JP6120213B2 - Method for producing fine structure, method for producing composite - Google Patents

Description

  The present invention relates to a method for producing a microstructure comprising a metal oxide and a composite obtained using the production method.

At present, a structure in which fine structures having a size of several nanometers to several tens of nanometers are regularly arranged on a conductive substrate (for example, a nanodot array, a nanorod array, Line & Space (LS), etc.). In other words, optical devices, magnetic devices, field emission devices, field electrodes and the like are attracting attention.
As a method of forming the ordered arrangement structure, a method of manufacturing by a metal organic vapor phase epitaxy (MO-VPE) (see Non-Patent Document 1), a method of manufacturing by a vapor-solid-liquid method (VLS). (Refer nonpatent literature 2), the method of producing by the electrolytic deposition method, etc. are proposed. As a method of producing by electrolytic deposition, a method that does not use a mask (see Non-Patent Document 3), a method that uses porous alumina as a mask (see Non-Patent Document 4), and a block copolymer are used. A method of using a membrane having a microphase separation structure as a mask (see Non-Patent Document 5 and Patent Document 1) has been proposed.

Among the above, in Non-Patent Document 1 using MO-VPE, a SiO ₂ thin film is formed on a GaN substrate, the SiO ₂ film is patterned by a top-down method by electron beam lithography, and ZnO is MO— By growing by CVD, regularly arranged ZnO nanorod arrays, nanotube arrays, and nanowalls are fabricated.
In Non-Patent Document 2 using VLS, an epitaxial growth layer of AlGaN is first formed on a sapphire substrate, and an Au thin film is formed thereon. The substrate and an equal amount of mixed powder of ZnO and graphite were loaded into a chamber in which Ar containing 2% O ₂ was supplied as a carrier gas, heated to 850 ° C., and the Au thin film as a catalyst by VLS growth. A nanorod array of ZnO with an irregular arrangement of 30 to 40 nm is fabricated. Further, the density of the nanorod array is controlled by changing the thickness of the Au thin film between 1 and 8 nm.
In Non-Patent Document 3 using an electrolytic deposition method without using a mask, a Ti electrode is used as a working electrode, a graphite electrode is used as a counter electrode, and an Ag / AgCl electrode is used as a reference electrode, and 10 mM cerium nitrate and 50 mM KCl are used. A CeO ₂ nanorod array having a diameter of about 200 nm is manufactured by applying an electric field at 70 ° C. for 120 minutes under a constant current condition of 0.5 mA / cm ^{2 using} an aqueous solution containing ammonium chloride as an electrolytic solution.
In Non-Patent Document 4 using an electrolytic deposition method using porous alumina as a mask, a working electrode is formed by vapor-depositing gold on one side using a pore obtained by anodizing Al as a mask, and a graphite electrode as a counter electrode. Using a calomel electrode as the reference electrode and applying an electric field at a constant voltage of -3 to -9 V for 60 minutes using an ethanol solution of 0.3MCeCl ₃ · 7H ₂ O as an electrolyte, a cerium hydroxide rod is produced. doing. Moreover, the rod of cerium oxide is produced by baking the obtained rod of hydroxide at 500 degrees.
In Non-Patent Document 5 using an electrolytic deposition method using a microphase separation structure formed by a block copolymer as a mask, a block copolymer made of polystyrene (PS) and polymethyl methacrylate (PMMA) is used as a gold substrate. A cylinder structure made of PMMA by applying a Kapton sheet deposited with aluminum to the surface of the formed film and bonding it with aluminum, and heating at 165 ° C. for 14 hours while applying an electric field of 30 to 40 V / μm. Form a microphase-separated structure perpendicular to the substrate and arranged in a hexagonal manner. The film on which the microphase separation structure is formed is irradiated with ultraviolet rays and rinsed with acetic acid to remove the PMMA domain in the film, thereby producing a nanoporous PS film. Thereafter, using a nanoporous PS film as a mask, Co or Cu is deposited in the porous by electrolytic plating to produce a metal nanorod array. In the example of Patent Document 1, a block copolymer composed of polyethylene oxide (PEO) and a polymer of methacrylate having a liquid crystalline mesogen chain in the side chain is formed on a conductive substrate and heat-treated at 140 degrees. Thus, a micro layer separation structure in which the cylinder structure made of PEO is arranged in a hexagonal manner perpendicular to the substrate is formed. And the metal nanorod array is produced by performing electroplating with respect to the film | membrane in which this micro phase separation structure was formed, and depositing a metal in the position of the said cylinder structure.

ADV. Mater. , 2009, 21, 222-226 J. et al. AM. CHEM. SOC. 2005, 127, 7920-7923. Chem. Commun. , 2010, 46, 7721-7723 Electrochemical and solid-state letters, 11 (9) K93-K97 (2008) Science, 290, 2126 (2000)

JP 2012-1787 A

However, all of the methods of Non-Patent Documents 1 to 5 are costly, time-consuming, and labor-intensive to form regularly arranged nanometer-scale microstructures made of metal oxides on a conductive substrate. There is such a problem.
For example, the method described in Non-Patent Document 1 requires a top-down process such as electron beam lithography or direct drawing in order to produce a mask that provides a regular arrangement. In addition, the top-down process requires a very expensive apparatus such as an electron beam drawing apparatus, which increases the cost. Further, since the patterns are drawn one by one, a great amount of time is required even in the process.
The VLS method of Non-Patent Document 2 does not require a mask, but requires a catalyst to grow a rod. Moreover, the rod array obtained by this method grows at random, and the arrangement cannot be given regularity. Furthermore, it is difficult to remove the catalyst from the produced rod.
In the electrolytic deposition method that does not use the mask of Non-Patent Document 3, the structure to be formed depends on the composition (type of additive, etc.), temperature, type of electrode substrate, etc. of the electrolyte used when forming the fine structure. Different like rods, particles, sheets, etc. Therefore, it is necessary to search for and optimize conditions for forming a target structure, and the versatility with respect to various types of metal hydroxides or metal oxides is low. Furthermore, in this method, since the rods grow at random, the arrangement cannot have regularity.
The electrolytic deposition method using porous alumina as a mask described in Non-Patent Document 4 requires a long time because it requires a step of immersing the electrolyte in the electrolyte for 2 hours or more and allowing the electrolyte to penetrate into the pores. . When porous alumina is used as an electrode, a gold thin film is formed by vapor deposition to give conductivity to the bottom of the porous alumina. However, if the porous alumina is removed after forming the microstructure, the gold thin film cannot maintain the structure. Since the regular arrangement structure is broken, it is difficult to obtain a structure in which the obtained fine structure is maintained on the electrode substrate while maintaining the regular arrangement.
The method described in Non-Patent Document 5 uses a self-organization phenomenon of a block copolymer to form a microphase separation structure in the block copolymer film, and uses this as a mask, so a top-down process is required. There are advantages to not. However, this method requires the application of an electric field to induce self-assembly of the block copolymer. In addition, when using the block copolymer film formed with microphase separation as a mask, it is necessary to remove the PMMA in the cylinder part by irradiating it with VUV, so that a multi-step process is required. And
On the other hand, since the method described in Patent Document 1 does not require a step of selectively removing the cylinder structure, it is simpler and requires less cost and time than the conventional method. However, in this method using an electroplating method in which a cathodic reaction (reduction reaction) proceeds electrochemically on the electrode substrate surface on which a mask having a microphase separation structure of a block copolymer is formed, the metal oxide that can be formed There are restrictions on things. For example, metal oxides such as MnO ₂ and Co ₃ O ₄ cannot be deposited by electrolytic plating.

  The present invention has been made in view of the above circumstances, and a method for manufacturing a microstructure that can be manufactured by regularly arranging a microstructure made of a metal oxide on a conductive substrate, and the manufacture It aims at providing the composite_body | complex obtained using a method.

The present invention for solving the above problems has the following aspects.
[1 ] An amphiphilic block copolymer film is formed on a conductive substrate by applying a solution in which an amphiphilic block copolymer having a liquid crystalline molecular structure in the side chain is dissolved in a solvent. A phase separation step in which the inside of the amphiphilic block copolymer membrane is phase-separated into a hydrophilic phase and a hydrophobic phase;
The amphiphilic block copolymer film, contacted Al, Ti, Cr, Mn, Fe, Co, an electrolyte of metal salts dissolved in a solvent selected from the group consisting of Ni and V, the conductive substrate By applying an oxidization voltage to the electrophilic treatment, MnO ₂ , Mn ₂ O ₃ , Al ₂ O ₃ , TiO ₂ , Cr ₂ O ₃ , at the position of the hydrophilic phase of the amphiphilic block copolymer film , An electrolytic deposition treatment step of depositing a metal oxide selected from the group consisting of Fe ₂ O ₃ , Co ₃ O ₄ , Ni ₂ O ₃ and V ₂ O ₅ to form a microstructure formed of the metal oxide; ,
A method for producing a fine structure characterized by comprising:
[2] An organic film forming step of forming an organic film on the conductive substrate;
On the organic film, a solution obtained by dissolving an amphiphilic block copolymer having a liquid crystalline molecular structure in the side chain in a solvent is applied to form an amphiphilic block copolymer film, followed by heat treatment, A phase separation step of separating the inside of the amphiphilic block copolymer membrane into a hydrophilic phase and a hydrophobic phase;
Contacting the amphiphilic block copolymer film with an electrolytic solution in which a metal salt selected from the group consisting of Al, Ti, Cr, Mn, Fe, Co, Ni and V is dissolved in a solvent, the conductive substrate By applying an oxidization voltage to the electrophilic treatment, MnO ₂ , Mn ₂ O ₃ , Al ₂ O ₃ , TiO ₂ , Cr ₂ O ₃ , at the position of the hydrophilic phase of the amphiphilic block copolymer film , An electrolytic deposition treatment step of depositing a metal oxide selected from the group consisting of Fe ₂ O ₃ , Co ₃ O ₄ , Ni ₂ O ₃ and V ₂ O ₅ to form a microstructure formed of the metal oxide; ,
A method for producing a fine structure characterized by comprising:
[3] The conductive substrate is an organic film formed thereon,
The fine film according to [2], wherein the organic film is a self-assembled monolayer, a Langmuir-Blodgett film, an acrylic polymer thin film, an amphiphilic random copolymer thin film, or an amphiphilic block copolymer thin film. Manufacturing method of structure.
[4] The method for producing a microstructure according to [2] or [3], wherein the organic film is a self-assembled monolayer formed using a compound represented by the following general formula (2): .
[Wherein, Z ′ represents a liquid crystalline mesogenic chain, E represents a silyl group, thiol group, disulfide group or phosphonic acid group having an alkoxy group or a chlorine atom as a substituent bonded to a silicon atom, and D represents an ester. A bond, a urethane bond, a urea bond, an ether bond or an alkylene group is represented, p ′ represents an integer of 4 to 30, and r represents an integer of 1 to 30. ]
[ 5 ] The method for manufacturing a microstructure according to any one of [1] to [4], wherein the electrolytic treatment is performed by a constant potential method, a constant current method, or a pulse method.
[6] The electrolytic treatment is performed by a pulse method,
The method for producing a fine structure according to any one of [1] to [5], wherein the time for applying the oxidation voltage is 0.1 second to 10 seconds.
[ 7 ] The method for producing a microstructure according to any one of [1] to [6], wherein the amphiphilic block copolymer is represented by the following general formula (1).

[In the formula, A represents a hydrophilic polymer chain, Z represents a liquid crystalline mesogenic chain, B represents a halogen atom, R ¹ represents a hydrogen atom or an alkyl group, and p represents an integer of 4 to 30. , Q represents an integer of 5 to 500, R ² represents a hydrogen atom or an alkyl group, and R ³ represents a methyl group. ]

[ 8 ] The method for producing a microstructure according to [ 7 ], wherein Z in the general formula (1) is represented by the following general formula (z1).
_{^{-X- (R 4 -Y) m -R}} 5 ... (z1)
[Wherein, X and Y each independently represent a divalent hydrocarbon cyclic group or a heterocyclic group which may have a substituent, and R ⁴ represents a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —C (═O) O—, —OC (═O) —, —C≡C—, —CH═CH—, —CF═CF—, — (CH _{2 ) 4 -, - CH 2 CH} 2 CH 2 O -, - OCH 2 CH 2 CH 2 -, - CH = CH-CH 2 CH 2 -, - CH 2 CH 2 -CH = CH -, - N = N- , —CH═CH—COO—, —OCO—CH═CH—, —CH═CH—CO— or —CO—CH═CH—, wherein R ⁵ represents a hydrogen atom, a halogen, an alkyl group, an alkoxy group, cyano Represents a group, a mercapto group, a nitro group or an amino group, and m represents an integer of 1 to 4. ]

[ 9 ] The conductive substrate is a glass substrate, a gold substrate, a silicon substrate having a film of tin oxide or indium-tin oxide formed on the surface, or a flexible substrate having a film formed of indium-tin oxide or gold on the surface. The manufacturing method of the fine structure according to any one of [1] to [ 8 ].
[ 10 ] The microstructure according to any one of [1] to [ 9 ], further including a film removal step of removing only the amphiphilic block copolymer film after the electrolytic deposition treatment step. Body manufacturing method.
[ 11 ] The film removing step includes a method of dissolving the amphiphilic block copolymer film with a solvent, a method of decomposing the amphiphilic block copolymer film by irradiation with vacuum ultraviolet light, and the amphiphilic block. A method of irradiating and decomposing the copolymer film with an electron beam, a method of irradiating the amphiphilic block copolymer film with reactive ions and etching, or a temperature of 450 ° C. or higher for the amphiphilic block copolymer film The method for producing a fine structure according to [ 10 ], which is performed by a method of thermally decomposing by performing a treatment.
[1 2 ] A microstructure is manufactured on a conductive substrate by the method for manufacturing a microstructure according to any one of [1] to [ 9 ], and the microstructure is formed on the conductive substrate. Is formed, and the microstructure is a method for producing a composite to obtain a composite in which the microstructure is disposed in the amphiphilic block copolymer film.
[1 3 ] A composite in which a fine structure is produced on a conductive substrate by the fine structure production method according to [ 10 ] or [ 11 ], and the fine structure is formed on the conductive substrate. The manufacturing method of the composite_body | complex which obtains a body .

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the fine structure which can be produced by arranging regularly the fine structure which consists of metal oxides on a conductive substrate, and the composite_body | complex obtained using this manufacturing method are provided. it can.

It is process drawing which shows typically one Embodiment of the manufacturing method of this invention. It is a schematic sectional drawing of the composite_body | complex obtained by the manufacturing method of embodiment shown in FIG. It is process drawing which shows typically one Embodiment of the manufacturing method of this invention. It is a schematic sectional drawing of the composite_body | complex obtained by the manufacturing method of embodiment shown in FIG. It is the AFM image before electrolytic deposition of the surface of the amphiphilic block copolymer film formed in Example 1, and its Fourier transform image. One side of the AFM image is 1 μm. It is the FE-SEM image which observed the composite_body | complex after the electrolytic deposition process produced in Example 1 from the cross-sectional direction. It is the FE-SEM image which observed the surface of the composite_body | complex after removing the film | membrane produced in Example 1 from diagonally upward. It is a cross-sectional FE-SEM image of the amphiphilic block copolymer film (before electrolytic deposition treatment) formed in Production Example 1.

The manufacturing method of the microstructure of the present invention is as follows:
An amphiphilic block copolymer film is formed by applying a solution obtained by dissolving an amphiphilic block copolymer having a liquid crystal molecular structure in the side chain in a solvent on a conductive substrate on which an organic film may be formed. After the formation, a phase separation step of separating the inside of the amphiphilic block copolymer membrane into a hydrophilic phase and a hydrophobic phase by heat treatment;
The amphiphilic block copolymer film is brought into contact with an electrolytic solution in which a metal salt is dissolved in a solvent and subjected to electrolytic treatment by applying an oxidation voltage to the conductive substrate. An electrolytic deposition treatment step of depositing a metal oxide at the position of the hydrophilic phase of the film and forming a microstructure formed of the metal oxide;
Have

  In the production method, in the electrolytic deposition treatment step, a microstructure made of a metal oxide is formed in the hydrophilic phase portion of the amphiphilic block copolymer film in a shape corresponding to the hydrophilic phase. Thereby, a fine structure is formed on the conductive substrate, and a composite in which the fine structure is disposed in the amphiphilic block copolymer film is obtained. Although details will be described later, the shape of the hydrophilic phase in the amphiphilic block copolymer film, the interval between the plurality of hydrophilic phases, and the like are determined by the amphiphilic block copolymer used. Therefore, by selecting the amphiphilic block copolymer to be used, a complex in which a plurality of fine structures are regularly arranged on a conductive substrate can be easily produced, and the shape and interval thereof can be easily adjusted.

In the method for manufacturing a microstructure of the present invention, a film removal step for removing only the amphiphilic block copolymer film may be further performed after the electrolytic deposition treatment step. By performing the film removal step, the fine structure formed in the amphiphilic block copolymer film is exposed, and a composite in which the fine structure is formed on the conductive substrate is obtained.
Hereinafter, the manufacturing method of the microstructure of the present invention and the composite obtained by the manufacturing method will be described with reference to the accompanying drawings.

<First embodiment>
In the manufacturing method of the microstructure of the present embodiment, an amphiphilic block copolymer film is formed directly on a conductive substrate on which an organic film is not formed in the phase separation step.
FIG. 1 is a process diagram schematically showing this embodiment. FIG. 2 shows a schematic cross-sectional view of the composite obtained by the production method of the present embodiment.

In the present embodiment, first, the phase separation structure film 14 is formed on the conductive substrate 13 by the following procedure (phase separation step).
As shown in FIG. 1A, an amphiphilic block copolymer film 11 is formed on a conductive substrate 13 by applying a solution obtained by dissolving an amphiphilic block copolymer in a solvent. Next, heat treatment is performed on the conductive substrate 13 on which the amphiphilic block copolymer film 11 is formed. When heat treatment is performed, the hydrophilic polymer chain (for example, the A portion in the general formula (1) described later) and the hydrophobic polymer chain (for example, the general formula (1) described later) in the amphiphilic block copolymer are formed. As shown in FIG. 1 (b), the amphiphilic block copolymer film 11 has a hydrophilic phase 15 and a hydrophobic phase 15 ′ by repulsive interaction with Z). And phase separation. Hereinafter, the amphiphilic block copolymer film phase-separated into the hydrophilic phase 15 and the hydrophobic phase 15 ′ is referred to as a phase separation structure film 14.

Next, an electrolytic deposition process is performed by applying an oxidation voltage to the conductive substrate 13 on which the phase separation structure film 14 is formed (electrolytic deposition process step).
In the electrolytic deposition process, the phase separation structure film 14 functions as a mask, and in the hydrophilic phase 15, as shown in FIG. It is formed in a shape corresponding to the shape.
That is, the solvent that dissolves the metal salt that is the electrolyte of the electrolytic solution is usually an aqueous solvent (water, a hydrophilic organic solvent such as alcohol, a mixture thereof, or the like). Since the hydrophilic phase 15 of the phase separation structure film 14 is composed of hydrophilic polymer chains, the electrolyte can easily enter the hydrophilic phase 15 in a short time. Thus, when an oxidation voltage is applied to the conductive substrate 13 in a state where the electrolytic solution has entered the hydrophilic phase 15, the electrolyte contained in the electrolytic solution is electrochemically oxidized and a metal oxide is deposited. As a result, a metal oxide is selectively deposited in the hydrophilic phase 15 and deposited on the conductive substrate 13 to form a microstructure 16 made of the metal oxide.
The oxidation number of the metal in the metal oxide to be deposited can be controlled by the pH of the electrolyte, the additive, the applied voltage, and the like.
At this time, the hydrophilic polymer chain in the hydrophilic phase 15 is pushed away by the deposited metal oxide as the electrolytic deposition process proceeds, and moves to the vicinity of the interface with the hydrophobic phase 15 ′. On the other hand, the hydrophobic phase 15 ′ is difficult for the electrolytic solution to enter and is insulative, so that no electrolytic deposition is performed on the inside or the surface of the hydrophobic phase 15 ′.
Thus, the composite shown in FIG. 1C, that is, the composite 10 shown in FIG. 2A is obtained. In the composite 10, a plurality of fine structures 16 are regularly arranged on a conductive substrate 13, and the fine structures 16 are arranged in the phase separation structure film 14.

In the present embodiment, after the electrolytic deposition process, a film removal process for removing only the phase separation structure film 14 may be performed. Thereby, the fine structure 16 is exposed, and a composite as shown in FIG. 1D, that is, a composite 20 as shown in FIG. 2B is obtained.
The composite 20 is a structure in which a plurality of fine structures 16 are regularly arranged on the conductive substrate 13, the phase separation structure film 14 is not present, and the fine structures 16 are exposed. Is different.

[Phase separation process]
In the phase separation step, first, an amphiphilic block copolymer film 11 is coated on a conductive substrate 13 by applying a solution obtained by dissolving an amphiphilic block copolymer having a liquid crystal molecular structure in the side chain in a solvent. Form.
As the conductive substrate 13, it is sufficient that at least the surface on which the amphiphilic block copolymer film 11 is provided is made of a conductive material. With such a substrate, electrolytic deposition can be performed in a subsequent electrolytic deposition process.
The conductive material is not particularly limited. For example, metals such as gold, silver, copper, nickel, lead, cobalt, titanium, and silicon; indium tin oxide (ITO), zinc oxide, and titanium oxide And the like, and the like. Among these, gold or ITO is preferable in terms of high transparency and conductivity. In particular, ITO is preferable because a hydroxyl group can be formed by a hydrophilization treatment described later.
The conductive substrate 13 may be made of a conductive material, or may be formed by depositing a conductive material on the surface of an arbitrary substrate, and is appropriately selected from known substrates according to the purpose. it can. The material constituting the substrate used in the latter case may be a conductive material or a non-conductive material.
Examples of the conductive substrate 13 include a glass substrate (ITO-coated glass, hereinafter referred to as an ITO glass substrate) having an ITO film formed thereon, a gold substrate, a silicon substrate, or a flexible substrate having an ITO or gold film formed on the surface. preferable.
The conductive substrate 13 may be subjected to a surface treatment on the surface on which the amphiphilic block copolymer film 11 is provided in order to improve adhesion with the amphiphilic block copolymer film 11. Good.

The “amphiphilic block copolymer” is a block copolymer in which a hydrophobic polymer chain and a hydrophilic polymer chain are bonded. Since the hydrophobic polymer chain and the hydrophilic polymer chain are incompatible with each other, when the amphiphilic block copolymer film 11 is heat-treated using the amphiphilic block copolymer, the hydrophobic polymer chain is highly hydrophobic. Phase separation into molecular chain phase and hydrophilic polymer chain phase. Specifically, the liquid crystal molecular structure is aligned in the direction perpendicular to the surface of the conductive substrate 13 by heat treatment to form a liquid crystal phase, that is, a hydrophobic polymer chain phase (hydrophobic phase 15 ′). Therefore, a hydrophilic polymer chain phase (hydrophilic phase 15) is formed.
“Liquid crystal molecules” are molecules that can be aligned in a certain direction to form liquid crystals. Since the liquid crystalline molecular structure is introduced into the amphiphilic block copolymer, the orientation becomes high, and a structure with high reproducibility and high alignment can be induced.
The amphiphilic block copolymer used in the present invention usually contains a liquid crystalline molecular structure in a hydrophobic polymer chain.

The amphiphilic block copolymer is not particularly limited as long as it has the above function, but is a block copolymer represented by the following general formula (1) (hereinafter referred to as block copolymer (1)). Is preferred.
The block copolymer (1) includes a hydrophobic polymer chain composed of a repeating unit having a liquid crystalline mesogenic chain (Z in the formula (1)) at a side chain terminal, and a hydrophilic polymer chain (formula (1). ) Is a block copolymer bonded with A). The liquid crystalline mesogenic chain corresponds to the liquid crystalline molecular structure. Since the hydrophobic polymer chain and the hydrophilic polymer chain are incompatible with each other, when the heat treatment is performed on the amphiphilic block copolymer film 11 using the block copolymer (1), the hydrophobic polymer chain and the hydrophilic polymer chain are hydrophobic. Phase separation into a polymer chain phase and a hydrophilic polymer chain phase.

[In the formula, A represents a hydrophilic polymer chain, Z represents a liquid crystalline mesogenic chain, B represents a halogen atom, R ¹ represents a hydrogen atom or an alkyl group, and p represents an integer of 4 to 30. , Q represents an integer of 5 to 500, R ² represents a hydrogen atom or an alkyl group, and R ³ represents a methyl group. ]

In the formula (1), as a hydrophilic polymer chain preferable as A, for example, the formula — (O—R ¹¹ ) _n1 — [wherein R ¹¹ is an alkylene group, and n1 is the degree of polymerization. ] Or a formula — (CH ₂ —C (R ¹² ) (R ¹³ )) _n2 — [wherein R ¹² is a hydrogen atom or an alkyl group] R ¹³ is a hydrophilic group and n2 is the degree of polymerization. And a polymer chain represented by the formula (hereinafter referred to as polymer chain (a2)) in the structure.
The polymer chain containing these polymer chains (a1) or (a2) is higher in hydrophilicity than poly (alkyl acrylate) such as PMMA, and the hydrophilic chain is not removed by VUV irradiation or the like. The fine structure 16 can be formed by electrolytic deposition in the hydrophilic phase portion. This is considered because the formed hydrophilic phase 15 is liquid at a temperature at which electrolytic deposition is performed (for example, 10 to 50 ° C.). For example, the freezing point of poly (ethylene oxide) having a phase-separated structure is approximately −20 ° C. depending on the degree of polymerization, but when the hydrophilic polymer chain is poly (ethylene oxide), the hydrophilic phase 15 is −20 It becomes liquid at a temperature not lower than 115 ° C and not higher than 115 ° C.
In addition, the phase transition temperature of the liquid crystal formed by the liquid crystalline mesogenic chain is usually about 115 ° C., and the phase separation structure is destroyed when the temperature is exceeded.
Each of the freezing point of a hydrophilic polymer chain such as poly (ethylene oxide) and the phase transition temperature of liquid crystal can be measured by DSC (differential scanning calorimetry).

In the polymer chain (a1), the alkylene group for R ¹¹ is preferably a linear or branched alkylene group having 1 to 4 carbon atoms, and particularly preferably an ethylene group.
Specific examples of the polymer chain (a1) include poly (ethylene oxide), poly (propylene oxide), poly (butylene oxide), poly (tetramethylene ether) and the like. Of these, poly (ethylene oxide) is preferred.
n1 is the degree of polymerization. n1 is preferably an integer of 5 to 500, and more preferably an integer of 40 to 500. When the value of n1 is within the above range, the moldability of the phase separation structure is stabilized.
The polymer chain (a1) is bonded to the carbon atom adjacent to A (the carbon atom to which R ² and R ³ are bonded) via —O—CO— from the viewpoint of ease of synthesis and the like. Is preferred.

In the polymer chain (a2), the alkyl group for R ¹² is preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.
R ¹² is preferably a hydrogen atom or a methyl group.
Examples of the hydrophilic group for R ¹³ include —OH, —COOH, —CO—NH ₂ , —CO—R ¹⁴ , wherein R ¹⁴ is a cyclic ether group or a sugar chain. ] Etc. are mentioned. Examples of the cyclic ether group for R ¹⁴ include a group obtained by removing one hydrogen atom from a crown ether, a group obtained by removing one hydrogen atom from a cryptand, and the like.
Specifically, the polymer chain (a2) is poly (vinyl alcohol), poly (acrylic acid), poly (methacrylic acid), poly (acrylamide), poly (methacrylate) having a crown ether, cryptand or sugar chain in the side chain. ) Or poly (acrylate).
n2 is the degree of polymerization, and its preferred range is the same as the preferred range of n1.

Among the above, A includes a polymer chain (a1) from the viewpoint of forming a phase separation structure, and is preferably represented by the general formula R ^10- (O—R ¹¹ ) _b —O—CO— R ¹⁰ is a hydrogen atom or an alkyl group, R ¹¹ is an alkylene group, and b is an integer of 5 to 500. ] Is more preferable.
In the formula, as R ¹⁰ , a hydrogen atom or an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group is particularly preferable. R ¹¹ is the same as described above. The preferable range of b is the same as the preferable range of n1.

In formula (1), Z represents a liquid crystalline mesogenic chain. When heat treatment is performed on the amphiphilic block copolymer film 11, the liquid crystalline mesogen chains are aligned in the direction perpendicular to the surface of the conductive substrate 13 to form a liquid crystal phase. Thereby, a hydrophilic polymer chain phase (hydrophilic phase 15) is formed.
The liquid crystalline mesogenic chain of Z is not particularly limited as long as it has the above function, and a known mesogenic chain possessed by the liquid crystalline polymer can be used.
Preferable examples of the liquid crystalline mesogenic chain of Z include those represented by the following general formula (z1).
_{^{-X- (R 4 -Y) m -R}} 5 ... (z1)
[Wherein, X and Y each independently represent a divalent hydrocarbon cyclic group or a heterocyclic group which may have a substituent, and R ⁴ represents a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —C (═O) O—, —OC (═O) —, —C≡C—, —CH═CH—, —CF═CF—, — (CH _{2 ) 4 -, - CH 2 CH} 2 CH 2 O -, - OCH 2 CH 2 CH 2 -, - CH = CH-CH 2 CH 2 -, - CH 2 CH 2 -CH = CH -, - N = N- , —CH═CH—COO—, —OCO—CH═CH—, —CH═CH—CO— or —CO—CH═CH—, wherein R ⁵ represents a hydrogen atom, a halogen, an alkyl group, an alkoxy group, cyano Represents a group, a mercapto group, a nitro group or an amino group, and m represents an integer of 1 to 4. ]

In formula (z1), X and Y each independently represent a divalent hydrocarbon cyclic group or heterocyclic group which may have a substituent.
The divalent hydrocarbon cyclic group may be an aromatic hydrocarbon cyclic group or an aliphatic hydrocarbon cyclic group, and the aliphatic hydrocarbon cyclic group may be saturated or unsaturated.
Specific examples of the hydrocarbon cyclic group include 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6. -Diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, 1,4-bicyclo [2.2.2] octylene and the like. These groups may have a substituent. Examples of the substituent include an alkyl group and a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
As the heterocyclic group, those having an oxygen atom or a nitrogen atom in the ring skeleton are preferable. For example, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrazine-2,5-diyl, Pyridazine-3,6-diyl, pyrimidine-2,5-diyl and the like can be mentioned. These groups may have a substituent. Examples of the substituent include the same as those mentioned as the substituent that the hydrocarbon cyclic group may have.
X and Y are each independently a divalent aromatic hydrocarbon cyclic group which may have a substituent, and 1,4-phenylene is particularly preferable.

In the formula (z1), R ⁴ is a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —C (═O) O—, —OC (═O) —, —C≡. C—, —CH═CH—, —CF═CF—, — (CH ₂ ) ₄ —, —CH ₂ CH ₂ CH ₂ O—, —OCH ₂ CH ₂ CH ₂ —, —CH═CH—CH ₂ CH _{2 -, - CH 2 CH 2} -CH = CH -, - N = N -, - CH = CH-COO -, - OCO-CH = CH -, - CH = CH-CO- or -CO-CH = CH -Represents.
Among the above, those having a carbon-carbon double bond or a nitrogen-nitrogen double bond are preferred, and —CH═CH—, —N═N—, —CH═CH—CO— or —COCH═CH— is preferred. More preferred. When R ⁴ has a carbon-carbon double bond or a nitrogen-nitrogen double bond, the liquid crystalline mesogenic chain of Z becomes excellent in reactivity, and block co-polymerization is caused by ultraviolet irradiation, electron beam irradiation, or the like. The phase separation structure 15 can be immobilized by causing cross-linking by a dimerization reaction between the double bonds between the molecules of the coalescence (1).
R ⁵ represents a hydrogen atom, a halogen, an alkyl group, an alkoxy group, a cyano group, a mercapto group, a nitro group or an amino group. Among these, an alkyl group or an alkoxyl group is preferable. As for carbon number of this alkyl group or alkoxyl group, 1-10 are preferable. The alkyl group or alkoxyl group may be linear or branched.
m is an integer of 1 to 4, and 1 is particularly preferable.

In formula (1), B is a halogen atom, preferably a chlorine atom or a bromine atom.
R ¹ represents a hydrogen atom or an alkyl group. The alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group. R ¹ is preferably a hydrogen atom or a methyl group.
p is an integer of 4 to 30, and an integer of 11 to 20 is preferable.
q is an integer of 5 to 500, and is appropriately set so that the volume fraction of the hydrophilic polymer chain (A) in the block copolymer (1) becomes a desired value. The volume fraction will be described later in detail.
The amphiphilic block copolymer is not limited to the block copolymer (1), and any amphiphilic block copolymer other than the block copolymer (1) may be used as long as it has a liquid crystal molecular structure. A coalescence may be used.

The number average molecular weight (Mn) of the amphiphilic block copolymer is preferably from 5,000 to 100,000, more preferably from 10,000 to 50,000. When Mn is not less than the lower limit of the above range, the film formability is improved, and when it is not more than the upper limit, the ordered arrangement of the phase separation structure is improved.
The molecular weight dispersity (weight average molecular weight (Mw) / Mn) of the amphiphilic block copolymer is preferably 1.0 to 1.5, more preferably 1.0 to 1.2.
The Mn and Mw are each measured by gel permeation chromatography using polystyrene as a standard substance.

The amphiphilic block copolymer has a volume fraction of a hydrophilic polymer chain in the amphiphilic block copolymer (for example, A in the block copolymer (A)) of 8 to 99%. Is preferable, and 8 to 82% is more preferable. If the volume fraction is less than 8%, it may be difficult to form the hydrophilic phase 15 penetrating the amphiphilic block copolymer film 11 in the direction perpendicular to the conductive substrate 13. On the other hand, if it exceeds 99%, a phase separation structure may not be formed.
The hydrophilic phase 15 in the phase separation structure film 14 is composed of a hydrophilic polymer chain of an amphiphilic block copolymer, and the hydrophobic phase 15 ′ is composed of a hydrophobic polymer chain. Therefore, by adjusting the volume fraction of the hydrophilic polymer chain in the amphiphilic block copolymer to be used, the shape and size of the formed hydrophilic phase 15, the arrangement interval, and the like can be adjusted.
For example, the shape of the hydrophilic phase 15 formed within the above range can be a cylindrical shape or a lamellar shape (layered shape) oriented in a direction substantially perpendicular to the surface of the conductive substrate 13 by the volume fraction. For example, in the case of the block copolymer (1), when the volume fraction of the hydrophilic polymer chain is 8% or more and less than 53%, the formed hydrophilic phase 15 tends to be cylindrical. When the volume fraction is 53% or more and 82% or less, the formed hydrophilic phase 15 tends to be lamellar. When the volume fraction is more than 82% and less than 99%, the regularity of the phase separation structure may be deteriorated as compared with the case where the volume fraction is 82% or less.
Further, when the volume fraction of the hydrophilic polymer chain is reduced, the width of the hydrophilic phase 15 (cylinder diameter, layer thickness, etc.) can be reduced, and the interval between the plurality of hydrophilic phases 15 can be increased. On the contrary, when the volume fraction of the hydrophilic polymer chain is increased, the width of the hydrophilic phase 15 can be increased or the interval between the plurality of hydrophilic phases 15 can be reduced.
The volume fraction of the hydrophilic polymer chain in the amphiphilic block copolymer is the weight fraction of each hydrophilic polymer chain and hydrophobic polymer chain in the amphiphilic block copolymer. It is calculated | required by converting into the volume fraction using the density of the homopolymer of a chain | strand.

The amphiphilic block copolymer can be produced by a known method. For example, the block copolymer (1) can be produced by the method described in JP 2004-124088 A, WO 2007/055371, etc.
For example, a monomer represented by the formula CH ₂ ═C (R ¹ ) —CO—O— (CH ₂ ) _p —OZ is polymerized at a desired degree of polymerization to synthesize a hydrophobic polymer chain. When the hydrophobic polymer chain is reacted with a compound represented by CH ₂ ═C (R ² ) —CO—O— (O—R ¹¹ ) _b —R ¹⁰ , in the general formula (1), A block copolymer in which A is R ¹⁰ — (O—R ¹¹ ) _b —O—CO— is obtained.

The amphiphilic block copolymer film 11 can be formed by applying a solution obtained by dissolving an amphiphilic block copolymer in a solvent onto the conductive substrate 13 and drying it.
The solvent is not particularly limited as long as it can dissolve the amphiphilic block copolymer to be used. For example, benzene, toluene, xylene, chloroform, dichloromethane, tetrahydrofuran, dioxane, carbon tetrachloride, ethylbenzene, propyl Examples include benzene, ethylene dichloride, and methyl chloride.
The concentration of the amphiphilic block copolymer in the solution may be appropriately set in consideration of the film thickness of the amphiphilic block copolymer film 11 to be formed, the applicability of the resulting solution, and the like. Usually, about 0.1-5 mass% is preferable.

A polyalkylene oxide may be further added to the solution of the amphiphilic block copolymer. The addition of polyalkylene oxide is effective for increasing the size of the hydrophilic phase 15.
As the polyalkylene oxide, for example, the general formula _{^{R 15 - (OR 17) n4}} -OR 16 [ ^wherein, each ^{R 15} and ^{R 16} independently represents a hydrogen atom or an alkyl ^{group, R 17} is C2-4 It is a linear alkylene group, n4 represents the integer of 1-20. ] Is represented. In the formula, the alkyl group for R ¹⁵ and R ¹⁶ is preferably an alkyl group having 1 to 10 carbon atoms. As the alkylene group for R ¹⁷ , an ethylene group is particularly preferable.
The amount of polyalkylene oxide added to the amphiphilic block copolymer solution is such that the volume fraction of polyalkylene oxide with respect to the hydrophilic polymer chain of the amphiphilic block copolymer is 80% or less. preferable.
The volume fraction of polyalkylene oxide with respect to the hydrophilic polymer chain of the amphiphilic block copolymer is the volume fraction of the hydrophilic polymer chain in the amphiphilic block copolymer determined by the above-described procedure. It is calculated | required from the compounding quantity of a property block copolymer and a polyalkylene oxide, and the density of a polyalkylene oxide.

As a method for applying the solution of the amphiphilic block copolymer, known methods such as a spin coating method, a casting method, a dip method, and a bar coating method can be used.
Drying can be carried out by natural drying or vacuum drying.
The film thickness of the amphiphilic block copolymer film 11 is set according to the height of the microstructure 16 to be formed, and is usually preferably in the range of about 30 nm to about 10 μm. The film thickness is a film thickness after drying and can be measured by an atomic force microscope (AFM).

Next, heat treatment is performed on the conductive substrate 13 on which the amphiphilic block copolymer film 11 is formed. When the heat treatment is performed, as described above, the amphiphilic block copolymer film 11 is formed by the repulsive interaction between the hydrophilic polymer chain and the hydrophobic polymer chain constituting the amphiphilic block copolymer. The inside is phase-separated into a hydrophilic phase 15 and a hydrophobic phase 15 ′ to form a phase-separated structure film 14.
As described above, the hydrophilic phase 15 has a cylindrical or lamellar shape depending on the volume fraction of the hydrophilic polymer chain of the amphiphilic block copolymer to be used. Further, by adjusting the volume fraction, the width of the hydrophilic phase 15 and the interval between the hydrophilic phases 15 (the width of the hydrophobic phase 15) can be adjusted.
The heat treatment temperature is preferably in the temperature range of −20 to + 40 ° C. of the melting point (usually 50 to 150 ° C.) of the amphiphilic block copolymer, and more preferably in the temperature range of −10 to + 20 ° C. of the melting point. When the heat treatment temperature is -20 ° C or higher, the fluidity of the amphiphilic block copolymer is good. When the melting point is 40 ° C or lower, the structural stability of the amphiphilic block copolymer is improved. It is good.
The melting point of the amphiphilic block copolymer can be measured by differential scanning calorimetry.

When the hydrophilic phase 15 has a cylindrical shape, the cylinder diameter is preferably 3 to 40 nm, and more preferably 3 to 20 nm. The interval between the plurality of hydrophilic phases 15 is preferably 60 nm or less, and particularly preferably in the range of 15 to 40 nm. Within this range, it is useful in terms of forming a regular array.
When the hydrophilic phase 15 is lamellar, the thickness of the layer is preferably 3 to 20 nm. Further, the interval between the plurality of hydrophilic phases 15, that is, the thickness of the hydrophobic polymer chain layer is preferably 20 nm or less, and more preferably 3 to 20 nm. Within this range, it is useful in terms of forming a regular array.
However, the present invention is not limited to this, and the size and interval thereof can be freely designed according to the application.

[Electrolytic deposition treatment process]
In the electrolytic treatment for the conductive substrate 13 on which the phase separation structure film 14 is formed, an electrolytic solution in which a metal salt corresponding to the metal oxide constituting the microstructure to be formed is dissolved in a solvent is used. When the electrolytic solution is brought into contact with the phase separation structure film 14 and an oxidation voltage is applied to the conductive substrate 13 in this state, the electrolyte that has entered the hydrophilic phase 15 near the surface of the conductive substrate 13 as described above. The electrolyte contained in the liquid is electrochemically oxidized to deposit a metal oxide. By utilizing this phenomenon, the microstructure 16 made of a metal oxide can be formed in the hydrophilic phase 15 portion.

The electrolytic treatment using the oxidation voltage can be performed by a known method.
Specific examples of the metal constituting the metal salt used in the electrolytic solution include Al, Si, Ti, Cr, Mn, Fe, Co, Ni, and V.
In the metal salt, any counter ion capable of forming a salt with a metal ion may be used as long as it can form a salt soluble in a solvent.
As a solvent for dissolving the metal salt, water may be used, an organic solvent may be used, or a mixture thereof may be used. Any organic solvent may be used as long as it has affinity with the hydrophilic phase 15 (affinity with the hydrophilic polymer chain of the amphiphilic block copolymer), and examples thereof include alcohols such as methanol, ethanol, and isopropanol. Can be mentioned. As the solvent, ethanol is most preferable.
Components other than metal salts may be added to the electrolytic solution. Examples of such components include lithium perchlorate and tetrabutylammonium salt (an electrolyte for increasing the conductivity of the solution).

The oxidation voltage means a voltage at which electrons can be directly extracted from a target metal ion, that is, the oxidation number increases. When an oxidation voltage is applied to the conductive substrate 13 as a working electrode to electrolyze the electrolyte (metal salt), the metal ion (M ^{n +} ) derived from the electrolyte is converted into a metal oxide ( ^{Mn +} ) by the reaction shown in the following reaction formula (r1). M _x O _y ). The oxidation number (2y / x) of the metal in the generated metal oxide is a value larger than the oxidation number (n) of the metal ion before applying the oxidation voltage.
xM ^{n +} + yH ₂ O → M _x O _y + 2yH ⁺ + ze ⁻ Reaction formula (r1)

The oxidation voltage applied in the electrolytic treatment varies depending on the metal species to be deposited and the oxidation number, and can be determined with reference to the oxidation-reduction potential of metal ions obtained by the cyclic voltammetry method.
Measurement of the redox potential of metal ions by cyclic voltammetry is performed by measuring the current value while sweeping the voltage in the electrolyte containing the target metal ion and observing the oxidation current and reduction current. Can do. The applied oxidation voltage may be selected to be equal to or higher than the oxidation-reduction potential obtained by cyclic voltammetry.

Various methods such as a constant potential method, a constant current method, and a pulse method can be used for the electrodeposition treatment, which can be selected depending on the metal species to be deposited and the oxidation number. The constant potential method is an electrolytic deposition method in which an applied potential is fixed and applied at an oxidation voltage determined by a cyclic voltammetry method, and the amount of electrodeposition is controlled by the application time. The constant current method is a method in which electrolytic deposition is performed at a constant current value at which the voltage applied to the conductive substrate 13 as the working electrode is equal to or higher than the oxidation-reduction potential obtained by the cyclic voltammetry method. The pulse method is an electrolytic deposition method in which an oxidation voltage and a non-oxidation voltage (voltage that does not cause an oxidation reaction and is lower than the oxidation-reduction potential) are applied alternately.
In the electrodeposition process, it is preferable to use a pulse method in that the fine structure 16 can be efficiently formed with low defects in the hydrophilic phase 15 portion of the phase separation structure film 14. In the pulse method, the time for applying the oxidation voltage is preferably 0.1 seconds or more and 10 seconds or less. If the application time of the oxidation voltage is longer than 10 seconds, electrolytic deposition may proceed at the interface between the phase separation structure film 14 and the conductive substrate 13, and the phase separation structure film 14 may peel off.
The oxidation number of the metal oxide deposited by the electrolytic treatment can be confirmed by X-ray photoelectron spectroscopy.

Preferable specific examples of the metal oxide deposited by electrolytic deposition using an oxidation voltage include metal oxides represented by the following general formula (3).
M _a O _b (3)
[In Formula (3), M is a transition metal selected from the group consisting of Al, Ti, Cr, Mn, Fe, Co, Ni, and V, and 1 ≦ a ≦ 3 and 1 ≦ b ≦ 5. ]

In formula (3), when a is 2 or more, a M may be the same or different.
b is a value that satisfies the oxidation number of a M.
Specific examples of the metal oxide represented by the formula (3) include MnO ₂ , Mn ₂ O ₃ , Al ₂ O ₃ , TiO ₂ , Cr ₂ O ₃ , Fe ₂ O ₃ , Co ₃ O ₄ , and Ni _2. Examples include O ₃ and V ₂ O ₅ .

[Membrane removal process]
In the present embodiment, after the electrolytic deposition treatment step, only the phase separation structure film 14 can be removed in order to obtain the composite 20 by exposing the fine structure 16 of the obtained composite 10.
As a method of removing only the phase separation structure film 14, a method of dissolving the phase separation structure film 14 with a solvent, a method of irradiating the phase separation structure film 14 with vacuum ultraviolet light and decomposing it, an electron beam on the phase separation structure film 14 Examples include a method of irradiating and decomposing, a method of irradiating reactive ions to the phase separation structure film 14 and etching, a method of thermally decomposing the phase separation structure film 14 by performing a high temperature treatment at 450 ° C.
Examples of the solvent used for dissolving the phase separation structure film 14 include the same solvents as those mentioned as the solvent capable of dissolving the amphiphilic block copolymer in the description of the phase separation step.
Examples of reactive ions used for etching include oxygen plasma.

<Second Embodiment>
In the method for manufacturing a microstructure of the present embodiment, an amphiphilic block copolymer film is formed on the organic film of the conductive substrate on which the organic film is formed in the phase separation step.
Since the adhesion between the conductive substrate and the amphiphilic block copolymer film is not so strong, when the amphiphilic block copolymer film is directly formed on the conductive substrate, during the electrolytic deposition treatment, Electrolyte solution may enter the part other than the hydrophilic phase at the interface between the phase-separated amphiphilic block copolymer film and the conductive substrate, and the shape of the fine structure may deteriorate. Thus, since the adhesion between the hydrophobic phase of the amphiphilic block copolymer film after phase separation and the organic film is good, a fine structure can be formed in a good shape.
The manufacturing method of the present embodiment is an organic film forming step of forming an organic film on a conductive substrate before performing a phase separation step, that is, before applying a solution in which an amphiphilic block copolymer is dissolved in a solvent. Except for the above, the same procedure as in the first embodiment can be performed.
FIG. 3 is a process diagram schematically showing this embodiment. FIG. 4 shows a schematic cross-sectional view of the composite obtained by the production method of the present embodiment.
In the embodiments described below, the same reference numerals are given to the components corresponding to the above-described components, and the detailed description thereof is omitted.

In this embodiment, first, the organic film 12 is formed on the conductive substrate 13 (organic film forming step).
Next, the phase separation structure film 14 is formed on the organic film 12 by the following procedure (phase separation step).
As shown in FIG. 3A, a solution obtained by dissolving an amphiphilic block copolymer in a solvent is applied on a conductive substrate 13 on which an organic film 12 is formed, and the amphiphilic block copolymer film 11 is applied. Form. Next, heat treatment is performed on the conductive substrate 13 on which the amphiphilic block copolymer film 11 is formed. When heat treatment is performed, as shown in FIG. 3B, the inside of the amphiphilic block copolymer film 11 is phase-separated into a hydrophilic phase 15 and a hydrophobic phase 15 ′, and a phase-separated structure film 14 is formed.
Next, an electrolytic deposition process is performed by applying an oxidation voltage to the conductive substrate 13 on which the phase separation structure film 14 is formed (electrolytic deposition process step). As a result, a fine structure 16 made of a metal oxide is formed in the shape corresponding to the shape of the hydrophilic phase 15 in the hydrophilic phase 15 of the phase separation structure film 14 as shown in FIG.
Thus, the composite shown in FIG. 3C, that is, the composite 30 shown in FIG. 4A is obtained. In the composite 30, a plurality of fine structures 16 are regularly arranged on the conductive substrate 13 via the organic film 12, and the fine structures 16 are arranged in the phase separation structure film 14. .

In the present embodiment, after the electrolytic deposition process, a film removal process for removing only the phase separation structure film 14 may be performed. Thereby, the fine structure 16 is exposed, and a composite as shown in FIG. 3D, that is, a composite 40 as shown in FIG. 4B is obtained.
In the composite 40, a plurality of fine structures 16 are regularly arranged on the conductive substrate 13 via the organic film 12, the phase separation structure film 14 is not present, and the fine structures 16 are exposed. In that it is different from the composite 30.

  Among the above, the phase separation step, the electrolytic deposition treatment step, and the film removal step are the same as those in the first embodiment, and thus detailed description thereof is omitted. Hereinafter, the organic film formation step will be described in more detail.

[Organic film formation process]
In the organic film forming step, the organic film 12 is formed on the conductive substrate 13.
As the conductive substrate 13, the same one as described above can be used.
The conductive substrate 13 may be subjected to a surface treatment on the surface on which the organic film 12 is provided in order to improve adhesion with the organic film 12. For example, when forming a self-assembled monomolecular film as the organic film 12 using a compound represented by the general formula (2) described later, it is preferable to perform a hydrophilic treatment for forming a hydroxyl group on the substrate surface. Since the hydroxyl group can react with E in the formula (2) of the compound to form a chemical bond, the hydrophilic treatment improves the adhesion between the conductive substrate 13 and the organic film 12, As a result, the adhesion between the conductive substrate 13 and the phase separation structure film 14 is improved, and the electrolytic deposition treatment can be performed satisfactorily. As the conductive substrate 13 used in this case, an ITO glass substrate, a silicon substrate, or a flexible substrate in which ITO is formed on the surface is preferable. The hydrophilization treatment can be performed by ozone treatment, VUV treatment or the like.

The organic film 12 is provided in order to improve the adhesion between the conductive substrate 13 and the phase separation structure film 14 and to form the fine structure 16 in a favorable shape corresponding to the shape of the hydrophilic phase 15.
The organic film 12 is not particularly limited as long as it can improve the adhesion between the conductive substrate 13 and the phase separation structure film 14, but is preferably a self-assembled monomolecular film (hereinafter abbreviated as SAM). ), Langmuir-Blodgett film (Langmuir-Bloggett film; hereinafter abbreviated as LB film), acrylic polymer thin film, amphiphilic random copolymer thin film, amphiphilic block copolymer thin film and the like. .
Since each of the SAM and LB films is a monomolecular film and has a small film thickness, the hydrophilic phase 15 of the amphiphilic block copolymer film 11 is not deteriorated in the electrolytic deposition treatment step without impairing the conductivity of the conductive substrate 13. Inside, the fine structure 16 can be satisfactorily formed by electrolytic deposition.
The “thin film” in the acrylic polymer thin film, the amphiphilic random copolymer thin film, and the amphiphilic block copolymer thin film is thin enough that the film thickness does not impair the conductivity of the conductive substrate 13. Means that. Thereby, in the electrolytic deposition treatment step, the fine structure 16 can be formed in a favorable shape by electrolytic deposition in the hydrophilic phase 15 of the amphiphilic block copolymer film 11.
From the above viewpoint, the thicknesses of the acrylic polymer thin film, the amphiphilic random copolymer thin film, and the amphiphilic block copolymer thin film are each preferably 20 nm or less, and more preferably 10 nm or less. The lower limit of the film thickness is not particularly limited, but is preferably 3 nm or more, more preferably 5 nm or more in consideration of uniform film formability.
The film thickness of the organic film 12 can be measured by an atomic force microscope (AFM).

Among the above, SAM is preferable as the organic film 12 because it is excellent in the effect of improving the adhesion and can easily form a thin film having a thickness of nanometer order.
The SAM is a monomolecular layer formed by spontaneously chemisorbing molecules on the surface of a solid (here, the conductive substrate 13).
In the SAM, for example, an organic compound forming the SAM is dissolved in a solvent such as chloroform or toluene, and this solution is heated to room temperature or a temperature at which the organic compound is not decomposed to be brought into contact with the conductive substrate 13 for a certain period of time. It can be formed by rinsing with a solvent.
As the organic compound used for forming the SAM, a compound having a portion that is chemically adsorbed on the surface of the conductive substrate 13 and a portion having an affinity for the hydrophobic polymer chain of the amphiphilic block copolymer is used. . Examples of such sites include those having a liquid crystal molecular structure similar to the liquid crystal molecular structure of the hydrophobic polymer chain.
For example, when the block copolymer (1) is used as the amphiphilic block copolymer, a compound represented by the following general formula (2) (hereinafter sometimes referred to as compound (2)) is preferably used.
In the SAM (organic film 12) formed using the compound (2), the Z ′ (liquid crystal mesogen chain) side terminal is disposed on the surface opposite to the conductive substrate 13. Since a stacking structure by a high affinity π-π interaction is formed between this Z ′ and Z (liquid crystal mesogen chain) of the block copolymer (1), the organic film 12 and the phase separation structure film 14 Adhesion with is improved.

[Wherein, Z ′ represents a liquid crystalline mesogenic chain, E represents a silyl group, thiol group, disulfide group or phosphonic acid group having an alkoxy group or a chlorine atom as a substituent bonded to a silicon atom, and D represents an ester. A bond, a urethane bond, a urea bond, an ether bond or an alkylene group is represented, p ′ represents an integer of 4 to 30, and r represents an integer of 1 to 30. ]

In the formula (2), Z ′ represents a liquid crystal mesogenic chain. Examples of the liquid crystal mesogen chain include the same ones as mentioned for the liquid crystal mesogen chain of Z in the formula (1) in the description of the block copolymer (1).
In the present invention, it is particularly preferable that Z ′ is the same as Z in the formula (1). When the structure of the liquid crystal mesogen chain is the same, the adhesion between the organic film 12 and the phase separation structure film 14 becomes higher.
E represents a silyl group, thiol group, disulfide group or phosphonic acid group having an alkoxy group or a chlorine atom as a substituent bonded to a silicon atom. The alkoxy group of the silyl group is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group or an ethoxy group. The number of alkoxy groups or chlorine atoms bonded to the silicon atom of the silyl group is 1 to 3, particularly preferably 3.
E is a site that reacts with the surface of the conductive substrate 13 to form a chemical bond (covalent bond, hydrogen bond, etc.), and is selected according to the conductive substrate 13 to be used. For example, when a hydroxyl group is present on the surface of the conductive substrate 13, a covalent bond can be formed with the hydroxyl group by a dehydration reaction. Therefore, a silyl group having an alkoxy group or a chlorine atom as a substituent bonded to a silicon atom, Acid groups are preferred. For example, in the silyl group, an alkoxy group or a chlorine atom bonded to a silicon atom becomes -OH by hydrolysis, and a silanol group (Si-OH) is generated. This silanol group dehydrates with the hydroxyl group on the substrate surface to form a covalent bond. When the surface of the conductive substrate 13 is made of gold, a thiol group or a disulfide group is preferable.

In the compound (2), Z ′ and E are bonded via — (CH ₂ ) _r —D— (CH ₂ ) _{p ′} —O—.
D represents an ester bond, a urethane bond, a urea bond, an ether bond or an alkylene group. By having D, the thermal stability of the compound (2) is improved. Therefore, heat treatment is performed at about 140 ° C. in order to form the hydrophilic phase 15, but the bond is kept stable even at that temperature. Further, in the synthesis of the compound, the reaction proceeds easily with a high yield.
Further, by providing an alkyl chain (— (CH ₂ ) _r —, — (CH ₂ ) _{p ′} —), the molecules constituting the SAM retain fluidity in the solution or in the phase separation structure membrane 14. It can be made easier to interact in the film, and the adhesion is improved. Moreover, the film thickness of SAM formed can be adjusted by adjusting the chain length of an alkyl chain.
p 'represents the integer of 4-30, and the integer of 11-20 is preferable.
r represents an integer of 1 to 30, and an integer of 3 to 10 is preferable.

As described above, the manufacturing method of the microstructure of the present invention and the composite manufactured by using the manufacturing method have been described in detail with reference to the embodiment. However, the present invention is not limited to the above-described embodiment. Of course, various improvements and changes may be made without departing from the spirit of the invention.
For example, after the composites 10 and 30 are manufactured, the phase separation structure film 14 may be peeled off from the conductive substrate 13 together with the fine structure 16 without performing the film removal step. The film thus obtained includes the regularly arranged microstructures 16. Further, when only the amphiphilic block copolymer film is removed from the film, a plurality of independent fine structures 16 are obtained.
Further, the fine structure 16 may be peeled off from the conductive substrate 13 after the composites 20 and 40 are manufactured. Thereby, a plurality of independent fine structures 16 are obtained.
The microstructure 16 obtained as described above can be used as a positive electrode material for a lithium ion battery, for example, when manganese oxide is selected as the metal oxide.

According to the method for manufacturing a fine structure of the present invention described above, the fine structure can be easily arranged regularly on a conductive substrate.
In addition, in this manufacturing method, compared with the conventional method, a microstructure made of a metal oxide and a complex in which a plurality of the microstructures are regularly arranged on a conductive substrate are very inexpensive and easy. Can be made. For example, the manufacturing method of the present invention does not require a process such as electron beam lithography that is required in Non-Patent Document 5 for manufacturing a mask for electrolytic deposition treatment for forming a fine structure. Further, the phase separation structure film used as a mask for electrolytic deposition treatment in the present invention requires a step of immersing the electrolytic solution into the pores by immersing it in the electrolytic solution as in Non-Patent Document 4 for 2 hours or more. Moreover, the process of selectively removing the polymer (PMMA) of the cylinder domain as in Non-Patent Document 5 is not required.
In addition, in the production method of the present invention, metal oxide precipitation accompanied by an oxidation reaction is possible by applying an oxidation potential, and a metal oxide microstructure that cannot be produced by the method described in Patent Document 1 is easy. Can be produced.

The composites obtained as described above can be expected to be used in fields such as optical devices, magnetic devices, field emission devices, field electrodes, sensing devices, solar cells, lithium ion batteries, and fuel cells. In particular, it is useful as an electrode material in the field of battery devices that require large capacity, high-speed charging, and high-efficiency energy conversion.
In addition, the composite from which the phase separation structure film is removed can use the gaps between the regularly arranged microstructures as microchannels, and can be expected to be used for various sensing using microfluids.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited by the following description.
<Synthesis Example 1: Synthesis of SAM-forming molecule>
A compound (2-1) represented by the following chemical formula (2-1) was synthesized by the following procedure. The compound (2-1) is a compound in which Z ′ in the general formula (2) is a liquid crystalline mesogenic chain containing azobenzene, E is a triethoxysilyl group, and D is a urethane bond.
The azo compound (2-1a) represented by the following chemical formula (2-1a) is used as a starting material, sodium hydroxide is added to the isopropanol (IPA) solution, hydrolyzed at 60 ° C. for 12 hours, and the azo compound ( The compound (2-1b) represented by the following chemical formula (2-1b) was obtained by hydroxylating the terminal of 2-1a). Thereafter, 40 equivalents of 3-triethoxysilylpropyl isocyanate was added, and a urethane bond was formed by stirring overnight in dehydrated tetrahydrofuran to synthesize Compound (2-1).

<Synthesis Example 2: Synthesis of amphiphilic block copolymer>
The block copolymers (1-1) and (1-2) respectively represented by the following chemical formulas (1-1) and (1-2) are respectively used by an atom transfer radical polymerization method using a copper complex as a catalyst. And synthesized. The block copolymer (1-1) has —CO—O— (CH ₂ CH ₂ O) ₁₁₄ CH ₃ as a hydrophilic site (A in the general formula (1)), and is on the hydrophobic site side. It has a liquid crystalline mesogenic chain containing azobenzene at the chain end. The block copolymer (1-1) had an Mn of 32100, an Mw / Mn of 1.08, a polymethacrylate (MA) content of 86% by mass, and a melting point of 120 ° C. Moreover, the volume fraction of the hydrophilic site | part in a block copolymer (1-1) was 13%.
The block copolymer (1-2) has —CO—O— (CH ₂ CH ₂ O) ₂₇₂ CH ₃ as a hydrophilic moiety, and a liquid crystalline mesogenic chain containing azobenzene at the side chain end of the hydrophobic moiety. It is what you have. The block copolymer (1-1) had an Mn of 18634, an Mw / Mn of 1.104, a polymethacrylate (MA) content of 34% by mass, and a melting point of 120 ° C. Moreover, the volume fraction of the hydrophilic site | part in a block copolymer (1-2) was 63%.

<Example 1>
First, a composite having the same configuration as that of the composite 30 shown in FIG. 4 was produced by the following procedure.
The ITO glass substrate was ultrasonically cleaned with ethanol for 5 minutes, and after natural drying, the ITO surface was hydrophilized with a VUV irradiation apparatus for 30 minutes. Thereafter, the ITO glass substrate was immersed in a chloroform solution in which the compound (2-1) synthesized in Synthesis Example 1 was dissolved at a concentration of 1 mM for 12 hours. Thereafter, the ITO surface of the ITO glass substrate was rinsed with a chloroform solvent to form a SAM on the ITO surface of the ITO glass substrate.
Next, 0.0101 g of the block copolymer (1-1) obtained in Synthesis Example 2 was dissolved in toluene to obtain a 4% by mass solution. This solution was spin-coated on the ITO glass substrate on which SAM was formed as described above to form an amphiphilic block copolymer film having a thickness of about 200 nm. This ITO glass substrate was heat-treated at 140 ° C. for 1 hour.
FIG. 5 shows an AFM (atomic force microscope) image of the surface of the amphiphilic block copolymer film after the heat treatment. In FIG. 5, one side of the AFM image is 1 μm. A Fourier transform image of the AFM image is shown in the upper right corner of the AFM image. In the Fourier transform image, a signal resulting from the hexagonal regular arrangement of the microphase separation structure is obtained, and a cylindrical microphase separation structure is arranged as a hydrophilic phase in the amphiphilic block copolymer film. It was shown that

The ITO glass substrate obtained above was used as a working electrode, electrolytic deposition treatment was performed using a Pt electrode as a counter electrode and Ag / AgCl as a reference electrode. As an electrolytic solution, a solution in which 0.05 M of manganese (II) chloride tetrahydrate (MnCl ₂ .4H ₂ O, oxidation-reduction potential: 0.85 V) was dissolved in ethanol was used. The application of the oxidation voltage in the electrolytic deposition treatment was performed under the condition that the process of applying the voltage for 5 seconds at a pulse voltage of 1.0 V and 20 seconds at 0.0 V was repeated for 20 cycles with Ag / AgCl as a reference. .
FIG. 6 shows an image obtained by observing the cross section of the ITO glass substrate after the electrolytic deposition treatment with FE-SEM (Field Emission-Scanning Electron Microscopy). As shown in FIG. 6, an amphiphilic block copolymer film is laminated on an ITO glass substrate via an organic film, and in the amphiphilic block copolymer film, an array of microphase separation structures is arranged. Reflecting this, the cylindrical microstructures were regularly arranged.

Next, from the composite obtained above, a composite having the same configuration as that of the composite 40 shown in FIG.
The amphiphilic block copolymer film was removed by irradiating the surface of the ITO glass substrate after the electrolytic deposition treatment with oxygen plasma. The irradiation conditions were a chamber internal pressure of 10 Pa, an RF bias of 250 W, and an oxygen flow rate of 12 sccm.
FIG. 7 shows an image obtained by observing the surface of the ITO glass substrate thus obtained obliquely from above with an FE-SEM. From this result, an ordered manganese (IV) (MnO ₂ ) array was formed on the ITO glass substrate, reflecting the arrangement of the microphase separation structure in the amphiphilic block copolymer film. It could be confirmed.
From the above results, it was shown that a regularly arranged microstructure can be formed by the method for producing a microstructure of the present invention.

<Production Example 1>
In Example 1, except that the block copolymer (1-2) was used instead of the block copolymer (1-1), and the thickness of the amphiphilic block copolymer film was about 1000 nm, the example In the same manner as in Example 1, SAM formation, amphiphilic block copolymer film formation, and heat treatment were performed.
The FE-SEM image of the cross section of the amphiphilic block copolymer film after the heat treatment is shown in FIG. From the FE-SEM image, it was confirmed that a phase separation structure in which lamellar hydrophilic phases and hydrophobic phases were regularly arranged alternately was formed.
By performing electrolytic deposition treatment on the ITO glass substrate thus obtained, a metal oxide is deposited on the hydrophilic phase portion, and a regularly arranged lamellar microstructure can be formed.

  DESCRIPTION OF SYMBOLS 10 ... Composite, 11 ... Amphiphilic block copolymer film, 12 ... Organic film, 13 ... Conductive substrate, 14 ... Phase separation structure film, 15 ... Hydrophilic phase, 15 '... Hydrophobic phase, 16 ... Fine structure 20 ... complex, 30 ... complex, 40 ... complex

Claims (13)

By applying a solution obtained by dissolving an amphiphilic block copolymer having a liquid crystal molecular structure in the side chain in a solvent on a conductive substrate to form an amphiphilic block copolymer film, followed by heat treatment A phase separation step of separating the inside of the amphiphilic block copolymer membrane into a hydrophilic phase and a hydrophobic phase;
The amphiphilic block copolymer film, contacted Al, Ti, Cr, Mn, Fe, Co, an electrolyte of metal salts dissolved in a solvent selected from the group consisting of Ni and V, the conductive substrate By applying an oxidization voltage to the electrophilic treatment, MnO ₂ , Mn ₂ O ₃ , Al ₂ O ₃ , TiO ₂ , Cr ₂ O ₃ , at the position of the hydrophilic phase of the amphiphilic block copolymer film , An electrolytic deposition treatment step of depositing a metal oxide selected from the group consisting of Fe ₂ O ₃ , Co ₃ O ₄ , Ni ₂ O ₃ and V ₂ O ₅ to form a microstructure formed of the metal oxide; ,
A method for producing a fine structure characterized by comprising: An organic film forming step of forming an organic film on the conductive substrate;
On the organic film, a solution obtained by dissolving an amphiphilic block copolymer having a liquid crystalline molecular structure in the side chain in a solvent is applied to form an amphiphilic block copolymer film, followed by heat treatment, A phase separation step of separating the inside of the amphiphilic block copolymer membrane into a hydrophilic phase and a hydrophobic phase;
Contacting the amphiphilic block copolymer film with an electrolytic solution in which a metal salt selected from the group consisting of Al, Ti, Cr, Mn, Fe, Co, Ni and V is dissolved in a solvent, the conductive substrate By applying an oxidization voltage to the surface of the amphiphilic block copolymer film, MnO ₂ , Mn ₂ O ₃ , Al ₂ O ₃ TiO ₂ , Cr ₂ O ₃ , Fe ₂ O ₃ , Co ₃ O ₄ , Ni ₂ O ₃ And V ₂ O ₅ An electrolytic deposition treatment step of depositing a metal oxide selected from the group consisting of, and forming a microstructure comprising the metal oxide;
A method for producing a fine structure characterized by comprising: The organic layer is self-assembled monolayer, Langmuir - Blodgett film, acrylic polymer film, an amphiphilic random copolymer film or amphipathic block copolymers films, according to claim 2 A manufacturing method of a fine structure. Before SL organic film is a self-assembled monolayer film formed by using a compound represented by the following general formula (2), method for manufacturing a microstructure according to claim 2 or 3.
[Wherein, Z ′ represents a liquid crystalline mesogenic chain, E represents a silyl group, thiol group, disulfide group or phosphonic acid group having an alkoxy group or a chlorine atom as a substituent bonded to a silicon atom, and D represents an ester. A bond, a urethane bond, a urea bond, an ether bond or an alkylene group is represented, p ′ represents an integer of 4 to 30, and r represents an integer of 1 to 30. ] The method for manufacturing a microstructure according to any one of claims 1 to 4, wherein the electrolytic treatment is performed by a constant potential method, a constant current method, or a pulse method. The electrolytic treatment is performed by a pulse method,
The manufacturing method of the microstructure according to any one of claims 1 to 5, wherein a time for applying the oxidation voltage is 0.1 second or more and 10 seconds or less. The manufacturing method of the microstructure according to any one of claims 1 to 6, wherein the amphiphilic block copolymer is represented by the following general formula (1).
[In the formula, A represents a hydrophilic polymer chain, Z represents a liquid crystalline mesogenic chain, B represents a halogen atom, R ¹ represents a hydrogen atom or an alkyl group, and p represents an integer of 4 to 30. , Q represents an integer of 5 to 500, R ² represents a hydrogen atom or an alkyl group, and R ³ represents a methyl group. ] The manufacturing method of the microstructure according to claim 7 , wherein Z in the general formula (1) is represented by the following general formula (z1).
^{_{-X- (R 4 -Y) m -R}} 5 ... (z1)
[Wherein, X and Y each independently represent a divalent hydrocarbon cyclic group or a heterocyclic group which may have a substituent, and R ⁴ represents a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —C (═O) O—, —OC (═O) —, —C≡C—, —CH═CH—, —CF═CF—, — (CH _{2 ) 4 -, - CH 2 CH} 2 CH 2 O -, - OCH 2 CH 2 CH 2 -, - CH = CH-CH 2 CH 2 -, - CH 2 CH 2 -CH = CH -, - N = N- , —CH═CH—COO—, —OCO—CH═CH—, —CH═CH—CO— or —CO—CH═CH—, wherein R ⁵ represents a hydrogen atom, a halogen, an alkyl group, an alkoxy group, cyano Represents a group, a mercapto group, a nitro group or an amino group, and m represents an integer of 1 to 4. ] The conductive substrate is a glass substrate, a gold substrate, a silicon substrate having a film of tin oxide or indium-tin oxide formed on a surface thereof, or a flexible substrate having a film of indium-tin oxide or gold formed on a surface thereof. Item 9. The method for producing a microstructure according to any one of Items 1 to 8 . The method for producing a microstructure according to any one of claims 1 to 9 , further comprising a film removal step of removing only the amphiphilic block copolymer film after the electrolytic deposition treatment step. The film removal step includes a method of dissolving the amphiphilic block copolymer film with a solvent, a method of decomposing the amphiphilic block copolymer film by irradiation with vacuum ultraviolet light, and the amphiphilic block copolymer. A method in which the film is irradiated with an electron beam for decomposition, a method in which the amphiphilic block copolymer film is irradiated with reactive ions and etching, or a process at a high temperature of 450 ° C. or higher is performed on the amphiphilic block copolymer film. The method for producing a microstructure according to claim 10 , wherein the method is performed by thermal decomposition. A fine structure is manufactured on a conductive substrate by the method for manufacturing a fine structure according to any one of claims 1 to 9 , and the fine structure is formed on the conductive substrate. The manufacturing method of the composite_body | complex which obtains the composite_body | complex in which the structure is arrange | positioned in the said amphiphilic block copolymer membrane. A composite body obtained by manufacturing a microstructure body on a conductive substrate by the method for manufacturing a microstructure body according to claim 10 or 11 to obtain a composite body in which the microstructure body is formed on the conductive substrate . Manufacturing method .