TW201700183A - Film forming method and film forming apparatus comprising a substrate, a vacuum pump, a storage container, a nozzle, and a liquid pressurizing unit - Google Patents

Abstract

The present invention provides a method for forming a film having endurance at a low cost. The film-forming method uses a film-forming apparatus (1) comprising a substrate (100) configured at the internal lower side of a vacuum container (11), a vacuum pump (15) for exhausting the inside of container (11), a storage container (23) disposed outside the container (11) and storing a film-forming agent solution (21) therein, a nozzle 17 provided with a discharging unit (19) for discharging film-forming agent solution (21) at one end, and a liquid pressurizing unit (gas supply source (29), etc.) for pressurizing the film-forming agent solution (21) which is stored in the storage container (23). The film-forming agent solution (21) is a solution composed of two or more materials, the solution comprising a first material (S1) and a second material (P2) having a vapor pressure (P2) higher than the vapor pressure (P1) of the first material (S1), and the concentration of the first material is 0.01wt% or more. The film-forming agent solution (21) is discharged onto the substrate at a discharge pressure of 0.05 to 0.3 MPa in an atmosphere at a pressure of P2 or more (excluding a pressure one magnitude of order higher than P2).

Description

Film forming method and film forming device

The present invention relates to a film forming method and apparatus capable of forming a film in a vacuum. The thin film includes, for example, an organic film, an inorganic film, or the like.

A wet method such as a coating method or a dipping method is known as a film forming method for forming a thin film, for example, an organic film or an inorganic film, on the surface of a substrate. For example, Patent Document 1 proposes a film forming method in which a mark (scratch) having a depth of 10 to 400 nm is formed on a surface of a substrate such as glass or plastic in the atmosphere to have a stripe having a predetermined direction. A fine uneven surface of a shape is formed, and then a coating liquid (diluted solution) prepared by a predetermined composition is applied and dried to form an antifouling film (organic film) having a predetermined composition on the fine uneven surface. Further, Patent Document 2 proposes a film forming method in which a titanium oxide particle is mixed in water to form a suspension, and after further adjusting to a specific pH, the suspension is applied onto a support and dried. Thus, an inorganic titanium oxide film (inorganic film) was formed.

Prior art literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. Hei 9-309745

Patent Document 2: Japanese Patent Laid-Open No. Hei 6-293519

The coating liquid and the suspension used in the wet method use a dilute solution having a low solute concentration. Therefore, the density of the film obtained after heat drying is low, and there is a problem that the function of the formed film is likely to disappear. For example, in the antifouling film coated by the wet method, the film formed on the outermost surface is easily scraped off by wiping, and the oil repellency sometimes disappears.

On the other hand, a film forming method of forming a thin film on a substrate by a vacuum vapor deposition method (dry method) is also considered. When this method is used, it is necessary to form a high vacuum condition at the time of film formation, and an expensive vacuum exhaust system is required. As a result, it is difficult to achieve film formation at a low cost.

According to an aspect of the invention, it is possible to provide a film forming method and apparatus capable of forming a film having durability at a low cost.

The term "discharge" as used in the present invention means that the liquid is directly ejected in a liquid state. "Discharge" also includes a "spray" that allows the liquid to be dispersed. Further, in the "discharge", the physical state and the chemical state of the raw material in the liquid do not change before and after the discharge. Therefore, the principle of "discharge" differs from the principle of CVD in which the physical state of the raw material changes from liquid or solid to vapor deposition of the gas and chemical state of the raw material changes.

The present inventors have found that, at a specific pressure (Pc) (a pressure of P2 or more (excluding a pressure higher than one order of P2), and discharge of a solution at a predetermined discharge pressure, A film having durability is formed, and the solution is composed of two or more materials including a first material (S1) and a second material (S2) having a vapor pressure (P2) higher than a vapor pressure (P1) of the S1. The concentration of the first material (hereinafter also referred to as "S1 concentration") is adjusted. Also found that Since the specific pressure Pc discharged from the solution is mostly in a medium vacuum or a low vacuum region, the film having durability can be formed at a low cost as compared with the vapor deposition method in which high vacuum conditions are required at the time of film formation, thereby completing the present invention. invention.

According to the first aspect of the invention (first invention), it is possible to provide a film formation method of a film having the following constitution. This film formation method is premised on forming a thin film on a substrate in a vacuum. Therefore, the solution contains two or more kinds of materials (for example, the first material (S1), the second material (S2), the third material (S3), ..., etc.. The same applies to the solution). In the atmosphere of the pressure (Pc) set by the vapor pressure (for example, P1, S2, S3, ..., etc.) of each material (for example, S1, S2, S3, ..., etc.) This solution is discharged onto the substrate.

According to the second aspect (second invention) of the present invention, it is possible to provide a film forming apparatus having a film having the following configuration. The film forming apparatus is configured to form a thin film on a substrate in a vacuum, and includes a vacuum container in which a substrate as a film forming article is disposed, an exhaust unit that exhausts the inside of the vacuum container, and two or more types of storage. A storage container for the solution of the material, and a nozzle for discharging the solution onto the substrate disposed inside the vacuum container. The apparatus is characterized in that when the pressure in the vacuum vessel reaches a pressure (Pc) set based on the vapor pressure of each material constituting the solution, the solution is discharged from the nozzle onto the substrate.

In addition to the above, in the present invention (the first invention and the second invention), as the solution discharged onto the substrate, a vapor pressure including the first material (S1) and having a vapor pressure (P1) higher than the S1 is used. The second material (S2) of (P2) is used as a material constituting the solution, and a solution having a S1 concentration of a predetermined value (0.01% by weight or more) is adjusted. Therefore, it is characterized in that when the atmospheric pressure (Pc) is P2 or more (excluding a pressure higher than one order of magnitude higher than P2), the row is within a predetermined range (0.05 to 0.3 MPa). The solution was discharged onto the substrate under pressure.

In the second aspect of the invention, the substrate as the film formation article may be disposed below the inside of the vacuum container (that is, below the vertical direction) and on the side of the inside of the vacuum container (that is, the side in the horizontal direction). For the front end (discharge portion) of the nozzle, when the substrate is disposed below the inside of the vacuum container, it is provided so that the solution can be discharged downward (vertical or oblique) (hereinafter also referred to simply as "the discharge direction of the solution faces downward". Further, when the substrate is disposed on the side of the inside of the vacuum container, it is only necessary to discharge the solution in the lateral direction (level or inclination) (hereinafter also referred to simply as "the discharge direction of the solution is in the lateral direction"). That is, in the second invention, the installation position of the discharge portion is not limited.

The same applies to the first invention, and the discharge direction of the solution may be either downward or in the transverse direction.

In the second aspect of the invention, an in line method including a transport mechanism for transporting the substrate may be employed. In the first invention, if the film formation is performed by an automated method having a transport mechanism, productivity is improved, which is advantageous.

According to the first aspect of the invention, the solution containing the two or more materials including S1 and S2 (wherein the relationship between P1 of S1 and P2 of S2 is P1 < P2) and the concentration of S1 is adjusted is equal to or higher than the atmospheric pressure Pc (P2). When the pressure is not more than one order of magnitude higher than P2, it is discharged to the film formation target (substrate) at a discharge pressure of a predetermined range. When the solution is discharged under the pressure Pc, S2 is volatilized on the substrate, but S1 does not volatilize. Therefore, the film formed on the substrate has a high density. In other words, according to the first aspect of the invention, it is possible to form a film having durability at a low cost.

According to the second invention, it is configured to include S1 and S2 (where The relationship between the P1 of S1 and the P2 of S2 is two or more materials of P1<P2), and the solution adjusted with the S1 concentration is specified when the atmospheric pressure is P2 or more (excluding a pressure higher than one order of P2). The discharge pressure of the range is discharged from the nozzle to the film formation target (substrate). When the pressure in the vacuum vessel is Pc, even if the solution is discharged, S2 will volatilize, but S1 will not volatilize. Therefore, the film formed on the substrate has a high density. In other words, according to the second aspect of the invention, it is possible to form a film having durability at a low cost.

1‧‧‧ film forming device

11‧‧‧Vacuum container

13‧‧‧Pipe

15‧‧‧Vacuum pump (exhaust unit)

16‧‧‧ Controller

17‧‧‧Nozzles

18‧‧‧ Pressure detection unit

19‧‧‧Exporting Department

21‧‧‧filming agent solution

23‧‧‧ storage container

25‧‧‧ Infusion tube

26‧‧‧ Valve

27‧‧‧Pipe

29‧‧‧ gas supply

31‧‧‧Substrate support

33‧‧‧Roll (transport mechanism)

100‧‧‧Substrate

Fig. 1 is a schematic cross-sectional view showing an example of a film forming apparatus which can carry out the method of the present invention.

Hereinafter, embodiments of the above invention will be described based on the drawings.

<Configuration Example of Film Forming Apparatus>

First, an example of the film forming apparatus (the apparatus of the present invention) of the present invention (the case where the discharge direction of the solution faces downward) will be described.

As shown in Fig. 1, a film forming apparatus 1 as an example of the apparatus of the present invention includes a vacuum vessel 11 in which a substrate 100 as a film-forming object is disposed. In the present embodiment, the vacuum vessel 11 is formed of a hollow body having a substantially rectangular parallelepiped shape, but the present invention is not limited to this shape.

An exhaust port for exhaust gas (not shown) is provided in the vicinity of the lower end of the side wall of the vacuum vessel 11. The exhaust port is connected to one end of the pipe 13, and the other end of the pipe 13 is connected to a vacuum pump 15 (exhaust unit). For the vacuum pump 15, in this example, it is a pump capable of producing a vacuum state of about atmospheric pressure to medium vacuum (0.1 Pa to 100 Pa). For example, a rotary pump (oil rotary vacuum pump) or the like. Although a turbo molecular pump (TMP), an oil diffusion pump, or the like can produce a vacuum state of a high vacuum (less than 0.1 Pa), it is not necessary to use a pump that introduces a high cost. Therefore, in this example, the device can be made inexpensive.

The vacuum pump 15 is operated in accordance with a command from the controller 16 (control unit), and the degree of vacuum (pressure) in the container 11 is lowered by the pipe 13. The vacuum vessel 11 is provided with a pressure detecting unit 18 (pressure gauge or the like) that detects the pressure in the container 11. The information of the pressure in the container 11 detected by the pressure detecting unit 18 is sequentially output to the controller 16. When the controller 16 determines that the pressure in the container 11 has reached a predetermined value, it transmits an operation command to the gas supply source 29 (see below).

In addition, for example, a flow rate adjustment unit such as a mass flow controller (Mass Flow Controller: MFC) is monitored under the supervision of a pressure control unit (not shown) such as an automatic pressure controller (APC). The gas in the container 11 can be controlled by introducing a gas such as argon into the container 11. Further, a configuration in which a valve (not shown) is provided in a line connecting the exhaust port of the container 11 and the pipe 13 of the pump 15 can be used to control the container 11 by adjusting the opening degree of the valve while the pump 15 is operating. The pressure inside.

In this example, an opening/closing door (not shown) as an insulating unit that can be opened and closed may be provided below the side wall of the vacuum container 11, and a load lock chamber (not shown) may be connected through the opening and closing door. ).

In this example, one end of the nozzle 17 is inserted downward in the upper portion of the inside of the vacuum container 11, and the other end of the nozzle 17 is exposed outside the container 11. One end of the nozzle 17 existing inside the container 11 is connected to the discharge portion 19. It should be noted that the number (number) of the nozzles 17 inserted into the container 11 is not limited. According to the size of the container 11, Two or more nozzles 17 are sometimes used in the single container 11. In this example, when the extending direction of the nozzle 17 is the central axis, the discharge portion 19 can be configured to be able to form the film forming agent solution 21 at an angle θ of, for example, 30 degrees or more and 80 degrees or less with respect to the central axis. Shape or fan shape spray. Solution-like particles having a size of, for example, several hundred μm are discharged from the discharge portion 19.

The other end of the nozzle 17 exposed to the outside of the container 11 is connected to the other end of the infusion tube 25. One end of the infusion tube 25 is inserted into the inside of the storage container 23 in which the film-forming agent solution 21 is sealed. Therefore, when the valve 26 is opened, the film forming agent solution 21 is sent out from the storage container 23 through the infusion tube 25, and is discharged from the discharge portion 19 connected to one end of the nozzle 17 to the inside of the container 11.

In the present example, one end of the gas supply pipe 27 for pressurizing the liquid surface in the container 23 is connected to the storage container 23, and the other end thereof is connected to the gas supply source 29.

The gas supply source 29 is operated in accordance with a command from the controller 16, and supplies gas to the inside of the pipe 27 to pressurize the liquid surface of the storage container 23. Thus, in this example, the liquid level of the storage container 23 is pressurized, and the film forming agent solution 21 is pressure-fed into the infusion tube 25. In the present invention, the method of outputting the solution 21 by such pressure is not limited.

A substrate holder 31 that holds the substrate 100 as a film formation target is disposed below the inside of the vacuum container 11. In this example, the substrate holder 31 is supported by a transport mechanism including two or more rollers 33, 33, ..., etc., and the substrate holder 31 can be moved inside the container 11 by the operation of the transport mechanism. It should be noted that in addition to the movement of the straight line (this example), the movement here also includes rotation. In the case of rotation, for example, the substrate holder 31 may be configured in the form of a turntable or the like. Inside the substrate holder 31 The surface has a concave substrate holding surface, and when the film is formed, the back surface of the substrate 100 (either single or two or more) as a film formation is brought into contact with the substrate 100 to hold the substrate 100.

In the present invention, the distance D between the discharge portion 19 and the substrate 100 is not particularly limited as long as the film forming agent solution 21 discharged from the discharge portion 19 in a liquid form can reach the substrate 100 in a liquid form. This is because the film forming agent solution 21 can reach the substrate 100 from the discharge portion 19 by the direction of the discharge portion 19, the initial velocity of the film forming agent solution 21 when discharged from the discharge portion 19, and the film forming agent solution 21. The second material (S2, described later) contained therein changes in vapor pressure (P2) at normal temperature for various reasons.

In the present example in which the discharge direction of the film forming agent solution 21 is downward, by adjusting the arrangement of the discharge portion 19 and the substrate holder 31, the distance D is about 300 mm or less, and it is easy to achieve sufficient film strength of the obtained film, and it is easy to make it possible. Increased durability.

In the present example in which the discharge direction of the film forming agent solution 21 is downward, by arranging the discharge portion 19 so that the distance D to the substrate 100 is 150 mm or more, a sufficient effective discharge range of the film forming agent solution 21 can be secured, which is advantageous. The useless consumption of the film forming agent solution 21 is suppressed, and as a result, the cost reduction of the film formation can be more advantageous.

In the case of the present example in which the discharge direction of the film forming agent solution 21 is downward, when the distance D is too far, the diluent (solvent) of the film forming agent solution 21 is volatilized during discharge, and after reaching the substrate, The leveling becomes difficult to occur, whereby the film distribution becomes uneven, and the film properties sometimes decrease. When the distance D is too close, the effective discharge region becomes narrow, and thus the useless consumption of the film-forming agent solution 21 increases, and film spots may also occur.

The controller 16 first has a pressure control function inside the container to make true The air pump 15 and the pressure detecting unit 18 operate to adjust the degree of vacuum inside the container 11 (i.e., the pressure at the start of film formation) to an appropriate state. At the same time, it also has a liquid level pressure control function for adjusting the pressure applied to the gas supplied from the gas supply source 29 to the liquid surface in the storage container 23. In addition, the controller 16 also has a function of controlling the operation and stop of the transport mechanism including two or more rollers 33 and the like.

<film formation example>

Next, an example of the film formation method (method of the present invention) of the present invention using the film formation apparatus 1 will be described.

(1) First, the film forming agent solution 21 is prepared. In this example, a case where the film forming agent solution 21 is composed of a solution containing two materials of the first material (S1) and the second material (S2) will be described as an example, and in the following description, S1 and S2 are passed. In the comparison, the component of the film-forming material (constituting material of the film) is S1, and the component (liquid) in which S1 is dissolved is referred to as S2.

It should be noted that S1 also includes a liquid in addition to a solid such as a powder.

In the case where the solution 21 is composed of a mixed system of a liquid (for example, liquid A) and a liquid (for example, liquid B), in the solution 21, the concentration (presence or ratio) of the liquid A is higher than the concentration of the liquid B (specifically When the concentration of the liquid A is a high concentration of more than 50% by weight, the liquid A constitutes S1 as long as the liquid A is a component of a film-forming material (constituting material of the film). That is, the concentration in the solution itself does not determine the difference between S1 and S2.

As an example of a film, an organic film and an inorganic film exist. Further, an organic-inorganic hybrid film formed of a material having both an organic component and an inorganic component is also included. As such a film, there are an antifouling film, a waterproof film, a moisture proof film, An organic EL film, a titanium oxide film, or the like, as a constituent raw material (corresponding to S1 of the present example), for example, a hydrophobic reactive organic compound (having at least one hydrophobic group in one molecule and at least one capable of binding to a hydroxyl group) An organic compound of a reactive group), a water repellent material, a moisture proof material, an organic EL material, titanium oxide, or the like.

For example, the hydrophobic reactive organic compound which can form a material of the antifouling film which is an example of the organic-inorganic hybrid film may, for example, be an organofluorene compound containing a polyfluoroether group or a polyfluoroalkyl group. As an example of the product, there are OF-SR (oil repellent), OF-110 (water repellent), and the like of Canon Optron.

Among the above hydrophobic reactive organic compounds, in particular, a substance having a low vapor pressure (P1) at normal temperature can be selected, for example, about 10 ^-4 Pa or less (preferably 0.8 × 10 ^-5 Pa to 3 × 10 ^-4 Pa). More preferably, it is 10 ^-4 Pa or less (liquid at normal temperature).

The S2 which can be used is not particularly limited as long as it is a component S1 which can dissolve the constituent raw materials of the above various films. When a hydrophobic reactive organic compound containing fluorine is used as the S1, a solvent (fluorine-based solvent) containing fluorine in the same manner can be used as the S2 in order to improve the affinity.

The fluorine-based solvent may, for example, be a fluorine-modified aliphatic hydrocarbon solvent (perfluoroheptane or perfluorooctane) or a fluorine-modified aromatic hydrocarbon solvent (hexafluoro-xylene or trifluorotoluene). Fluorine-modified ether solvent (methyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), etc.), fluorine-modified alkylamine solvent (perfluorotributylamine, perfluorotributylamine) and many more.

In the above-mentioned fluorine-based solvent, in particular, a substance having a very high vapor pressure (P2) at normal temperature can be selected, and is, for example, 10 ³ Pa or more (preferably 0.8 × 10 ³ Pa or more and less than atmospheric pressure (1.01325 × 10 ⁵ Pa). The degree is more preferably 6.0 × 10 ³ Pa to 1.6 × 10 ⁴ Pa), and is excellent in volatility at normal temperature.

The fluorine-based solvent may be used singly or in combination of two or more. When two or more types are used in combination, the mixture may be selected in the above vapor pressure range.

In the present invention, the film forming agent solution 21 to be used is required to have a concentration (S1 concentration) of S1 of 0.01% by weight or more, and when the concentration of S1 is too low, the film forming start pressure (hereinafter referred to as the following) is P2 or more. In the present invention (excluding a pressure of more than one order of magnitude higher than P2), even if the discharge pressure of the liquid is appropriately adjusted, an undesired film former solution 21 may be generated from the discharge portion 19 before the film formation starts. Dropping, it is not possible to form a film properly. Further, even if film formation is possible, it is difficult to prevent a decrease in film density of the film.

In the present invention, the concentration of S1 of the film-forming agent solution 21 may be 0.01% by weight or more, and further preferably 0.03% by weight or more, and more preferably 0.05% by weight or more. When the film forming agent solution 21 having an S1 concentration of 0.03% by weight or more is used, even if the film forming start pressure is set to P2 or more (excluding a pressure higher than one order of P2), the durability of the obtained film is easily obtained. The standard has improved.

The upper limit of the S1 concentration can be considered in consideration of the types of S1 and S2 used, the inner diameter and length of the infusion tube 25, the configuration of the discharge portion 19, and the like, so as not to be caused by fixation inside the infusion tube 25 and the discharge portion 19. The upper limit is determined by the range of the liquid clogging. For example, when a hydrophobic reactive organic compound is used as S1 and a fluorine-based solvent is used as S2, the S1 concentration is not 100% by weight (that is, S2 is 0, only S1), even if the upper limit is close to 100% by weight (in a trace amount) The state in which S2 is diluted) can be prevented from occurring in the infusion tube by the pressure at the start of film formation, the discharge pressure of the liquid, the inner diameter and length of the infusion tube 25, and the configuration of the discharge portion 19. 25. The liquid inside the discharge portion 19 is clogged to form a film, and sufficient film performance can be obtained. Therefore, in this example, the upper limit of the S1 concentration may be preferably less than 100% by weight, preferably 70% by weight, more preferably 40% by weight, still more preferably 10% by weight.

It is particularly preferably, for example, 2% by weight or less, preferably 1% by weight or less, and more preferably 0.1% by weight or less. When the S1 concentration is 2% by weight or less, film formation is less likely to occur on the film formation surface of the film formation target (two or more substrates 100) (the remaining material is not deposited), and the use of the film formation agent solution 21 is finally suppressed. By consuming, it is easier to reduce the cost of film formation.

In addition, when the concentration of S1 is high, the S1 component may be fixed inside the infusion tube 25 and the discharge portion 19 due to the film formation start pressure and the discharge pressure of the liquid, and so-called liquid clogging may occur.

The viscosity of the film-forming agent solution 21 to be used is not particularly limited, and the inner diameter and length of the infusion tube 25, the configuration of the discharge portion 19, and the like are appropriately adjusted so that the solution 21 flows smoothly in the infusion tube 25, and can be appropriately obtained from The discharge portion 19 is discharged, and the solution 21 is not fixed to the inside of the infusion tube 25 or the discharge portion 19, and the so-called liquid clogging may be performed.

(2) Next, the prepared film forming agent solution 21 is added to the storage container 23. Further, in the present example, two or more substrates 100 are held at the concave portion of the substrate holder 31 outside the container 11.

As each of the substrates 100 that can be fixedly held by the substrate holder 31, a plastic substrate or the like can be given in addition to the glass substrate and the metal substrate. Depending on the type of the substrate 100, it is also possible to select a film without heating (the method of not heating the inside of the container 11 at the time of film formation). Selecting a glass substrate or a metal substrate without heating film formation In addition, plastic substrates can also be used. Further, as each of the substrates 100, a substrate whose shape is processed into, for example, a plate shape or a lens shape can be used. It should be noted that the substrate 100 may be wet-washed before being fixed to the substrate holder 31, or may be wet-washed after being fixed and before film formation starts.

(3) Next, the substrate holder 31 holding the two or more substrates 100 is placed inside the container 11 (in the case of batch processing). At this time, the opening and closing door (see above) provided under the side wall of the container 11 may be opened, and the substrate holder 31 holding the substrate 100 may be moved from the load lock chamber to be placed in the container 11 by operating the transport mechanism (roller 33). . Thereafter, the pump 15 is operated in accordance with a command from the controller 16, and the exhaust in the vacuum chamber 11 is started.

In the film formation to be described later, it is not necessary to make the substrate holder 31 stand still in the container 11 and, in the case of continuous processing, even in the film formation, the container 11 may be moved at a predetermined conveyance speed (automatic mode). ). From the aspect of productivity, it is advantageous to carry it quickly. However, from the viewpoint of effective use of the film-forming agent (film forming material of the film, which corresponds to S1 of the present example), film properties, and the like, it is preferably, for example, about 50 to 90 mm/sec.

The controller 16 successively detects the pressure (Pc) in the container 11 based on the output from the pressure detecting unit 18. Then, in this example, when it is judged that the pressure Pc in the container 11 reaches the vapor pressure (P2) or more (P2≦Pc) of S2 contained in the film forming agent solution 21, the function based on the pressure control inside the container is controlled. The control maintains this state, and an instruction to start the operation can be sent to the gas supply source 29. The gas supply source 29 that has received the operation command supplies the gas into the pipe 27, and pressurizes the liquid surface of the storage container 23 by the gas. Thus, the film forming agent solution 21 is pressure-fed through the inside of the infusion tube 25, introduced into the nozzle 17, and discharged from the discharge portion 19 to the inside of the container 11.

In the present invention, the pressure Pc in the container 11 from which the film forming agent solution 21 is discharged can be set to be less than one order of magnitude higher than P2. By such setting, it is possible to effectively prevent the occurrence of film defects.

In addition, when the film formation is performed under an excessively high pressure (for example, a pressure higher than one order of P2) in comparison with the vapor pressure P2 at a normal temperature of the solvent S2, the drying process after the film formation is performed. The solvent remaining in the film formation can be removed, but the film is not formed in this portion (the solute component is not uniformly adhered to form a film defect). When the solute component is not uniformly adhered to the substrate 100, there is a portion where the film is not formed on the substrate 100, and film peeling occurs from the non-existing portion of the film at the time of rubbing, and finally, it is not expected to improve durability.

In the present invention, a pressure (discharge pressure) can be applied to the film forming agent solution 21 when discharged from the discharge portion 19. This is because in the present invention in which the film formation start pressure is P2 or more (excluding a pressure of more than one order of magnitude higher than P2), the form of liquid discharge (discharge shape) is the most effective diffusion form by applying the discharge pressure. The discharge of the showerhead reduces the use of liquid waste, thereby reducing the cost of film formation and improving production efficiency. Among them, from the viewpoint of stabilizing the discharge shape, it is preferable to use a spray nozzle, and the film-forming agent solution 21 can be discharged at a discharge pressure (gauge pressure) of 0.05 to 0.3 MPa. By discharging it at a specific discharge pressure, the discharge shape is further stabilized, and the generation of liquid useless consumption is further reduced, whereby the cost of film formation is further reduced, and the production efficiency can be further improved. When the film forming agent solution 21 is discharged at the specific discharge pressure, the gas is supplied to the pipe 27, and the pressure of the liquid surface of the storage container 23 can be 0.05 to 0.3 MPa.

The discharge time of the film forming agent solution 21 from the discharge portion 19 is not limited. This is because it varies depending on the size, the number, and the like of the substrate 100. The thickness of the film formed on the substrate 100 is also not limited because it varies depending on the kind of the material contained in the film forming agent solution 21, the discharge time of the solution 21, and the like.

In the present example, when the film forming agent solution 21 is discharged from the discharge portion 19 at the position of the distance D with respect to the substrate 100, the pressure Pc in the container 11 at the start of discharge (ie, film formation) is controlled to a predetermined range (P2). In the case of ≦ and <pressure of more than one order of magnitude higher than P2, the S1 concentration and the discharge pressure of the film forming agent solution 21 are adjusted to a predetermined range (S1 concentration: 0.01% by weight or more, discharge pressure: 0.05 to 0.3 MP) In this case, when the pressure Pc in the container 11 at the start of discharge is P2 or more, if the S1 concentration and the discharge pressure of the film forming agent solution 21 are not adjusted, the film of the film formed on the substrate 100 cannot be prevented. The density is lowered and good film formation cannot be performed.

The mechanism of the film density reduction of the film is as follows. In other words, when the pressure Pc in the container 11 at the start of discharge is equal to or greater than P2, if the S1 concentration and the discharge pressure of the film forming agent solution 21 are not adjusted, S2 in the film forming agent solution 21 may remain on the substrate. 100 on. The S2 remaining on the substrate 100 is volatilized during drying in the subsequent step, thereby inducing a release state, and as a result, the film density of the film is lowered.

In this example, the film forming agent solution 21 having the S1 concentration adjusted to a predetermined range is used, and is discharged at a predetermined discharge pressure. Therefore, even if the pressure Pc in the container 11 at the start of discharge is controlled to be P2 or more, the film forming agent is used. S2 in the solution 21 does not remain on the substrate 100, and the release state can be avoided. As a result, the film density of the film can be prevented from decreasing.

As described above, for the film formed in this example, as an example, There are an antifouling film, a water repellent film, a moisture proof film, an organic EL film, a titanium oxide film, and the like. The present invention is a film forming method to which all of the compounds can be applied, and the above compounds include organic materials, inorganic materials, organic-inorganic hybrid materials, and the like. Hereinafter, a case where the film formed in this example is an antifouling film (an example of an organic-inorganic hybrid film) will be described as an example.

The antifouling film is a film having water repellency and oil repellency, and has a function of preventing oil stain from adhering. Here, the term "preventing oil stain adhesion" means not only that the oil does not adhere, but also that it can be easily wiped off even if it adheres. That is, the antifouling film maintains oil repellency. Specifically, the durability level of the antifouling film is maximally improved, and even if the steel wool #0000 based on the load of 1 kg/cm ² is reciprocated more than 2000 times (preferably 4000 times, more preferably 6000 times), the oiliness can be wiped off. Pen ink.

The durability is improved because the film forming agent solution 21 having the S1 concentration and the discharge pressure adjusted to a predetermined range is used, and when it is discharged from the discharge portion 19 at the position of the distance D with respect to the substrate 100, the discharge is started. When the pressure Pc in the container 11 is adjusted to a predetermined range (P2≦, and <pressure higher than P2 by more than one order of magnitude), the surface of the substrate 100 is indeed filled with constituent molecules (thin film molecules) of the S1 component, and there is no film. Non-existent part.

As described above, in the film forming apparatus 1 of the present embodiment, in the film forming method in the case where the discharge direction of the film forming agent solution 21 is downward, S1 and S2 are mixed, and a film forming agent solution whose S1 concentration is adjusted is used. 21, discharging it at a specific pressure Pc of a pressure higher than a vapor pressure P2 of S2 (excluding a pressure higher than one order of P2) under a discharge pressure of a predetermined range (0.05 to 0.3 MPa) A film is formed on the substrate 100. According to the film forming method of this example, the film forming agent solution 21 discharged from the discharge portion 19 reaches the substrate 100 while maintaining the solution state. Thereafter, the solvent component evaporates, causing the film (film) to form and forming a high density. Finally, a film having an improved durability level can be formed on each of the substrates 100 at a low cost.

When the film formed by the method of the present example is an antifouling film, according to the antifouling film, even if a heavy load (for example, a load of about 1 kg/cm ² ) is wiped off, the oil such as a fingerprint attached to the surface can be wiped off. The constituent components of the antifouling film effectively remain.

The film formed by the method of this example is not limited to the antifouling film. There are also film formation examples of inorganic films. When the titanium oxide particles were mixed in water to prepare 4 g/liter of a suspension (S1 is titanium oxide particles and S2 is water. The vapor pressure at normal temperature of water is about 3,000 Pa), the pressure Pc in the vessel 11 is set to 3000 Pa. When the film was discharged by discharging at a discharge pressure of 0.2 MPa of the suspension, a titanium oxide film having a refractive index of 2.400 for light having a wavelength of 550 nm and having good optical characteristics was formed. It is considered that by using a suspension in which the concentration of the titanium oxide particles is adjusted to a predetermined range, when the pressure Pc in the vessel is 3,000 Pa, the discharge is discharged at a discharge pressure of 0.2 MPa, whereby a dense inorganic titanium oxide film can be formed and obtained well. Optical properties.

<Other Embodiments>

The film forming apparatus of the present invention is not limited to the above-described film forming apparatus 1 (the discharge direction of the film forming agent solution 21 is downward), and the arrangement direction of the nozzles 17 can be arranged in the lateral direction (the discharge direction of the film forming agent solution 21 toward Horizontal). When it is set to the horizontal direction, for example, one end of the nozzle 17 can be inserted from the inner side horizontal direction of the vacuum container 11, and the other end of the nozzle 17 can be exposed to the outside of the side wall of the container 11. Alternatively, a rotating member (not shown) that can rotate a front portion (including the discharge portion 19) in the vicinity of the middle of the longitudinal direction of the nozzle 17 to rotate by, for example, about 90 degrees, may be used. The discharge portion 19 is connected thereto) from the vacuum vessel 11 The inside is inserted downward, and the other end of the nozzle 17 is exposed to the outside of the container 11 to be disposed. In either case, when the orientation of the nozzles 17 is set to the lateral direction, the substrate holder 31 is disposed on the inner side of the vacuum vessel 11 so as to hold the surface of the substrate 100 and the end connected to the nozzle 17 . The discharge portion 19 is opposed to each other.

Further, the substrate holder 31 may be configured to be movable while the nozzle 17 is configured to be movable by a transporter (not shown). Alternatively, the nozzle 17 can be moved by a transport mechanism (not shown). In this case, the film forming method can be applied even if the nozzle 17 side is moved.

Example

Next, the embodiment of the invention will be described in more detail, and the present invention will be described in further detail.

[Experimental Examples 1 to 6] <1. Production of antifouling film samples>

Using the film forming apparatus 1 shown in FIG. 1, two substrates 100 (glass substrates, size: 50 mm × 100 mm) were provided on the substrate holding surface of the substrate holder 31.

The film former solutions a to e having the compositions described in Table 1 were prepared.

In addition, in Table 1, "oilproof agent 1" is a surface antifouling coating agent (manufactured by Daikin Industries, Ltd., trade name: Optool DSX, component name: fluorine-containing organic antimony compound), and "oil repellent 2" It is a fluorine-based antifouling coating agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KV-178, component name: fluorine-containing organic antimony compound), and "solvent 1" is a fluorine-based solvent (manufactured by Sumitomo 3M Co., Ltd., trade name: Novec 7200) "Solvent 2" is a fluorine-based solvent (manufactured by Sumitomo 3M, trade name: Novec 7300).

Table 2 shows other film forming conditions such as the pressure Pc and the distance D in the container 11 at the start of film formation. In addition, a spray nozzle which can discharge the solution-like particle of 140-260 micrometer size is used as a discharge part of a nozzle, and the discharge time of a film-forming agent solution is set to 30 second. Then, samples of each experimental example in which an antifouling film having a thickness of 10 to 15 nm was formed on the substrate 100 were obtained.

In the experimental examples 1 to 3, the anti-fouling film (batch processing) was formed in a state in which the substrate holder 31 provided with the substrate 100 was stationary in the vacuum container 11. In Experimental Examples 4 to 6, film formation (continuous processing) was performed while transporting the substrate holder 31 on which the substrate 100 was placed in the vacuum chamber 11.

<2. Evaluation> 2-1. Durability of antifouling film

On the surface of the antifouling film of each of the obtained experimental samples, 1 cm ² of steel wool (SW) #0000 was loaded, and a load of 1 kg/cm ² was applied to make the reciprocation at a speed of 1 second at 50 mm. Reciprocating (friction) on a straight line. After 3,500 such reciprocating operations, the contact angle of the pure water on the antifouling film surface was measured. The contact angle of the pure water on the antifouling film surface immediately after the film formation was also measured. Regarding the value of the contact angle, the measured value of the contact angle after adding 1 point to the pure water drop was measured by repeating five times and measuring the average value of the obtained measured values. The results are listed in Table 2.

2-2. Maximum number of scratches and reciprocating times of antifouling film

On the surface of the antifouling film of each of the obtained experimental samples, 1 cm ² of steel wool (SW) #0000 was loaded, and a load of 1 kg/cm ² was applied to make the reciprocation at a speed of 1 second at 50 mm. Reciprocating (friction) on a straight line. For every 100 reciprocating operations, an oil-based universal pen (organic solvent type marker, trade name: Mckee, fine, Zebra) was used to scribe the test surface (antifouling film surface), and it was evaluated whether it could be wiped with a dry cloth. An organic solvent-based ink for oil-free universal pens. As a result, the maximum number of scratches and reciprocating times capable of erasing the organic solvent type ink is shown in Table 2.

<3. Investigation> 3-1. Cases of batch processing (Experimental Examples 1 to 3b)

As shown in Tables 1 and 2, in Experimental Examples 1 and 2 (discharge under low vacuum), the S1 concentration and the discharge pressure of the film forming agent solution and the pressure Pc at the time of discharging the film forming agent solution were appropriately adjusted, which was just completed. The contact angle of the surface of the antifouling film after the film hardly decreases after the SW rubbing, and the durability is extremely excellent. In addition, the maximum number of scratches is 3,500. More than this time, it is sufficient, and it is confirmed that it has a practical friction resistance.

On the other hand, in Experimental Example 3 (Purification at atmospheric pressure) in which Pc was higher than P2 and Experimental Example 3a in which the pressure was higher than one order of P2, the contact angle of the surface of the antifouling film immediately after film formation was in SW friction. After a sharp drop. In addition, the maximum number of scratches and reciprocations was extremely small, and it was confirmed that it did not have durability.

Further, Pc was in an appropriate range, but when the discharge pressure of the film-forming agent solution was too low (Experimental Example 3b), it was impossible to obtain a sufficient contact angle on the surface of the anti-fouling film immediately after film formation. In addition, the maximum number of scratches and reciprocations was extremely small, and it was confirmed that it did not have durability.

3-2. Case of continuous processing (Experimental Examples 4 to 6)

When the conveyance speed of the substrate is increased, the durability of the antifouling film is lowered, and it is confirmed that the maximum number of scratches and reciprocations tends to decrease. A good balance of film properties and productivity is Experimental Example 5.

1‧‧‧ film forming device

11‧‧‧Vacuum container

13‧‧‧Pipe

15‧‧‧Vacuum pump (exhaust unit)

16‧‧‧ Controller

17‧‧‧Nozzles

18‧‧‧ Pressure detection unit

19‧‧‧Exporting Department

21‧‧‧filming agent solution

23‧‧‧ storage container

25‧‧‧ Infusion tube

27‧‧‧Pipe

29‧‧‧ gas supply

31‧‧‧Substrate support

33‧‧‧Roll (transport mechanism)

100‧‧‧Substrate

Claims (4)

A film forming method for forming a film on a substrate in a vacuum, characterized by: a vapor pressure (P2) for containing a first material (S1) and having a vapor pressure (P1) higher than the S1 The solution of the second material (S2) composed of two or more materials and having a concentration of the first material of 0.01% by weight or more is discharged to the substrate at a discharge pressure of 0.05 MPa to 0.3 MPa in an atmosphere of a pressure of P2 or higher. Above, wherein the pressure above P2 does not include a pressure higher than P2 by more than one order of magnitude. The film forming method according to claim 1, wherein the film forming method is performed by an automated method having a transport mechanism. A film forming apparatus for forming a film on a substrate in a vacuum, comprising: a vacuum container in which a substrate as a film forming object is disposed; and exhausting the inside of the vacuum container a storage container for storing a solution composed of two or more materials, wherein the two or more materials include the first material (S1) and the vapor pressure (P2) having a vapor pressure (P1) higher than the S1. a material (S2), wherein the concentration of the first material in the solution is 0.01% by weight or more; a nozzle for discharging the solution onto the substrate; and pressurizing the liquid surface stored in the storage container a unit configured to pressurize the liquid surface in the storage container to 0.05 MPa to 0.3 MPa when the pressure in the vacuum container reaches a pressure equal to or higher than P2 The solution is discharged from the nozzle onto the substrate, wherein the pressure above P2 does not include a pressure above the order of P2. The film forming apparatus according to claim 3, wherein the film forming apparatus is an automated method including a transport mechanism for transporting a substrate.