TW201701387A - Filming formation method and filming formation device for thin film for producing thin film with durability at low cost - Google Patents

Abstract

The invention provides a filming formation method for thin film with durability at low cost. The filming formation method utilizes a filming formation device (1). The device (1) comprises a vacuum container (11) for arranging a substrate (100) at the lower side of the interior, a vacuum pump (15) for exhaust of the container (11), a storage container (23) disposed outside the container (11) for storing filming formation agent solution(21), and a nozzle (17) having one end formed as a discharge portion for discharging filming formation agent solution (21). The filming formation agent solution (21) uses more than two types of material. The filming formation agent solution (21) is discharged onto a substrate at a set pressure according to the vapor pressure of each material constituting the solution.

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 score (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 shape in a predetermined direction. The fine uneven surface is then coated with a coating liquid (diluted solution) prepared in a predetermined composition 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 applied by the wet method, the film formed on the outermost surface is easily scraped off by wiping, and the oil repellency may be lost.

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.

By "discharging" in the present invention, it is meant 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 chemical state of the raw material in the liquid before and after the discharge did not change. 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 when a solution is discharged in an atmosphere of a specific pressure (Pc) set based on vapor pressures (P1, P2, P3, ...) of two or more materials constituting a solution, even if the solute concentration of the solution is low ( That is, even if the discharged solution is a dilute solution, a film having durability can be formed. Further, it has been found that the specific pressure Pc for discharging the solution mostly belongs to a medium vacuum or a low vacuum region, so that a film having durability can be formed at a low cost as compared with a vapor deposition method in which a high vacuum condition is required at the time of film formation. Thus, the present invention has been completed.

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.) The pressure set by the vapor pressure (for example, P1, P2, P3, ..., etc., the same below) of each material (for example, S1, S2, S3, ..., etc.) of the solution (Pc) The solution was discharged onto the substrate under an atmosphere.

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 premised on forming 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 types of storage. A storage container of the solution of the above material, and a nozzle for discharging the solution onto a substrate disposed inside the vacuum container. The film forming apparatus is configured to discharge the solution from the nozzle onto the substrate when the pressure in the vacuum container reaches a pressure (Pc) set based on the vapor pressure of each material constituting the solution.

In the present invention (the first invention and the second invention), each material constituting the solution discharged onto the substrate includes the first material (S1) and a vapor pressure (P2) having a vapor pressure (P1) higher than the S1. In the case of the second material (S2), it is preferred that the pressure (Pc) in the atmosphere in which the solution is discharged is higher than P1 and lower than P2. In the present invention, even if the pressure (Pc) in the atmosphere in which the solution is discharged is P1 or less or P2 or more, a film which is considered to be practically durable can be formed.

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, the substrate When it is disposed under the inside of the vacuum container, it is disposed so that the solution can be discharged downward (vertical or oblique) (hereinafter also referred to as "the discharge direction of the solution is downward"), and the substrate is disposed inside the vacuum container. In the case of the side, it is only necessary to discharge the solution in the lateral direction (level or inclination) (hereinafter also referred to as "the discharge direction of the solution toward the lateral direction"). That is, in the second aspect of the invention, the setting 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 lateral 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 vapor pressure of each material (for example, S1, S2, etc.) in the constituent material of the solution discharged to the substrate (for example, P1 of S1, P2 of S2, etc.), P1 < P2 And the set pressure Pc (for example, in an atmosphere higher than P1 (P1 < Pc) and lower than P2 (Pc < P2)), a solution composed of two or more materials containing S1 and S2 is discharged to the pressure. On the film object (substrate). 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 becomes high in 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 aspect of the invention, when the pressure in the vacuum container reaches the pressure Pc set based on the vapor pressure of each material in the constituent material of the solution discharged to the substrate, the solution composed of two or more materials is discharged from the nozzle to the nozzle. On the film-forming object (substrate). When the pressure inside the vacuum container is Pc, even if it is discharged Liquid, S2 will also volatilize, but S1 will not volatilize. Therefore, the film formed on the substrate becomes high in 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.

In addition, according to the present invention, by appropriately adjusting the solute concentration (for example, 0.01% by weight or more) of the discharged solution, the durability of the obtained film can be further improved, and the cost of film formation can be further reduced. .

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. The vacuum container 11 is constituted by a hollow body having a substantially rectangular parallelepiped shape in this example, 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 vacuum state capable of producing an atmospheric pressure to a medium vacuum (0.1 Pa to 100 Pa). The pump can be used, such as a rotary pump (oil rotary vacuum pump). 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 an instruction from the controller 16 (control unit), and the degree of vacuum (pressure) in the container 11 is lowered by the pipe 13. The vacuum container 11 is provided with a pressure detecting unit 18 (a 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 it is judged by the controller 16 that the pressure in the container 11 reaches a predetermined value, the operation command is transmitted 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 illustration is omitted. When a gas such as argon gas is introduced into the container 11, the pressure inside the container 11 can also be controlled. 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, The number (number) of the nozzles 17 inserted into the container 11 is not limited. Depending on the size of the container 11, more than two 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. Thereby, the liquid level of the storage container 23 is pressurized, and in this example, 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 linear movement (in 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. The inner surface of the substrate holder 31 has a concave substrate holding surface. 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 in the second material (S2) is changed by various factors such as the vapor pressure (P2) at normal temperature.

In the present example in which the discharge direction of the film forming agent solution 21 is downward, the arrangement of the discharge portion 19 and the substrate holder 31 is adjusted so that the distance D is 300 mm or less, so that the obtained film can easily achieve sufficient film strength and is easy. Increase the durability level.

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, it is possible to secure a sufficient effective discharge range of the film forming agent solution 21, which is advantageous. The useless consumption of the film forming agent solution 21 is suppressed, and finally, the cost of film formation can be more favored.

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 domain becomes narrow corresponding to this, and thus the film former solution 21 is useless. The consumption is increased, and in addition, film spots are sometimes generated.

First, the controller 16 is provided with a pressure control function in the container to operate the vacuum pump 15 and the pressure detecting unit 18, and adjusts 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 composed of a solution containing two materials of the first material (S1) and the second material (S2) is described as an example, and in the following description, S1 is used as The solute (the component dissolved in the solvent) and the S2 as the solvent (the component which dissolves the solute. Liquid).

It should be noted that the solute also includes a liquid in addition to a solid such as a powder. When the solution 21 is composed of a mixture of a liquid and a liquid, the component present in the solution 21 in a large amount or in a ratio is a solvent, and in this example, S2 is formed.

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 water repellent film, a moisture proof film, an organic EL film, a titanium oxide film, etc., and as a constituent raw material (corresponding to S1 of this example), for example, a hydrophobic reactive organic compound (one) Have at least a molecule An organic compound having a hydrophobic group and at least one reactive group capable of binding to a hydroxyl group), a water repellent material, a moisture proof material, an organic EL material, titanium oxide, or the like.

For example, as the hydrophobic reactive organic compound (solute S1) capable of forming an antifouling film which is an example of the organic-inorganic hybrid film, an organic ruthenium compound containing a polyfluoroether group or a polyfluoroalkyl group may, for example, be mentioned. . 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 solvent S2 which can be used is not particularly limited as long as it can dissolve the solute S1. When a hydrophobic reactive organic compound containing fluorine is used as the solute S1, a solvent (fluorine-based solvent) containing fluorine in the same manner can be used 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, a substance having a very high vapor pressure (P2) at normal temperature can be selected, and for example, it is about 10 ³ Pa or more (preferably 0.8 × 10 ³ Pa or more and less than atmospheric pressure (1.01325 × 10 ⁵ Pa)). Further, it 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. use. When two or more types are used in combination, the mixture may be selected in the above vapor pressure range.

The concentration (solute concentration) of S1 in the film-forming agent solution 21 to be used may be 0.01% by weight or more, more preferably 0.03% by weight or more, and still more preferably 0.05% by weight or more. When the film-forming agent solution 21 having a solute concentration of 0.01% by weight or more is used, the durability level of the obtained film is easily improved. In addition, when the solute concentration is too low, even if the film formation start pressure (see below) and the liquid discharge pressure are appropriately adjusted, an undesired film former solution may be generated from the discharge portion 19 before the film formation starts. The dropping of 21 does not form a film properly.

The upper limit of the solute concentration can be considered in consideration of the type of the solute S1 and the solvent S2 to be 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 fixed inside the infusion tube 25 and the discharge portion 19. The upper limit is determined by the range of so-called liquid clogging. When a hydrophobic reactive organic compound is used as the solute S1 and a fluorine-based solvent is used as the solvent S2, the solute concentration in the film-forming agent solution 21 can be, for example, 2% by weight or less, preferably 1% by weight or less, more preferably 0.1% by weight or less. When the solute concentration is 2% by weight or less, the film formation surface of the film formation target (two or more substrates 100) is less likely to cause film spots (remaining material remaining without film formation), and finally the useless consumption of the film forming agent solution 21 is suppressed. This makes it easier to reduce the cost of film formation. In addition, when the solute concentration is too high, even if the film formation start pressure and the liquid discharge pressure are appropriately adjusted, the solute component may be fixed inside the infusion tube 25 and the discharge portion 19 to cause so-called liquid clogging.

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. It is sufficient that the solution 21 flows smoothly in the infusion tube 25, can be appropriately discharged from the discharge portion 19, and does not cause so-called liquid clogging caused by the solution 21 being fixed inside the infusion tube 25 and the discharge portion 19.

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

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). When a film is formed without heating, a plastic substrate can be applied in addition to the glass substrate or the metal substrate. Further, as each of the substrates 100, a substrate which is processed into a shape such as 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 conveying mechanism (roller 33). Inside. Thereafter, the pump 15 is operated in accordance with an instruction from the controller 16, and the exhaust in the vacuum chamber 11 is started.

In the case of the substrate holder 31, it is not necessary to make it stand still in the container 11 in the film formation described below, and in the case of continuous processing, the film holder 31 may be moved in the container 11 at a predetermined conveyance speed even during film formation. (automated mode). From the aspect of productivity, it is advantageous to carry it quickly. However, from the film former (thin Film forming material of the film. It is preferable to set it as 50 to 90 mm/sec, for example, from the viewpoint of effective use of S1) of this example, film performance, and the like.

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 a prescribed pressure which is most effective for improving the durability of the formed film, that is, a pressure in a specific range is reached, which is higher than that contained in the film forming agent solution 21. The vapor pressure (P1) of S1 (P1 < Pc) is lower than the vapor pressure (P2) (Pc < P2) of S2 contained in the film forming agent solution 21, at this time, by the pressure control function based on the inside of the container The control is maintained in 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, and is introduced into the nozzle 17, and then discharged to the inside of the container 11 by the discharge portion 19.

It is not necessary to apply a pressure (discharge pressure) to the film forming agent solution 21 when it is discharged from the discharge portion 19. This is because even if the discharge pressure is not applied to the film forming agent solution 21, as long as the pressure Pc in the container 11 is maintained within the above range (see above, greater than P1 and smaller than P2), the liquid discharge mode (discharge shape) is the most The effective diffusion method (sprinkler-like) discharge reduces the occurrence of useless consumption of the liquid, thereby achieving cost reduction of the film formation of the film, and easily improving production efficiency. In addition, from the viewpoint of stabilizing the discharge shape, the spray nozzle 21 can be further 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 more stabilized, and the occurrence of useless consumption of the liquid is further reduced, whereby the cost of film formation is further reduced, and the production efficiency can be further improved. For making the film former solution 21 specific as described above The discharge pressure is discharged, and the gas may be sent to the inside of the pipe 27 so that the pressure of the liquid surface of the storage container 23 reaches 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 (that is, film formation) can be controlled to a predetermined range. (greater than P1 and smaller than p2), when the pressure Pc in the container 11 at the start of discharge is equal to or lower than the vapor pressure P1 at normal temperature of S1, even if the solute concentration of the film-forming agent solution 21 to be used is appropriately adjusted, The solute component may be fixed to the inside of the infusion tube 25 and the discharge portion 19, and so-called liquid clogging may occur. On the other hand, when the pressure Pc in the container 11 at the start of discharge is equal to or higher than the vapor pressure P2 at the normal temperature of S2, even if the solute concentration of the film-forming agent solution 21 to be used is appropriately adjusted, the solvent S2 after reaching the substrate 100 is At the same time, it is not volatilized due to the high atmospheric pressure, and remains, so that the film density sometimes becomes low.

In the case where Pc is equal to or less than P1 (≦P1), the possibility of preventing the occurrence of the liquid clogging can be increased by appropriately adjusting the discharge amount and discharge pressure of the film forming agent solution 21, and the like. Good film formation (that is, a film which is practically considered to have durability is formed by film formation. The same applies hereinafter). When Pc is equal to or higher than P2 (P2≦), it is possible to prevent thin film formation on the substrate 100 by appropriately adjusting the concentration of the film forming agent solution 21, the discharge pressure, and the like. The film density of the film is lowered, and good film formation can be performed.

Therefore, in the present invention, the timing at which the controller 16 transmits the command to start the operation to the gas supply source 29 is not limited to the case where it is determined that the pressure Pc in the container 11 has reached the above range (P1 < Pc < P2). The predetermined pressure which is most effective in improving the durability of the formed film is the above range (P1 < Pc < P2).

In the case where the film is formed under an excessively low pressure (for example, a pressure lower than one order of P1) as compared with the vapor pressure P1 at a normal temperature of the solute S1, the solute which constitutes the film is deposited on the substrate 100. When the components evaporate, the final solute components sometimes become dense and uniformly adhere to all of the substrates 100. When the non-existing portion of the film is present, film peeling occurs from the portion at the time of rubbing, and ultimately, the durability of the film cannot be expected to be improved.

Further, in the case of film formation under an excessively high pressure (for example, a high pressure higher than one order of P2) as compared with the vapor pressure P2 at a normal temperature of the solvent S2, it is possible to pass a drying step after film formation or the like. The solvent remaining in the film formation was removed, but no film was formed in this portion (the solute component did not uniformly adhere to the film defect). When the solute component is not uniformly adhered to the substrate 100, the film 100 has a portion where the film is not formed, and when the film is rubbed, the film is peeled off from the non-existing portion of the film, and finally, durability is not expected to be improved.

As described above, the film formed in the present example is, for example, an antifouling film, a water repellent film, a moisture proof film, an organic EL film, a titanium oxide film, or 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.

In this way, the durability is most improved because 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 is adjusted to The durability of the formed film is increased by the most effective predetermined pressure (P1 < Pc < P2), so that the surface of the substrate 100 is surely filled with constituent molecules (thin film molecules) of the solute component, and there is no non-existing portion of the film.

In addition, although the above description was made, the pressure Pc in the container 11 when the film-forming agent solution 21 was discharged was not equal to P1 < Pc < P2, but was equal to or less than P1 (≦P1) and P2 or more (P2≦). In this case, good film formation can also be performed, and the obtained film can be made into a film which is practically considered to have durability.

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 the solute concentration thereof is adjusted as needed, and the film is used. The film solution 21 is discharged onto the substrate 100 at a specific pressure Pc which is preferably higher than the vapor pressure P1 of S1 and lower than the vapor pressure P2 of S2, and film formation is performed. According to the film forming method of the present example, the film forming agent solution 21 discharged from the discharge portion 19 reaches the substrate 100 while maintaining the solution state, and by appropriately controlling the pressure Pc in the container 11, reaching the substrate 100, the solvent component evaporates, causing the solvent component to evaporate. Film (film) is formed and forms a high density Chemical. Finally, the film having the highest durability can be formed on each of the substrates 100 at a low cost.

It is presumed that such an effect is obtained by the fact that the evaporation of S1 can be prevented by appropriately controlling the pressure Pc in the container 11 at the start of discharge, and the film molecules constituting the film can be surely adhered to the substrate densely and uniformly. At 100, there is no portion on the substrate 100 where no film is formed.

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

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. In the case of a 4 g/liter suspension prepared by mixing titanium oxide particles in water, when the pressure Pc in the container 11 is set to 1000 Pa to form a film, the refractive index for light having a wavelength of 550 nm is 2.400. A titanium oxide film having good optical properties. It is considered that by setting Pc to 1000 Pa, Pc is higher than the vapor pressure at room temperature of titanium oxide (no measurement data, predicted from the external interpolation value of 10 ^-10 Pa or less), and vapor pressure lower than the normal temperature of water (about 3,000 Pa) As a result, a dense inorganic titanium oxide film is formed, and good optical characteristics are obtained.

<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 is directed to the lateral direction). ). In the case of being oriented in the lateral direction, for example, the nozzle can be inserted from the inner side of the vacuum vessel 11 in the horizontal direction One end of the nozzle 17 exposes the other end of the nozzle 17 to the outside of the side wall of the container 11. Alternatively, the front portion (including the discharge portion 19) may be attached to the middle portion in the longitudinal direction of the nozzle 17 to rotate a rotating member (not shown) of, for example, about ±90 degrees, on the basis of which one end of the nozzle 17 is attached ( The discharge portion 19 is connected thereto, and is inserted downward from the inside of the vacuum chamber 11, 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 portions 19 are 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 transport mechanism (not shown), or the nozzle 17 may be separately 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 present invention will be further described in detail by way of examples in which the embodiments of the invention are embodied.

[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 forming agent solutions a to d of the composition 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, a sample of each experimental example in which an antifouling film having a thickness of 10 to 15 nm was formed on the substrate 100 was obtained.

In the experimental examples 1 to 3, the deposition of the antifouling film (batch processing) is performed in a state where the substrate holder 31 on which the substrate 100 is placed is placed in the vacuum container 11. In the experimental examples 4 to 6, the substrate holder 31 on which the substrate 100 is placed is conveyed in the vacuum chamber 11, and film formation (continuous processing) is performed.

<2. Evaluation>

2-1. Durability of antifouling film

1 cm ² of steel wool (SW) #0000 was placed on the surface of the obtained antifouling film of each experimental sample, and a load of 1 kg/cm ² was applied to make it reciprocate once in 1 second on a straight line of 50 mm. Speed reciprocating (friction). 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 the average value of the measured values obtained by repeating the dropping and measuring five times. The results are listed in Table 2.

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

1 cm ² of steel wool (SW) #0000 was placed on the surface of the antifouling film of each of the obtained experimental samples, and the load was applied at a load of 1 kg/cm ² to make a reciprocation of 1 second on a straight line of 50 mm. Speed reciprocating (friction). 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 3)

As shown in Tables 1 and 2, in Experimental Examples 1 and 2 (discharge under low vacuum), rows When the film forming agent solution is discharged, the pressure Pc is higher than the vapor pressure P1 of S1 and the vapor pressure P2 lower than S2, and the contact angle of the surface of the antifouling film immediately after the film formation is hardly lowered after the SW rubbing, and the durability is extremely excellent. . In addition, it is sufficient that the maximum number of scratches and reciprocating times is 3,500 or more, and it is confirmed that it has a practical abrasion resistance.

In addition, although not shown in Table 2, in the case of discharging under 10 Pa (medium vacuum) under the same conditions as Experimental Examples 1 and 2 (Experimental Examples 1a and 2a), the solute concentration was lowered to 0.01. In the case of the weight % (Experimental Examples 1b and 2b), when the solution c or d of Table 1 was used as the film-forming agent solution (Experimental Examples 1c and 2c), results substantially similar to those of Experimental Examples 1 and 2 were also obtained. Further, in the case where the solute concentration was lowered to 0.005% by weight under the same conditions as in Experimental Examples 1 and 2 (Experimental Examples 1d, 2d), the durability of the antifouling film was slightly lowered as compared with Experimental Examples 1 and 2, but It is also confirmed that it has durability that can withstand practical use.

On the other hand, in Experimental Example 3 (spray at atmospheric pressure) in which Pc was higher than P2, the contact angle of the surface of the antifouling film immediately after film formation was largely lowered after SW rubbing. 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 (7)

A film forming method for forming a film on a substrate in a vacuum, characterized in that a solution containing two or more kinds of materials is subjected to a pressure set based on a vapor pressure of each material constituting the solution. Drain onto the substrate. The film forming method according to claim 1, wherein each of the materials constituting the solution contains the first material (S1) and the vapor pressure (P2) having a vapor pressure (P1) higher than the S1. At the time of the material (S2), the above solution was discharged under an atmosphere of a low pressure higher than P1 and lower than P2. The film forming method according to claim 1, wherein each of the materials constituting the solution contains the first material (S1) and the vapor pressure (P2) having a vapor pressure (P1) higher than the S1. In the case of the material (S2), the solution is discharged under an atmosphere of a pressure of P2 or higher. The film forming method according to claim 1, wherein each of the materials constituting the solution contains the first material (S1) and the vapor pressure (P2) having a vapor pressure (P1) higher than the S1. In the case of the material (S2), the solution is discharged under an atmosphere of a pressure of P1 or less. The film forming method according to any one of claims 1 to 4, wherein the film forming method is carried out in an automated manner 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 formation object is disposed inside, a venting unit that exhausts a vacuum container, a storage container that stores a solution containing two or more materials, and a nozzle that discharges the solution onto the substrate, wherein the pressure in the vacuum container is based on constituting the solution When the vapor pressure of each material is set to a pressure, the solution is discharged from the nozzle onto the substrate. The film forming apparatus according to claim 6, wherein the film forming apparatus is an automated method including a transport mechanism for transporting the substrate.