Film formation method

Abstract

To provide a film deposition method for forming a precise surface treatment layer containing a fluorine-containing compound by vacuum vapor deposition.SOLUTION: A film deposition method for forming a vapor-deposited film by vapor-depositing a deposit material on a surface of a substrate includes the steps of: preparing the deposit material containing a fluorine-containing compound represented by formula (1); and forming the vapor-deposited film by vapor-depositing the deposit material on the surface of the substrate. In the step of forming the vapor-deposited film, a vapor of the heated deposit material is irradiated with a thermoelectron and the vapor irradiated with the thermoelectron is brought into contact with the surface of the substrate to form the vapor-deposited film. In the formula, R1 indicates a group containing a fluoroalkyl group, R2 indicates an alkyl group or an alkoxyalkyl group, each of R3 and R4 independently indicates a hydrogen atom or a monovalent organic group, x is an integer of 1-100, and y is an integer of 0-100.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a method for forming a film by vapor deposition of a fluorine-containing compound on the surface of a substrate. [Background technology]

[0002] It is known that certain fluorine-based compounds, when used in the surface treatment of a substrate, can exhibit excellent water repellency, oil repellency, and antifouling properties, as well as electrical properties such as insulation and optical properties such as antireflection. Surface treatment layers containing such fluorine-based compounds are provided as functional thin films, such as antifouling layers, on a wide variety of substrates, including glass, plastics, fibers, and building materials (see Patent Document 1). The surface treatment layers are formed, for example, by wet processes, such as spin coating and impregnation, in which a surface treatment agent prepared by dissolving a fluorine-based compound in a solvent is applied to the surface of the substrate (see Patent Document 2). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-196432 [Patent Document 2] Japanese Patent Application Publication No. 11-342371 Summary of the Invention [Problem to be solved by the invention]

[0004] Many of the fluorine-based compounds have the property of easily condensing when exposed to the air, and therefore, when attempting to form the surface treatment layer by the wet process, particularly in a thickness of about 100 nm, the fluorine-based compounds aggregate, making it difficult to form a dense surface treatment layer.

[0005] In order to form the surface treatment layer densely, it is conceivable to form the surface treatment layer by a so-called dry process such as a vacuum deposition method of the fluorine-based compound, but the dry process also has the problem of the fluorine-based compound agglomerating over time, which is particularly likely to occur in the fluorine-based compound having a molecular weight in the oligomer range (e.g., a molecular weight of 1000 or less).

[0006] In view of the above problems, an object of the present invention is to provide a film forming method for forming a dense surface treatment layer containing a fluorine-containing compound by vacuum deposition. [Means for solving the problem]

[0007] In order to solve the above problems, the present invention provides a film-forming method for forming a vapor-deposited film by depositing a vapor deposition material on a surface of a substrate, the method comprising: 3 and a step of depositing the deposition material onto the surface of the substrate to form the deposition film, wherein in the step of forming the deposition film, the vapor of the heated deposition material is irradiated with thermoelectrons, and the vapor irradiated with the thermoelectrons is brought into contact with the surface of the substrate to form the deposition film.

[0008] [ka] The above formula ( 3 ) inside, x' is 2 or 3 is.

[0009] The deposition Forming a membrane In the step of irradiating the vapor of the deposition material with the thermoelectrons generated from a thermoelectron generating unit provided between the surface of the base material and the deposition material, the thermoelectron generating unit may be located between the surface of the base material and the deposition material and may have an opening through which the vapor of the deposition material passes, an anode located so as to surround the periphery of the opening, and a cathode located so as to surround the anode and generating the thermoelectrons; Forming a membrane In the step of irradiating the vapor of the deposition material passing through the opening with the thermoelectrons generated from the cathode and emitted toward the anode. [Effects of the Invention]

[0013] According to the present invention, it is possible to provide a film forming method for forming a dense surface treatment layer containing a fluorine-containing compound by vacuum deposition. [Brief explanation of the drawings]

[0014] [Figure 1] FIG. 1 is a schematic diagram illustrating the configuration of a vacuum deposition apparatus according to one embodiment of the present invention. [Figure 2] FIG. 2 is a perspective view schematically showing a thermoelectron generating device according to one embodiment of the present invention. [Figure 3A] FIG. 3A shows infrared absorption spectra of thin films of the surface treatment layers of Samples 1, 3, 4, and 5 in Test Example 1. [Figure 3B] FIG. 3B shows infrared absorption spectra of thin films of the surface treatment layers of Samples 2, 4, 5, and 9 in Test Example 1. [Figure 3C] FIG. 3C shows infrared absorption spectra of thin films of the surface treatment layers of Samples 4 to 8 in Test Example 1. [Figure 4A] FIG. 4A is an X-ray photoelectron spectroscopy spectrum of Sample 1 in Test Example 2. [Figure 4B] FIG. 4B is an X-ray photoelectron spectroscopy spectrum of Sample 3 in Test Example 2. [Figure 4C] FIG. 4C is an X-ray photoelectron spectroscopy spectrum of Sample 4 in Test Example 2. [Figure 4D] FIG. 4D is an X-ray photoelectron spectroscopy spectrum of Sample 5 in Test Example 2. [Figure 5A] FIG. 5A is an X-ray photoelectron spectroscopy spectrum of Sample 1 in Test Example 2. [Figure 5B] FIG. 5B is an X-ray photoelectron spectroscopy spectrum of Sample 3 in Test Example 2. [Figure 5C] FIG. 5C is an X-ray photoelectron spectroscopy spectrum of Sample 4 in Test Example 2. [Figure 5D] FIG. 5D is an X-ray photoelectron spectroscopy spectrum of Sample 5 in Test Example 2. [Figure 6A] FIG. 6A is an X-ray photoelectron spectroscopy spectrum of Sample 1 in Test Example 2. [Figure 6B] FIG. 6B is an X-ray photoelectron spectroscopy spectrum of Sample 3 in Test Example 2. [Figure 6C] FIG. 6C is an X-ray photoelectron spectroscopy spectrum of Sample 4 in Test Example 2. [Figure 6D] FIG. 6D is an X-ray photoelectron spectroscopy spectrum of Sample 5 in Test Example 2. [Figure 7A] FIG. 7A is an X-ray photoelectron spectroscopy spectrum of Sample 1 in Test Example 2. [Figure 7B] FIG. 7B is an X-ray photoelectron spectroscopy spectrum of Sample 3 in Test Example 2. [Figure 7C] FIG. 7C is an X-ray photoelectron spectroscopy spectrum of Sample 4 in Test Example 2. [Figure 7D] FIG. 7D is an X-ray photoelectron spectroscopy spectrum of Sample 5 in Test Example 2. [Figure 8A] FIG. 8A is a graph showing the measurement results of the reflectance of the thin film of the surface treatment layer of Samples 1 to 5 and the glass substrate of Reference Sample 1 in Test Example 4. [Figure 8B] FIG. 8B is a graph showing the measurement results of the reflectance of the thin film of the surface treatment layer of Sample 9 in Test Example 4. [Figure 8C] FIG. 8C is a graph showing the measurement results of the transmittance of the thin film of the surface treatment layer of Samples 1 to 5 and the glass substrate of Reference Sample 1 in Test Example 4. [Figure 8D] FIG. 8D is a graph showing the measurement results of the transmittance of the thin film of the surface treatment layer of Sample 9 in Test Example 4. [Figure 9] FIG. 9 is a graph showing the measurement results of the impedance and the dielectric loss tangent (tan δ) of the thin film of the surface treatment layer of Sample 1 in Test Example 5. DETAILED DESCRIPTION OF THE INVENTION

[0015] A film forming method according to one embodiment of the present invention will be described. FIG. 1 is a schematic diagram illustrating a vacuum deposition apparatus capable of carrying out the film formation method according to this embodiment, and FIG. 2 is a perspective view illustrating a thermoelectron generating apparatus according to this embodiment.

[0016] The film forming method according to the present embodiment includes the steps of preparing a deposition material containing a fluorine-containing compound and depositing the deposition material onto a surface of a substrate to form a deposition film. The fluorine-containing compound contained in the deposition material has a structure represented by the following formula (1):

[0017] [ka] In formula (1), R 1 represents a group containing a fluoroalkyl group, and R 2 represents an alkyl group or an alkoxyalkyl group, and R 3 and R 4 each independently represents a hydrogen atom or a monovalent organic group; x is an integer of 1 to 100; and y is an integer of 0 to 100.

[0018] In formula (1), R 1 Examples of the group containing a fluoroalkyl group represented by the formula (I) include -CF3, -C2F5, -C3F7, -CF 13 , -C7F 15 Etc.-C q F 2q+1 Examples include a fluoroalkyl group represented by (q=1 to 10); an oxyfluoroalkylene group, and among these, an oxyfluoroalkylene group represented by the following formula (2) is preferred.

[0019] [ka] In formula (2), p is an integer of 0 to 2.

[0020] In formula (1), R 2 Examples of the alkyl group represented by R include alkyl groups having 1 to 2 carbon atoms, such as a methyl group and an ethyl group. 2 Examples of the alkoxyalkyl group represented by the formula (I) include alkoxyalkyl groups having 2 to 4 carbon atoms, such as a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, and an ethoxyethyl group. 2 The group represented by the formula (I) is preferably an alkyl group, and particularly preferably a methyl group.

[0021] In formula (1), R 3 and R 4 Examples of the organic group represented by the formula (i) include groups represented by the following formulas (i) to (v).

[0022] [ka]

[0023] In formula (1), a trialkoxysilyl group or a trialkoxyalkoxysilyl group (—Si(OR 2 The number x of intermediate chains (-CH2-CH-) to which the intermediate chains (-CH2-CR3) are bonded is 1 to 100, preferably 1 to 50, more preferably 1 to 10, and particularly preferably 2 to 3. 3 R 4 The number y of -) is 0 to 100, preferably 0 to 50, more preferably 0 to 10, and particularly preferably 0.

[0024] Examples of compounds suitable as the fluorine-containing compound include compounds represented by the following formulas (3) to (7): In particular, when the fluorine-containing compound is a compound represented by formula (3) or formula (6) (a compound in which y=0 in formula (1)), the proportion of fluorine atoms per molecule is large.

[0025] [ka] In formula (3), x' is 2 or 3.

[0026] [ka]

[0027] [ka] In formula (4) and formula (5), R 1’ is a group represented by -CF(CF3)OCF2CF(CF3)OC3F7. In formula (4), xa is an integer of 1 to 100. In formula (5), xb is an integer of 1 to 100, and yb is an integer of 1 to 500.

[0028] [ka] In formula (6), xc is an integer of 1 to 10, and yc is an integer of 0 to 100.

[0029] [ka] In formula (7), xd is an integer of 1 to 10, and yd is an integer of 0 to 100.

[0030] The fluorine-containing compound represented by the formula (1) above can be obtained by polymerizing a monomer represented by the formula (Ib) below and a monomer represented by the formula (Ic) below in the presence of a fluorine-containing peroxide represented by the formula (Ia) below. Note that this reaction product (fluorine-containing compound) contains a group (R 1 ) may be introduced at only one end of the oligomer in any proportion.

[0031] [ka] In formulas (Ia) to (Ic), R 1represents a group containing a fluoroalkyl group, and R 2 represents an alkyl group or an alkoxyalkyl group, and R 3 and R 4 each independently represents a hydrogen atom or a monovalent organic group.

[0032] The substrate onto which a vapor deposition film is formed by vapor deposition of a vapor deposition material is not particularly limited, and examples thereof include glass substrates such as quartz glass substrates; resin substrates such as polyimide substrates, polyethylene substrates, polyethylene terephthalate substrates, polypropylene substrates, and polycarbonate substrates; metal substrates such as aluminum substrates; and semiconductor substrates such as silicon substrates, GaAs substrates, and InP substrates. In the film formation method according to this embodiment, a vapor deposition film can be formed under relatively low temperature conditions, and therefore a resin substrate such as a polyethylene terephthalate substrate, which has relatively low heat resistance, is suitable as the substrate.

[0033] The step of depositing a deposition material onto the surface of a substrate to form a deposition film can be carried out using, for example, a film forming apparatus 1 described below.

[0034] The film forming apparatus 1 includes a vacuum chamber 2, a film forming source 3, a thermoelectron generating unit 4, and a substrate holder 5. The vacuum chamber 2 is capable of maintaining a reduced pressure inside the vacuum chamber 2. A vacuum pump is connected to the vacuum chamber 2 via an exhaust pipe, and a vacuum of, for example, 1.0×10 -5 ~1.0×10 -2 The vacuum chamber 2 can be evacuated to a predetermined pressure of about 100 Pa and maintained at that pressure. If gas is present in the vacuum chamber 2, the deposition material evaporated from the film formation source 3 may collide with gas molecules in the vacuum chamber 2, which may prevent the deposition material from adhering to the surface 61 of the substrate 6. However, by maintaining the interior of the vacuum chamber 2 at a predetermined pressure, the deposition material can be effectively adhered to the surface 61 of the substrate 6. The film formation apparatus 1 may also be provided with a gas supply mechanism (not shown) capable of supplying gas from outside the vacuum chamber 2 into the vacuum chamber 2.

[0035] The film formation source 3 is provided at or near the bottom of the vacuum chamber 2. The film formation source 3 has an evaporation container such as a crucible, and the fluorine-containing compound is contained in the evaporation container as a deposition material. A heating device such as a heater is provided around the evaporation container, and the fluorine-containing compound contained in the evaporation container is heated. When the fluorine-containing compound contained in the evaporation container is heated, the fluorine-containing compound evaporates from the evaporation container toward the surface 61 (deposition surface) of the substrate 6.

[0036] The thermoelectron generating unit 4 includes an anode 43 and a cathode 44. An anode power supply 45 that applies a voltage to the anode 43 is connected to the anode 43, and a cathode power supply 46 that applies a voltage to the cathode 44 is connected to the cathode 44. The cathode 44 includes a conductive filament (e.g., a tungsten filament) as a thermoelectron generating member, and the conductive filament of the cathode 44 is heated by applying a predetermined voltage from the cathode power supply 46 to the cathode 44. As a result, thermoelectrons are emitted from the conductive filament of the cathode 44 toward the anode 43. At this time, in order to accelerate the emitted thermoelectrons, the anode power supply 46 is connected to the cathode 44 and a voltage is applied thereto.

[0037] The thermoelectron generating unit 4 includes a substrate 41 having an opening 42 that opens substantially at the center. The anode 43 and the cathode 44 are provided on the substrate 41 to surround the opening 42. The opening 42 is located between the film formation source 3 and the substrate 6 held by the substrate holder 5. The vapor of the fluorine-containing compound evaporated from the evaporation container of the film formation source 3 passes through the opening 42 and reaches the surface 61 of the substrate 6. The cathode 44 is provided to surround the outside of the anode 43 that is provided around the opening 42. With this configuration, thermoelectrons emitted from the conductive filament of the cathode 44 toward the anode 43 are irradiated onto the vapor of the fluorine-containing compound passing through the opening 42, and the vapor irradiated with the thermoelectrons adheres to the surface 61 of the substrate 6. In this way, the fluorine-containing compound irradiated with the thermoelectrons adheres to the surface 61 of the substrate 6, forming a dense surface treatment layer (fluorine-containing compound layer) having the desired function on the surface 61 of the substrate 6.

[0038] When a current flows through the cathode 44, the conductive filament of the cathode 44 is heated, which can cause thermions to be emitted from the conductive filament of the cathode 44. For example, when the conductive filament of the cathode 44 is heated to about 800 to 1300°C, thermions can be emitted from the conductive filament.

[0039] The voltage applied to the anode 43 may be, for example, within a range of 50 to 500 V. If the voltage applied to the anode 43 is less than 50 V, it may be difficult to extract thermoelectrons from the conductive filament of the cathode 44, and if it exceeds 500 V, the fluorine-containing compound may be easily decomposed. The current value flowing through the anode 43 may be, for example, within a range of 10 to 30 mA. In particular, when the current value flowing through the anode 43 is within the above range, the function of the fluorine-containing compound can be exhibited and a dense surface treatment layer can be formed as a thin film (with a thickness of about 100 to 200 nm).

[0040] According to the film formation method of the present embodiment described above, the vapor of the fluorine-containing compound evaporated from the film formation source 3 is irradiated with thermoelectrons, and the vapor of the fluorine-containing compound irradiated with the thermoelectrons can be attached to the surface 61 of the substrate 6. As a result, as will be apparent from the examples described later, a thin film of a surface treatment layer (fluorine-containing compound layer) that is dense and has desired functions can be formed on the surface 61 of the substrate 6.

[0041] The above-described embodiments have been described to facilitate understanding of the present invention, and are not intended to limit the present invention. Therefore, each element disclosed in the above embodiments is intended to include all design modifications and equivalents that fall within the technical scope of the present invention. [Example]

[0042] The present invention will be explained in more detail below by giving Production Examples, Test Examples, etc., but the present invention is not limited to the following Production Examples, Test Examples, etc.

[0043] [Production Example 1] Using the film formation apparatus 1 shown in Figure 1, a fluorine-containing compound represented by the above formula (3) was placed as a deposition material in a crucible serving as a film formation source 3 and heated, forming a thin film of a surface treatment layer (sample 1) on the surface 61 of a glass substrate 6 held by a substrate holder 5. The film thickness of the thin film was measured using an ellipsometer (manufactured by JASCO Corporation, product name: Ellipsometer M-150, measurement wavelength: 632.8 nm, incident angle: 45°, substrate refractive index: 1.515%), and was found to be 138.7 nm. The film formation conditions were as follows:

[0044] [Film formation conditions] Film forming time: 80min Starting temperature: 100℃ Heating rate: 1.5 to 2.0°C / min Vacuum degree: 7.5×10 -6 ~1.6×10 -5 Torr Anode voltage: 150V Anode current: 10mA Cathode current: 3.5A Cathode conductive filament (tungsten filament) diameter: 0.2 mm

[0045] [Production Example 2] A thin film of the surface treatment layer (sample 2) was formed on the surface 61 of the glass substrate 6 in the same manner as in Production Example 1, except that the anode current as a film formation condition was changed to 20 mA. The film thickness measured using the above-mentioned ellipsometer was 130.7 nm.

[0046] [Production Example 3] A thin film of the surface treatment layer (Sample 3) was formed on the surface 61 of the glass substrate 6 in the same manner as in Production Example 1, except that the anode current as a film formation condition was changed to 30 mA. The film thickness measured using the above-mentioned ellipsometer was 137.6 nm.

[0047] [Production Example 4] A thin film of the surface treatment layer (sample 4) was formed on the surface 61 of the glass substrate 6 in the same manner as in Production Example 1, except that the anode current as a film formation condition was changed to 0 mA.

[0048] [Production Example 5] A fluorine-containing compound solution was prepared by adding 100 mg of the fluorine-containing compound represented by the above formula (3) to 5 g of a solvent (ethanol) and stirring at room temperature for 10 minutes. The obtained fluorine-containing compound solution was applied to the surface 61 of the glass substrate 6 by spin coating and dried to form a thin film of the surface treatment layer (sample 5).

[0049] [Production Example 6] A thin film of the surface treatment layer (sample 6) was formed on the surface 61 of the glass substrate 6 in the same manner as in Production Example 3, except that the anode voltage as a film formation condition was changed to 200V.

[0050] [Production Example 7] A thin film of the surface treatment layer (sample 7) was formed on the surface 61 of the glass substrate 6 in the same manner as in Production Example 6, except that the anode current as a film formation condition was changed to 40 mA.

[0051] [Production Example 8] A thin film of the surface treatment layer (sample 8) was formed on the surface 61 of the glass substrate 6 in the same manner as in Production Example 6, except that the anode current as a film formation condition was changed to 50 mA.

[0052] [Production Example 9] A thin film of the surface treatment layer (sample 9) was formed on the surface 61 of the glass substrate 6 in the same manner as in Production Example 2, except that the anode voltage as a film formation condition was changed to 100V.

[0053] [Test Example 1] Infrared absorption spectrum measurement test The infrared absorption spectra of the thin film surface treatment layers of Samples 1 to 9 were measured using a Fourier transform infrared spectrophotometer (manufactured by Horiba, Ltd., product name: FT-730) to analyze the film formation state of the thin film surface treatment layers. The results are shown in Figures 3A to 3C.

[0054] 3A to 3C show the infrared absorption spectra of the thin films of the surface treatment layers of Samples 1 to 9. It was confirmed that the infrared absorption spectra of Samples 1 and 2 and Samples 6 to 8 were different from those of Sample 4, which was vacuum-deposited without being irradiated with thermoelectrons, and Sample 5, which was formed by spin coating.

[0055] In samples 1-2 and 6-8, the peaks at 1350 cm were higher than those in samples 4-5. -1 CF3 stretching vibration and 1250cm -1 It was confirmed that the intensity of the peak indicating the stretching vibration of CF2 was weak. On the other hand, it was confirmed that Sample 3, which was formed using an anode current of 30 mA as the film formation condition, exhibited an infrared absorption spectrum similar to that of Samples 4 and 5.

[0056] [Test Example 2] X-ray photoelectron spectroscopy measurement test X-ray photoelectron spectroscopy spectra were measured using an X-ray photoelectron spectrometer (manufactured by Shimadzu Corporation, product name: AXIS-NOVA) for the thin films of the surface treatment layers of Sample 1 and Samples 3 to 5. The results are shown in Figures 4A to 7D.

[0057] 5A to 5D, it was confirmed that absorption (290 to 295 eV) due to the fluorine-containing groups of CF3 and CF2 appeared in Samples 3 to 5, but absorption due to the fluorine-containing groups of CF3 and CF2 did not appear in Sample 1. Although the measurement results for Sample 2 are not shown, Sample 2 also did not appear to exhibit absorption due to the fluorine-containing groups of CF3 and CF2, just like Sample 1.

[0058] [Test Example 3] Water contact angle measurement test Water was dropped onto the thin film of the surface treatment layer of Samples 1 to 5, and the water contact angle (deg) was measured using a contact angle meter (manufactured by First Ten Angstrom, product name: FTA188). The results are shown in Table 1.

[0059] [Table 1]

[0060] As is clear from the results shown in Table 1, it was confirmed that the thin film surface treatment layers of Samples 1 to 3 exhibited water contact angles equivalent to those of the thin film surface treatment layers of Samples 4 to 5.

[0061] [Test Example 3] Observation of the thin film surface of the surface treatment layer The surfaces of the thin films of the surface treatment layers of Samples 1 to 5 were observed using an optical microscope immediately after deposition and 7 days after deposition. As a result, the surfaces of the thin films of the surface treatment layers of Samples 1 to 3 remained unchanged both immediately after deposition and 7 days after deposition. On the other hand, the surfaces of the thin films of the surface treatment layers of Samples 4 to 5 showed aggregation of the fluorine-containing compound 7 days after deposition, partially exposing the surface 61 of the glass substrate 6. These results confirmed that a dense thin film of the surface treatment layer can be formed by irradiating the fluorine-containing compound evaporated from the crucible serving as the film-forming source 3 with thermoelectrons and causing the fluorine-containing compound irradiated with the thermoelectrons to adhere to the surface 61 of the glass substrate 6. The irradiation of the thermoelectrons imparts energy to the evaporated fluorine-containing compound. It is believed that the adhesion of the energized fluorine-containing compound to the surface 61 of the substrate 6 results in the formation of a dense thin film of the surface treatment layer, although the detailed mechanism is unknown. From the above results, it is possible to predict that a dense thin film of the surface treatment layer will be formed by depositing the film formation material to which energy has been applied. Therefore, it is conceivable to form a dense thin film of the surface treatment layer by applying energy, such as by irradiating electrons onto the thin film of the surface treatment layer formed by adhering the film formation material to the surface 61 of the substrate 6. However, if energy is applied to the thin film of the surface treatment layer formed on the surface of the substrate 6, there is a risk of damaging the substrate itself. Furthermore, because energy can be applied to the evaporated material by simply irradiating the evaporated material with thermoelectrons, no plasma is generated. Therefore, damage to the substrate can also be suppressed.

[0062] [Test Example 4] Optical property evaluation test The reflectance and transmittance of the thin surface treatment layers of Samples 1 to 5 and Sample 9, as well as the glass substrate 6 (Reference Sample 1) without a thin surface treatment layer, were measured using an ultraviolet-visible spectrophotometer (manufactured by JASCO Corporation, product name: V-550). The results are shown in Figures 8A to 8D.

[0063] 8A and 8C are graphs showing the reflectance (FIG. 8A) and transmittance (FIG. 8C) of the thin surface treatment layers of Samples 1 to 5 and the glass substrate of Reference Sample 1. FIGS. 8B and 8D are graphs showing the reflectance (FIG. 8B) and transmittance (FIG. 8D) of the thin surface treatment layer of Sample 9. As shown in FIGS. 8A to 8D, Sample 3 exhibited high transmittance and low reflectance. These results confirmed that irradiating the emitted thermoelectrons onto a fluorine-containing compound at an anode current of 30 mA and depositing the compound on the surface 61 of the substrate 6 provided particularly excellent light transmittance and anti-reflection effects. Furthermore, when comparing Sample 3 and Sample 5, Sample 3 exhibited higher transmittance and lower reflectance than Sample 5. This is presumably due to the fact that the surface of the thin surface treatment layer of Sample 3 has higher flatness and lower scattering loss than the surface of a thin surface treatment layer formed by spin coating, such as Sample 5.

[0064] [Test Example 5] Electrical insulation evaluation test The impedance (Ω) and dielectric loss tangent (tan δ) of the thin film of the surface treatment layer of Sample 1 were measured using an impedance analyzer (manufactured by Solartron, product name: S1260). The results are shown in FIG. 9, the plots of black circles indicate impedance (Ω), and the plots of white circles indicate dielectric loss tangent (tanδ). From the results shown in Fig. 9, it was confirmed that the thin film of the surface treatment layer formed by irradiating the fluorine-containing compound with thermoelectrons and depositing it on the surface 61 of the substrate 6 exhibits excellent electrical insulation properties. [Explanation of symbols]

[0065] 1...Film deposition equipment 2...Vacuum chamber 3…Film formation source 4...Thermionic generating section 5...Substrate holder

Claims

1. A film-forming method for forming a vapor-deposited film by depositing a vapor deposition material on a surface of a substrate, comprising: preparing the deposition material containing a fluorine-containing compound represented by the following formula (3); depositing the deposition material on the surface of the substrate to form the deposition film; Including, A film forming method characterized in that, in the step of forming the vapor deposition film, the vapor of the heated vapor deposition material is irradiated with thermoelectrons, and the vapor irradiated with the thermoelectrons is brought into contact with the surface of the substrate to form the vapor deposition film. 【Chemistry 1】 In the above formula (3), x' is 2 or 3.

2. 2. The film forming method according to claim 1, wherein in the step of forming the vapor deposition film, the thermoelectrons generated from a thermoelectron generating unit provided between the surface of the substrate and the vapor deposition material are irradiated onto the vapor of the vapor deposition material.

3. the thermoelectron generating unit is located between the surface of the base material and the deposition material and includes an opening through which vapor of the deposition material passes, an anode located so as to surround the periphery of the opening, and a cathode located so as to surround the anode and generating the thermoelectrons; 3. The film forming method according to claim 2, wherein in the step of forming the vapor deposition film, the thermoelectrons generated from the cathode and emitted toward the anode are irradiated onto the vapor of the deposition material passing through an opening.

Images