JP5511345B2 - Metal structure-containing polymer film, method for producing metal structure-containing polymer film, method for producing pattern structure - Google Patents

Description

  The present invention relates to a metal structure-containing polymer film, a method for producing a metal structure-containing polymer film, and a method for producing a pattern structure.

  In Patent Document 1 and Patent Document 2, an optical recording medium has a microphase separation structure formed by a block copolymer in which polymer chains incompatible with each other are bonded, and one of the microphase separation structures An organic thin film containing ultrafine metal particles in the phase is described.

  Further, in Non-Patent Document 1, a film having a microphase separation structure formed by a block copolymer in which incompatible polymer chains are bonded to each other, and containing one of the phases of the microphase separation structure containing osmium oxide. And a method of forming a pattern by etching a structure comprising a substrate and a substrate using the phase as a mask.

JP 2004-306404 A JP 11-60891 A

Miri Park et al., Science, 276, 1401-1404 (1997)

  However, in the pattern forming method described in Non-Patent Document 1, the difference in etching rate between the polystyrene phase and the phase containing osmium oxide in polybutadiene, which form the microphase separation structure, is small. There is a problem that the aspect ratio becomes small.

  Therefore, in the present invention, a manufacturing method of a pattern structure for manufacturing a pattern structure with a higher aspect ratio, a metal structure-containing polymer film that can be used when manufacturing the pattern structure, and a manufacturing method thereof I will provide a.

The first of the present invention comprises a block copolymer having an ion conductive segment and a non-ion conductive segment, a polymer membrane having a microphase separation structure comprising an ion conductive domain and a non-ion conductive domain, a metal structure localized at the ion conductive domain, Tona is, the metal structure is at least partially located in the surface of the two main surfaces of the polymer film, to the surface The part which is not located is also a metal structure-containing polymer film characterized in that it continues from the part located on the surface .

The second aspect of the present invention is a polymer membrane comprising a block copolymer having an ion conductive segment and a non-ion conductive segment, and having a microphase separation structure comprising an ion conductive domain and a non-ion conductive domain. A process to prepare;
Performing electrolytic plating on the polymer film to localize and deposit a metal structure in the ion conductive domain;
It is a manufacturing method of the metal structure containing polymer film characterized by having.

The third aspect of the present invention is a step of preparing a composite comprising the metal structure-containing polymer film obtained by the second of the present invention and the metal structure-containing polymer film;
Etching the substrate using the metal structure as a mask;
It is a manufacturing method of the pattern structure which has this.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the pattern structure which can manufacture the pattern structure which has a fine pattern, the metal structure containing polymer film which can be used when manufacturing the said pattern structure, and its manufacturing method are provided. can do.

It is a schematic diagram which shows the cross section of the metal structure containing polymer film of an example of this invention. It is a schematic diagram which shows an example of the block copolymer used for this invention. It is a schematic diagram which shows the manufacturing method of the pattern structure of an example of this invention. It is a schematic diagram which shows the manufacturing method of the pattern structure of an example of this invention. 3 is an atomic force microscope phase image of the polymer film obtained in Reference Example 1. 2 is a transmission electron microscope image of the polymer film obtained in Reference Example 1. 4 is a scanning electron microscope image of a cross section of a metal structure-containing polymer film in which the metal structure obtained in Example 2 is exposed. 4 is a scanning electron microscope image of a cross section of a metal structure-containing polymer film in which the metal structure obtained in Example 2 is exposed. It is a scanning electron microscope image of the cross section of the metal structure containing polymer film which exposed the metal structure obtained in Example 3. FIG. It is a scanning electron microscope image of the surface and cross section of the metal structure containing polymer film which exposed the metal structure obtained in Example 4. FIG. It is a scanning electron microscope image of the surface of the metal structure containing polymer film which exposed the metal structure obtained in Example 5 and Reference Example 2. It is an atomic force microscope shape image of the metal structure containing polymer film which exposed the metal structure obtained in Example 5 and Reference Example 2. 6 is a scanning electron microscope image of the pattern structure obtained in Example 5. FIG. 2 is a scanning electron microscope image of the pattern structure obtained in Comparative Example 1. FIG.

The first of the present invention comprises a block copolymer having an ion conductive segment and a non-ion conductive segment, a polymer membrane having a microphase separation structure comprising an ion conductive domain and a non-ion conductive domain, a metal structure localized at the ion conductive domain, Tona is, the metal structure is at least partially located in the surface of the two main surfaces of the polymer film, to the surface The part which is not located is also a metal structure-containing polymer film characterized in that it continues from the part located on the surface .

  FIG. 1 is a schematic view showing a cross section when an example of the first metal structure-containing polymer film of the present invention is cut in parallel to the thickness direction of the film, wherein 1 is a metal structure-containing polymer film, 2 is a polymer film having a microphase separation structure, 3 is a metal structure, 4 is an ion conductive domain, and 5 is a non-ion conductive domain.

  Hereafter, the part which comprises the 1st of this invention is demonstrated.

  Reference numeral 2 denotes a polymer membrane having a microphase separation structure composed of an ion conductive domain and a non-ion conductive domain.

  The microphase separation structure of the polymer membrane 2 may be a cylinder structure composed of a cylinder portion and a matrix portion whose length direction is the thickness direction of the polymer membrane 2 as shown in FIG. Further, it may be a cylinder structure composed of a cylinder portion and a matrix portion whose length direction is parallel to the film surface of the polymer film 2. Furthermore, a co-continuous structure or a lamellar structure may be used. One of the phases forming these structures is an ion conductive domain, and the other is a non-ion conductive domain. Among these, the polymer film 2 preferably has a cylinder structure composed of a cylinder part and a matrix part whose length direction is the thickness direction of the polymer film 2 as shown in FIG.

  The size of such a microphase separation structure is preferably 1-50 nm. Here, the size of the microphase separation structure indicates, for example, the distance between one cylinder and the cylinder closest to the cylinder when the microphase separation structure is a cylinder structure, and is one when the structure is a sea-island structure. The distance between one island and the island closest to the island is indicated. In the case of a lamellar structure, the distance between one layer and the closest layer formed by the same segment as the layer is indicated.

  The polymer membrane 2 having a microphase separation structure is composed of a block copolymer 6 composed of an ion conductive segment A7 and a non-ion conductive segment B8 as shown in FIG. Between different block copolymers, ion-conductive segments A7 and non-ion conductive segments B8 interact with each other. Thereby, the ion conductive domain and non-ion conductive domain which the polymer film 2 has are formed, and the micro phase separation structure is formed. Since the block copolymer is formed by linking different polymer chains, it is difficult to make a phase separation structure larger than the spread of each polymer chain. Thereby, a micro phase separation structure which is a periodic self-assembled structure of about 1 nm to 50 nm is formed. In addition, it is preferable that the ratio (ion conductive domain / non-ion conductive domain) of the ionic conductivity between the ion conductive domain and the non-ion conductive domain is 10 or more, and more preferably 100 or more.

  Moreover, it is preferable that the ion conductive segment A which forms a block copolymer has an ion exchange group. The ion exchange group is preferably an acidic group from the viewpoint of conducting metal ions. Examples of such acidic groups include sulfonic acid, carboxylic acid, phosphoric acid, phosphonic acid, phosphonous acid and the like. Among these, sulfonic acid is preferable from the viewpoint of ease of synthesis and high degree of acid dissociation. These polymers may contain one type of ion exchange group or two or more types of ion exchange groups.

  As an example of the monomer constituting the ion conductive segment A, a diene monomer or an olefin monomer added with an ion exchange group is preferable. More specifically, styrene, (meth) acrylate, (meth) acrylamide, butadiene, isoprene, ethylene, propylene and the like containing an ion exchange group (or a salt thereof) are exemplified. Further, in order to improve the film strength, dimensional stability, acid dissociation degree of the polymer film, and to form a clearer phase separation structure, those monomers introduced with fluorine may be used.

  The non-ion conductive segment B only needs to be capable of binding to the ion conductive segment A and forming a microphase separation structure.

Examples of monomers constituting such a non-ion conductive segment B include heavy polymers synthesized from monomers such as acrylic acid esters, methacrylic acid esters, styrene and derivatives thereof, conjugated dienes, and vinyl ester compounds. Coalescence is mentioned. More specifically, styrene, α-, o-, m-, p-alkyl, alkoxyl, halogen, haloalkyl, nitro, cyano, amide, ester-substituted product of styrene;
2,4-dimethylstyrene, paradimethylaminostyrene, vinylbenzyl chloride, vinylbenzaldehyde, indene, 1-methylindene, acenaphthalene, vinylnaphthalene, vinylanthracene, vinylcarbazole, 2-vinylpyridine, 4-vinylpyridine, 2- Polymerizable unsaturated aromatic compounds such as vinyl fluorene;
Alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate;
Unsaturated monocarboxylic acid esters such as methyl crotonate, ethyl crotonate, methyl cinnamate, ethyl cinnamate; trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, heptafluorobutyl (meth) acrylate Fluoroalkyl (meth) acrylates such as;
Siloxanyl compounds such as trimethylsiloxanyldimethylsilylpropyl (meth) acrylate, tris (trimethylsiloxanyl) silylpropyl (meth) acrylate, di (meth) acryloylpropyldimethylsilyl ether;
Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate , Amine-containing (meth) acrylates such as t-butylaminoethyl (meth) acrylate;
Hydroxyalkyl esters of unsaturated carboxylic acids such as 2-hydroxyethyl crotonic acid, 2-hydroxypropyl crotonic acid, 2-hydroxypropyl cinnamate; unsaturated alcohols such as (meth) allyl alcohol;
Unsaturated (mono) carboxylic acids such as (meth) acrylic acid, crotonic acid and cinnamic acid; glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, α-n-butyl Glycidyl acrylate, (meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzylglycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, (meth) acrylic acid-β-methyl glycidyl, (meth) acrylic acid-β-ethyl glycidyl, (meth) acrylic acid-β-propyl glycidyl, α-ethyl Acrylic acid-β-methylglycidyl, (meth) acrylic acid-3-methyl-3,4 Epoxybutyl, (meth) acrylic acid-3-ethyl-3,4-epoxybutyl, (meth) acrylic acid-4-methyl-4,5-epoxypentyl, (meth) acrylic acid-5-methyl-5,6 Epoxy hexyl, (meth) acrylic acid-β-methylglycidyl, (meth) acrylic acid-3-methyl-3,4-epoxybutyl-containing (meth) acrylic acid esters; and their mono and diesters Kind;
N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N-o-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, N-o-hydroxyphenylmaleimide, Nm -Hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenylmaleimide, N-o-chlorophenylmaleimide, Nm-chlorophenylmaleimide, N -P-chlorophenylmaleimide, N-o-carboxyphenylmaleimide, Np-carboxyphenylmaleimide, Np-nitrophenylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-isopropyl Maleimides and (meth) acrylonitrile, such as maleimide, and vinyl chloride.

  In FIG. 2, as a block copolymer constituting the polymer film 2, an AB diblock copolymer that is a copolymer composed of an ion conductive segment A <b> 7 and a non-ion conductive segment B <b> 8 is described. A-B-X or B-A-X type block copolymer in which another segment (polymer) X is linked to the end of one segment (polymer chain) of the AB diblock copolymer It does not matter. In such a case, X may be a segment (polymer) C different from the segments A and B, or may be a diblock copolymer of segments C and D different from the segments A and B. X may be segment A or segment B, and the block copolymer may be an ABA type or BAB type block copolymer. The ABA type or BAB type block copolymer is preferable because the mechanical strength of the film is stronger than that of the AB type diblock copolymer.

  The block copolymer constituting the polymer film 2 is a star block copolymer in which a plurality of different polymers are linked to one chemical bonding point, and a plurality of different polymers are linked to the side chain of one polymer chain. It may be a graft copolymer. Further, it may be a gradient copolymer in which the composition of the monomer of segment A and the monomer of segment B changes continuously along the block copolymer chain.

  The molecular weight of the block copolymer constituting the polymer film 2 may be any molecular weight capable of forming a microphase separation structure, but the higher the molecular weight, the higher the film strength of the polymer film. 1,000 or more is desirable.

  The composition ratio of each segment in the block copolymer is not particularly limited as long as the continuity of the ion conductive domain is not extremely impaired, for example, the ion conductive segment A forms a spherical domain.

  The metal structure 3 may have any metal as a main component, but from the viewpoint of ease of preparation, the metal structure 3 has any element of Ni, Ag, Sn, Cu, Zn, Cr, Au, Co, and Fe as a main component. It is preferable. Although the metal structure 3 may have any shape, the metal structure 3 has a length in a direction perpendicular to the main surface of the polymer film 2 that is longer than a length in a direction horizontal to the main surface of the polymer film 2. Is also preferably long. Here, the main surface of the polymer film refers to the surface having the largest area among the surfaces of the polymer film. For example, when the first metal structure-containing polymer film of the present invention is used as an anisotropic conductive film, at least a part of the metal structure 3 is at least one main surface of the polymer film. It is preferable that the part which is located on the surface and not located on the surface is continuous from the part located on the surface.

  The reason why it is preferable to be located on the surface of at least one main surface can be explained as follows. For example, when making contact with a metal-specific property (for example, high conductivity, heat transfer) on the surface, if a part of the metal structure is located on the surface, the contact can be made with less obstructive factors. it can. For example, if a part of the metal structure is located on the surface, the contact point is not affected by the resistance component caused by the polymer as compared with the case where the metal structure is buried in the polymer. Can be taken. Moreover, the reason why it is preferable that the portion not located on the surface is continuous from the portion located on the surface can be explained as follows. For example, when it is desired to exhibit a property specific to a metal (for example, high conductivity, heat conductivity) through the metal structure, if the metal structure is continuous, the property can be exerted with few obstruction factors. . As an example, when the metal structure is continuous, the metal structure is disconnected, and each of the disconnected structures is covered with another substance (for example, an organic substance such as a dispersant). Compared to the above, it can be energized without being affected by resistance components caused by other substances. That a part of this metal structure is located on the surface can be easily confirmed by external observation, microscopic observation, or the like. Moreover, it can confirm that a metal structure is continuing by cross-sectional observation, cross-sectional microscope observation, etc. In addition, a metal structure in which at least a part thereof is located on the surface of at least one main surface of the polymer film, and a portion that is not located on the surface is continuous from a portion located on the surface An example of the body forming method is a method in which one main surface is brought into contact with a conductor, and a metal is deposited by electrolytic plating from a metal ion-containing electrolyte. In this case, since the metal is deposited on the surface of the conductor through electrons provided from the conductor, the metal is necessarily positioned on the surface of the main surface. In addition, since the portion not located on the surface is also given electrons from the deposited metal through the electrons given from the conductor and is deposited on the surface of the deposited metal (there is no other electron source) Inevitably, it is formed continuously.

  The concept that “the metal structure 3 is in contact with at least one main surface of the polymer film” includes the concept that the metal structure 3 is in contact with two main surfaces of the polymer film. Needless to say.

  In addition, the metal structure 3 is localized in the ion conductive domain 4. The metal structure 3 may exist on the surface of the polymer film 2 and the non-ion conductive domain 5. This means that the body exists inside the ion conductive domain 4. In addition, the majority means 80% or more of the total metal structure existing inside or on the surface of the polymer film 2.

Patent Document 1 discloses an organic thin film containing metal ultrafine particles protected with a dispersant only in one separated layer of a block copolymer that forms a microphase-separated structure. The difference between the present invention and Patent Document 1 will be described below.
The configuration includes the following two points.
1. The metal contained in this organic thin film is a metal ultrafine particle, and it is difficult to say that it is a metal structure.
2. The metal fine particles contained in the organic thin film must be protected by a dispersant and not a continuum.

The following points can be cited as effects resulting from the above configuration.
1. Since the metal contained in the organic thin film is a metal ultrafine particle protected by a dispersing agent, there is an inhibitory factor between the metal fine particles when it is desired to exert a characteristic characteristic of the metal as described above. On the other hand, in the present invention, since the metal structure is a continuum as a preferable configuration, the properties can be exhibited without being affected by the inhibition factor.

Next, the second aspect of the present invention will be described.
The second of the present invention is
(I) a step of preparing a polymer film having a microphase separation structure composed of a block copolymer having an ion conductive segment and a non-ion conductive segment and having an ion conductive domain and a non-ion conductive domain; ,
(Ii) a step of localizing and depositing a metal structure on the ion conductive domain;
It is a manufacturing method of the metal structure containing polymer film characterized by having.

Hereinafter, each step will be described.
Step (i) In step (i), a microphase comprising a block copolymer having an ion conductive segment A and a non-ion conductive segment B, and comprising an ion conductive domain and a non-ion conductive domain. A polymer membrane having a separation structure is prepared.

  Examples of a method for preparing a polymer film having a microphase separation structure composed of an ion conductive domain and a non-ion conductive domain include a block copolymer having an ion conductive segment A and a non-ion conductive segment B. A method of forming a polymer film by applying a solution containing a solution on the surface of a substrate and evaporating the solvent, or a method of extruding a block copolymer melt in one direction using an extrusion molding machine or an injection molding machine Can be used.

  In the case of using the former method, a bar coating method, a gravure coating method, a spin coating method can be used as a method for applying a solution containing a block copolymer composed of an ion conductive segment A and a non-ion conductive segment B to the surface of a substrate. Application means such as a dip coating method, a roll coating method, a spray method, and a casting method can be used.

  In that case, as a solvent used for the solution containing the block copolymer consisting of the ion conductive segment A and the non-ion conductive segment B, for example, N, N-dimethylformamide (DMF), N-methyl-2-pyrrolidone ( NMP), dimethyl sulfoxide (DMSO), γ-butyrolactone, tetrahydrofuran, 1,4-dioxane, dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl Ether, propylene glycol monoethyl ether, methanol, ethanol, propanol and the like can be used. Moreover, you may use the mixed solvent which mixed 2 or more types of the above-mentioned solvent.

  When forming a film using a mixed solvent, the morphology of the block copolymer can be controlled by precisely controlling the mixing ratio of the mixed solvent under dry conditions such as dry air, nitrogen and argon. Is easily controlled, and a microphase separation structure is easily formed. In such a case, it is preferable to remove as many water molecules as possible in the solution comprising the block copolymer.

  When the ion conductive segment A has a rich volume composition (the volume fraction of the ion conductive segment A is higher than the volume fraction of the non-ion conductive segment B), the ion conductive segment A has a matrix phase. It is preferred to select a solvent that does not form.

  In addition, components other than the block copolymer may be added to the solution made of the block copolymer. For example, additives such as homopolymers of the same component as the polymer chain constituting the block copolymer, plasticizers, antioxidants, radical scavengers, light stabilizers, dyes, cross-linking agents, and various catalysts are added. Also good.

  In the case of using the latter method, the melt of the block copolymer is affected by the shear stress at the time of extrusion, whereby a microphase separation structure in which the cylinder structure is oriented in the extrusion direction can be obtained. Thereafter, the obtained film may be cut perpendicularly to the extrusion direction to obtain a polymer film.

  Regardless of which method is used, heating may be performed after film formation. By heating, it can be transferred to a more ordered microphase separation structure. In addition, by applying an external field when heating, it is possible to obtain a microphase separation structure with better orientation. Here, the external field means an electric field, a magnetic field, a share, and the like. The heating temperature is preferably a temperature not lower than the glass transition temperature of the block copolymer, but may be a temperature not higher than the glass transition temperature when an external field is applied.

  The microphase separation structure of the polymer membrane can be confirmed with a transmission electron microscope, an atomic force microscope, or the like.

Step (ii) In the step (ii), the metal structure is localized in the ion conductive domain and deposited.

  Examples of the method for localizing and depositing the metal structure on the ion conductive domain include a method of plating the ion conductive domain of the polymer film obtained in (i).

  Examples of the type of plating include electrolytic plating, electroless plating, displacement plating and the like. Among them, it is preferable to use electrolytic plating from the viewpoint that the selection range of the type of metal structure to be deposited is wide and the film thickness can be controlled by the amount of charge.

As a specific method of electrolytic plating, the polymer film obtained in (i) is formed on the surface of the working electrode, the polymer film is brought into contact with a solution made of metal ions, and an electrode containing a metal element is formed. Examples thereof include a method in which a constant potential, a constant voltage, a constant current, a pulse, and the like are applied to the working electrode as a counter electrode. Among them, it is preferable to apply constant current electrolysis to the working electrode because the thickness of the metal structure can be easily controlled. By such a method, the metal ion in the solution containing the metal ion moves to the ion conductive domain of the polymer film and is reduced to form a metal structure. At this time, metal ions are supplied through the ion conductive domain (because they are ions) and are hardly supplied through the non-ion conductive domain. As a result, the deposited metal grows along the ion conductive domain, which is the ion supply route, and finally forms a metal structure-containing polymer film in which the metal structure is localized in the ion conductive domain. become. The working electrode can be used as long as it does not corrode in a solution containing metal ions and conducts electricity. For example, noble metals, Ni, Sn, Cu, Zn, Cr, Fe, and alloys thereof, carbon, semiconductors doped with impurities, conductive metal oxides such as ITO, and the like can be used. In addition, when applying the solution containing the block copolymer to the surface of the substrate in the step (i), using the working electrode as the substrate, the obtained polymer film is contained without moving the polymer film. A polymer membrane can be obtained. Moreover, as a counter electrode, it is preferable to use the electrode containing the metal which forms a metal structure. This is because the frequency of the work of supplying metal ions from the outside to the solution containing metal ions is reduced. The preferred metal ion concentration in the polymer film is 0.5M or less and 0.001M or more, and more preferably 0.1M or less and 0.01M or more. Moreover, as an example of the preferable current density of a polymer film, it is 100 mAcm ^-2 or less and 0.1 mAcm ^-2 or more, More preferably, it is 30 mAcm ^-2 or less and 1 mAcm ^-2 or more. When the metal ion strength and the current density are within these ranges, uniform plating is facilitated.

  Moreover, when performing electroplating, you may use a reference electrode in addition to these. By using the reference electrode, potential control electrolysis can be performed, and there is an advantage that the potential can be monitored even when current control electrolysis is performed.

  Furthermore, when there is a gap between the polymer film and the working electrode, the possibility that a metal structure is formed in the gap is increased. Examples of a method for reducing the gap between the working electrode and the polymer film include a method in which a polymer film is formed on the surface of the working electrode and then pressure is applied to the polymer film from the outside.

  As a method of performing electroless plating, for example, it can be performed by performing a pretreatment that gives a reaction point when a metal is deposited on a surface of an electrode or a polymer film that contacts the electrode or polymer film. . By performing the pretreatment, the metal structure can be localized in a region near the surface in the ion conductive domain. Examples of the pretreatment method include a method of providing a substance that becomes a catalyst for an electroless deposition reaction such as palladium. In addition, examples of a method for applying a substance serving as a catalyst include methods such as dip coating, screen printing, and sputtering.

  As a method for performing displacement plating, for example, the following method can be used. First, an element having a relatively high ionization tendency, such as nickel, iron, or silicon, is applied to the surface of the polymer film by a method such as sputtering, plating, printing, dip coating, or bar coating, or from the polymer film and these elements. These elements are made to exist on the surface of the polymer film by a method such as contacting with an electrode. Next, a polymer film having these elements on the surface is brought into contact with a solution containing ions of elements having a relatively small ionization tendency such as gold and copper. Thereby, an element having a relatively high ionization tendency and an ion of an element having a relatively low ionization tendency are replaced, and an element having a relatively high ionization tendency becomes an ion and an ion having an element having a relatively low ionization tendency becomes an element. When displacement plating is used, it is easy to form a thin metal structure in the ion conductive domain.

  In addition, even if it is a case where any plating method is used, an additive can be added to the solution containing the metal ion made to contact with a polymer film as needed. Examples of the additive include a supporting salt, a surfactant, a buffering agent, a chelating agent, and a brightening agent.

  In addition, regardless of which plating method is used, the metal structure is deposited on the ion conductive domain of the polymer film from the surface in contact with the electrode. It grows from near the inner surface.

  In addition, the formed metal structure can be simply confirmed by visually observing the appearance. More specifically, it can be confirmed by observing the surface and cross section of the metal structure-containing polymer film using an electron microscope, particularly a scanning electron microscope. At this time, the surface and cross-sectional metal structures are exposed and observed by immersing the polymer film of the metal structure-containing polymer film in a solvent that can be dissolved, baking the metal structure-containing polymer film, etc. It can be made easier. Confirmation that the metal structure is contained in the polymer film is performed by an energy dispersive X-ray fluorescence spectrometer or inductively coupled plasma spectroscopy by decomposing the metal structure-containing polymer film. be able to.

  In addition, when peeling the obtained metal structure containing polymer film from an electrode, you may form the peeling film in order to peel easily on the electrode surface previously. In such a case, a release film may remain on the surface of the obtained metal structure-containing polymer film.

  Patent Document 2 is characterized by forming micropores by decomposing and eluting one phase of a block polymer that forms a microphase separation structure, and then depositing metal fine particles by a plating method. A method for producing a composite is disclosed.

The difference between the present invention and Patent Document 2 will be described below.
1. In the process of Patent Document 2, pores are formed by decomposing and eluting one phase of the block polymer, and metal fine particles are deposited in the pores. That is, the metal fine particles are deposited in the space from which the polymer is removed. In contrast, in the present invention, metal is deposited on the ion conductive domain of the polymer film having a microphase separation structure composed of an ion conductive domain and a non-ion conductive domain.
2. Compared with the process of patent document 2, the process of this invention does not require the process of forming a void | hole by decomposing | dissolving and eluting one phase of a block polymer separately. (Patent Document 2 includes, as an example of this process, processes such as oxidative decomposition of one phase of the polymer film and washing with concentrated acid.) Therefore, the process cost is reduced due to the small number of processes. The deterioration of the microphase separation structure is suppressed by eliminating the need for a process that causes degradation of the microphase separation structure of the polymer (which can never be degraded at all). This is because, for example, in the case of forming a pattern structure using a metal structure prepared from this microphase-separated structure as a mask, the mask shape has not deteriorated. Gives advantages such as clarification of shape.

Next, the third aspect of the present invention will be described.
The third aspect of the present invention is
(I) preparing a composite comprising a metal structure-containing polymer film obtained by the second of the present invention and a base material in contact with the metal structure-containing engineered film;
(II) etching the base material using the metal structure as a mask;
It is a manufacturing method of the pattern structure characterized by having.

  FIG. 3 is a schematic diagram for explaining a third example of the present invention, in which step (I) is shown in FIGS. 3 (a) to 3 (b), and step (II) is shown in FIGS. It is shown in (c).

  In step (I), a composite comprising a base material 9 to be a pattern formation target and a metal structure-containing polymer film 1 in contact with the base material 9 and obtained by the second method of the present invention is prepared. (FIGS. 3A to 3B). Examples of the material constituting the base material 9 that is the target of pattern formation include semiconductors such as Si, GaAs, and InP, dielectrics such as glass, quartz, and boron nitride, and carbon. In addition, the substrate is composed of a plurality of layers, the layers other than the outermost surface are made of these materials, and the outermost layer is made of a polymer, spin-on-glass, metal, oxide, nitride, magnetic material, etc. It may be a layer. In addition, in the case where plating is used in the second step (ii) of the present invention, and the electrode used when performing plating is used as a substrate that is a target for forming a pattern, By performing the second, step (I) is achieved. However, when the electrode used for plating and the substrate are different from each other, the metal structure-containing polymer film and the substrate are brought into contact after the second of the present invention.

  In step (II), the base material 9 is etched using the metal structure 3 of the metal structure-containing polymer film 1 as a mask to obtain a pattern structure 10 having the metal structure 3 on the surface (FIG. 3C). ).

  3B to 3C, the base material 9 is etched at the same time that the ion conductive domain 4 and the non-ion conductive domain 5 of the metal structure-containing polymer film 1 are removed. . However, as shown in FIG. 4, a composite comprising the metal structure-containing polymer film 1 and the substrate 9 is prepared (FIG. 4B), and the polymer film constituting the metal structure-containing polymer film 1 is prepared. After removing the ion-conductive domain 4 and the non-ion-conductive domain 5 (FIG. 4C), the substrate 9 may be etched (FIG. 4D). Note that, in the process of FIG. 4C, it is assumed that both the ion conductive domain 4 and the non-ion conductive domain 5 of the polymer film 2 are removed, but the non-ion conductive domain is removed. If so, the ion conductive domain 4 may remain.

When the former method is used, dry etching can be used as the etching method. Examples of the etching gas at this time include Ar, O ₂ , CF ₄ , H ₂ , C ₂ F ₆ , CHF ₃ , CH ₂ F ₂ , CF ₃ Br, N ₂ , NF ₃ , Cl ₂ , CCl ₄ , HBr, SF ₆ or the like can be used.

  When the latter method is used, the base material 9 can be etched using the above etching method after the polymer film 2 is removed by a dry process, a wet process, baking by heating, or the like. Specific examples of the dry process include ozone, UV ozone ashing, oxygen plasma ashing, and the like. As a specific example of the wet process, there is a method of immersing in a solvent in which the polymer film of the metal structure-containing polymer film can be dissolved.

  Moreover, you may have the process of removing the metal structure 3 after process (I) and process (II). By removing the metal structure 3, a pattern structure 11 having a pattern formed on the substrate 9 can be obtained (FIG. 3D).

  Next, a method for manufacturing an antireflection structure as an example of the pattern structure 11 will be described. Here, the antireflection structure is a structure that can reduce reflection of light incident on the surface of the structure. For example, an antireflection structure for a lens such as a lens having an uneven pattern on the surface and a film having an uneven pattern for coating the lens surface can be used. Such an antireflection structure can be manufactured by a method similar to the method shown in FIGS. 3 and 4 if a lens material or a material for coating the lens surface is used as the substrate 9. As a material for coating the lens material and the lens surface, various materials can be used depending on the application as long as they can be etched. For example, a glass material, a polymer material, a crystalline material, or a composite thereof. Examples include the body as the main component. The material of the metal structure 3 and the block copolymer can be selected from the aforementioned materials according to the characteristics of the material of the lens serving as the base material.

  Further, a mold for a lens having an uneven pattern or a mold for a film having an uneven pattern for coating the lens surface is manufactured by the same method as the method for manufacturing the antireflection structure, and these molds are used. May be used to manufacture the antireflection structure. Examples of the template material include a material mainly containing a metal, a carbon material, a polymer material, a crystalline material, or a composite thereof.

  Here, when the irregularities on the surface of the antireflection structure are arranged at intervals equal to or less than the wavelength of light for which reflection is to be reduced, the effect of reducing reflection is enhanced. Therefore, the metal structure 3 as a mask is preferably present at an interval of 1/100 to 1 times the wavelength of light for which reflection is to be reduced, more preferably 1/10 to 1 times the wavelength of light. As shown in the examples described later, the block copolymer phase separation structure described in the present invention is used, and through the above steps, 1/100 to 1 of the wavelength of infrared light, visible light, and ultraviolet light. Since the metal structures 3 are arranged at double intervals, an antireflection structure for infrared light, visible light, and ultraviolet light can be formed. The method for manufacturing the antireflection structure is not limited to the above.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in more detail, the method of this invention is not limited only to these Examples.

Example 1
1- (1)
A commercially available block copolymer represented by the general formula (0) (manufactured by Kuraray, Septon SEEPS (Septon is a trade name of Kuraray Co., Ltd.)) in 200 ml of dichloroethane in 200 ml of dichloroethane (0.76 ml) in 50 ml of dichloroethane In addition, sulfonation was performed for 2 hours. The reaction solution was reprecipitated in hexane, washed and dried to obtain a compound represented by the general formula (1).

1- (2)
Acetoxystyrene (30 g), Dimethyl-2,6-dibromoheptanedioate (201 μL), Pentamethylenediethylenediamine (386 μL) and Copper (I) bromide (265 mg) were mixed, and the polymerization reaction was terminated at 100 ° C./2.5 hours. The product was diluted with chloroform, and then the catalyst was removed with an alumina column and purified by reprecipitation into cold methanol. 2.5 g of this compound, 11.6 g of styrene, 232 μL of pentamethylenediethyleneamine, and 160 mg of copper (I) bromide were mixed, degassed, polymerized (110 ° C./1.3 hours), stopped, and purified. To a 1,4-dioxane solution of 2.0 g of this compound, 4.0 mL of hydrazine monohydrate was stirred for 2 hours, and then reprecipitated, washed and dried in water. To a DMF solution of this compound 1.10 g, add 523 mg of NaH and 6.38 mg of propanesulfone, react at 65 ° C. for 3 hours, add again 523 mg of NaH and 6.38 mg of propanesultone, and further react for 2 hours with purified water. Was added, and then reprecipitated with methanol, filtered, dried and dispersed in tetrahydrofuran. An ion exchange resin was added thereto, followed by reprecipitation with hexane and drying to obtain a compound represented by the general formula (2).

1- (3)
30 g of tert-butyl acrylate, dimethyl-2,6-dibromoheptanedioate 509 μl, hexmethyltriethyletraamine 254 μl, DMF 8.1 g, copper bromide (I) 254 mg were mixed, and polymerization was performed at 70 ° C./2. 4.0 g (0.381 mmol) of the obtained compound, 23.8 g of styrene, 207 μl of hexamethylethylenetetraamine, and 109 mg of copper (I) bromide were mixed, frozen / degassed, polymerized (100 ° C./3.75 hours), stopped, and purified. Went. To a 1,4-dioxane solution of 2.0 g of this compound, 4.0 ml of hydrazine monohydrate was stirred for 2 hours, and then reprecipitated, washed and dried in water. To this DMF solution of 1.10 g of this compound, 523 mg of NaH and 6.38 mg of Propanesultone were added and reacted at 65 ° C. for 3 hours. Further, 523 mg of NaH and 6.38 mg of Propanesultone were added again, followed by further 2 hours of reaction and purification. After adding water, it was reprecipitated with methanol, filtered, dried and dispersed in THF. An ion exchange resin was added thereto, followed by reprecipitation with hexane and drying to obtain a compound represented by the formula (3).

  In Examples 1- (1) to (3), the block copolymer was identified by NMR, gel permeation chromatography, inductively coupled plasma analysis, and the like.

Reference example 1
A solution in which a block copolymer represented by the general formulas (1) to (3) is contained in a solvent of methanol: tetrahydrofuran = 8: 2 is applied to a substrate obtained by sputtering Ti / Au on a commercially available slide glass by a bar coating method. Thus, a polymer film composed of an ion conductive domain and a non-ion conductive domain was obtained. FIG. 5 shows an atomic force microscope phase image of the obtained polymer film. 5 (1) is a block copolymer represented by the general formula (1), FIG. 5 (2) is a block copolymer represented by the general formula (2), and FIG. 5 (3) is a general formula (3). 3 shows a polymer film formed from the block copolymer shown. In FIG. 5 (1), the relatively soft part shown by the dark color has shown the non-ion conductive domain, and the relatively hard part shown by the light color has shown the ion conductive domain. On the other hand, in FIGS. 5 (2) and (3), the relatively soft part indicated by the dark color indicates the ion conductive domain, and the relatively hard part indicated by the light color indicates the non-ion conductive domain. ing. From these, it was confirmed that a microphase separation structure was formed in any polymer membrane.

  Further, a solution obtained by adding a block copolymer represented by the general formulas (1) to (3) in a solvent of methanol: tetrahydrofuran = 8: 2 on a substrate obtained by sputtering Ti / Au on a commercially available slide glass is cast. Coating, a polymer film composed of an ion conductive domain and a non-ion conductive domain was obtained. The transmission electron microscope image which peeled off the obtained polymer film from the board | substrate and cut out with the microtome is shown in FIG. 6 (1) is a block copolymer represented by the general formula (1), FIG. 6 (2) is a block copolymer represented by the general formula (2), and FIG. 6 (3) is a general formula (3). 3 shows a polymer film formed from the block copolymer shown. The polymer film was dyed using an aqueous phosphotungstic acid solution. In FIG. 6, the dark colored portion indicates an ion conductive domain having a strong affinity with the phosphotungstic acid aqueous solution used for dyeing, and the light color indicates a non-ion conductive domain. From these photographs, it can be seen that a microphase separation structure is formed in any polymer membrane. In addition, when these polymer films were observed in a vacuum, it was found that there existed micropaths due to continuously connected ion conductive domains.

Example 2
A solution in which a block copolymer represented by the general formulas (1) to (3) is contained in a solvent of methanol: tetrahydrofuran = 8: 2 is applied to a substrate obtained by sputtering Ti / Au on a commercially available slide glass by a bar coating method. A polymer film composed of an ion conductive domain and a non-ion conductive domain was formed. A bipolar cell having a substrate on which the polymer film was formed as a working electrode (electrode area 0.48 cm 2) and a metal wire as a counter electrode was formed. Pt was used for the metal wire of the counter electrode, and 0.05 M AgNO ₃ aqueous solution was used as the electrolyte to be injected into the cell.

  The electrode was connected to a potentio / galvanostat, and electrolytic plating was performed at room temperature and in the atmosphere at -2 V for 20 seconds. A substrate on which a metal structure-containing polymer film obtained by depositing Ag on a polymer film made of a block copolymer represented by the general formulas (1) to (3) by electrolytic plating is formed is washed with water. FIGS. 7 (1) to (6) show scanning electron microscopic images of the cross section of the metal structure-containing polymer film that was dried and then immersed in dimethylacetamide overnight to expose Ag. FIGS. 7 (1) and (4) are a polymer film composed of a block copolymer represented by the general formula (1) and a metal structure-containing polymer film composed of Ag, and FIGS. 7 (2) and (5) are general structures. A polymer film comprising a block copolymer represented by the formula (2) and a metal structure-containing polymer film comprising Ag, FIGS. 7 (3) and (6) are block copolymers represented by the general formula (3) 3 shows a polymer film made of Ag and a metal structure-containing polymer film made of Ag. From the comparison of the shapes of the atomic force microscope phase image of FIG. 5 and the transmission electron microscope image of FIG. 6, it is confirmed that the metal is deposited on the ion conductive domain by electrolytic plating. That is, the metal structure of the metal structure-containing polymer film formed here is localized in the ion conductive domain of the polymer film. Further, from the images of the interface with the substrate (the upper part is the deposited metal and the lower part is the substrate) shown in FIGS. 7 (4) to (6), these metal structures are at least partially made of a polymer film. It is confirmed that a portion that is located on the surface (here, the interface with the substrate) of at least one main surface and that is not located on the surface is continuous from the portion located on the surface. This is because the metal is deposited on the surface of the conductor through the electrons provided from the conductor, so the portion that is necessarily located on the surface of the main surface is also provided from the conductor. This is because electrons are given from the deposited metal through the generated electrons and deposited on the surface of the deposited metal. FIG. 8 shows low-magnification (20,000 times) images of the polymer film made of the block copolymer represented by the general formula (2) and the metal structure-containing polymer film made of Ag. Here, the dark color part at the bottom of the image is glass of the electrode, the light color part above is gold of the electrode, Ag on which the light color part is deposited, the polymer where the dark color part above remains, The black part above it indicates that it is a space.

Example 3
2. Ni in the metal wire of the counter electrode, 11 gL ⁻¹ NiSO ₄ , 1.9 gL ⁻¹ NiCl ₂ , 0.0015 gL ⁻¹ boric acid aqueous solution as the electrolyte to be injected into the cell, at room temperature and in the atmosphere; A metal structure-containing polymer film was obtained in the same manner as in Example 2 except that constant current electrolytic plating was performed at 25 mA for 20 seconds.

  Next, an electrode having a metal structure-containing polymer film on the surface using a film made of a block copolymer represented by the general formula (1) as the polymer film was immersed in dimethylacetamide overnight, washed with water and dried. . Moreover, the metal structure containing polymer film using the film | membrane which consists of a block copolymer shown to General formula (2), (3) as a polymer film was baked at 450 degreeC for 30 minutes. By these methods, Ni contained in the metal structure-containing polymer film was exposed. Scanning electron microscope images of the cross section of the obtained metal structure are shown in FIGS. 9 (1) and 9 (4) show a metal structure in which the polymer film is removed from the polymer film made of the block copolymer represented by the general formula (1) and the metal structure-containing polymer film made of Ni. Ni), FIG. 9 (2) shows a metal structure (Ni) obtained by removing the polymer film from the polymer film made of the block copolymer represented by the general formula (2) and the metal structure-containing polymer film made of Ni. 9 (3) shows a metal structure (Ni) in which the polymer film is removed from the polymer film made of the block copolymer represented by the general formula (3) and the metal structure-containing polymer film made of Ni. It is. From the comparison of the shapes of the atomic force microscope phase image of FIG. 5 and the transmission electron microscope image of FIG. 6, it is confirmed that the metal is deposited on the ion conductive domain by electrolytic plating. That is, the metal structure of the metal structure-containing polymer film formed here is localized in the ion conductive domain of the polymer film. Further, from the image of the interface with the substrate shown in (4) of FIG. 9 (the upper part is the deposited metal and the lower part is the substrate), these metal structures are at least partially composed of at least one main polymer film. It is confirmed that the portion that is located on the surface of the surface (here, the interface with the substrate) and is not located on the surface is continuous from the portion located on the surface. This is because the metal is deposited on the surface of the conductor through the electrons provided from the conductor, so the portion that is necessarily located on the surface of the main surface is also provided from the conductor. This is because electrons are given from the deposited metal through the generated electrons and deposited on the surface of the deposited metal. From these, it was shown that the ion conductive domain can be replicated by electrolytic plating even when Ni is used as the deposited metal.

Example 4
Spin as a method for applying a solution comprising a block copolymer, using a substrate obtained by depositing Cu on a Si wafer as a substrate, using only a block copolymer represented by the general formula (1) as a block copolymer, Electrolytic plating was carried out in the same manner as in Example 2 except that the coating method was used, Pt was used as the metal wire of the counter electrode, and 0.05 M SnSO ₄ aqueous solution was used as the electrolytic solution to be injected into the cell. went.

  The electrolytic plating was performed at room temperature and in the air under the conditions of 1.92 mA and 20 seconds. After depositing Sn on the polymer film made of the block copolymer represented by the general formula (1) by electrolytic plating to obtain a metal structure-containing polymer film, the block copolymer represented by the general formula (1) is obtained as the polymer film. A metal structure-containing polymer film using a polymer film was immersed in tetrahydrofuran overnight to expose Sn. A scanning electron microscope image of the surface of the obtained metal structure is shown in FIG. 10 (1), and a scanning electron microscope image of the cross section is shown in FIG. 10 (2). From these, it was shown that even when Sn is used as the deposited metal, the ion conductive domain can be replicated by electrolytic plating, and the negative electrode of the lithium ion battery can be prepared.

Example 5
The use of an n-Si wafer as a substrate, the use of only the block copolymer represented by the general formula (1) as a block copolymer, and the use of spin coating when applying a solution comprising the block copolymer In addition, an n-Si wafer having Ni as a metal structure on its surface was obtained in the same manner as in Example 3 except that the metal structure-containing polymer film was baked at 450 ° C. for 30 minutes. FIG. 11 (1): Oblique observation image, (2): Upper surface observation image show a scanning electron microscope image of the surface of the fired metal structure-containing polymer film. FIG. 12 (1) shows an atomic force microscope shape image (height scale is 6 nm) of the fired metal structure-containing polymer film. From these images, at least a part of these metal structures is located on the surface (here, the interface with the substrate) of at least one main surface of the polymer film, and is not located on the surface. It is confirmed that the part is also continuous from the part located on the surface.

Next, an oxygen plasma treatment is performed on an n-Si wafer that is in contact with the fired metal structure-containing polymer film using Ni as a mask of the fired metal structure-containing polymer film as a substrate on which a pattern is to be formed. Then, ion etching was performed to obtain a pattern structure. The plasma treatment conditions were O ₂ = 50, 0.5 Pa, 500/0 W, 10 seconds, and the etching conditions were SF ₆ / CHF ₃ = 4/46, 1 Pa, 250/20 W, 10-30 seconds. .

  FIG. 13 shows a scanning electron microscope image (oblique observation) of the obtained pattern structure.

Reference example 2
An n-Si wafer having a polymer film formed thereon was prepared in the same manner as in Example 5 except that Ni was not electroplated. Further, in order to observe the surface of the n-Si wafer, a sample was prepared by baking at 450 ° C. for 30 minutes and removing the polymer film.

  FIG. 11 (3) shows a scanning electron microscope image of the surface of the n-Si wafer that has been baked and from which the polymer film has been removed. FIG. 12 (2) shows an atomic force microscope shape image (height scale is 6 nm) of the obtained fired n-Si wafer.

Comparative Example 1
Using the Si substrate on which the polymer film obtained in Reference Example 2 was formed as an object for forming a pattern, oxygen plasma treatment and ion etching were performed in the same manner as in Example 5. FIG. 14 shows a scanning electron microscope image (oblique observation) of the obtained pattern structure. In this case, it was shown that no pattern was formed on the surface of the Si substrate.

  From Example 5 and Comparative Example 1, it is possible to form a fine pattern structure by performing etching by forming a metal structure-containing polymer film on a substrate and using the metal structure as a mask. It has been shown.

  The metal structure-containing polymer film of the present invention can be used as an anisotropic conductive film, anisotropic heat transfer film, information recording medium, battery electrode, optical material, and the like.

  In addition, it is possible to evaluate the morphology of the domain of the polymer film having a microphase separation structure with the metal structure-containing polymer film of the present invention.

  Furthermore, the pattern structure obtained by the present invention can be used as an antireflection structure, an electronic circuit, a mold for producing a molded body, and the like.

DESCRIPTION OF SYMBOLS 1 Metal structure containing polymer film 2 Polymer film which has micro phase-separation structure 3 Metal structure 4 Ion conductive domain 5 Non-ion conductive domain 6 Block copolymer 7 Ion conductive segment A
8 Non-ion conductive segment B
9 Substrate 10 Pattern structure with metal structure on its surface 11 Pattern structure

Claims (7)

A polymer membrane comprising a block copolymer having an ion conductive segment and a non-ion conductive segment, having a microphase separation structure composed of an ion conductive domain and a non-ion conductive domain, and localized in the ion conductive domain. a metal structure for standing, Tona is, the metal structure is at least partially located in the surface of the two main surfaces of the polymer film, even the portion not located in said surface, A metal structure-containing polymer film which is continuous from a portion located on the surface . The metal structure-containing polymer film according to claim 1, wherein the ion conductive domain has a co-continuous structure in relation to the non- ion conductive segment. A step of preparing a polymer film having a microphase separation structure composed of a block copolymer having an ion conductive segment and a non-ion conductive segment and having an ion conductive domain and a non-ion conductive domain;
Performing electrolytic plating on the polymer film to localize and deposit a metal structure in the ion conductive domain;
A process for producing a metal film containing a metal structure, comprising: A step of bringing the metal structure- containing polymer film according to claim 1 or 2 into contact with a substrate to produce a composite composed of the metal structure- containing polymer film and the substrate;
Etching the substrate using the metal structure as a mask;
The manufacturing method of the pattern structure which has. And a step of removing the polymer film of the metal structure-containing polymer film between the step of producing the composite and the step of etching the base material using the metal structure as a mask. The manufacturing method of the pattern structure of Claim 4 . 6. The method for manufacturing a pattern structure according to claim 4 , further comprising a step of removing the metal structure after the step of etching the base material using the metal structure as a mask. A method of manufacturing a pattern structure that reduces reflection of incident light,
7. The method of manufacturing a pattern structure according to claim 6 , wherein the metal structures are arranged at an interval of 1/100 to 1 times the wavelength of incident light.

Images