JP2763357B2 - Manufacturing method of substrate with fine pattern - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[Industrial applications]

The present invention relates to a method for manufacturing a substrate with a fine pattern, and more particularly to a method for manufacturing a substrate with a fine pattern useful as an optical disk substrate, a diffraction grating, and the like.

[Prior art]

Conventionally, as a method of manufacturing a substrate with a fine pattern, a plastic coating film is formed by applying a solution containing a metal organic compound onto a substrate such as glass, and the coating film is pressed against a mold having fine irregularities. There is known a method of manufacturing a substrate with a fine pattern, in which a groove shape corresponding to a peak shape of a mold is transferred, and then, the coating film on which the fine irregularities are transferred is baked and solidified. (For example, Japanese Patent Application Laid-Open No.
−225273, JP-A-63-158168)

[Problems to be solved by the invention]

However, in the case of a substrate with a fine pattern manufactured by the above-described conventional method, in a long-term use, the refractive index of the fine unevenness film changes or the film thickness changes, and a change in optical characteristics based on this change occurs. There was a problem. Further, when another film body is further laminated on the fine uneven film, there is a problem that the adhesion between the films is reduced with time and the film is peeled off in a long-term use. The above problem is an extremely serious problem particularly when the above-mentioned basic with a fine pattern is used as a substrate for an optical disc, because it causes deterioration of an electric signal.

[Means for Solving the Problems]

The present invention has been made in order to solve the above-mentioned conventional problems, and the fine-patterned substrate is formed on a substrate by a sol-gel method using a solution containing a metal compound. In the basic manufacturing method with a fine pattern for forming a coating of an organic-inorganic composite material or an inorganic material having a projection and a depression, the coating having the projection and the depression is formed by M
(OR) after being formed from at least one metal compound selected from the group consisting of a metal alcoholate represented by _n , a chelate complex, and an organometallic compound containing a general functional group that undergoes polycondensation or cross-linking reaction, General formula XMR _n-1 (X: functional group reacting with metal-hydroxyl bond such as halogen, M: valence of n so that difference in change in refractive index when desorbing adsorbed water is performed is 0.04 or less A metal having R, a hydrophobic organic functional group in which hydrogen of an alkyl group or an alkyl group is partially substituted with a halogen), X ₂ MR _n-2 (X: an alkoxyl group, or a reaction with a metal-hydroxyl bond such as a halogen) Functional groups,
M: a metal having a valence of n, R: an alkyl group, or a hydrophobic organic functional group in which hydrogen of an alkyl group is partially substituted with halogen, or R _n-1 MNHMR _n-1 (a valence of M: n A metal having a structure, R: an alkyl group, or a hydrophobic organic functional group in which hydrogen of an alkyl group is partially substituted with halogen, N: nitrogen, H: hydrogen) or a solution of an organometallic compound having a structure of the organometallic compound. It can be produced by performing a capping treatment in which the film is brought into contact with steam or a steam treatment to reduce the hygroscopicity in the film and to set the final heat treatment temperature of the film to 600 ° C. or lower. Further, for example, X _n-1 MR (X: an alkoxy group or a functional group crosslinked by hydrolysis such as halogen, M: metal, n: a natural number representing the valency of the metal, R: an alkyl group, or hydrogen of an alkyl group Can be produced by using a solution containing a hydrolyzed / condensed polymer of an organometallic compound having a hydrophobic organic group represented by the general formula (functional group partially substituted with halogen). Further, it can also be produced by including an organic polymer in the coating. The basic concavo-convex film with a fine pattern produced in the present invention is a film in which the difference in refractive index change when desorbing moisture adsorbed in the film is 0.04 or less. The change in the refractive index when performing, for example, the coated substrate under a reduced pressure of 10 ^-5 Torr, once held at 150 ℃ for about 30 minutes, then cooled to 25 ℃, under the reduced pressure, By measuring the refractive index of the film in a dry state without, then at 25 ° C., held in the atmosphere at a relative temperature of 90 ° C. for a few minutes, measure the refractive index of the film in the hygroscopic state under the above conditions, and determine the difference Can be measured. In addition, for simplicity, the coated substrate is usually placed in an atmosphere.
It can be measured by heating to about 150 ° C., immediately holding in a vortex of a dry nitrogen flow to obtain a refractive index, then flowing air, obtaining a refractive index in a normal atmosphere, and calculating a difference between the two refractive indexes. In a substrate with a fine pattern having a film produced so as to satisfy the conditions of the present invention, deterioration of characteristics due to a weather resistance test (accelerated test) is remarkably improved. Even if the hygroscopicity of the film is reduced from the hygroscopicity of a film prepared by a conventional method, when the refractive index change due to the water adsorption is larger than 0.04, particularly when used as a substrate for an optical disc, a weather resistance test is performed. Deterioration of the electrical signal has occurred. As the substrate used in the present invention, any substrate such as glass, ceramic, metal, and plastic can be used depending on the use of the substrate with the fine pattern. However, adhesion to the film, optical properties, and mechanical properties For example, glass is preferably used. Among them, when used as an optical disk substrate, soda lime glass, which can be chemically strengthened, is inexpensive, and is not easily heat-treated at a temperature higher than 600 ° C., is particularly preferably used. Also, by preventing the diffusion of alkali in the glass substrate on the soda-lime glass substrate, the film-coated glass substrate that reduces the burn of the glass substrate, particularly when used as a glass substrate for optical discs from the viewpoint of reliability, preferable. Various shapes can be used as the fine pattern of the mold.For example, it can be used as a pit pattern of a read-only optical disk, a fine pattern with a width of about 0.7 μm and a height of about 150 nm, and a guide groove for an optical disk A fine pattern having a possible width of about 1 μm and a depth of 50 to 200 nm or a pattern having a shape of several hundred nm that can be used as a diffraction grating or a grating lens can be used. The metal compound used in the present invention may be any compound that increases the viscosity of a solution by a polycondensation or crosslinking reaction. For example, Si (OCH ₃ ) ₄ , Si (OC ₂ H ₆ ) ₄ , Ti (OC ₃ H ₇ ) ₄ , Ti
(OC ₄ H ₉ ) ₄ , Zr (OC ₃ H ₇ ) ₄ , Zr (OC ₄ H ₉ ) ₄ , Al (OC ₃ H ₇ ) ₃ ,
M (OR) _{n of} Al (OC ₄ H ₉ ) ₃ , NaOC ₂ H ₆ etc. [M is Si, Ti, Zr, C
a, Al, Na, Pb, B, Sn, Ge, etc., a metal such as R, an alkyl group such as methyl, ethyl, etc., and n is an integer of 1-4]. chelate complexes, and _{-Cl, -COOH, -COOR, -NH 2} , Metal organic compounds containing a general functional group that undergoes a polycondensation or cross-linking reaction. Among them, metal alcoholates are preferably used. Further, as a metal compound other than the metal organic compound,
(CH ₃ O) ₃ SiCH ₃ , (C ₂ H ₅ O) ₃ SiCH ₃ , (CH ₃ O) ₃ SiC ₂ H ₅ , (C
_{2 H 5 O) 3 SiC 2} H 5, (CH 3 O) 3 SiC 6 H 5, (C 2 H 5 O) 3 SiC 6 H 5, Cl 3
SiCH ₃ , Cl ₃ SiC ₂ H ₅ , Cl ₃ SiC ₆ H ₅ , (CH ₃ O) ₂ Si (CH ₃ ) ₂ , Cl ₂ S
i (CH ₃ ) ₂ , (CH ₃ O) ₂ Si (CH ₂ CF ₃ ) ₂ , Cl ₂ Si (CH ₂ CF ₃ ) ₂ ,
(CH ₃ O) Si (CH ₃ ) ₃ , ClSi (CH ₃ ) ₃ , (CH ₃ O) Si (CH ₂ C
F ₃ ) ₃ , ClSi (CH ₂ CF ₃ ) ₃ , (CH ₃ O) ₃ Si (CH ₂ CF ₃ ), Cl ₃ Si
(CH ₂ CF ₃ ), (CH ₃ O) ₃ TiCH ₃ , (C ₂ H ₅ O) ₃ TiCH ₃ , (CH
_{3 O) 2 Ti (CH 3} ) 2, (C 2 H 5 O) 2 Ti (CH 3) 2, Cl 3 TiCH 3, Cl 2 Ti (CH 3) 2, (CH 3 O) 3 Ti (CH 2 CF ₃ ), Cl ₃ Ti
(CH ₂ CF ₃ ) and other X _nm MR _m (X: alkoxy group or functional group cross-linkable by hydrolysis such as halogen, X: metal, n: natural number representing the valency of metal, m: 1 or more (n− 1) An organic metal compound having a hydrophobic organic group represented by the general formula of the following natural numbers (R: an alkyl group or a functional group in which hydrogen of an alkyl group is partially substituted with halogen) can be exemplified. The above-mentioned metal compound is mixed with an organic solvent such as water and alcohol, and, if necessary, with an acid or alkali hydrolysis catalyst as one or a mixture of two or more kinds to form a coating solution. Further, in particular, in the present invention, it has the effect of increasing the viscosity of the solution containing the metal compound, facilitates the formation of a coating film, and at the same time, when performing the step of pressing the substrate and the mold under reduced pressure, A thickener that has the effect of maintaining the coating film in a soft state (a moderately viscous state) for a long time even under reduced pressure and that facilitates patterning is often used. As the thickener, a polymer material that is water-soluble and soluble in an organic solvent is preferably used. Among them, chain polyethers such as polyethylene glycol and polytetramethylene ether glycol are preferably used. The amount of the polyethylene glycol, polytetramethylene ether glycol or the like to be added is preferably about 0.25 to 1.8 times the weight of the metal oxide produced by the coating solution. (If the addition amount is less than 0.25 times, the coating film is likely to be hardened at the time of decompression and patterning tends to be difficult. Conversely, if the addition amount is more than 1.8 times, the coating film becomes too soft and loses shape. It is considered that the change in the refractive index due to moisture absorption can be reduced to 0.04 or less by reducing the concentration of the metal-hydroxyl group acting as a water adsorption site in the fired film, for example. Reduction of the hydroxyl group concentration can be achieved by capping treatment, steam treatment, chlorination treatment, high-temperature heat treatment, or the like. The chlorination treatment and the high-temperature heat treatment require heating the substrate to about 600 ° C. or more, though depending on the composition of the coating, in order to change the refractive index of the coating due to the moisture adsorption to 0.04 or less. It can be used when there is no limitation on the heating temperature of the substrate. However, when the heating temperature is limited to a high temperature such as the above-mentioned soda-lime glass and plastic, it cannot be carried out, and capping treatment and steam treatment are effective means. Capping treatment is performed using XMR _n-1 (X: metal such as halogen).
A functional group that reacts with a hydroxyl bond, M: a metal having a valence of n, R: an alkyl group, or a hydrophobic organic functional group in which hydrogen of an alkyl group is partially substituted with halogen, X ₂ MR _n-2 (X : An alkoxyl group, or a functional group that reacts with a metal-hydroxyl bond such as halogen, M: a metal having a valence of n, R: an alkyl group, or a hydrophobic organic functional group in which hydrogen of an alkyl group is partially substituted with halogen ) Or R _n-1 MNHMR _n-1 (M: metal having a valence of n, R: an alkyl group, or a hydrophobic organic functional group in which hydrogen of an alkyl group is partially substituted with halogen, N: nitrogen, H : Hydrogen) by bringing an organometallic compound having a structure such as a solution or a vapor into contact with the coating. The steam treatment can be performed by baking, in particular, exposing the film to steam of 100 kPa or more. The temperature of the steam treatment is 10
Performing at 0 ° C. or higher is efficient in terms of reaction time and the like. The change in refractive index due to moisture absorption can be reduced to 0.04 or less, for example, by reducing pores in the fired film. The pores in the fired film can be reduced by capping treatment, steam treatment, chlorine treatment, high-temperature heat treatment, or by actively remaining or impregnating an organic substance in the film. Examples of the remaining organic substance include water and organic polymers having solubility in alcohol. The thickness of the fired film body with a fine pattern provided on the substrate in the present invention is preferably about 0.1 to 5 μm.

[Action]

The present invention is a conventional refractive index change of the uneven coating, a change in film thickness,
Adhesive strength reduction, and electrical signal degradation when used as an optical disc substrate, etc., was considered in view of the fact that it is caused by moisture absorption of the fired film, and as the film body, a film having low hygroscopicity was used. I'm using According to the present invention, since the hygroscopicity of a fired film having a fine pattern is reduced, problems such as a change in the refractive index or a change in the film thickness of the fired film with a fine pattern with time, which have conventionally occurred, are avoided. it can. When another film body is further laminated on the coating,
It is possible to avoid the problems that have conventionally occurred, such as a decrease in the adhesive force of the film and the peeling of the film over time. In particular, when the substrate with a fine pattern is used as a substrate for an optical disk, the above-mentioned causes do not cause deterioration of an electric signal.

【Example】

Example 1 0.05 mol of silicon tetraethoxide is weighed, and a 5-fold molar ratio of ethanol and 6-fold water (containing 3 wt% HCl) are added thereto, followed by stirring at room temperature for 1 hour. 2 in this solution
Dilute by adding twice the volume of ethanol, and further add an average molecular weight of 20.
0 or 600 polyethylene glycol (hereinafter PEG2
(PEG, abbreviated as PEG 600) was added to the final product, SiO _{2, in} a weight ratio of (PEG) / (SiO ₂ ) = 1.0 and uniformly dissolved. did. Into this coating solution 1 or coating solution 2, an outer diameter of 130m
After a disk substrate made of chemically strengthened glass having a thickness of 1.2 mm and a thickness of 1.2 mm was immersed, it was slowly pulled up to form a coating film on the substrate. Then, the width of about 0.7μm, a large number of fine pit patterns of about 150nm height in the range of 25mm to 60mm radius 130mm outside diameter, 1.2mm thick resin mold and this glass substrate to prevent air from entering I pressed. Thereafter, heating was performed in this state, and firing was performed at 100 ° C. for 10 minutes. At that time, the mold and the glass disk were released, and further, the glass disk was fired at 350 ° C. for 15 minutes. By this baking operation, the coating film becomes an amorphous film having a thickness of about 0.2 μm similar to glass due to the scattering of ethanol, moisture and the like. Next, a capping process was performed for the purpose of reducing the hygroscopicity of the fired film on the surface of the glass disk with a fine pattern manufactured by the above operation. The capping treatment was performed using the following treatment solutions 1 and 2. Treatment solution 1. 2.5 wt% hexane solution of chlorotrimethylsilane. Treatment solution 2. 2.5 wt% hexane solution of dimethoxydimethylsilane. Above the glass substrate with the fine pattern obtained by baking at 350 ° C for 15 minutes. To get rid of
After drying again at 200 ° C., immediately after drying, it was immersed in one of the treatment solutions 1 and 2, refluxed near the boiling point of hexane for 60 minutes, and finally dried at 200 ° C. to perform a capping treatment. The effect of reducing the hygroscopicity by the capping treatment was better when the treatment solution 2 and then the treatment solution 1 were used. The refractive index change due to moisture absorption of a fired film having fine irregularities on a glass substrate for an optical disk manufactured using the processing solution 2 using dimethoxydimethylsilane was determined by adding PEG200.
1.426 to 1.432 (variation 0.006) for SiO ₂ fired film, P
1.408 to 1.416 for the baked SiO ₂ film with EG600 added
(Variation 0.008). The change in the refractive index of a fired film having fine irregularities on a glass substrate for an optical disk produced by using the treatment solution 1 using chlorotrimethylsilane due to moisture absorption was caused by the addition of PEG200 to Si.
1.388 to 1.416 (change amount 0.028) for baked O ₂ film, PEG
In the case of the SiO ₂ fired film to which 600 was added, the value was 1.363 to 1.388 (change amount: 0.025). The measurement of the refractive index change due to moisture absorption is performed by measuring the above-mentioned coated substrate.
After once holding at 150 ℃ for about 15 minutes under reduced pressure of 10 ^-5 Torrb
Cool to 25 ° C., measure the refractive index of the dried film without adsorbed moisture under the reduced pressure, and then hold for 4 minutes in the atmosphere at 25 ° C. and a relative humidity of 60%, then measure the refractive index again (Other conditions are constant). These results are shown in Table 1. Comparative Example 1 Using the glass disk with a fine pattern produced in Example 1, a change in refractive index due to moisture absorption was measured. The change in the refractive index due to moisture absorption was from 1.334 to 1.424 when the PEG 200 prepared in Example 1 was added and left in the air.
(Change amount 0.08), whereas in the case of adding PEG600, it changed from 1.300 to 1.395 (change amount 0.095). These results are shown in Table 1 as blanks. Comparative Example 2 A capping process was performed in the same manner as in Example 1, using the glass disk with a fine pattern manufactured in Example 1. The following treatment solutions a and b were used as capping treatment solutions. Treatment solution a. 2.5 wt% hexane solution of dichlorodimethoxysilane Treatment solution b. 2.5 wt% hexane solution of methoxytrimethylsilane When the above treatment solutions a and b were used, the change in refractive index due to moisture absorption due to capping was 0.04. Did not go below. These results are shown in Table 1. An Au-based metal reflective film was formed on the disk substrate with the fine pattern of Sample Nos. 1 to 10 shown in Table 1 and the weather resistance test was conducted.
The evaluation was performed for 24 hours under the conditions of ° C. and 80% relative humidity (RH), and the electric signal was evaluated. The results are shown in Table 2. In Table 2, 信号, △, △, ×, and XX in the signal evaluation indicate good characteristics in the order of ＞>○>△>×> xx, and ◎ indicates 10 ⁻⁵ to 10 ^−. The increase of the block error rate by about ⁴ and the mark XX indicate that the reflection film was peeled off visually, indicating a signal decrease in which the error rate could not be measured. From Table 2, it can be seen that the capping treatment was performed with the treatment solutions 1 and 2, and the deterioration of the electric signal and the like was hardly recognized on the substrate with the fine pattern having a change in the refractive index of 0.04 or less. Example 2 0.167 mol of silicon tetraethoxide is weighed, and 4 times ethanol and 4 times water (containing 3 wt% HCl) are added thereto in a molar ratio, and the mixture is stirred at room temperature for 30 minutes. A solution prepared by diluting 0.033 mol of titanium tetranormal butoxide with ethanol is gradually added to the solution, and the mixture is stirred at room temperature for 30 minutes. The solution was diluted by adding two volumes of ethanol, further polyethylene glycol having a molecular weight of 600 (PEG _600), in a weight ratio SiO ₂ + TiO ₂ as the final product _{(PEG 600) / (SiO 2} + TiO 2) = 1.0 was added and uniformly dissolved to obtain a coating solution 3. A disk substrate made of chemically strengthened glass having an outer diameter of 130 mm and a thickness of 1.2 mm was immersed in this coating solution, and then slowly pulled up to form a coating film on the substrate. Next, Example 1
Transfer and firing of the fine pit pattern were performed in the same manner. The resulting TiO ₂ -SiO ₂ based porous fired film was subjected to the same capping process using the processing solution 2 of Example 1. It has fine irregularities on a glass substrate for an optical disk manufactured using the processing solution 2 using dimethoxydimethylsilane.
The refractive index change of the TiO ₂ -SiO ₂ based fired film due to moisture absorption was 1.49.
It was from 0 to 1.528 (change amount 0.038). An Au-based metal reflective film was formed on a glass substrate for an optical disk prepared using the treatment solution 2 using dimethoxydimethylsilane, and a weather resistance test (60 ° C., 80% RH, 24 hours) was performed. After the test, almost no deterioration of the electric signal of the disk substrate was recognized. The coating solution 2 of SiO ₂ containing PEG600 prepared in Example -3 previous example -1 was used. The coating solution was dropped on a chemically strengthened glass disk having a diameter of 120 mm, and the substrate was rotated to perform spin coating. The fine pit pattern was transferred and baked on the coating film thus obtained on the glass disk substrate in the same manner as in Example-1. The obtained porous SiO ₂ fired film having fine irregularities
Drying was performed at 4 × 10 ⁻⁵ torr and 120 ° C. for 15 minutes. Then
Hexamethyldisilazane was introduced into the vessel, kept at 1 torr for 5 minutes, and evacuated (<10 ^-2 torr). Further, introduction, holding and exhaust of hexamethyldisilazane were repeated twice, and the product was taken out after leaking. The refractive index change due to moisture absorption of the fired film having fine irregularities of the glass substrate for an optical disk produced by the capping treatment with paper using hexamethyldisilazane was 1.368 to 1.395 (change amount 0.027). An Au-based metal reflective film was formed on a glass substrate for an optical disk produced by capping with paper using the above hexamethyldisilazane, and a weather resistance test (60 ° C, 80%
RH, 24 hours). After the test, almost no deterioration of the electric signal of the disk substrate was recognized. Example-4 Using the coating solution 1 and the coating solution 2 prepared in the previous Example-1, a substrate was immersed in a solution on a quartz substrate and pulled up to form a coating film. An acetylcellulose mold having fine irregularities was pressed against the coating film, dried at 100 ° C., released, and baked at 350 ° C. to produce a diffraction grating having a depth of about 100 nm. By the above method, quartz substrate and porous Si with fine irregularities
Steam treatment was performed by maintaining the diffraction grating composed of the O ₂ film at 135 ° C. and 90% relative humidity for 170 hours. The refractive index change due to moisture absorption of the fired film having fine irregularities of the SiO ₂ diffraction grating produced by performing the steam treatment was 1.360 to 1.384 (change amount 0.024) when PEG200 was added, and PEG600 was added. From 1.357 in case of things
It was 1.378 (change amount 0.021).

【The invention's effect】

According to the method for manufacturing a substrate with a fine pattern of the present invention,
As is clear from the examples, the hygroscopicity is lower than that of the conventional fine-patterned substrate without any treatment for reducing moisture absorption, and the refractive index of the fine-pattern fired film changes or the film thickness changes with time. Thus, a substrate with a fine pattern having no problem of producing a substrate can be manufactured. Further, when another film body is laminated on the fired film, a substrate with a fine pattern can be manufactured without the problem that the adhesion between the films decreases with time and the film peels off. . In particular, when a substrate with a fine pattern formed by the method for manufacturing a substrate with a fine pattern is used as a substrate for an optical disk, electric signal deterioration due to the above-described causes does not occur. Therefore, a substrate for an optical disk such as a read-only optical disk, a recordable optical disk, a rewritable optical disk, and a phase-change optical disk, or an optical disk that can be used as a micro optical element such as a diffraction grating or a lens, which requires reliability. A substrate can be made.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Shinya Katayama 3-5-1, Doshu-cho, Chuo-ku, Osaka-shi, Osaka Inside Nippon Sheet Glass Co., Ltd. (72) Inventor Toshio Kado 3-chome, Doshu-cho, Chuo-ku, Osaka-shi, Osaka No. 5-11 Nippon Sheet Glass Co., Ltd. (72) Inventor Fumitake Watanabe 5-33-1, Shiba, Minato-ku, Tokyo NEC Corporation (72) Inventor Mikiko Saito 5-3-1, Shiba, Minato-ku, Tokyo NEC Corporation (72) Inventor Hirotaka Yamaguchi 5-33-1, Shiba, Minato-ku, Tokyo NEC Corporation (72) Inventor Masahiro Yanagisawa 5-33-1, Shiba, Minato-ku, Tokyo NEC Corporation (56) References JP-A-63-153746 (JP, A) JP-A-63-225536 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G11B 7/26 G11B 7 / 24 G02B 5/18 B32B 3/30 B32B 7/02 1 03 B32B 31/24

Claims (2)

(57) [Claims] 1. A basic method for forming a coating of an organic-inorganic composite material or an inorganic material having an uneven surface on a substrate, which is formed by a sol-gel method using a solution containing a metal compound on a substrate. In the method, the coating having the uneven shape is formed by forming at least one selected from the group consisting of a metal alcoholate represented by M (OR) _n , a chelate complex, and an organometallic compound containing a general functional group that performs a polycondensation or crosslinking reaction. After forming from two metal compounds, the general formula XMR _n-1 (X: metal-hydroxyl group such as halogen, etc.) such that the difference in the change in refractive index when desorption of water adsorbed in the film is performed on the film is 0.04 or less. A functional group that reacts with a bond, M: a metal having a valence of n, R: an alkyl group, or a hydrophobic organic functional group in which hydrogen of an alkyl group is partially substituted with halogen), X ₂ MR
_n-2 (X: alkoxyl group, or a functional group that reacts with a metal-hydroxyl bond such as halogen, M: a metal having a valence of n,
R: an alkyl group or a hydrophobic organic functional group in which hydrogen of the alkyl group is partially substituted with halogen), or R _n-1 MNHMR _n-1
(M: metal having a valence of n, R: an alkyl group, or a hydrophobic organic functional group in which hydrogen of an alkyl group is partially substituted with halogen, N: nitrogen, H: hydrogen) Capping treatment to be brought into contact with the solution or the vapor of the organometallic compound, or steam treatment to reduce the hygroscopicity in the film, and the final heat treatment temperature of the film is set to 600 ° C. or less. A method for producing a patterned substrate. 2. The method for producing a substrate with a fine pattern according to claim 1, wherein the steam treatment is a method of maintaining the atmosphere at a steam pressure of 100 kPa or more.