JP5286266B2 - Preparation method of organic thin film on substrate - Google Patents

Abstract

A clean organic thin film free from liquid stains and liquid-flow marks is formed on a surface of a substrate. The method of organic-thin-film formation is characterized by comprising (a) placing a substrate having a hydrophilic surface on a horizontal table or rotatable horizontal table and fixing the substrate to the table, (b) dropping a water-repellent-group-containing solution for organic-thin-film formation onto the substrate just in an amount sufficient for covering the substrate surface, and (c) allowing the covered table to stand for a time period sufficient to enable the solution to form an organic thin film on the substrate, and then tilting the table or rotating the table to remove the excess solution for organic-thin-film formation, and by optionally including (d) dropping a cleaning solvent onto the substrate, holding the table for a certain time period, and then tilting the table or rotating the table to remove the cleaning solvent.

Description

  The present invention relates to a method for producing an organic thin film on a substrate, and more particularly to a method suitable for producing a monomolecular film on a substrate such as a wafer.

Conventionally, the surface of a substrate made of glass, metal, plastic, ceramics or the like is modified in various fields according to the purpose. For example, in order to impart water repellency and oil repellency to the surface of glass or plastics, a coating with a silane coupling agent may be mentioned.
Examples of the method for coating the silane coupling agent include the following methods.
After washing the untreated substrate with pure water, alcohols, etc., the surface of the substrate is activated by a method such as UV ozone treatment. Thereafter, the substrate is immersed in a tank containing a silane coupling agent, and the substrate is coated with the silane coupling agent.
For example, when producing a monomolecular film made of a silane coupling agent on the surface of a substrate such as a silicon wafer, immerse the silicon wafer in a tank containing the silane coupling agent, pull it up, and drain the liquid. Air blow is performed for this purpose.
However, in the dipping method (dip method), the processing liquid also contacts the back surface of the substrate. Therefore, when air is blown to remove the liquid, the processing liquid attached to the back surface wraps around the surface, causing the substrate surface to reach the surface. It was difficult to finish cleanly.

On the other hand, methods for applying a liquid material on a substrate include a dipping method, a spray method, a roll coating method, a spin coating method, a slit die method, a bar coating method, an ink jet method, and a spinless method. Is a method in which a solution is dropped from a nozzle (Patent Documents 1, 2, 3, etc.).
In order to solve the problems of the above-described dip method, the inventors worked on coping with a method of dropping droplets.
Among the methods performed by dropping droplets, the spin coating method is to adsorb a substrate such as a silicon wafer on a rotating stage, and to drop the thin film forming solution on the center of the substrate and rotate the rotating stage. There is a problem as a method of manufacturing a thin film, such as unevenness or irregularities on the film surface caused by the liquid flow caused by centrifugal force.
Also, among the methods that are performed by dropping droplets, the method that is performed without rotating the substrate is to arrange the nozzles for dropping the thin film forming solution in a line and move the nozzles to drop the solution onto the substrate. There are a method (for example, Patent Document 2) and a method of dropping in a spiral shape from the outside toward the center (for example, Patent Document 3).
However, none of these methods is sufficient as a method for producing a monomolecular film having excellent quality.

JP 2007-44691 A JP 2003-124108 A JP 2005-327879 A

  The present invention has been made in view of such circumstances, and the thin film forming solution adhering to the back surface of the base material does not go around the surface, so that the surface of the base material is liquid and no clean film is present. The purpose is to finish.

  As a result of intensive studies to solve the above problems, the inventors have determined that when the substrate surface is hydrophilic and the thin film has a water-repellent group, an appropriate amount is sufficient to cover the horizontally placed substrate surface. The film formation solution was dropped and allowed to stand, and then the excess film formation solution on the substrate was removed to find that no liquid spots or liquid flow traces were generated on the surface, and the present invention was completed. It was.

That is, the present invention
(1) (a) After a substrate having a hydrophilic surface is placed on a horizontal base and fixed,
(B) An organic thin film forming solution having a water-repellent group is dropped on the substrate in an amount capable of covering the substrate surface;
(C) After standing for a time sufficient to form an organic thin film on the substrate, the table is tilted to remove excess organic thin film forming solution, and if necessary,
(D) A method for producing an organic thin film characterized in that after the cleaning solvent is dropped on the substrate and held for a certain period of time, the cleaning solvent is removed by tilting the table, or
(2) (a) After the substrate having a hydrophilic surface is placed and fixed on a horizontally rotatable table,
(B) An organic thin film forming solution having a water repellent group is dropped on the substrate in an amount that can cover the substrate surface;
(C) After standing for a time sufficient to form an organic thin film on the substrate, the table is rotated to remove excess organic thin film forming solution, and if necessary,
(D) The present invention relates to a method for producing an organic thin film characterized in that a cleaning solvent is dropped on a substrate and held for a certain period of time, and then the cleaning solvent is removed by rotating a table.

(1) Organic thin film preparation method In the present invention, a substrate having a hydrophilic surface is placed on a horizontal base and fixed, and a solution for forming an organic thin film having a water-repellent group is dropped onto the surface of the substrate. The organic thin film is formed by allowing the organic thin film forming solution to diffuse by itself on the substrate. After the thin film is formed on the substrate, the table on which the substrate is placed is tilted or the table is rotated to remove the excess thin film forming solution on the substrate from the substrate. In this invention, since it is a water-repellent thin film, after forming a water-repellent thin film on a base material, an excess thin film formation solution can be removed only by inclining a base material.
If necessary, the cleaning solvent is then dropped to dissolve the remaining thin film forming solution or excess organic thin film on the substrate, and the table is tilted or the table is rotated to remove the cleaning solvent from the substrate. remove.
Examples of the solvent used for washing include paraffins, aromatic hydrocarbons, alicyclic hydrocarbons, halogen compounds, and ketones. Specifically, pentane, hexane, heptane, octane, isooctane, benzene, Toluene, xylene, diethylbenzene, Solvesso (registered trademark), cyclohexane, ligroin, petroleum ether, chloroform, methylene chloride, acetone and the like are used.
In the present invention, “the amount of the organic thin film forming solution that can cover the surface of the substrate” varies depending on the size of the substrate to which the present invention can be applied, but the area of the substrate to which the present invention can be applied is usually 1 cm ^2. Since it is ˜4 m ² , it means an amount that can cover the area.
The “time sufficient for forming the organic thin film on the base material” is usually 30 seconds to 3 hours, although it varies depending on the type of the organic thin film forming solution and the size of the base material.
In addition, the “time for dropping and holding the cleaning solvent on the substrate” can be appropriately set, but is usually 1 minute to 30 minutes.

(2) Apparatus required for carrying out the above method 1) In the case of the method described in paragraph (0007 ) (1) , a device on which the substrate is placed and a device for dropping the thin film forming solution on the surface of the substrate are required. To do. The platform is not particularly limited as long as it has a width on which the substrate can be placed and can be tilted.
As the dropping device, a manual dropping means such as a burette or an automatic dropping device used for spin coating or the like can be used.
Further, the surface of the table needs to be horizontal, and it is necessary to have means for fixing the substrate.
2) In the case of the method described in paragraph 0007 (2) , a rotatable table on which the substrate is placed, a rotating means for rotating the substrate, and a device for dropping the thin film forming solution on the surface of the substrate are required. To do.
The rotatable base in the present invention is a base having a width on which a substrate can be placed and can be rotated. For example, a spin coat turntable, a magnetic stirrer, or the like can be used. it can.
As in the case of 1), the dropping device can be a manual dropping means such as a burette or an automatic dropping device used for spin coating or the like.
Further, the plane of the table needs to be horizontal, and it is necessary to have means for fixing the substrate.

(3) Substrate In the present invention, a substrate having a hydrophilic surface is used.
The base material used in the method for producing an organic thin film of the present invention is not particularly limited in material, shape, etc., but has a functional group on the surface that can interact with molecules forming the organic thin film in the organic solvent solution of the present invention. A substrate is preferred, and a substrate having active hydrogen on the surface is particularly preferred. When a substrate having active hydrogen on the surface is used, the active hydrogen on the surface of the substrate and the molecules in the organic solvent solution of the present invention are chemically bonded, and a chemisorbed film can be easily formed on the substrate surface.

As functional groups containing active hydrogen, hydroxyl group (—OH), carboxyl group (—COOH), formyl group (—CHO), imino group (═NH), amino group (—NH ₂ ), thiol group (—SH) Among them, a hydroxyl group is preferable.

Specifically, as a base material having a hydroxyl group on the surface of the base material, a base material made of metal such as aluminum, copper, stainless steel, glass, silicon wafer, ceramics, paper, natural fiber, leather, other hydrophilic substance, etc. Is mentioned.
Even if the substrate is made of a material having no hydroxyl group on its surface, such as plastic or synthetic fiber, the substrate surface is treated in advance in a plasma atmosphere containing oxygen (for example, 100 W for 20 minutes) or corona treatment. It can be preferably used by introducing a hydrophilic group by performing UV ozone treatment, treatment with hydrogen peroxide solution, treatment with hydrogen peroxide solution and sulfuric acid, or the like. A substrate made of a polyamide resin or a polyurethane resin has an imino group on the surface, and the active hydrogen of the imino group and the alkoxysilyl group of the metal-based surfactant undergo a dealcoholization reaction to form a siloxane bond (- Since SiO-) is formed, no surface treatment is required.
As a base material used for the manufacturing method of the organic thin film of this invention, the base material comprised from at least 1 chosen from the group which consists of a metal, glass, a silicon wafer, ceramics, and a plastic is preferable.

In the case of using a substrate that has no active hydrogen on the surface, the surface of the substrate, previously _{SiCl 4, SiHCl 3, SiH 2} Cl 2, Cl- (SiCl 2 O) b -SiCl 3 ( wherein, b It is also possible to form a silica underlayer having active hydrogen on the surface thereof by contacting with at least one compound selected from (natural number) and then dehydrochlorinating.
Note that the substrate may be previously cleaned with pure water, alcohol, or the like.
The size of the substrate applicable to the present invention, a method of the present invention is not limited as long as applicable, is generally 1cm ² ~4m ^2.

(4) Organic thin film and organic thin film forming solution The organic thin film referred to in the present invention is an organic thin film composed of a metal surfactant having a water-repellent group, and includes a monomolecular film and a multilayer film. It is particularly suitable for the production of monomolecular films. A self-assembled film may also be used. Here, the self-assembled film means a film formed with an ordered structure without external forcing.
The organic thin film produced by this invention is demonstrated below.

The organic thin film is an organic thin film forming solution containing, in an organic solvent, a metal-based surfactant having at least one hydrolyzable group or hydroxyl group and water-repellent group, and a catalyst capable of interacting with the metal-based surfactant. To the substrate.
The details of the mechanism by which the metal surfactant is adsorbed on the surface of the substrate are not clear, but in the case of a substrate having active hydrogen on the surface, it can be considered as follows. That is, in the solution for forming an organic thin film, the hydrolyzable group of the metal surfactant is hydrolyzed with water. The metal surfactant in this state reacts with active hydrogen on the surface of the base material to form a thin film that forms a strong chemical bond with the substrate.
Although there is no restriction | limiting in particular in content of the metal-type surfactant in the solution for organic thin film formation used for this invention, In order to manufacture a dense monomolecular film, the range of 0.1 to 30 weight% is preferable. .
The amount of the catalyst that can interact with the metal-based surfactant is not particularly limited as long as it does not affect the physical properties of the monomolecular organic thin film to be formed, but with respect to 1 mol of the metal-based surfactant. The number of moles in terms of oxide is usually within the range of 0.001 to 1 mole, preferably within the range of 0.001 to 0.2 mole.
The organic solvent, metal surfactant, catalyst, base material and the like used here will be described below.

(Metal surfactant)
As the metal surfactant having at least one or more hydrolyzable groups or hydroxyl groups contained in the organic thin film forming solution, at least one or more hydrolyzable functional groups or hydroxyl groups and water-repellent groups are contained in the same molecule. If it has, it will not be restrict | limited especially, However, The thing which has a hydrolyzable group and hydroxyl group which can react with the active hydrogen on the base-material surface and can form a bond is preferable. Here, the water repellent group means a hydrocarbon group, a halogenated hydrocarbon group or the like.
Specific examples of such a metal surfactant include compounds represented by the formula (II).
R ¹ _n MX _mn (II)
In the formula, R ¹ is a hydrocarbon group which may have a substituent, a halogenated hydrocarbon group which may have a substituent, a hydrocarbon group including a linking group, or a halogenated group including a linking group. Represents a hydrocarbon group, M represents at least one metal atom selected from the group consisting of a silicon atom, a germanium atom, a tin atom, a titanium atom, and a zirconium atom, and X represents a hydroxyl group or a hydrolyzable group. , N represents an integer of 1 to (m−1), m represents a valence of M, and when n is 2 or more, R ¹ may be the same or different, and (m When -n) is 2 or more, X may be the same or different.

  Examples of the hydrocarbon group that may have a substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. Group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-decyl group and the like. An alkenyl group having 2 to 30 carbon atoms such as a vinyl group, a propenyl group, a butenyl group or a pentenyl group; an aryl group such as a phenyl group or a naphthyl group;

  Examples of the halogenated hydrocarbon group of the halogenated hydrocarbon group which may have a substituent include a halogenated alkyl group having 1 to 30 carbon atoms, a halogenated alkenyl group having 2 to 30 carbon atoms, and a halogenated aryl group. Etc. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned, A fluorine atom is preferable. Specific examples include groups in which one or more of the hydrogen atoms in the hydrocarbon groups exemplified above are substituted with a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom.

  Among these, the halogenated hydrocarbon group is preferably a group in which two or more of the hydrogen atoms in the alkyl group having 1 to 30 carbon atoms are substituted with halogen atoms, and in the alkyl group having 1 to 30 carbon atoms, More preferred is a fluorinated alkyl group in which two or more of the hydrogen atoms are substituted with fluorine atoms. In addition, when the fluorinated alkyl group has a branched structure, the branched portion is preferably a short chain having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms.

The fluorinated alkyl group is preferably a group in which one or more fluorine atoms are bonded to the terminal carbon atom, more preferably a group having a CF ₃ group part in which _three fluorine atoms are bonded to the terminal carbon atom, and the terminal is a fluorine atom. May be a carbon chain in which a fluorine atom is substituted on an internal carbon chain with a hydrocarbon group that is not substituted. The terminal portion has a perfluoroalkyl portion in which all the hydrogen atoms of the alkyl group are substituted with fluorine atoms, and-(CH ₂ ) _h- (wherein h is 1) with the metal atom M described later. Represents an integer of ˜6, preferably an integer of 2 to 4.), and particularly preferred is a group having an alkylene group.

  The number of fluorine atoms in the fluorinated alkyl group is [(number of fluorine atoms in fluorinated alkyl group) / (number of fluorine atoms in fluorinated alkyl group + number of hydrogen atoms in fluorinated alkyl group)] × 100%. When expressed, it is preferably 60% or more, and more preferably 80% or more.

  Examples of the substituent of the hydrocarbon group that may have a substituent or the halogenated hydrocarbon group that may have a substituent include a carboxyl group; an amide group; an imide group; an ester group; a methoxy group, and an ethoxy group. An alkoxy group such as a group; or a hydroxyl group. The number of these substituents is preferably 0-3.

  Specific examples of the hydrocarbon group including a linking group include the same hydrocarbon groups as those described above as the hydrocarbon group of the hydrocarbon group which may have a substituent.

  In addition, as the halogenated hydrocarbon group of the halogenated hydrocarbon group containing a linking group, specifically, those listed as the halogenated hydrocarbon group of the halogenated hydrocarbon group which may have the above substituent The same thing is mentioned.

The linking group is preferably present between carbon-carbon bonds of a hydrocarbon group or a halogenated hydrocarbon group, or between carbon of the hydrocarbon group and a metal atom M described later.
Specific examples of the linking group include —O—, —S—, —SO ₂ —, —CO—, —C (═O) O— or —C (═O) NR ⁵¹ — (wherein R ⁵¹ represents A hydrogen atom; an alkyl group such as a methyl group, an ethyl group, an n-propyl group or an isopropyl group).

Among these, as R ¹ , from the viewpoint of water repellency and durability, an alkyl group having 1 to 30 carbon atoms, a fluorinated alkyl group having 1 to 30 carbon atoms, or a fluorinated group having 1 to 30 carbon atoms including a linking group. An alkyl group is preferred.

  M represents one kind of atom selected from the group consisting of a silicon atom, a germanium atom, a tin atom, a titanium atom, and a zirconium atom. Among these, a silicon atom is particularly preferable from the viewpoints of availability of raw materials and reactivity.

  X represents a hydroxyl group or a hydrolyzable group, and the hydrolyzable group is not particularly limited as long as it is a group that reacts with water and decomposes. Specifically, the C1-C6 alkoxy group which may have a substituent, the alicyclic hydrocarbon oxy group which may have a substituent, and the aromatic which may have a substituent. Having a substituent such as an aromatic hydrocarbonoxy group, an alkenyloxy group which may have a substituent, an alkynyloxy group which may have a substituent, an aralkyloxy group which may have a substituent. Optionally substituted hydrocarbonoxy group; acyloxy group optionally having substituent; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; isocyanate group; cyano group; amino group; or amide group Etc. can be illustrated.

  Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, n-pentyloxy group, and n-to. A xyloxy group etc. are mentioned.

Examples of the alicyclic hydrocarbon oxy group include cyclopropyloxy group, cyclopropylmethyloxy, cyclohexyl group, norbornyloxy group and the like.
Examples of the aromatic hydrocarbon oxy group include a phenoxy group and a naphthyloxy group.
Examples of the alkenyloxy group include a vinyloxy group and an allyloxy group.
Examples of the alkynyloxy group include a prop-1-in-1-yloxy group and a but-1-in-1-yloxy group.
Examples of the aralkyloxy group include a benzyloxy group and a phenethyloxy group.
Examples of the acyloxy group include an acetoxy group, a propionyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, and an n-butylcarbonyloxy group.

Examples of these substituents include a carboxyl group, an amide group, an imide group, an ester group, and a hydroxyl group.
Among these, X is preferably a hydroxyl group, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an acyloxy group, or an isocyanate group, and more preferably an alkoxy group having 1 to 4 carbon atoms or an acyloxy group.

m represents the valence of the metal atom M.
n represents any integer of 1 to (m−1). In producing a high-density organic thin film, n is preferably 1.
When n is 2 or more, R ¹ may be the same or different.
When (mn) is 2 or more, Xs may be the same or different.

(Catalyst that can interact with metal surfactant)
The catalyst contained in the organic thin film forming solution and capable of interacting with the metal-based surfactant includes a metal part or a hydrolyzable group part of the metal-based surfactant, via a coordination bond, a hydrogen bond, etc. The catalyst is not particularly limited as long as it is a catalyst having an action of activating a hydrolyzable group or hydroxyl group and promoting condensation by interacting. Among them, a metal oxide; a metal hydroxide; a metal alkoxide; a chelated or coordinated metal compound; a metal alkoxide partial hydrolysis product; and a metal alkoxide treated with two or more equivalents of water. The obtained hydrolysis product; organic acid; at least one compound selected from the group consisting of a silanol condensation catalyst and an acid catalyst is preferable, and metal alkoxides and metal alkoxide partial hydrolysis products are more preferable.

(Organic solvent used for organic thin film forming solution)
As the organic solvent used in the organic thin film forming solution, it is preferable that the hydrolysis product of the metal alkoxide is dispersed in the organic solvent, and the metal surfactant is treated with water. Therefore, a solvent that has high water solubility and does not solidify at a low temperature is more preferable.

  Specific examples of the organic solvent used include alcohol solvents such as methanol, ethanol and isopropanol; halogenated hydrocarbon solvents such as methylene chloride, chloroform and chlorobenzene; hydrocarbon solvents such as hexane, cyclohexane, benzene, toluene and xylene. Ether solvents such as tetrahydrofuran, diethyl ether and dioxane; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; amide solvents such as dimethylformamide and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; methyl polysiloxane , Silicones such as octamethylcyclotetrasiloxane, decamethylcyclopentanesiloxane, and methylphenylpolysiloxane (JP-A-9-208438). .

These solvents can be used alone or in combination of two or more.
When used as a mixed solvent, a combination of a hydrocarbon solvent such as toluene or xylene and a lower alcohol solvent system such as methanol, ethanol, isopropanol, or t-butanol is preferable. In this case, the lower alcohol solvent is more preferably a secondary or higher alcohol solvent such as isopropanol or t-butanol. The mixing ratio of the mixed solvent is not particularly limited, but it is preferable to use a hydrocarbon solvent and a lower alcohol solvent in a volume ratio of 99/1 to 50/50.

(5) Method of dropping a solution onto a substrate As a dropping method of the present invention, in the case of a small scale, a manually operable instrument such as a bullet can be used, and the dropping amount can be controlled industrially and continuously. It is possible to use an automatic dripping apparatus capable of dripping.
In order to drop an appropriate amount of the thin film forming solution onto the base material, for example, as shown in JP-A-8-318200, several sensors are arranged on the table, and the thin film forming solution on which the sensor has been dropped is detected. The dripping of the thin film forming solution can also be stopped.
Moreover, it can be dripped only a fixed amount continuously, transferring the base which can be rotated by means, such as a conveyor belt, to the lower part of a dripping apparatus. Conversely, the dropping port may be moved.
The dripping amount is at least an amount sufficient to coat a necessary portion on the substrate.
One or a plurality of dripping ports can be installed. When a plurality of dripping ports are provided, one drip port may be provided for each substrate, or a plurality of dripping ports may be provided for one substrate. You may do it.
In the case of one dripping port with respect to one base material, it positions so that the front-end | tip of a dripping port may come to the center of a base material. Further, when a plurality of dropping ports are provided for one base material, the position of the dropping port is set so that the dropped solution is equally coated.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, the technical scope of this invention is not limited to these illustrations.

[Example 1]
A double-sided tape for fixing is stuck on the cross-shaped stirrer chip and placed in a 1 L SUS container. After placing the SUS container on a magnetic stirrer, a diameter: 2 inch (50 mm) Si wafer subjected to UV / O ₃ cleaning treatment for 10 minutes was fixed on a cross-shaped stirrer chip with double-sided tape.
An organic thin film forming solution (SAMLAY (registered trademark) manufactured by Nippon Soda Co., Ltd.) was gently spread over the entire surface of the Si wafer so as not to spill from the wafer, and held for 1 minute. After 1 minute, the magnetic stirrer was operated to rotate the Si wafer, and the organic thin film forming solution on the Si wafer was shaken off.
Thereafter, a cleaning solvent (NS Clean 100 (registered trademark) manufactured by Nikko Petrochemical Co., Ltd.) was gently spread on the Si wafer and held for 1 minute. After 1 minute, the magnetic stirrer was operated to rotate the Si wafer, and the cleaning solvent on the Si wafer was shaken off.
The shaken Si wafer was placed in a dryer at 60 ° C., the solvent on the substrate was dried, and an organic thin film was produced on the Si wafer.

[Example 2]
A double-sided tape for fixing the Si wafer was attached to the center fixing position of the spin coater, and a diameter / 8 inch (200 mm) Si wafer subjected to UV / O ₃ cleaning treatment for 10 minutes was fixed on the double-sided tape.
An organic thin film forming solution (SAMLAY (registered trademark) manufactured by Nippon Soda Co., Ltd.) was gently spread over the entire surface of the Si wafer so as not to spill from the wafer, and held for 1 minute. After 1 minute, the spin coater was operated to rotate the Si wafer, and the organic thin film forming solution on the Si wafer was shaken off.
Thereafter, the cleaning solvent (NS Clean 100 (registered trademark) manufactured by Nikko Petrochemical Co., Ltd.) was gently spread on the Si wafer and held for 1 minute. After 1 minute, the spin coater was operated to rotate the Si wafer, and the cleaning solvent on the Si wafer was shaken off.
The shaken Si wafer was placed in a dryer at 60 ° C., the solvent on the substrate was dried, and an organic thin film was produced on the Si wafer.

  By using the method of the present invention, the treatment liquid does not adhere to the back surface of the base material, and the organic thin film forming solution attached to the back surface of the base material does not wrap around the surface. A clean thin film with no trace of liquid flow can be produced. Moreover, since the method of the present invention produces an organic thin film having a water-repellent group on a hydrophilic substrate, it is not necessary to rotate the stage or move the dropping port, and the organic thin film is easily produced. be able to.

Claims (2)

(A) After the substrate having a hydrophilic surface is placed and fixed on a horizontal table,
(B) An organic thin film forming solution having a water repellent group is dropped on the substrate in an amount that can cover the substrate surface;
(C) A method for producing an organic thin film, wherein the organic thin film is allowed to stand for a period of time sufficient to form an organic thin film on a substrate, and then the excess organic thin film forming solution is removed by tilting the table. 2. The method for producing an organic thin film according to claim 1 , wherein the organic thin film is a monomolecular film.