JP4863428B2 - Metal particle array sheet - Google Patents

Description

  The present invention relates to a polymer sheet in which metal fine particles are two-dimensionally arranged at a nano level and a metal fine particle array substrate having a two-dimensional superlattice of metal dots using the sheet. This metal dot can be used for a quantum device using a single electron tunnel effect such as a single electron transistor or a single electron memory as a quantum dot.

When an amphiphilic block copolymer is formed into a film, a domain centering on a hydrophobic or hydrophilic portion is formed, and a cylindrical hydrophilic domain having a diameter of 3 to 15 nm is spaced at a distance of 10 to 50 nm in a hydrophobic substrate. It is known to take a form existing in large numbers (Patent Document 1). A film having such minute hydrophilic regions at minute intervals has not been obtained so far, and its utilization is greatly expected.
As one example of such utilization, extremely minute metal dots arranged on a substrate can be considered. Such a metal dot can be applied to an element using a single electron tunnel effect.
Even if electron beam lithography, which has been practically the most advanced as a microfabrication method, is used, it is difficult to achieve a processing accuracy of 20 nm or less, and single atom operation using a scanning tunneling microscope has poor productivity. It was not practical. In addition, in the droplet epitaxy method, the size and density of dots can be controlled, but the arrangement cannot be controlled.
Currently, the processing dimensions of semiconductor devices are becoming less than 100 nm, and are expected to be several nm in the near future. With semiconductor devices of this size, device operation based on the conventional principle is difficult, and devices based on new operation principles such as single-electron transistors and single-electron memories using the single-electron tunnel effect have been developed. It is attracting attention (Non-Patent Document 1, Patent Document 2). In order to operate such an element at room temperature, it is necessary to dispose quantum dots made of extremely fine metal dots of 10 nm or less on an insulator, electron beam lithography, atomic manipulation with a scanning tunneling microscope, Microfabrication technology such as droplet epitaxy has been studied.

JP2004-124088 JP2003-51498 Hitachi review vol.86, No.7, 55-58 (2004.7)

The present invention provides a substrate such as a silicon wafer on which metal dots of 10 nm or less, which have been difficult to manufacture, are arranged, and means for forming such a substrate with high productivity.
Metal nanoparticles with controlled orientation are attracting a great deal of attention because they have new electronic and optical properties that are not seen with nanoparticles alone. Localized plasmon light, including nanoelectronic devices that use single electrons, is attracting attention. Applications to nano-optical devices using an enhanced electric field are expected. Currently, the two-dimensional orientation control of metal nanoparticles is often performed by a self-organization method such as dropping the dispersion on a smooth substrate and then drying. However, this limits the formation of complex patterns.
Therefore, the present invention focuses on the nano-order structure formed by the amphiphilic block copolymer for the purpose of developing a new method for controlling the orientation of metal nanoparticles, and organizes the metal nanoparticles using this as a template. Provide a means to

  First, an amphiphilic block copolymer was self-assembled to form a microphase separation membrane (Patent Document 1). This microphase separation membrane has a large number of approximately circular hydrophilic regions of 3 to 15 nm on the surface at intervals of 10 to 50 nm. On the other hand, a core-shell type spherical micelle solution in which metal fine particles with a diameter of 1 to 5 nm are covered with an organic ligand and a water-permeable group is exposed on the outside is prepared, and the above-described microphase separation membrane is immersed in the solution. Depending on the structure, it was possible to obtain a polymer sheet in which ultrafine metal particle micelles were arranged in the hydrophilic region of the microphase separation membrane in solution. Furthermore, by moving this sheet onto a substrate such as a silicon wafer and decomposing and removing organic substances, it was possible to obtain a substrate on which nanometer-sized dots were formed. That is, the fine metal fine particle dots have been successfully controlled on the substrate at fine intervals.

That is, the present invention provides a metal particle-containing sphere in the substantially circular region on the microphase separation membrane having a large number of substantially circular hydrophobic or hydrophilic regions having a diameter of 3 to 15 nm at intervals of 10 to 50 nm on the surface. A metal fine particle arrangement sheet in which one micelle is arranged, wherein the metal fine particle-containing spherical micelle is a core-shell type spherical micelle in which metal fine particles having a diameter of 1 to 5 nm are covered with an organic ligand, When the substantially circular region on the phase separation membrane is hydrophilic, it is a hydrophilic group, and when the substantially circular region on the micro phase separation membrane is hydrophobic, it is a spherical micelle with the hydrophobic group exposed to the outside. It is a metal fine particle arrangement sheet.

The present invention also includes a step of casting a solution containing an amphiphilic block copolymer on a substrate to form a microphase separation membrane, and immersing the microphase separation membrane in a dispersion in which spherical particles containing metal fine particles are dispersed. And the step of removing the microphase separation membrane from the dispersion and drying, wherein the amphiphilic block copolymer is composed of a hydrophilic polymer component (A) and a hydrophobic polymer component (B). Amphiphilicity in which the molecular weight distribution (Mw / Mn) of the hydrophilic polymer component (A) and the hydrophobic polymer component (B) is 1.3 or less, which is formed by covalently bonding compatible polymers. In the process for producing a metal fine particle array sheet, which is a block copolymer, and wherein the metal fine particle-containing spherical micelle is a core-shell type spherical micelle in which a metal fine particle having a diameter of 1 to 5 nm is covered with an organic ligand. That.
Furthermore, the present invention provides a method for producing the metal fine particle arrangement sheet, further comprising the steps of laminating the metal fine particle arrangement sheet on a substrate, and removing the microphase separation film and the organic ligand. It is a manufacturing method.

  The metal fine particle arrangement sheet and the metal fine particle arrangement substrate of the present invention are obtained by forming metal dots in a wide area on any substrate regardless of the material and shape, and the size of the metal fine particles is 1 to 5 nm. Therefore, the electrostatic energy of the free electrons is higher than the thermal excitation level of the electrons at room temperature, and such ultrafine metal particles were deposited on a substrate such as a silicon wafer at nanometer scale intervals. Metal dots can be applied to quantum devices that operate at room temperature.

The microphase separation membrane used in the present invention has a large number of substantially circular hydrophobic or hydrophilic regions having a diameter of 3 to 15 nm at intervals of 10 to 50 nm on the surface. The phase separation membrane may have this region only on the surface, or the region may be one in which a substantially cylindrical domain is present in the membrane and its cross section appears on the membrane surface. . In the present invention, the chemical composition of the microphase separation membrane is not particularly limited as long as it has such a form.
In the present invention, a film made of an amphiphilic block copolymer, in which such a substantially cylindrical domain is self-assembled, can be used. This amphiphilic block copolymer is a block copolymer in which a hydrophilic polymer component (A) and a hydrophobic polymer component (B) are incompatible with each other by a covalent bond. The component (A) and the hydrophobic polymer component (B) are preferably amphiphilic block copolymers having a molecular weight distribution (Mw / Mn) of 1.3 or less.
From the quantitative relationship between the hydrophilic component and the hydrophobic component, either the hydrophilic component or the hydrophobic component constitutes an island region (substantially cylindrical domain) and the other constitutes a sea region. It is considered to be taken.
The thickness of the film to be formed is usually about 50 nm to 1 μm.

The molecular weight distribution (Mw / Mn) refers to a value calculated from the weight average molecular weight Mw in terms of polyethylene and the number average molecular weight Mn measured by gel permeation chromatography.
The molecular weight of the block copolymer is preferably 5,000 to 100,000, more preferably 10,000 to 50,000.

Examples of the hydrophilic polymer component (A) include poly (ethylene oxide), poly (propylene oxide), poly (vinyl alcohol), poly (acrylic acid), poly (methacrylic acid), poly (acrylamide), and oligo (ethylene oxide). And crown ether, cryptand, poly (methacrylate) or poly (acrylate) having a sugar chain in the side chain.
Examples of the hydrophobic polymer component (B) include poly (methacrylate), poly (acrylate), poly (styrene), vinyl polymer having a mesogenic side chain, a long-chain alkyl side chain, or a hydrophobic side chain. Is mentioned. The mesogenic side chain refers to a highly oriented molecular chain such as a liquid crystal molecule.

This block copolymer is preferably represented by the following general formula (1).
Formula _{(1): CH 3 (OCH} 2 CH 2) m O COC (CH 3) 2 (CH 2 C (CH 3) COOR) n -X
(In the formula, m and n may be the same or different and each is an integer of 5 to 500; R is a substituent represented by the following general formula (2) or (3); X represents a hydrogen atom or a halogen atom.)
Formula (2): —CH ₂ (CH ₂ ) _a CH ₂ OBN = NBR ¹
(In the formula, a represents an integer of 0 to 20, R ¹ represents hydrogen or an alkyl group having 1 to 22 carbon atoms, and B represents a p-phenylene group.)
Formula (3): —CH ₂ (CH ₂ ) _b CH ₂ OB—CH═CH—BR ²
(In the formula, b represents an integer of 0 to 20, R ² represents hydrogen or an alkyl group having 1 to 22 carbon atoms, and B represents a p-phenylene group.)

The metal fine particle-containing spherical micelle used in the present invention is a core-shell type spherical micelle in which metal fine particles are covered with an organic ligand.
Examples of the metal include gold, silver, platinum, and rhodium. The diameter of the metal fine particles is usually 1 to 5 nm, although it is determined by the mixing ratio of metal ions and organic ligands and the reducing power and addition rate of the reducing agent.

The organic ligand has a hydrophilic group when the substantially circular region on the microphase separation membrane is hydrophilic, and has a hydrophobic group when the substantially circular region on the microphase separation membrane is hydrophobic. Designed to be exposed outside the micelle.
As the organic ligand, one having a thiol group (—SH), a disulfide group (—S—S—) or a thioether group (—S—) at one end is preferable. In addition, the other end can be any functional group as long as it is modified with a functional group capable of selectively binding to the hydrophilic or hydrophobic part on the microphase separation membrane. Examples thereof include an ethylene oxide group, a hydroxyl group, an amino group, and a carboxyl group, and examples of the hydrophobic group include an alkyl group, an aryl group, and a cholesteryl group.
In the case of exposing a hydrophilic group as this ligand, in particular, (R ³ O (R ⁴ O) _c R ⁵ S) ₂ (wherein R ³ is a hydrogen atom or an alkyl group, and R ⁴ is a carbon number. Is an alkylene group having 2 or 3, c is an integer of 1 to 10, and R ⁵ is an alkylene group having 2 to 4 carbon atoms.
This ligand forms a core-shell type spherical micelle having a diameter of about 170 to 200 nm when S is bonded to a metal, and a plurality of metal fine particles and the ligand are further bonded to form a diameter of usually 180 to 200 nm. A spherical micelle containing fine metal particles of about 220 nm is formed. In this metal microparticle-containing spherical micelle, there are cases where the metal microparticles are encapsulated in the ligand and cases where the metal microparticles surround the outside of the ligand, and when a plurality of metal microparticles are encapsulated, the metal The diameter of the part is about 30 to 60 nm.

In the present invention, a metal fine particle array sheet is prepared in which metal fine particle-containing spherical micelles are arranged in the substantially circular region on the microphase separation membrane. Examples of the production method are shown below.
First, a microphase separation membrane is prepared. The preparation method is not particularly limited, although it depends on the chemical composition of the microphase separation membrane.
When the amphiphilic block copolymer of the present invention is used, since the hydrophilic domain and the hydrophobic domain are separated in a self-assembled manner, the self-assembled or heated in solution can be arranged by self-assembly. It is preferable to promote.
As an example, a film containing an amphiphilic block copolymer can be dropped onto a substrate to form a film, or a film can be formed by injecting this solution into a mold. As this substrate, a substrate having high smoothness is preferable. For example, a mica plate, a silicon wafer, or the like can be used.
When the block copolymer of the general formula (1) is used as an amphiphilic block copolymer, a film or film having a thickness of about 50 nm to 1 μm and an area of about several m ² can be obtained. This is shown in FIG.

On the other hand, there is no particular limitation on the production method of the spherical micelles containing fine metal particles. Usually, by adding an organic ligand to a salt solution containing a metal, the organic ligand is coordinated with the metal to form core-shell type fine particles.
A dispersion in which the metal fine particle-containing spherical micelles are dispersed is prepared. As the solvent, ethanol, ether or the like is preferably used. The concentration of the metal fine particle-containing spherical micelles in the dispersion is about 0.5 to 2.5 wt%, and the temperature of the dispersion is usually kept at about −80 ° C. to room temperature, preferably about 20 to 25 ° C.
The microphase separation membrane is immersed in this dispersion, and the microphase separation membrane is taken out from this dispersion. This is shown in FIG.

  Further, using this dispersion, spherical fine micelles containing metal fine particles may be deposited on the microphase separation film by spin coating. For example, a dispersion liquid in which the concentration of metal fine particle-containing spherical micelles is adjusted to about 0.05 to 0.5 wt% is dropped on a microphase separation membrane and rotated at about 500 to 2000 rpm for about 5 to 30 seconds.

As a result, spherical micelles bind to the island region (hydrophobic region or hydrophilic region) on the microphase separation membrane. This coupling is due to non-covalent bonds such as van der Waals forces, dipole-dipole interactions, electrostatic attraction. Since this binding force is weak, for example, if the concentration of the dispersion is too high, spherical micelles may not selectively bind to the island region, so the desired occupation ratio (ratio of micelle binding to the island region) It is preferable to adjust the concentration of the spherical micelles appropriately so that the above can be obtained. The same consideration is preferable for other conditions (immersion time, temperature, rotation speed, etc.).
Thereafter, the membrane may be dried as necessary. Drying is preferably performed at room temperature and under reduced pressure.

Next, a method for producing a metal fine particle array substrate having a two-dimensional superlattice of metal dots will be described. The microphase separation membrane obtained as described above is taken out and laminated on the substrate. As this substrate, a substrate that is not easily oxidized by ozone (O ₃ ) is preferable. For example, a substrate such as a silicon wafer, glass, or metal can be used. If an appropriate substrate is used in the above method, this operation may be omitted.
Next, the microphase separation membrane and the organic ligand are removed. Examples of the removing means include ultraviolet irradiation, heating, and plasma etching.
When ultraviolet rays are used, the organic matter can be decomposed and removed by irradiating ultraviolet rays having a wavelength of about 170 to 260 nm. As the light source, an excimer lamp, a low-pressure mercury lamp, or the like can be used.
When heating, it is preferable to carry out at 350-400 degreeC.
As a result of this operation, a metal fine particle array substrate in which a large number of metal fine particles having a diameter of 1 to 5 nm are arranged on the substrate at intervals of 10 to 50 nm can be obtained.

The following examples illustrate the invention but are not intended to limit the invention.
Production Example 1
An organic ligand was prepared by the following method. The synthesis reaction is shown in FIG. 4 (Scheme 1).
A mixed solution of triethylene glycol monomethyl ether (4 g, 0.024 mol), thionyl chloride (5.71 g, 0.048 mol) and pyridine (3.8 g, 0.048 mol) was heated and stirred at 80 ° C. for 6 hours. After completion of the reaction, the reaction solution was allowed to cool to room temperature and concentrated under reduced pressure at 50 ° C. Methylene chloride was added to the resulting residue to remove thionyl chloride. After removal, the residue was cooled in a refrigerator for 3 hours and washed with diethyl ether to give compound 2 as a yellow liquid (3.55 g, 81% yield).
¹ H-NMR (DMSO): δ 3.230 (3H, s), 3.424 (2H, m), 3.522 (6H, m), 3.666 (4H, m)
Compound 2 (1.0 g, 5.5 mmol) and potassium thioacetate (1.8 g, 16.5 mmol) were dissolved in 30 ml of DMF, and the mixture was heated and stirred at 60 ° C. for 17 hours. The mixture was allowed to cool to room temperature and extracted with diethyl ether. The extracted diethyl ether was concentrated under reduced pressure. Thereafter, separation by column chromatography (silica gel, 3% methanol / methylene chloride) was performed to obtain Compound 3 as a yellow liquid (912 mg, yield 75%).
¹ H-NMR (DMSO): δ 2.320 (3H, s), 3.001 (2H, t, J = 6.59), 3.229 (3H, s), 3.309 (2H, m), 3.490 (8H, m) IR ( cm ^-1 ): 1692 (CO)
Compound 3 (100 mg, 0.45 mmol) and NaOMe (72.87 mg, 1.349 mmol) were dissolved in 5 ml of methanol and stirred at room temperature for 48 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure. The residue was extracted with diethyl ether and separated by column chromatography (silica gel, 3% methanol / methylene chloride) to obtain compound 4 (chemical formula: (MeO (C ₂ H ₄ O) ₂ C ₂ H and ₄ S) ₂₎ as a yellow liquid (115 mg, 72% yield).
¹ H-NMR (DMSO): δ 2.885 (4H, t, J = 6.34), 3.230 (6H, s), 3.313 (4H, m), 3.508 (12H, m), 3.626 (4H, t, J = 6.34) )

Production Example 2
Using the organic ligand obtained in Production Example 1, spherical micelles containing fine metal particles were prepared by the following method. The reaction is shown in FIG. 5 (Scheme 2).
4 ml of 40 mM HAuCl ₄ aqueous solution (66 mg, 0.1603 mmol) was added to 13 ml of 31 mM BrN (C ₈ H ₁₇ ) ₄ toluene solution (220 mg, 0.4.023 mmol) with stirring. The mixture was stirred until AuCl ₄ ⁻ moved to the organic layer, and the organic layer was separated. Compound 4 of Au: RSH = 1: 10 was added and stirred at room temperature for 10 minutes. After stirring, a fresh 0.4M NaBH ₄ aqueous solution was added dropwise in 1 second, and the mixture was stirred at room temperature for 12 hours. Then, the mixture of the precipitate, the toluene layer, and the aqueous layer was separated into the precipitate and the solution. The precipitate was dried overnight. After drying, methylene chloride was added to the residue to separate it into dissolved and insoluble materials. The dissolved material dissolved in methylene chloride was precipitated again by adding n-hexane to obtain a dark brown solid. The solution was separated into a toluene layer and an aqueous layer, the toluene layer was concentrated, and the resulting residue was dried overnight. After drying, the residue was dissolved in methylene chloride and precipitated again by adding n-hexane.

Production Example 3
A microphase separation membrane was prepared by the following method. This is shown in FIG.
(1) A block copolymer represented by the following formula (Chemical Formula 1) was used as a 2.0-5.0 wt% toluene solution.
(In this formula, m = 114 and n = 48 in the general formula (1), and R is the general formula (2).)
(2) The solution was filtered using a syringe filter (Whatman, mesh 0.45 μm).
(3) 200 μl of the filtrate was dropped on the entire 2 cm × 4 cm mica plate as flat as possible and applied using a bar coater (manufactured by Daiichi Rika Co., Ltd., counts 2, 10, 20).
(4) Thereafter, heat treatment was performed at 110 ° C. for 24 hours to obtain a sheet.
The obtained sheet was observed using an atomic force microscope (AFM) (manufactured by Seiko Instruments Inc., SPA400). The result is shown in FIG.

  From FIG. 6, approximately circular concave portions having a diameter of 10 nm are arranged in a hexagonal close-packed manner, and these concave substantially circular shapes are periodically arranged at intervals of 24 to 26 nm from observation of the height difference of the film surface. I understand that. That is, the substantially circular portion is a hydrophilic pEOm domain, and is phase-separated from the hydrophobic PMA (AZ) n domain in the peripheral portion to form a cylindrical cylinder array structure in a direction substantially perpendicular to the substrate. I understand that.

In this example, a metal fine particle array sheet was prepared by the following method. This is shown in FIG.
(1) The ethanol solution of the metal fine particle-containing spherical micelle obtained in Production Example 2 was prepared to 0.1 to 2.0 wt%.
(2) The microphase separation membrane obtained in Production Example 3 was cut out to about 1 cm × 2 cm.
(3) The phase separation membrane was immersed vertically in the solution of (1) at room temperature (25 ° C.) for 30 to 90 seconds.
(4) Then, it pulled up vertically and dried under reduced pressure for 1 hour.

The obtained sheet was observed using an atomic force microscope (SPA400). The result is shown in FIG. From FIG. 7, the substantially circular portion of the microphase separation membrane surface that was a concave portion was raised about 4 to 5 nm after the deposition of the gold nanoparticles (average particle size of about 5 nm), and one gold nanoparticle was It can be seen that they are deposited in a substantially circular portion . Furthermore, the gold nanoparticles are arranged at the same interval of 23 to 24 nm as the periodic structure of the film, and the gold nanoparticles whose surface is modified with hydrophilic groups are selectively deposited on the same hydrophilic pEOm domain. I understand that.

FIG. 8 shows the immersion time of the number of ultrafine gold particles arranged on the microphase separation membrane and the concentration dependence of the gold nanoparticles. The occupancy shown in FIG. 8 pays attention to pEOm domains existing within a certain area (100 × 100 nm ² ), and represents the number of PEOm domains on which gold nanoparticles are deposited as a percentage of the total number of PEOm domains. Is. It was found that when the immersion time was fixed at 10 seconds or 20 seconds, the gold nanoparticle was deposited more and the occupation ratio increased as the concentration of the gold nanoparticle solution to be immersed was higher. Moreover, when the density | concentration of the gold nanoparticle solution was made constant, it turned out that an occupation rate rises as immersion time is lengthened from 10 s to 20 seconds. However, it was found that when the gold nanoparticle solution having a high concentration of 2.0 wt% or more is immersed for a long time of 20 seconds or more, the occupation ratio increases, but at the same time, aggregation of the gold nanoparticles occurs. It is found that there is an appropriate immersion time and concentration for arranging the gold nanoparticles, and a relatively good occupation ratio (32%) can be obtained when immersed in a 0.5 wt% gold nanoparticle solution for 20 seconds. It was.

A silicon wafer in which only metal fine particles were arranged was prepared by the following method. This is shown in FIG.
(1) The metal fine particle array sheet obtained in Production Example 3 was placed on a silicon wafer.
(2) Ozone was generated by irradiating a VUV lamp under reduced pressure, and organic substances on the substrate were decomposed and lost. At this time, the substrate temperature was -80 to 30 ° C., and the air flow rate and the atmospheric pressure were 5 to 250 ml / min and 0.9 to 1.1 × 10 ³ Pa, respectively.
As a result, a metal fine particle array substrate in which a large number of metal fine particles were arranged on the substrate (silicon wafer) could be obtained (results are not particularly shown).

It is a figure which shows the mode of micro phase separation membrane formation. It is a figure which shows the mode of fine particle arrangement | sequence sheet | seat preparation. It is a figure which shows the mode of transcription | transfer. It is a figure which shows the synthesis | combination of a ligand. It is a figure which shows the synthesis | combination of a gold ultrafine particle. It is a figure which shows the AFM shape image of a micro phase separation membrane. It is a figure which shows the AFM shape image of the gold nanoparticle arranged on the micro phase separation membrane. It is a figure which shows the immersion time of the number of gold | metal ultrafine particles arranged on the micro phase separation membrane, and the density | concentration dependence of a gold nanoparticle.

Claims (7)

One spherical fine micelle containing metal fine particles is disposed on the surface of the micro-phase separation membrane having a large number of substantially circular hydrophobic or hydrophilic regions having a diameter of 3 to 15 nm at intervals of 10 to 50 nm on the surface. The metal fine particle-arranged sheet is a core-shell type spherical micelle in which the metal fine particle-containing spherical micelle is covered with an organic ligand and having a diameter of 1 to 5 nm. A metal fine particle array sheet, which is a hydrophilic group when the circular region is hydrophilic, and a spherical micelle with the hydrophobic group exposed to the outside when the substantially circular region on the microphase separation membrane is hydrophobic.
The microphase separation membrane is a block copolymer in which a hydrophilic polymer component (A) and a hydrophobic polymer component (B) are incompatible with each other by a covalent bond, and the hydrophilic polymer component (A) ) And the hydrophobic polymer component (B) are composed of amphiphilic block copolymers having a molecular weight distribution (Mw / Mn) of 1.3 or less. The metal fine particle arrangement sheet according to claim 2, wherein the block copolymer is represented by the following general formula (1).
Formula _{(1): CH 3 (OCH} 2 CH 2) m O COC (CH 3) 2 (CH 2 C (CH 3) COOR) n -X
(In the formula, m and n may be the same or different and each is an integer of 5 to 500; R is a substituent represented by the following general formula (2) or (3); X represents a hydrogen atom or a halogen atom.)
Formula (2): —CH ₂ (CH ₂ ) _a CH ₂ OBN = NBR ¹
(In the formula, a represents an integer of 0 to 20, R ¹ represents hydrogen or an alkyl group having 1 to 22 carbon atoms, and B represents a p-phenylene group.)
Formula (3): —CH ₂ (CH ₂ ) _b CH ₂ OB—CH═CH—BR ²
(In the formula, b represents an integer of 0 to 20, R ² represents hydrogen or an alkyl group having 1 to 22 carbon atoms, and B represents a p-phenylene group.)
The metal fine particle-containing spherical micelles are metal fine particles having a diameter of 1 to 5 nm, (R ³ O (R ⁴ O) _c R ⁵ S) ₂ (wherein R ³ is a hydrogen atom or an alkyl group, and R ⁴ is carbon. 2. A core-shell spherical micelle covered with a compound represented by 2 or 3 alkylene group, c is an integer of 1 to 10, and R ⁵ is an alkylene group of 2 to 4 carbon atoms. The metal fine particle arrangement | sequence sheet | seat as described in any one of -3. The metal fine particle arrangement sheet according to any one of claims 1 to 4 is laminated on a substrate, and the diameter is 1 to 5 nm on the substrate obtained by removing the microphase separation film and the organic ligand. A metal particle array substrate in which a large number of metal particles are arrayed at intervals of 10 to 50 nm. Casting a solution containing an amphiphilic block copolymer on a substrate to form a microphase separation membrane, immersing the microphase separation membrane in a dispersion in which metal microparticle-containing spherical micelles are dispersed, and The step comprises removing the microphase separation membrane from the dispersion and drying, wherein the amphiphilic block copolymer comprises a hydrophilic polymer component (A) and a hydrophobic polymer component (B) that are incompatible with each other. An amphiphilic block copolymer formed by covalent bonding and having a molecular weight distribution (Mw / Mn) of 1.3 or less of the hydrophilic polymer component (A) and the hydrophobic polymer component (B) There, the metal particles containing spherical micelles, diameter of core-shell type spherical micelles covered with organic ligands metal fine particles of 1 to 5 nm, the diameter of substantially circular 3~15nm hydrophobic or hydrophilic The symbolic circular region to the metal fine particle-containing spherical micelles one disposed metal particles array sheet manufacturing method each region on the micro phase separation membrane having a large number at intervals of 10 to 50 nm.
A method for producing a metal fine particle arrangement sheet according to claim 6, further comprising: laminating the metal fine particle arrangement sheet on a substrate; and removing the microphase separation film and the organic ligand. Manufacturing method.