JPH11271981A - Substrate with noble metallic colloid dispersed layer and pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a substrate coated easily and rapidly with a pattern contg. noble metallic colloid and having excellent optical function by disposing a silicon-contg. high molecular compd. layer contg. dispersed noble metallic colloid obtd. by bringing a noble metallic salt into contact and reduction with a silicon- contg. high molecular compd. having reducing property. SOLUTION: A polysilane film 2 is formed on a substrate 1 and selectively irradiated with light to form a pattern having Si-O bonds in the irradiated part and the substrate 1 is immersed in a soln. of a noble metallic salt 5 to form and disperse noble metallic colloid in the unexposed polysilane part. The objective substrate coated with a pattern of a noble metallic colloid dispersed high molecular compd. is obtd. through the easy and rapid steps.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substrate having a silicon-based polymer compound layer in which a noble metal colloid is dispersed, and a method for forming a pattern of the silicon-based polymer compound layer.

[0002]

2. Description of the Related Art It is well known that a substrate coated with a polymer compound in which a noble metal colloid is dispersed has specific electronic and optical functions. For example, A. W. Olesn et al. Report that when a gold colloid is dispersed in a diacetylene-based polymer compound, the third-order nonlinear characteristics are greatly improved (JA.
m. Chem. Soc. , 113 (1991) 775.
8).

[0003] Usually, a substrate coated with such a noble metal colloid is prepared by reacting a noble metal salt with a polymer compound capable of stabilizing the colloid and a reducing low molecular weight compound such as formalin or sodium borohydrate. It is produced by coating the colloid. However, the two actions of stabilizing the colloid and reducing the salt are performed by two materials, a high molecular compound and a low molecular weight compound, respectively. There is a disadvantage that it is difficult to obtain a substrate coated with the polymer compound dispersed in the polymer. Furthermore, in order to obtain a patterned dispersion substrate of a precious metal colloid, it is necessary to further combine a patterning material such as a resist,
The process was also very complicated.

By the way, polysilane is a very interesting polymer because of its metallicity and electron delocalization, high reducibility and flexibility, and good thin-film formation characteristics compared to carbon. Among those applications, researches using polysilanes have been actively conducted for the purpose of developing a photoresist capable of forming an extremely fine pattern with high precision (for example, Japanese Patent Application Laid-Open No. 6-291273). In addition, we have:
In Japanese Patent Application Laid-Open No. 9-327909, the production of metallic silver from a silver salt utilizing the reducing action of polysilane and the application of this and the optical circuit drawing properties of polysilane make it possible to produce a conductive circuit. Suggests what you can do. However, in order to exhibit high conductivity, contact between the generated metallic silver particles is necessary.
When a silver salt solution having a high concentration of weight% is used, a substrate coated with a polymer compound in which silver colloid is dispersed cannot be obtained. Further, the above proposal does not disclose the production of colloidal gold.

The present invention has been made in view of the above circumstances, and provides a substrate having a metal colloid dispersion layer in which a noble metal colloid is highly dispersed in a silicon-based polymer compound and which exhibits excellent optical functions, and a metal colloid. An object is to provide a pattern forming method for forming a pattern of a dispersion layer.

[0006]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted intensive studies in view of the fact that highly dispersed metal colloids are necessary for achieving optical functionality. In particular, when a noble metal salt is brought into contact with a silicon-based polymer compound having a reducing property, a silicon-based polymer compound having a reducing property has two effects of stabilizing a colloid and reducing a salt. Process and control are simplified, and when polysilane is used as the silicon-based polymer compound having a reducing property, patterning using light can be performed without using other materials such as a resist. And found the present invention.

That is, the present invention relates to [A] a silicon-based polymer compound layer in which the noble metal colloid obtained by contacting and reducing a noble metal salt with a silicon-based polymer compound having a reducing property is dispersed. A substrate, characterized by having
And [B] (1) a step of performing selective light irradiation after forming a polysilane film on the substrate to form a pattern having a Si—O bond in a light irradiation portion, and (2) dissolving a salt in a noble metal. A step of immersing the substrate in step (1) in a solution obtained by the step (1) to form and disperse the colloid of the noble metal in an unexposed part of the polysilane part.

According to the present invention, a substrate coated with a polymer compound in which a noble metal colloid is dispersed can be obtained by a simple and rapid process. In particular, when polysilane is used, a polymer in which a pattern of a noble metal colloid is formed can be obtained. A substrate coated with the compound can be obtained. This is a substrate coated with a polymer compound with a useful noble metal colloid pattern that can be applied to optical elements with various optical functions such as nonlinear optical characteristics and electronic elements with various electronic functions such as sensors. It can be widely used in electric, electronic and communication fields.

Hereinafter, the present invention will be described in more detail. A substrate coated with a polymer compound in which a noble metal colloid of the present invention is dispersed is formed by contacting a noble metal salt with a reducing silicon-based polymer compound. It was done.

Here, as the substrate, an insulator such as glass, ceramic or plastic, a semiconductor such as silicon, or a conductor such as aluminum is used.

In the present invention, as the silicon-based polymer compound having a reducing property, a silicon-based polymer compound having a Si—Si bond and / or a Si—H bond can be used. Polysiloxanes having directly bonded hydrogen atoms (ie, SiH groups) are preferred.

Here, as the polysilane, those represented by the following formula (1) are particularly preferred.

(R ¹ _m R ² _n X _p Si) _q (1) (wherein, R ¹ and R ² are a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, X is R ¹ , an alkoxy group, Represents a halogen atom, an oxygen atom or a nitrogen atom, and m is 0.1 ≦ m ≦
2, n is 0 ≦ n ≦ 1, p is 0 ≦ p ≦ 0.5, 1 ≦ m + n
+ P ≦ 2.5, q is 4 ≦ q ≦ 100,00
It is an integer satisfying 0. )

In the polysilane of the above formula (1),
R ¹ and R ² are a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and R ¹ and R ² may be the same or different from each other; Is an aliphatic, alicyclic or aromatic hydrocarbon group. In the case of an aliphatic or alicyclic hydrocarbon group, it has 1 to 12, preferably 1 to 6 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group And the like. Further, as the aromatic hydrocarbon group, those having 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms are suitable, for example, a phenyl group,
Examples include a tolyl group, a xylyl group, a naphthyl group, a benzyl group, and a phenethyl group. In addition, as the substituted hydrocarbon group, part or all of the hydrogen atoms of the unsubstituted hydrocarbon group exemplified above may be a halogen atom, an alkoxy group, an amino group,
Those substituted with an aminoalkyl group include, for example, a monofluoromethyl group, a trifluoromethyl group, an m-dimethylaminophenyl group and the like. X is, as described above, a group similar to R ¹ , an alkoxy group, a halogen atom, or the like. As the alkoxy group, those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, and an isopropoxy group; Represents a fluorine atom, a chlorine atom, a bromine atom or the like, and usually a methoxy group or an ethoxy group is used.

M is 0.1 ≦ m ≦ 2, especially 0.5 ≦ m ≦
2, n is 0 ≦ n ≦ 1, p is 0 ≦ p ≦ 0.5, especially 0 ≦ p
≦ 0.2 and 1 ≦ m + n + p ≦ 2.5, particularly 1.5 ≦ m + n + p ≦ 2, and q is 4 ≦
It is an integer in the range of q ≦ 100,000, particularly 10 ≦ q ≦ 10,000.

Examples of the polysiloxane having a hydrogen atom directly bonded to a Si atom include an organopolysiloxane represented by the following formula (2) having a SiH group in a side chain and a Si—O—Si bond in a main chain. Can be

[0017] ^{_{(R 3 a R 4 b H}} c SiO d) e (2) ( wherein, R ^3, R ⁴ represents a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group, an alkoxy group or a halogen atom ,
a is 0.1 ≦ a ≦ 2, b is 0 ≦ b ≦ 1, and c is 0.01 ≦
c ≦ 1, d is 0.5 ≦ d <1.95, 2 ≦ a + b + c +
a number satisfying d ≦ 2.5, e is 4 ≦ e ≦ 100,000
Is an integer that satisfies )

In the polysiloxane of the above formula (2),
R ³ and R ⁴ are a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and R ³ and R ⁴ may be the same or different from each other; Is an aliphatic, alicyclic or aromatic hydrocarbon group. In the case of an aliphatic or alicyclic hydrocarbon group, it has 1 to 12 carbon atoms, preferably 1 to 6; for example, a methyl group, an ethyl group, a vinyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentyl group And a cyclohexyl group. As the aromatic hydrocarbon group, those having 6 to 14, more preferably 6 to 10 carbon atoms are suitable, and examples thereof include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a benzyl group, and a phenethyl group. Examples of the substituted hydrocarbon group include those obtained by substituting a part or all of the hydrogen atoms of the unsubstituted hydrocarbon groups exemplified above with a halogen atom, an alkoxy group, an amino group, an aminoalkyl group, and the like, for example, monofluoromethyl. Group, trifluoromethyl group, m-dimethylaminophenyl group and the like. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, and an isopropoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Usually, a methoxy group and an ethoxy group are used.

A is 0.1 ≦ a ≦ 2, especially 0.5 ≦ a ≦
2, b is 0 ≦ b ≦ 1, c is 0.01 ≦ c ≦ 1, especially 0 ≦ b ≦ 1.
1 ≦ c ≦ 1, d is 0.5 ≦ d <1.95, and
2 ≦ a + b + c + d ≦ 2.5, especially 2 ≦ a + b + c + d
It is a number that satisfies ≦ 2.2. e is 4 ≦ e ≦ 100,0
00, especially an integer in the range of 10 ≦ e ≦ 10,000.

Specific examples of the organopolysiloxane include those of the following formulas. These may be partially crosslinked.

[0021]

Embedded image (Me represents a methyl group and Ph represents a phenyl group.)

In the present invention, a film of the above-mentioned silicon-based polymer compound is formed on the above-mentioned substrate, but the formation method is not particularly limited, and a spin coating method, a dipping method, a casting method, a vacuum deposition method, An ordinary thin film forming method such as the LB method (Langmuir-Blodget method) can be employed. In particular, a spin coating method in which a solution of a silicon-based polymer compound is formed while rotating at a high speed is preferably used.
Examples of the solvent for dissolving the silicon-based polymer compound include:
Aromatic hydrocarbons such as benzene, toluene and xylene, and ether solvents such as tetrahydrofuran and dibutyl ether are preferably used. After film formation, it is effective to leave the film in a dry atmosphere for a while or to leave it at a temperature of about 40 to 60 ° C. under reduced pressure for drying.

The concentration of the silicon-based polymer compound in the solvent solution can be 1 to 20% by weight, whereby a silicon-based polymer thin film having a thickness of 0.1 to 1,000 μm is formed. can do.

In the present invention, a salt of a noble metal is then brought into contact with the silicon-based polymer film. Among these noble metal salts, those having a standard oxidation-reduction potential of +0.54 V or more, particularly when converting ions into metal, are effective. More specifically, those that are platinum, gold, silver, and palladium are preferable.

The noble metal salt can be dissolved in a solvent to form a noble metal cation. Usually, M-Zn (n is M
) Or AM-Zm (A is an alkali metal or hydrogen, and m is an integer determined by the valency of M). In this case, Z is C
Halogen such as l, Br, I, acetate, trifluoroacetate, acetylacetonate, carbonate, perchlorate, nitrate, sulfate, cyanate, oxide and the like are used.

As an example of the gold salt, AuCl_Three, AuB
r _Three, HAuCl_Four, NaAuCl_Four, KAuCl_Four, Li
AuCl_Four, AuCNKAu (CN)_Three, As an example of silver salt
Is AgBF_Four, AgClO_Four, AgPF₆, AgBP
h_Four, Ag (CF_ThreeSO_Three), AgNO_ThreeThe palladium salt
For example, PdCl_Two, PdBr_Two, PdI_Two, Pd
(OCOCH_Three)_Two, Pd (OCOCF_Three)_Two, PdS
O_Four, Pd (NO_Three)_Two, PdO Examples of platinum salts include:
PtCl_Two, PtCl_Four, H_TwoPtCl₆, Na_TwoPtC
l₆, K_TwoPtCl₆, Pt (acetylacyton
ate)_TwoEtc. are preferably used.

As a contact method, a solution method in which a solution in which a noble metal salt is dissolved is brought into contact with the above-mentioned silicon-based polymer film is suitably used. In this solution method, a solvent that dissolves the noble metal salt well and hardly dissolves the silicon-based polymer compound is used. As such, water solubility or ketones such as acetone, methyl ethyl ketone, esters such as ethyl acetate, methanol, ethanol, etc. Examples of the solvent include aprotic polar solvents such as alcohols, dimethylformamide, dimethylsulfoxide, and hexamethylphosphoric triamide, and nitromethane and acetonitrile. Particularly, in the case of phenylmethylpolysilane, alcohols are preferably used.

In this case, the concentration of the noble metal salt in the solution is preferably 0.001 to 10% by weight, particularly preferably 0.1 to 5% by weight. If the concentration of the noble metal salt is too high, the surface is covered with the noble metal film and the noble metal colloid is not dispersed in the silicon-based polymer film.

After the contact, if necessary, 50-60
Heat treatment at a temperature of ° C. promotes adsorption of metal salts on the surface of the silicon-based polymer film and formation of metal colloids from the metal salts.

Next, a step of immersing the substrate in the solvent to wash and remove unnecessary metal salts is performed. As a removing method, the substrate can be immersed in the solvent for about 1 second to 10 minutes to remove unnecessary noble metal ions on the substrate.

Then, if necessary, by heating at a high temperature,
The formation of a metal colloid from the noble metal salt on the surface of the silicon-based polymer is promoted, and a substrate coated with a polymer compound in which the noble metal colloid is well dispersed can be obtained. The heating temperature is
Usually, it is preferably carried out at room temperature to 250 ° C. for 1 minute to 10 hours at normal pressure or reduced pressure. If the temperature exceeds 250 ° C., aggregation of the metal colloid starts, which is not desirable. Usually 80 to 20
What is necessary is just to heat at the temperature of 0 degreeC for 1 minute to 1 hour.

In the present invention, when the silicon-based polymer compound is polysilane, a substrate formed with a pattern of a noble metal colloid can be obtained because the photopatterning characteristic inherent to polysilane can be applied.

The patterning using this polysilane can be performed in the following steps. (1) A step of selectively irradiating a polysilane film formed on a substrate with light to form a pattern having a Si—O bond in a light-irradiated portion. (2) a step of immersing the substrate of step (1) in a solution in which a noble metal salt is dissolved to form a noble metal colloid in the unexposed portion of the polysilane portion.

In the pattern forming method of the present invention, first, a thin film containing this polysilane as a main component is formed on a substrate. From above the substrate on which this polysilane film is formed,
A step of performing non-selective light irradiation in the presence of oxygen to form a Si—O bond in part of the polysilane is performed. As a result, the surface of the portion irradiated with light has a Si--Si bond of Si
It is converted to a -O-Si bond or Si-OH and loses its reducing ability.

In this step, the same apparatus as in the step of drawing a photo-oxidation pattern of polysilane can be used. Usually 1μ
A light amount of 0.01 to 100 J / cm ² per m film thickness is used. In particular, a light amount of 0.1 to 10 J / cm ² is preferably used. As a result, the Si-
A substrate with an O bond formed is created and no longer produces metal colloids upon contact with a noble metal salt.

The light source may be a continuous spectrum light source such as a hydrogen discharge tube, a rare gas discharge tube, a tungsten lamp, a halogen lamp, or a discontinuous spectrum light source such as various lasers and a mercury lamp, but is inexpensive and easy to handle. A mercury lamp is preferably used.

Next, this substrate is immersed in a solution in which a noble metal salt is dissolved, and a noble metal colloid is formed in the unexposed portion of the polysilane portion. Thus, a substrate coated with the pattern of the noble metal colloid can be easily obtained, but this step and post-treatment can be performed in the same manner as described above.

FIG. 1 shows an example of polysilane patterning. An exposure step of forming a polysilane film 2 on a substrate 1 and irradiating the polysilane film 2 with ultraviolet rays 4 via a mask 3 is performed (FIG. 1A). )). As a result, the exposed portion of polysilane is converted into polysiloxane 2a, and the unexposed portion remains as polysilane 2b. Next, a step of bringing the noble metal salt 5 into contact with the exposed polysilane film is performed (FIG. 1).
(B)). As a result, the noble metal salt is attached or adsorbed as it is as the noble metal salt 5 in the polysiloxane portion 2a, while the noble metal ion is reduced to the noble metal by the action of the polysilane in the polysilane portion 2b, and the noble metal colloid 6 is formed. (FIG. 1 (C)). Next, the noble metal salt of the polysiloxane portion 2a is removed with a solvent (FIG. 1).
(D)), and by further heating, the polysilane portion 2b
Thus, a pattern in which the noble metal colloid 6 is dispersed is obtained (FIG. 1 (E)). In the example shown in the figure, when removing the noble metal salt, the polysiloxane portion was simultaneously removed using a solvent capable of dissolving the polysiloxane.

The substrate having a noble metal colloid-dispersed silicon-based polymer compound layer of the present invention exhibits characteristics from a high conductor to a semiconductor in Japanese Patent Application Laid-Open No. 9-327909, whereas The electric conductivity of the surface of the compound layer is 10 ⁶ to 10 ¹⁷ Ωcm / □, particularly 10 ⁹ to 10 ¹⁵ Ωcm /
□ indicates light absorption in the visible region while exhibiting characteristics as an insulator, and exhibits high third-order nonlinear optical characteristics.

[0040]

The substrate having a noble metal colloid-dispersed silicon-based polymer compound layer of the present invention has an excellent optical function. According to the present invention, the precious metal colloid-dispersed silicon polymer A substrate coated with a patterned pattern can be obtained, and a useful polymer-coated substrate applicable to electronic elements having various electronic functionalities such as sensors and various electronic functionalities such as non-linear optical characteristics can be obtained. it can.

[0041]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Synthesis Example] Production method of polysilane Metal sodium was added to toluene under a nitrogen stream.
Heat to 100-120 ° C while stirring at high speed to disperse. To this, dichlorodiorganosilane is slowly added dropwise with stirring. The addition amount is 1 mol of the silicon compound with respect to 2 to 3 mol of metallic sodium. 4 until the ingredients disappear
The mixture was stirred for an hour to complete the reaction. Then, after allowing to cool, the salt is filtered and concentrated, so that the polysilane can be easily obtained.

For example, a method for producing phenylmethylpolysilane was performed as follows. Under a nitrogen stream, 5.06 g (220 mmol) of metallic sodium was added to 60 ml of toluene.
The mixture was heated at 110 ° C. while stirring at a high speed to disperse. This was added to phenylmethyldichlorosilane 19.1.
g (100 mmol) was slowly added dropwise with stirring. The mixture was stirred for 4 hours until the raw materials disappeared to complete the reaction. Then, after cooling, the salt was filtered and concentrated to obtain a polysilane crude product 1.
0.0 g (83% crude yield) could be obtained. This polymer was dissolved again in 30 ml of toluene, 120 ml of hexane was added to the solution, and the solution was separated by precipitation to obtain phenylmethylpolysilane 6.6 having a weight average molecular weight of 45,000.
g (55% yield).

Using the toluene solution of the polymer synthesized in this way, a film is formed by spin coating to obtain a polymer having a desired film thickness.

[Examples and Comparative Examples 1 and 2] Polysilane (phenylmethylpolysilane produced in Synthesis Example) was dissolved in toluene to form a 7% solution. This polysilane solution was spin-coated on a glass plate at 3,000 rpm for 10 seconds, and dried at 2 mmHg / 50 ° C. to a thickness of 0.4 μm.
m was formed as a substrate for pattern formation.

A photomask is superimposed on this substrate,
UV light of 254 nm using a low pressure mercury lamp of 10 J / c
Irradiation was performed at a light amount of m ² , and a pattern was formed by the method as shown in FIG. 1 to prepare a glass substrate having a film on which an unexposed layer of polysilane and an exposed layer of polysiloxane were patterned.

Next, a 1.0% ethanol solution of sodium chloroaurate was prepared and brought into contact with a polysilane substrate by the following methods (1) and (2) to form a gold colloid pattern layer. Table 1 summarizes the data of the absorption spectrum of this substrate. (1): A glass substrate having a polysilane film on which a latent image is formed is immersed in a 1.0% ethanol solution of sodium chloroaurate for 1 minute, taken out of the solution, and 2 mmHg / 50 ° C.
And dried. As a result, the gold salt was adsorbed on the polysilane layer, then reduced, and a glass substrate coated with a polymer compound in which gold colloid was dispersed and having a characteristic maximum absorption spectrum at 550 nm was obtained. Next, it was immersed in ethanol for 1 minute to remove the gold salt which also adhered to the unexposed portion. (2): The glass substrate of (1) was heated at 100 ° C. for 10 minutes. When the absorption spectra of the glass substrates (1) and (2) were measured, a high absorption intensity at a wavelength of 550 nm characteristic of gold colloid was observed as described below. From this, it is clear that a pattern of a polymer compound in which gold colloid is dispersed is formed on the substrate.

For comparison, when the same operation was performed using ethanol instead of the gold salt or when the same operation was performed using phenylmethylpolysiloxane instead of polysilane, the high absorption intensity at a wavelength of 550 nm was obtained. Was not observed, and a substrate coated with colloidal gold could not be obtained.

[0049]

[Table 1]

[Brief description of the drawings]

FIG. 1 is an explanatory view of a manufacturing process of a substrate having a noble metal colloid pattern, wherein (A) is an exposure process, (B) is a noble metal salt treatment process, (C) is a noble metal colloid generation state, and (D) is a noble metal salt. The removal step (E) shows the state of formation of the noble metal colloid pattern.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Substrate 2 Polysilane film 2a Polysiloxane part 2b Polysilane part 3 Mask 4 Ultraviolet 5 Noble metal salt 6 Noble metal colloid

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI H01B 5/14 H01B 5/14 Z 13/00 503 13/00 503A H01L 51/00 H01L 29/28

Claims (9)

[Claims] 1. A substrate having a silicon-based polymer compound layer in which a noble metal colloid obtained by contacting and reducing a noble metal salt with a reducing silicon-based polymer compound is dispersed. . 2. The substrate according to claim 1, wherein the silicon polymer compound having a reducing property is a silicon polymer compound having a Si—Si bond and / or a Si—H bond. 3. The Si—Si bond and / or Si—H
3. The substrate according to claim 1, wherein the silicon-based polymer compound having a bond is polysilane or polysiloxane having a hydrogen atom bonded to a silicon atom. 4. The substrate according to claim 3, wherein the polysilane is represented by the following formula (1). (R ¹ _m R ² _n X _p Si) _q (1) (wherein, R ¹ and R ² are a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, X is R ¹ , an alkoxy group, a halogen atom, Represents an oxygen atom or a nitrogen atom, m is 0.1 ≦ m ≦
2, n is 0 ≦ n ≦ 1, p is 0 ≦ p ≦ 0.5, 1 ≦ m + n
+ P ≦ 2.5, q is 4 ≦ q ≦ 100,00
It is an integer satisfying 0. ) 5. The substrate according to claim 3, wherein the polysiloxane is represented by the following formula (2). (R ³ _a R ⁴ _{b Hc} SiO _d ) _e (2) (wherein R ³ and R ⁴ represent a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group, an alkoxy group or a halogen atom,
a is 0.1 ≦ a ≦ 2, b is 0 ≦ b ≦ 1, and c is 0.01 ≦
c ≦ 1, d is 0.5 ≦ d <1.95, 2 ≦ a + b + c +
a number satisfying d ≦ 2.5, e is 4 ≦ e ≦ 100,000
Is an integer that satisfies ) 6. The substrate according to claim 1, wherein the noble metal salt has a standard oxidation-reduction potential of +0.54 V or more when reducing ions to metal. 7. The substrate according to claim 6, wherein the noble metal salt is a platinum, gold, silver or palladium salt. 8. A step of (1) forming a polysilane film on a substrate and then selectively irradiating light to form a pattern having a Si—O bond in a light-irradiated portion; and (2) dissolving a salt of a noble metal. A step of immersing the substrate in step (1) in a solution obtained in step (1), and forming and dispersing the noble metal colloid in the unexposed part of the polysilane part. 9. The method according to claim 8, wherein the polysilane is represented by the following formula (1). (R ¹ _m R ² _n X _p Si) _q (1) (wherein, R ¹ and R ² are a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, X is R ¹ , an alkoxy group, a halogen atom, Represents an oxygen atom or a nitrogen atom, m is 0.1 ≦ m ≦
2, n is 0 ≦ n ≦ 1, p is 0 ≦ p ≦ 0.5, 1 ≦ m + n
+ P ≦ 2.5, q is 4 ≦ q ≦ 100,00
It is an integer satisfying 0. )