amount of compound (2) used, compound (1) having 5 to 6 alkyl groups in one molecule can be suitably obtained. For example, when the amount of the alkylating agent used is 7 to 8 times the amount of compound (2) used, compound (1) having 7 to 8 alkyl groups in one molecule can be suitably obtained. For example, when the amount of the alkylating agent used is 8 times or more the molar amount of the compound (2) used, the compound (1) having 8 alkyl groups in one molecule can be obtained in a higher yield.

[0044] The amount of the alkylating agent used may be, for example, 8 to 16 times the molar amount of the compound (2) used, and this means that such an amount is suitable, for example, when the number of substitutions is 8 (i.e., the number of alkyl groups in one molecule is 8).

[0045] The amount of the alkylating agent used described above is merely an example for obtaining the target compound (1) efficiently in a good yield, and the amount of the alkylating agent used can be appropriately adjusted taking into consideration the overall production conditions of compound (1). Furthermore, the amount of alkylating agent used as explained above means the total amount of all alkylating agents used when two or more alkylating agents are used.

[0046] [base] It is preferable to use a base during the reaction of compound (2) with an alkylating agent, since the amount of compound (1) produced can be significantly increased by using a base.

[0047] The base is preferably an organic base. The organic base is not particularly limited, but examples thereof include aromatic amines such as aniline, pyridine, and piperidine; and aliphatic amines such as triethylamine and diisopropylethylamine.

[0048] When the above bases are used, one type of base may be used alone, or two or more types may be used in combination. When two or more types are used in combination, the combination and ratio thereof can be appropriately adjusted depending on the purpose.

[0049] When the base is used, the amount of the base used can be adjusted depending on, for example, the amount of the alkylating agent used. In this case, the amount of the base used is preferably 0 to 2 times the molar amount of the alkylating agent used, and may be, for example, 0.85 to 1.5 times the molar amount. When the amount of the base used is 0.8 times or more, the amount of compound (1) produced is further increased. When the amount of the base used is 2 times or less, excessive use of the base is suppressed.

[0050] [solvent] The reaction of compound (2) with an alkylating agent may be carried out without using a solvent, but is preferably carried out using a solvent. By using a solvent, the fluidity of the reaction solution is improved, the reaction of compound (2) with an alkylating agent proceeds more smoothly, and the amount of by-products produced can be reduced.

[0051] The solvent is preferably one that has no reactivity with the components used in the reaction, such as compound (2) and an alkylating agent. The solvent is not particularly limited, but examples thereof include ethers (compounds having an ether bond) such as tetrahydrofuran (THF), 1,4-dioxane, tetrahydropyran, dibutyl ether, 1,2-dimethoxyethane, etc.; amides such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), etc.; esters such as ethyl acetate, butyl acetate, etc.; halogenated hydrocarbons (hydrocarbons having a halogen atom as a substituent) such as 1,2-dichloroethane, methylene chloride, chlorobenzene, etc.; nitriles (compounds having a cyano group) such as propionitrile, acetonitrile, etc.; and hydrocarbons such as toluene, n-hexane, methylcyclohexane, etc.

[0052] When a solvent is used, the solvent may be used alone or in combination of two or more kinds. When two or more kinds are used in combination, the combination and ratio thereof can be appropriately adjusted depending on the purpose.

[0053] When a solvent is used, the amount of the solvent used is not particularly limited, but is preferably, for example, (0 to 200 mL per 1 mmol of compound (2)), and more preferably (10 to 100 mL per 1 mmol of compound (2)). When the amount of the solvent used is equal to or more than the lower limit, the effect of using the solvent is more prominent. When the amount of the solvent used is equal to or less than the upper limit, excessive use of the solvent is suppressed.

[0054] [Other ingredients] When reacting compound (2) with an alkylating agent, a component other than compound (2), the alkylating agent, the base, and the solvent may be used within a range that does not impair the effects of the present invention. The types of the other components are not particularly limited and can be selected arbitrarily depending on the purpose.

[0055] When the other components are used, one type of the other components may be used alone, or two or more types may be used in combination. When two or more types are used in combination, the combination and ratio thereof can be appropriately adjusted depending on the purpose.

[0056] When using the other components, the amount of use of the other components is not particularly limited and can be arbitrarily selected according to the type of the other components.

[0057] [Other reaction conditions] The reaction temperature may be adjusted as appropriate and is not particularly limited. The reaction temperature is preferably 10 to 40°C, and may be room temperature such as 18 to 30°C, for example.

[0058] The reaction time should be adjusted as appropriate according to other conditions such as the reaction temperature so that the production amount of compound (1) increases. It is not particularly limited and may be adjusted as appropriate. For example, when the alkylating agent is alkyl triflate (methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, etc.), the reaction time is preferably 1 to 72 minutes, and more preferably 1 to 60 minutes. When the alkylating agent is alkyl halide (methyl chloride, methyl bromide, etc.), for example, the reaction time is preferably 1 to 72 hours, and more preferably 1 to 60 hours.

[0059] In this embodiment, after the reaction is completed, if necessary, after performing post-treatment by a known method, compound (1) can be taken out by a known method. For example, after the reaction is completed, if necessary, post-treatment operations such as filtration, washing, extraction, pH adjustment, dehydration, and concentration are performed either alone or in combination of two or more, and then compound (1) can be taken out by concentration, crystallization, reprecipitation, column chromatography, etc. In addition, the taken-out compound (1) may be further purified, if necessary, by performing any one of operations such as crystallization, reprecipitation, column chromatography, extraction, and stirring and washing of crystals with a solvent, either alone or in combination of two or more, once or twice or more. When continuing to perform other steps using compound (1) after the reaction is completed, after the reaction is completed, if necessary, after performing post-treatment by a known method, the other steps may be continued without taking out compound (1).

[0060] When multiple types of compound (1) are produced by the reaction of compound (2) with an alkylating agent, the desired compound (1) can be obtained by appropriately selecting either one or both of the above-mentioned post-treatment and purification operations. Even if multiple types of compound (1) are produced, the properties of the compound can be predicted from the structure of compound (1), and therefore the yield of the desired compound (1) can be improved by selecting a post-treatment or purification operation suitable for the properties. In addition, by adjusting the amount of alkylating agent used and other reaction conditions, the production rate of the target compound (1) can be increased, thereby improving the yield of compound (1).

[0061] The structure of compound (1) can be confirmed by known techniques such as nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry (MS), infrared spectroscopy (IR), ultraviolet-visible spectroscopy (UV-VIS absorption spectrometry), and elemental analysis. EXAMPLES

[0062] Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the examples, the various physical properties were measured by the following methods.

[0063] [Film density] The density of the film was measured based on structural data obtained by X-ray structural analysis. [Film thickness] The thickness of the films was measured by transmission electron microscope (TEM) imaging of the cross-sections of the films. [Dielectric constant of film] The dielectric constant of the film was calculated by first-principles calculation using the pseudopotential method.

[0064] <Synthesis of compound represented by formula (1)> [Synthesis Example 1] A compound represented by the following formula (1)-1, in which all R in formula (1) are methyl groups, was synthesized as a compound represented by formula (1) using a composition that is a mixed crystal containing a compound represented by the following formula (a) and N,N-dimethylacetamide (hereinafter also referred to as "DMAc"), as follows. [ka] The compound represented by the formula (a) and DMAc were dissolved in a composition (29.0 mg, 0.02 mmol as the compound represented by the formula (a)) in N,N-dimethylformamide (DMF) (1 mL), and the resulting solution was mixed with methyl trifluoromethanesulfonate (TfOMe) (27.7 mg, 0.168 mmol, 8.4 eq) and diisopropylethylamine (i-Pr 2 EtN) (24.2 mg, 0.188 mmol, 9.4 eq) was added and stirred for 15 minutes to obtain a colorless, transparent solution. The resulting colorless, transparent solution was subjected to an isolation procedure to obtain the compound represented by formula (1)-1 (composition formula: Si 8 O 20 C 8 H 24 , hereinafter "Q 8 Me 8 ") powder was obtained. Obtained Q 8 Me 8 The NMR data of is shown below. 1 H-NMR (DMF-d 7 ): 3.83ppm 13 C-NMR (DMF-d 7 ): 52.3 ppm 29 Si-NMR(DMF-d 7 ):-101.5ppm

[0065] [Example 1] The above synthesized Q 8 Me 8 A film was produced using the powder as follows. A Si substrate was prepared and placed in a vacuum chamber. The pressure in the vacuum chamber was increased to 10-3 The raw material was synthesized as above. 8 Me 8 was heated at 175°C to sublimate the source material, and the generated molecular beam was deposited on a Si substrate for 10 minutes. 8 Me 8 A film of was formed. X-ray diffraction (XRD) measurement was performed on the thin film obtained in Example 1. Figure 1 shows the results of the X-ray diffraction measurement of the obtained thin film. From this result, it was confirmed that X-ray diffraction accompanying the formation of the film was observed. In addition, Raman spectroscopy measurement was performed on the thin film obtained in Example 1. Figure 3 shows the obtained Raman spectroscopy spectrum. From the observed Raman modes, it was confirmed that the thin film formed in Example 1 had a Q 8 Me 8 The thin film obtained in Example 1 was measured by terahertz time-domain spectroscopy. Figure 4 shows the obtained terahertz transmission spectrum. As shown in the spectrum, no absorption occurred, and it was therefore confirmed that the thin film formed in Example 1 was a dielectric film. Q 8 Me 8 The dielectric constant of the structure in which Q is arranged was calculated by first-principles calculation using the pseudopotential method. 8 Me 8 The dielectric constant of quartz (SiO 2 ) and is estimated to be around 2.1 F / m. In addition, in the method of Example 1, Q 8 Me 8 Since a film could be formed by heating a substrate holder, which is smaller than the substrate holder used for forming a TEOS film by the conventional method, it is believed that power consumption can be reduced by heating a cell containing a deposition material at a lower temperature. In addition, the density of the thin film obtained in Example 1 was 1.77 g / cm. 3 The thickness of the thin film obtained in Example 1 was 80 nm.

[0066] [Example 2] The above synthesized Q 8 Me 8A film was produced using the powder as follows. A sapphire substrate was prepared and placed in a vacuum chamber. The pressure in the vacuum chamber was increased to 10 -3 The raw material was synthesized as above. 8 Me 8 was heated at 175°C to sublimate the raw material, and the generated molecular beam was deposited on a sapphire substrate for 10 minutes. 8 Me 8 The thin film of Example 2 was subjected to X-ray photoelectron spectroscopy (XPS) measurement. Figure 2 shows the results of the X-ray photoelectron spectroscopy measurement of the obtained thin film. From the measurement results, it was confirmed that a structure composed of Si was formed on the sapphire substrate. In the method of Example 2, Q 8 Me 8 Since a film could be formed by heating the substrate, it is considered that, for example, a cell containing a deposition material smaller than the substrate holder used for forming a TEOS film by a conventional method can be heated at a lower temperature, and therefore power consumption can be reduced. In addition, the density of the thin film obtained in Example 2 was 1.77 g / cm 3 The thickness of the thin film obtained in Example 2 was 80 nm.

[0067] [Example 3] The above synthesized Q 8 Me 8 A film was produced using the powder as follows. A 5 nm thick tungsten film was formed on a Si substrate by sputtering, and the substrate was placed in a vacuum chamber. The pressure in the vacuum chamber was increased to 10 -3 The raw material was synthesized as above. 8 Me 8 was heated at 175°C to sublimate the source material, and the generated molecular beam was deposited on a Si substrate for 10 minutes. 8 Me 8 A film of was formed. The cross section of the thin film of Example 3 was imaged by a transmission electron microscope (TEM). FIG. 5 shows a transmission electron microscope image of the cross section of the obtained thin film and the Si substrate. From the transmission electron microscope image of the cross section, the protective layer for analysis, the titanium layer, the Q 8 Me8 The structure is a layer of tungsten, a layer of silicon oxide, and a silicon substrate. 8 Me 8 It was confirmed that a thin film of 1000 nm was deposited on the substrate. In the method of Example 3, Q 8 Me 8 Since a film could be formed by heating the substrate, it is considered that, for example, a cell containing a deposition material smaller than the substrate holder used for forming a TEOS film by a conventional method can be heated at a lower temperature, and therefore power consumption can be reduced. In addition, the density of the thin film obtained in Example 3 was 1.77 g / cm 3 The thickness of the thin film obtained in Example 3 was 80 nm. [Industrial Applicability]

[0068] The method for producing the film of the present invention is to form a film using TEOS. 2 This is very useful, for example, for forming an electronic device. In addition, since the film of the present invention contains carbon atoms (C), it is possible to form a film at a lower temperature than SiO 2 Since it has a lower dielectric constant than SiO2 and has the same level of insulating properties, it can be used, for example, in high-frequency circuits and circuit technologies for next-generation communication standards.

Claims

1. A method for producing a film, comprising the steps of heating a raw material containing a compound represented by the following formula (1) in a temperature range of 150° C. or more and 250° C. or less to sublimate it, and depositing the generated molecular beam on a substrate to form a film containing the compound represented by the formula (1): 【Chemistry 1】 (In formula (1), R is a methyl group, an ethyl group, a normal propyl group, an isopropyl group, or a phenyl group.)

2. The density of the film is 1 g / cm 3 3g / cm or more 3 The method for producing the membrane according to claim 1, wherein the range is as follows:

3. The density of the film is 1 g / cm 3 2g / cm or more 3 The method for producing the membrane according to claim 1, wherein the range is as follows:

4. The method for producing a film according to claim 1 or 2, wherein the dielectric constant of the film is in the range of 1 F / m or more and 3 F / m or less.

5. The method for producing a film according to claim 1 or 2, wherein the dielectric constant of the film is in the range of 1 F / m or more and 2.5 F / m or less.

6. A film comprising a compound represented by the following formula (1): 【Chemistry 2】 (In formula (1), R is a methyl group, an ethyl group, a normal propyl group, an isopropyl group, or a phenyl group.)

7. Density is 1 g / cm 3 3g / cm or more 3 7. The membrane of claim 6, wherein the range is:

8. Density is 1 g / cm 3 2g / cm or more 3 7. The membrane of claim 6, wherein the range is:

9. 8. The film according to claim 6 or 7, having a dielectric constant in the range of 1 F / m to 3 F / m.

10. 8. The film according to claim 6 or 7, having a dielectric constant in the range of 1 F / m to 2.5 F / m.

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