Film forming method

Abstract

This invention discloses a film-forming method, which involves heat-treating mist in a film-forming section to form a film. The method includes: atomizing a raw material solution in an atomizing section to generate mist; conveying the mist from the atomizing section to the film-forming section via a carrier gas through a conveying section connecting the atomizing section and the film-forming section; and heat-treating the mist in the film-forming section to form a film on a substrate. When the flow rate of the carrier gas is set to Q (L / min) and the temperature of the carrier gas is set to T (°C), the flow rate and temperature of the carrier gas are controlled in the manner 7 < T + Q < 67. This provides a film-forming method with excellent film-forming speed.

Description

[0001] This invention is a divisional application of Chinese patent application No. 201980055286.4, filed on June 13, 2019, entitled "Method for Film Formation". This application claims priority to Japanese Patent Application No. 2018-158078, filed on August 27, 2018. Technical Field

[0002] This invention relates to a film-forming method using atomized raw materials to form films on a substrate. Background Technology

[0003] Previously, high-vacuum film deposition apparatuses capable of achieving non-equilibrium states using pulsed laser deposition (PLD), molecular beam epitaxy (MBE), sputtering, and other methods have been developed, enabling the fabrication of oxide semiconductors that could not be produced by previous melting methods. Furthermore, a mist chemical vapor deposition (Mist CVD, hereinafter also referred to as "mist CVD") method has been developed, which uses atomized raw materials to grow crystals on a substrate, thereby enabling the fabrication of gallium oxide (α-Ga₂O₃) with a corundum structure. As a semiconductor with a large band gap, α-Ga₂O₃ is expected to have applications in next-generation switching devices that achieve high voltage withstand, low loss, and high heat resistance.

[0004] Regarding atomization CVD, Patent Document 1 describes a tube furnace type atomization CVD apparatus. Patent Document 2 describes a microchannel type atomization CVD apparatus. Patent Document 3 describes a line source type atomization CVD apparatus. Patent Document 4 describes a tube furnace type atomization CVD apparatus, which differs from the atomization CVD apparatus described in Patent Document 1 in that it introduces carrier gas into the mist generator. Patent Document 5 describes an atomization CVD apparatus in which a substrate is provided above the mist generator, and the base is a rotating stage mounted on a heating plate.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 1-257337

[0008] Patent Document 2: Japanese Patent Application Publication No. 2005-307238

[0009] Patent Document 3: Japanese Patent Application Publication No. 2012-46772

[0010] Patent Document 4: Japanese Patent No. 5397794

[0011] Patent Document 5: Japanese Patent Application Publication No. 2014-63973 Summary of the Invention

[0012] The technical problem to be solved by the present invention

[0013] Unlike other CVD methods, atomization CVD does not require high temperatures and can also produce metastable crystal structures such as corundum structures of α-gallium oxide.

[0014] However, up to this point, the effect of carrier gas temperature has not been specifically considered. That is, it is known that if the carrier gas source is located outdoors or in an indoor room without air conditioning, the temperature of the carrier gas will change, which will have a significant impact on the film formation rate.

[0015] In response, the inventors of this invention discovered the following new problem: the generated mist condenses and condenses in the supply pipe before being transported to the substrate (the lifespan of the mist decreases), the condensed mist fails to be delivered to the film-forming section, the film-forming speed decreases, and it was found that the effect of this problem is more significant when the carrier gas flow rate is low.

[0016] Furthermore, the inventors of this invention discovered the following new problem: if the carrier gas is introduced into the supply pipe, the water vapor partial pressure in the pipe decreases, resulting in fog dissipation (evaporation), a decrease in the amount of fog participating in film formation, and a decrease in the film formation rate. Moreover, it was found that the effect of this problem is more significant when the carrier gas flow rate is large.

[0017] This invention was made to solve the above-mentioned problems, and its purpose is to provide a film-forming method with excellent film-forming speed.

[0018] Technical means to solve technical problems

[0019] The present invention was made to achieve the above-mentioned objective. The present invention provides a film-forming method, which is a film-forming method in which a mist is heat-treated in a film-forming section to form a film. The method includes: a step of atomizing a raw material solution in an atomizing section to generate mist; a step of conveying the mist from the atomizing section to the film-forming section via a conveying section connecting the atomizing section and the film-forming section by a carrier gas; and a step of heat-treating the mist in the film-forming section to form a film on a substrate. When the flow rate of the carrier gas is set to Q (L / min) and the temperature of the carrier gas is set to T (°C), the flow rate of the carrier gas and the temperature of the carrier gas are controlled in the manner of 7 < T + Q < 67.

[0020] Based on this film-forming method, the film-forming speed can be significantly improved through a simple approach.

[0021] At this point, a film-forming method can be set such that T+Q is 17 < T+Q < 57.

[0022] Therefore, it is possible to more effectively and significantly improve the film formation rate.

[0023] At this point, a film-forming method can be set such that T+Q is 27 < T+Q < 47.

[0024] This allows for a more stable increase in film formation rate.

[0025] Invention Effects

[0026] As described above, the film-forming method according to the present invention can significantly improve the film-forming speed through a simple method. Attached Figure Description

[0027] Figure 1 This is a schematic diagram illustrating an example of a film-forming apparatus used in the film-forming method of the present invention.

[0028] Figure 2 This is a diagram illustrating an example of an atomizing section in a film-forming apparatus.

[0029] Figure 3 This is a graph showing the relationship between carrier gas temperature T and film formation rate.

[0030] Figure 4 This is a graph showing the relationship between the sum of carrier gas temperature T and carrier gas flow rate Q (T+Q) and the film formation rate. Detailed Implementation

[0031] The present invention will now be described in detail, but it is not limited thereto.

[0032] As mentioned above, in the atomization CVD method, a film formation method that can significantly improve the film formation rate is sought.

[0033] The inventors of this invention have carefully studied the above-mentioned problems and found that the dissipation of mist in the conveying section can be easily suppressed by the following film-forming method, thereby extending the lifespan of the mist in the conveying section and increasing the film-forming speed, thus completing this invention. The film-forming method is a method of forming a film by heat-treating the mist in the film-forming section, which includes: a step of atomizing a raw material solution in an atomizing section to generate mist; a step of conveying the mist from the atomizing section to the film-forming section by a carrier gas via a conveying section connecting the atomizing section and the film-forming section; and a step of heat-treating the mist in the film-forming section to form a film on a substrate, wherein the flow rate of the carrier gas is set to Q (L / min) and the temperature of the carrier gas is set to T (°C), and the flow rate and temperature of the carrier gas are controlled in the manner of 7 < T + Q < 67.

[0034] The following explanation is based on the accompanying drawings.

[0035] In this invention, fog refers to the general term for liquid particles dispersed in a gas, including substances called fog, droplets, etc.

[0036] Figure 1 An example of a film-forming apparatus 101 that can be used in the film-forming method of the present invention is shown. The film-forming apparatus 101 includes: an atomizing section 120 for atomizing a raw material solution to generate mist; a carrier gas supply section 130 for supplying a carrier gas for conveying the mist; a film-forming section 140 for heat-treating the mist to form a film on a substrate; and a conveying section 109 connecting the atomizing section 120 and the film-forming section 140 and conveying the mist via the carrier gas. Furthermore, the film-forming apparatus 101 can be controlled by a control section (not shown) that controls all or part of the film-forming apparatus 101.

[0037] (Atomization Section)

[0038] In the atomizing unit 120, the raw material solution 104a is adjusted to atomize and generate mist. There are no particular limitations on the atomizing method, as long as it can atomize the raw material solution 104a; any known atomizing method can be used. However, atomizing methods utilizing ultrasonic vibrations are preferred because they allow for more stable atomization.

[0039] An example of such an atomizing section 120 is shown below. Figure 2 For example, it may include a mist source 104 containing a raw material solution 104a, a container 105 containing a medium, such as water 105a, capable of transmitting ultrasonic vibrations, and an ultrasonic vibrator 106 mounted on the bottom of the container 105. Specifically, the mist source 104, consisting of a container containing the raw material solution 104a, is housed within the container 105 containing water 105a using a support (not shown). An ultrasonic vibrator 106 is mounted on the bottom of the container 105 and connected to a vibrator 116. Furthermore, it is configured such that when the vibrator 116 is activated, the ultrasonic vibrator 106 vibrates, and ultrasonic waves are transmitted via the water 105a to the mist source 104, atomizing the raw material solution 104a.

[0040] (film-forming part)

[0041] Refer again Figure 1 In the film-forming section 140, the mist is heated to cause a thermal reaction, forming a film on a portion or the entire surface of the substrate 110. The film-forming section 140 may include, for example, a film-forming chamber 107, in which the substrate 110 is disposed, and may also include a heating plate 108 for heating the substrate 110. Figure 1The exhaust port 112 is provided on the outside of the film-forming chamber 107, as shown, or it can be provided inside the film-forming chamber 107. In addition, an exhaust port 112 is provided on the film-forming chamber 107 at a position that will not affect the supply of mist to the substrate 110.

[0042] In addition, in this invention, the substrate 110 can be disposed on the top of the film-forming chamber 107 with its surface facing down, or the substrate 110 can be disposed on the bottom surface of the film-forming chamber 107 with its surface facing up.

[0043] For thermal reactions, any reaction caused by heating of the mist is acceptable, and there are no special limitations on the reaction conditions. The temperature can be appropriately set according to the raw materials or film-forming material. For example, the heating temperature is in the range of 120–600°C, preferably in the range of 200°C–600°C, and more preferably in the range of 300°C–550°C.

[0044] The thermal reaction can be carried out under any of the following atmospheres: vacuum, oxygen-free atmosphere, reducing gas atmosphere, air atmosphere, and oxygen atmosphere. The atmosphere can be appropriately set according to the film-forming material. In addition, it can also be carried out under any of the following conditions: atmospheric pressure, pressurized atmosphere, or depressurized atmosphere. However, if film is formed under atmospheric pressure, the device structure can be simplified, so it is preferred.

[0045] (Conveying Department)

[0046] The delivery section 109 connects the atomizing section 120 and the film-forming section 140. Mist is transported by carrier gas from the mist generation source 104 of the atomizing section 120 to the film-forming chamber 107 of the film-forming section 140 via the delivery section 109. The delivery section 109 can be, for example, formed as a supply pipe 109a. For example, a quartz tube or a resin tube can be used as the supply pipe 109a.

[0047] (Raw material solution)

[0048] The raw material solution 104a is not particularly limited as long as it contains atomizable materials; it can be inorganic or organic. Metals or metal oxides are suitable, and substances containing one or more metals selected from gallium, iron, indium, aluminum, vanadium, titanium, chromium, rhodium, nickel, and cobalt can be used.

[0049] The raw material solution 104a is not particularly limited to any substance capable of atomizing the aforementioned metal, but it is suitable to use a substance that dissolves or disperses the aforementioned metal in an organic solvent or water in the form of a complex or salt as the raw material solution 104a. Examples of complex forms include acetylacetone complexes, carbonyl complexes, ammonia complexes, and hydrogenated complexes. Examples of salt forms include metal chloride salts, metal bromide salts, and metal iodide salts. Furthermore, an aqueous solution of the salt can also be used, formed by dissolving the aforementioned metal in hydrobromic acid, hydrochloric acid, hydroiodic acid, etc.

[0050] Furthermore, additives such as hydrohalic acid or oxidizing agents may be mixed into the raw material solution 104a. Examples of hydrohalic acids include hydrobromic acid, hydrochloric acid, and hydroiodic acid, with hydrobromic acid or hydroiodic acid being preferred. Examples of oxidizing agents include peroxides such as hydrogen peroxide (H₂O₂), sodium peroxide (Na₂O₂), barium peroxide (BaO₂), and benzoyl peroxide (C₆H₅CO)₂O₂, as well as organic peroxides such as hypochlorous acid (HClO), perchloric acid, nitric acid, ozone water, peracetic acid, or nitrobenzene.

[0051] Furthermore, the raw material solution may contain dopants. The dopants are not particularly limited. Examples include n-type dopants such as tin, germanium, silicon, titanium, zirconium, vanadium, or niobium, or p-type dopants such as copper, silver, tin, iridium, and rhodium. The concentration of the dopants may, for example, be approximately 1 × 10⁻⁶. 16 / cm 3 ~1×10 22 / cm 3 It can also be set to approximately 1×10 17 / cm 3 The following low concentrations can also be set to 1×10. 20 / cm 3 The above are high concentrations.

[0052] (Matrix)

[0053] The substrate 110 is not particularly limited as long as it can form a film and support the film. The material of the substrate 110 is also not particularly limited; known substrates can be used, including organic and inorganic compounds. Examples include polysulfone, polyethersulfone, polyphenylene sulfide, polyetheretherketone, polyimide, polyetherimide, fluoropolymer, iron or aluminum, stainless steel, gold and other metals, silicon, sapphire, quartz, glass, gallium oxide, etc., but it is not limited to these. The shape of the substrate is not limited to any shape; any shape is effective. Examples include plate-shaped (such as flat or round plates), fibrous, rod-shaped, cylindrical, prismatic, tubular, spiral, spherical, or annular shapes, but in this invention, a plate-shaped substrate is preferred. The thickness of the plate-shaped substrate is not particularly limited, but is preferably 10–2000 μm, more preferably 50–800 μm. When the substrate is plate-shaped, its area is preferably 100 mm². 2 More preferably, the diameter is 2 inches (50 mm) or more.

[0054] (Carrier Gas Supply Department)

[0055] The carrier gas supply unit 130 includes a carrier gas source 102a for supplying carrier gas, and may also include a flow regulating valve 103a for regulating the flow rate of the carrier gas (hereinafter referred to as "main carrier gas") output from the carrier gas source 102a. In addition, a dilution carrier gas source 102b for supplying dilution carrier gas and a flow regulating valve 103b for regulating the flow rate of the dilution carrier gas output from the dilution carrier gas source 102b may be included as needed.

[0056] There are no specific limitations on the type of carrier gas; it can be appropriately selected based on the film-forming material. Examples include inert gases such as oxygen, ozone, nitrogen, and argon, or reducing gases such as hydrogen or forming gases. Furthermore, there can be one or more types of carrier gas. For instance, a diluted gas (e.g., diluted 10 times) obtained by diluting the same gas as the first carrier gas with another gas can be used as a second carrier gas; air can also be used.

[0057] Furthermore, the carrier gas can be supplied from one location or more than two locations.

[0058] In this invention, the carrier gas flow rate Q refers to the total flow rate of the carrier gas. In the above example, the total flow rate of the main carrier gas output from carrier gas source 102a and the flow rate of the dilution carrier gas output from dilution carrier gas source 102b is defined as the carrier gas flow rate Q.

[0059] There is no particular limitation on the flow rate Q of the carrier gas. For example, when forming a film on a 30 mm square substrate, it is preferably set to 0.01 to 60 L / min, and more preferably to 1 to 30 L / min.

[0060] (Carrier Gas Temperature Control Unit)

[0061] The film-forming apparatus 101 includes a carrier gas temperature control unit 150 that allows for adjustment of the carrier gas temperature T. The method for controlling the carrier gas temperature T is not particularly limited. For example, a method of winding a pipe containing water at a regulated temperature around the carrier gas pipe section can be used. Alternatively, heating can be achieved by installing a heating jacket, heating the pipe section with infrared radiation, etc. Furthermore, when the control is at a low temperature, cooling can be achieved by arranging the carrier gas pipe in a freezing chamber, or by directly cooling the pipe section using refrigerants such as liquid nitrogen or Freon, or indirectly cooling it via the pipe. When the carrier gas sources 102a and 102b are containers, the temperature of the container itself can be controlled using the methods described above, or the carrier gas temperature T can be controlled by controlling the temperature of the chamber in which the container is located.

[0062] like Figure 1As shown, the temperature T of the carrier gas can be easily supplied to the conveying unit 109 by controlling the temperature of the carrier gas in the carrier gas supply unit 130. Therefore, it is preferred. However, as long as the temperature T of the carrier gas can be controlled quickly, the temperature of the carrier gas can also be controlled at the connection between the carrier gas supply unit 130 and the conveying unit 109 and / or at the connection between the carrier gas supply unit 130 and the atomizing unit 120.

[0063] The present invention is characterized by using the temperature T and flow rate Q of the carrier gas as parameters, controlling T and Q respectively, so that T+Q is within a specified range for film formation. T+Q will be described in detail later.

[0064] (Film-forming method)

[0065] Next, refer to the following: Figure 1 An example of the film-forming method of the present invention will be described below.

[0066] First, the raw material solution 104a is collected in the mist generation source 104 of the atomizing section 120, and the substrate 110 is placed directly on the heating plate 108 or placed on the heating plate 108 through the wall of the film forming chamber 107, so that the heating plate 108 is working.

[0067] In addition, the carrier gas temperature control unit 150 heats or cools the carrier gas to control the temperature T of the carrier gas.

[0068] Next, the flow regulating valves 103a and 103b are opened to supply the carrier gas from the carrier gas sources 102a and 102b into the film-forming chamber 107. The atmosphere in the film-forming chamber 107 is fully replaced by the carrier gas, and the flow rates of the main carrier gas and the dilution carrier gas are adjusted at the same time to control the flow rate Q of the carrier gas.

[0069] In the mist generation process, the ultrasonic vibrator 106 is vibrated, and its vibration is transmitted to the raw material solution 104a through water 105a, thereby atomizing the raw material solution 104a to generate mist. Next, in the mist conveying process via carrier gas, the mist is conveyed from the atomization section 120 to the film forming section 140 via the conveying section 109, and then introduced into the film forming chamber 107. In the film forming process, the mist introduced into the film forming chamber 107 is heat-treated by the heating plate 108 in the film forming chamber 107, thereby undergoing a thermal reaction and forming a film on the substrate 110.

[0070] The inventors of this invention investigated the effect of carrier gas flow rate Q and carrier gas temperature T on film formation rate, and the results are described here.

[0071] Using the above-described film formation method, the relationship between carrier gas flow rate Q (L / min), carrier gas temperature T (°C), and film formation rate (μm / hour) was investigated. Figure 3The results are shown in the figure. The vertical axis is taken as the film formation rate and the horizontal axis as the carrier gas temperature T, and plots are made for each carrier gas flow rate Q.

[0072] Assuming a carrier gas flow rate Q = 5.5 L / min, the film formation rate reaches its maximum at approximately 40°C, and then rapidly decreases between approximately 0°C and approximately 60°C. Similarly, at a carrier gas flow rate Q = 22 L / min, the rate reaches its maximum at approximately 20°C, and then rapidly decreases between approximately -15°C and approximately 45°C. At a carrier gas flow rate Q = 44 L / min, the rate reaches its maximum at approximately -5°C, and then rapidly decreases between approximately -35°C and approximately 25°C.

[0073] Therefore, the optimal temperature range of the carrier gas varies depending on the carrier gas flow rate Q.

[0074] However, when the carrier gas temperature is set to T (°C) and the carrier gas flow rate is set to Q (L / min), if the relationship between T+Q and film formation rate is adjusted, it is surprisingly found that regardless of the carrier gas flow rate Q and the carrier gas temperature T, the film formation rate reaches its maximum at around T+Q of 40°C, and the film formation rate drops rapidly when T+Q is below 7°C or above 67°C. Figure 4 In other words, it can be seen that when the carrier gas temperature is set to T (°C) and the carrier gas flow rate is set to Q (L / min), as long as the relationship 7 < T + Q < 67 is satisfied, a high film formation rate can be stably achieved regardless of the values ​​of T and Q.

[0075] As described above, according to the present invention, when the temperature of the carrier gas is set to T (°C) and the flow rate of the carrier gas is set to Q (L / min), by controlling the temperature T and the flow rate Q of the carrier gas in the manner of 7 < T + Q < 67, the condensation and evaporation of mist at the conveying section 109 can be suppressed, thereby improving the film formation rate. The range of T + Q is preferably 17 < T + Q < 57, which can more reliably and significantly improve the film formation rate. More preferably, it is 27 < T + Q < 47, which can further stabilize and increase the film formation rate.

[0076] When 7 ≥ T + Q, i.e., 7 - Q ≥ T, the water vapor in the pipeline of the conveying section 109 is supersaturated. The supersaturated water vapor condenses around the fog nucleus. It is assumed that the fog becomes thicker and the settling velocity increases. A large amount of fog settles and condenses in the pipeline, reducing the amount of fog sent to the film-forming section, resulting in a decrease in the film-forming velocity.

[0077] Furthermore, when T+Q≥67, i.e., T≥67-Q, the saturated water vapor pressure inside the pipe of the conveying section 109 increases. It is assumed that in order to utilize water vapor to evaporate the saturated mist inside the pipe, the amount of mist delivered to the film-forming section will decrease, resulting in a decrease in the film-forming rate. Although the total amount of water delivered to the film-forming section remains the same, the amount of mist capable of participating in film formation is reduced.

[0078] In addition, the temperature T of the carrier gas is the temperature of the carrier gas in the conveying section 109. In order to suppress the reduction of mist in the conveying section 109, it is desirable to satisfy the relationship 7 < T + Q < 67 throughout the entire area of ​​the conveying section 109.

[0079] For the temperature T of the carrier gas, it is preferable to directly measure the temperature of the carrier gas at the connection between the carrier gas supply section 130 and the conveying section 109 and / or the connection between the carrier gas supply section 130 and the atomizing section 120. However, under stable conditions, the temperature of the outer wall of the pipe at that location can also be used instead.

[0080] Sometimes, depending on the length of the conveying section 109 or the environment in which the conveying section 109 is installed, the temperature change of the carrier gas can be ignored, and it is not always necessary to adjust the temperature of the conveying section 109. However, if a temperature regulating device is provided in the conveying section 109 for temperature control, T+Q can be controlled more stably, which is therefore preferable. Furthermore, it is even more preferable to perform temperature measurement at the connection between the conveying section 109 and the film-forming section 140, thereby controlling the carrier gas temperature T. As a result, T+Q can be controlled more stably.

[0081] Furthermore, as long as the relationship 7 < T + Q < 67 is satisfied, it is not necessary for the carrier gas temperature T to remain constant throughout the entire conveying section. For example, 7 < T + Q < 67 can be modified to 7 - Q < T < 67 - Q, allowing variation within a range corresponding to the set carrier gas flow rate Q.

[0082] Example

[0083] The present invention will be described in detail below with reference to specific embodiments, but the present invention is not limited to these embodiments.

[0084] (Example 1)

[0085] According to the above film formation method, gallium oxide (α-Ga2O3) with a corundum structure is formed.

[0086] Specifically, firstly, a 0.1 mol / L gallium bromide aqueous solution is adjusted to contain 48% hydrobromic acid solution at a volume ratio of 10%, and this solution is used as the raw material solution 104a.

[0087] The raw material solution 104a obtained in the above manner is placed in the mist generation source 104. The temperature of the solution at this time is 25°C. Next, a 4-inch (100 mm in diameter) c-side sapphire substrate is placed as a substrate 110 in the film forming chamber 107 adjacent to the heating plate 108, and the heating plate 108 is activated to raise the temperature to 500°C.

[0088] Next, flow regulating valves 103a and 103b are opened to supply oxygen from carrier gas sources 102a and 102b into the film-forming chamber 107, fully replacing the atmosphere in the film-forming chamber 107. Simultaneously, the flow rate of the main carrier gas is adjusted to 5 L / min, and the flow rate of the dilution carrier gas is adjusted to 0.5 L / min. That is, the carrier gas flow rate Q = 5.5 L / min.

[0089] As a carrier gas temperature control unit 150, a pipe of water with regulated temperature is wound around the carrier gas supply pipe, thereby adjusting the carrier gas temperature T.

[0090] In Example 1, the temperature T of the carrier gas is set to 45°C. That is, T + Q = 50.5.

[0091] Next, the ultrasonic vibrator 106 is vibrated at 2.4 MHz, and the vibration is transmitted to the raw material solution 104a via water 105a, thereby atomizing the raw material solution 104a to generate mist. The mist is introduced into the film-forming chamber 107 via a carrier gas supply pipe 109a. Then, under atmospheric pressure and 500°C, the mist undergoes a thermal reaction in the film-forming chamber 107, forming a gallium oxide (α-Ga2O3) thin film with a corundum structure on the substrate 110. The film formation time is 30 minutes.

[0092] The growth rate was evaluated as follows: First, for the thin film on the substrate 110, 17 points within the surface of the substrate 110 were used as measurement sites, and the film thickness was measured using a profilometer. The average film thickness was calculated from the individual film thickness values. The film formation rate was obtained by dividing the obtained average film thickness by the film formation time.

[0093] (Comparative Example 1)

[0094] Except that the carrier gas temperature T was set to 74°C, i.e., T+Q=79.5, film formation and evaluation were carried out under the same conditions as in Example 1.

[0095] (Example 2)

[0096] Except that the flow rate of the main carrier gas was adjusted to 20 L / min and the flow rate of the dilution carrier gas was adjusted to 2 L / min, so that the carrier gas flow rate Q = 22 L / min, and the temperature of the carrier gas T was set to 10°C, i.e., T + Q = 32, the film formation and evaluation were carried out under the same conditions as in Example 1.

[0097] (Comparative Example 2)

[0098] Except that the temperature T of the carrier gas was set to 55°C, i.e., T+Q=77, film formation and evaluation were carried out under the same conditions as in Example 2.

[0099] (Example 3)

[0100] Except that the flow rate of the main carrier gas was adjusted to 40 L / min and the flow rate of the dilution carrier gas was adjusted to 4 L / min, so that the carrier gas flow rate Q = 44 L / min, and the temperature T of the carrier gas was set to 20°C, i.e., T + Q = 64, film formation and evaluation were carried out under the same conditions as in Example 1.

[0101] (Comparative Example 3)

[0102] Except that the temperature T of the carrier gas was set to 35°C, i.e., T+Q=79, film formation and evaluation were carried out under the same conditions as in Example 3.

[0103] Table 1 shows the conditions of Examples 1-3 and Comparative Examples 1-3, and the results of evaluating the film formation rate.

[0104] [Table 1]

[0105]

[0106] A comparison of Example 1 with Comparative Example 1, Example 2 with Comparative Example 2, and Example 3 with Comparative Example 3, all with the same carrier gas flow rate, clearly shows that the film formation rate differs significantly from other cases when 7 < T + Q < 67. Furthermore, as long as 7 < T + Q < 67 is satisfied, a high film formation rate can be achieved regardless of the values ​​of T and Q.

[0107] The film formation rate can be significantly improved through a simple method.

[0108] Furthermore, this invention is not limited to the embodiments described above. The embodiments described above are illustrative examples, and any technical solution having a structure substantially the same as the technical concept described in the claims of this invention and achieving the same effect is included within the technical scope of this invention.

Claims

1. A film-forming apparatus, wherein a film-forming apparatus is formed by heat-treating mist in a film-forming section, characterized in that, have: The atomizing section generates mist by atomizing the raw material solution. The carrier gas supply unit supplies the carrier gas used for transporting fog. Film-forming part that forms a film on a substrate by heat treatment of fog. A delivery unit that connects the atomizing section and the film-forming section and delivers the mist via a carrier gas, and A control unit that controls the film-forming apparatus. When the flow rate of the carrier gas supplied to the film-forming section is set to Q, in L / min, and the temperature of the carrier gas is set to T, in °C, the control unit controls the flow rate Q of the carrier gas supplied to the film-forming section and the temperature T of the carrier gas during film formation in a manner where 7 < T + Q < 67 and the flow rate Q is 0.01 to 60 L / min.

2. The film forming apparatus according to claim 1, wherein The control unit controls the flow rate Q and temperature T of the carrier gas supplied to the film-forming section in the manner of 17 < T + Q < 57.

3. The film forming apparatus according to claim 1, wherein The film-forming section includes a film-forming chamber, and a heating plate for heating the substrate is disposed outside or inside the film-forming chamber.

4. The film forming apparatus according to claim 1, wherein The carrier gas supply unit is equipped with a flow regulating valve for adjusting the flow rate of the carrier gas.

5. The film forming apparatus according to claim 1, wherein The film-forming apparatus has a carrier gas temperature control unit on the carrier gas supply pipeline for adjusting the temperature of the carrier gas.

6. The film-forming apparatus according to claim 1, characterized in that, The film-forming apparatus includes a carrier gas temperature control unit for adjusting the temperature of the carrier gas, and the carrier gas temperature control unit is disposed at the connection between the carrier gas supply unit and the conveying unit and / or the connection between the carrier gas supply unit and the atomizing unit.

7. The film-forming apparatus according to claim 1, characterized in that, The control unit controls the temperature T of the carrier gas based on the temperature measured at the outer wall of the pipe connecting the carrier gas supply unit and the delivery unit and / or the outer wall of the pipe connecting the carrier gas supply unit and the atomizing unit.

8. The film-forming apparatus according to any one of claims 1 to 7, characterized in that, The control unit further controls the temperature T of the carrier gas based on the temperature measured at the connection between the conveying unit and the film-forming unit.

9. A method for manufacturing a film-forming substrate, characterized in that, Using the film-forming apparatus according to any one of claims 1 to 8, gallium oxide having a corundum structure is formed on the substrate.

10. A method for manufacturing a film-forming substrate, wherein a film is formed on a substrate by heat-treating a mist in a film-forming section, characterized in that, include: The process of atomizing the raw material solution to generate mist in the atomization section; The process of conveying the mist from the atomizing section to the film-forming section via a carrier gas through a conveying section that connects the atomizing section and the film-forming section; as well as The process of heat-treating the mist in the film-forming section to form a film on the substrate. When the flow rate of the carrier gas is set to Q (in L / min) and the temperature of the carrier gas is set to T (in °C), the flow rate Q and the temperature T of the carrier gas are controlled in the manner of 7 < T + Q < 67. The heating temperature for heat treatment of the mist in the film-forming process is set to 120~600℃. The flow rate Q of the carrier gas is set to 0.01~60 L / min.

11. The method of manufacturing a film- forming substrate according to claim 10, wherein The temperature T of the carrier gas is controlled by controlling the temperature of the room containing the container for holding the carrier gas.

12. The method of manufacturing a film- forming substrate according to claim 10, wherein The raw material solution is a solution prepared by dissolving one or more metals selected from gallium, iron, indium, aluminum, vanadium, titanium, chromium, rhodium, nickel and cobalt in hydrobromic acid, hydrochloric acid or hydroiodic acid.

13. A semiconductor film manufacturing apparatus that performs heat treatment on mist at a film formation section to perform film formation of a semiconductor film, characterized by comprising: have: The atomizing section generates mist by atomizing the raw material solution. The carrier gas supply unit supplies the carrier gas used for transporting fog. Film-forming part that forms a film on a substrate by heat treatment of fog. A delivery unit that connects the atomizing section and the film-forming section and delivers the mist via a carrier gas, and A control unit that controls the manufacturing apparatus. The control unit controls the flow rate Q (in L / min) and temperature T (in °C) of the carrier gas in such a way that water vapor does not condense around the mist in the pipeline of the conveying unit and the mist does not evaporate.

14. A method for manufacturing a semiconductor film, which is a method for manufacturing a semiconductor film by heat-treating mist at a film formation portion, characterized by comprising: include: The process of atomizing the raw material solution to generate mist in the atomization section; The process of conveying the mist from the atomizing section to the film-forming section via a carrier gas through a conveying section that connects the atomizing section and the film-forming section; as well as The process of heat-treating the mist in the film-forming section to form a film on the substrate. In the manufacturing method, the flow rate Q of the carrier gas (in L / min) and the temperature T of the carrier gas (in °C) are controlled in such a way that water vapor will not condense around the mist in the pipeline of the conveying section and the mist will not evaporate.

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