KR20210114756A - Nanohybrids consisting of alternating-stacked conductive/nonconductive layers, the fabrication method of the nanohybrids and their applied products - Google Patents

Abstract

The present invention relates to composite material, and more specifically, to a conductive layer/non-conductive polymer layer laminated composite material, a method for manufacturing composite material, and application product including the composite material, which can check a state of the non-conductive polymer at the molecular level by applying electrical properties to the non-conductive polymers with insulator properties and measuring electrical signals.

Description

Nanohybrids consisting of alternating-stacked conductive/nonconductive layers, the fabrication method of the nanohybrids and their applied products

The present invention relates to a composite material, and more specifically, a conductive layer/non-conductive polymer capable of confirming the microchemical structural change of a non-conductive polymer by imparting electrical properties to a non-conductive polymer having an insulator property and measuring an electrical signal. It relates to a layer-laminated composite material, a method for manufacturing the composite material, and an application product comprising the composite material.

Block copolymers with controlled properties have been extensively studied in recent decades. In particular, atom transfer polymerization (ATRP), a type of controlled radical polymerization, has been widely used to make block copolymers with controlled components and degree of polymerization (DP). Advances in polymerization methods have made it possible to produce functional polymers for various applications. For example, stimulatory-responsive copolymers that are sensitive to changes in environmental parameters such as light, temperature, pH, and CO _{2 have been synthesized.} Selectivity can be imparted by incorporating functional groups that react under specific conditions into the polymer, and azobenzene, spiropyran, dithienylethene, and oxazolone are used as representative photoreactive functional groups. do. In addition, a material containing ionic acidic residues or basic residues has a characteristic of having pH reactivity.

The coulombic blockade of nanostructures has also attracted much attention in condensed matter physics. An example of a prototype is quantum dots separated from the source/drain leads by a tunnel junction in a transistor configuration, where electrons or holes can be individually injected into the quantum dots by varying the gate voltage. The intrinsic transport behavior of the coulombic containment regime can lead to coherent multibody interactions between single spin quantum bits or constrained spins and Fermi stores, depending on the tunnel coupling strength. Similarly, the coulombic blockade has been investigated mainly for small-area tunnel junctions in sophisticated microelectrode configurations.

However, most block copolymers are insulators, and due to these properties, it is not easy to analyze the state of the material through an electrical method. Insulators are not suitable for electronic material applications because electrical analysis mainly involves detecting changes in electron flow, identifying states, and converting them into signals.

Therefore, there is a need to develop a composite material that imparts electrical properties to the non-conductive polymer, and develop a technology capable of analyzing the state of the non-conductive polymer by measuring the electrical signal of the composite material.

Domestic Registered Patent No. 10-1295671

As a result of research efforts, the present inventors have completed the present invention by developing a composite material formed by inserting a non-conductive polymer into a two-dimensional structure having peelable conductor properties.

Therefore, it is an object of the present invention to form a laminate structure in which a non-conductive polymer is inserted between conductors using a laminate structure having peelable conductor properties and a non-conductive polymer, and a conductor layer capable of imparting electrical properties to the non-conductive polymer. / To provide a non-conductive polymer layer composite material.

Another object of the present invention is that a composite material formed in a laminated structure in which a non-conductive polymer is inserted between conductors can be manufactured through a simple process, so that it is easy to change the microchemical structure by controlling the molecular weight of the non-conductive polymer in a desired way It is to provide a method for manufacturing a composite material that can be controlled.

Another object of the present invention is to electrically detect external stimuli through a composite material formed by inserting a non-conductive polymer to observe electrical properties between the conductive layers, and the movement occurring inside the composite through post-processing of the obtained signal. The purpose of this study is to provide a method for observing electrical properties of amphiphilic block copolymers, which can confirm the microchemical structural change of non-conductive polymers by measuring electrical signals by analyzing them, and application products containing the composite material.

Objects of the present invention are not limited to the objects mentioned above, and other objects not mentioned will be clearly understood by those skilled in the art from the following description.

In order to achieve the object of the present invention described above, the present invention has a laminated structure composed of a conductive layer made of a conductive material and a non-conductive polymer layer made of an amphiphilic non-conductive polymer copolymer formed on the conductive layer, at least two or more. Provided is a conductive layer/non-conductive polymer layer laminated composite material sequentially included.

In a preferred embodiment, the conductive material is derived from a laminated structure having conductor characteristics made of a peelable two-dimensional structure, and the laminated structure having conductor characteristics is graphite, graphene, black phosphorus, molybdenum-based compound, metallic chalcogen-based compound. at least one selected from the group consisting of compounds.

In a preferred embodiment, the amphiphilic non-conductive polymer copolymer is an amphiphilic block copolymer in which a hydrophilic polymer and a hydrophobic polymer form a block through a copolymerization reaction, respectively.

In a preferred embodiment, the polymer constituting the amphiphilic block copolymer includes any one or more of a photoreactive functional group, a temperature-reactive functional group, a moisture-reactive functional group, and a pH-responsive functional group.

In a preferred embodiment, the photoreactive functional group is any one selected from the group consisting of cis-azobenzene, trans-azobenzene diarylethene, spiropyran, merocyanine, oxazolidine, oxazine, o-nitrobenzyl ester, fulgide, and spiroxazine.

In a preferred embodiment, the pH-reactive functional group is any one selected from the group consisting of a carboxyl group, a pyridine, a sulfonic group, a phosphate, and a tertiary amine.

In a preferred embodiment, the polymer having a temperature-reactive functional group is poly(N-isopropylacrylamide), poly(N-(2-hydroxypropyl)methacrylamide), poly (N,N-diethylacrylamide), poly (methylvinylether), poly(N -vinyl caprolactam), block copolymer of poly(ethylene oxide) and poly(propylene oxide), poly(N,N-dimethylaminoethyl methacrylate), poly(3-dimethyl (methacryloyloxy ethyl)ammonium propane sulfonate), poly(2-hydroxyethyl methacrylate), poly(methacrylamide), poly(N-acryloyl asparagine amide), poly(N-acryloyl glycinamide), and poly(6-(acryloyloxymethyl)uracil).

In a preferred embodiment, the two or more sequentially formed stacked structures exhibit Coulomb blockade oscillation when an external stimulus is applied.

In a preferred embodiment, the coulombic confinement vibration is controlled by controlling the degree of polymerization of the amphiphilic non-conductive polymer copolymer constituting the non-conductive polymer layer.

In a preferred embodiment, the conductive layer is made of any one of graphene, a molybdenum compound, or black phosphorus, and the non-conductive polymer layer is poly[(ethylene oxide) -b -poly[(3-vinylbenzyl ideneoxazolone)] (PEO- b -PVBO).

In a preferred embodiment, when the polymerization degree of the PVBO block in the PEO- b- PVBO is controlled, the photoreactivity and the Coulombic confinement vibration of the PEO- b-PVBO are controlled.

In addition, the present invention provides a method for producing any one of the above-described composite materials, comprising the steps of: synthesizing an amphiphilic block copolymer constituting a non-conductive polymer layer; A step of introducing a stimulus-responsive functional group into the amphiphilic block copolymer to obtain an amphiphilic stimulus-responsive block copolymer; after adding a conductor material forming a conductor layer to a dispersion solvent, the conductor material is peeled off into separate layers or each layer obtaining a dispersion solution in which the conductive material is dispersed by physically treating it to form a predetermined space therebetween; adding the amphiphilic stimulus-responsive block copolymer to the dispersion solution; The amphiphilic stimulus-responsive block copolymer surrounds a separate layer of the dispersed conductor material, or the amphiphilic block copolymer is inserted in a predetermined space formed between each layer of the conductor material, so that the conductor material and the amphiphilic block copolymer a bonding step of coalescing to form a laminated precursor; and a lamination step in which two or more laminated precursors dispersed in the solvent are laminated to form a laminated structure.

In a preferred embodiment, in the physically treating step, any one of ultrasonic treatment, agitator treatment, centrifugal separator treatment, and ball milling treatment is performed.

In a preferred embodiment, the lamination step is performed by removing the solvent to the lower side of the reactor.

In addition, the present invention comprises the steps of preparing the composite material of any one of claims 3 to 11 in which the amphiphilic block copolymer to be analyzed is inserted; measuring an electrical signal inside the composite material while applying an external stimulus to the composite material; and monitoring the change of the block copolymer by analyzing the measured electrical signal; provides an electrical property observation method for the amphiphilic block copolymer, including.

In a preferred embodiment, the change in the block copolymer is a change in the microchemical structure at the molecular level in response to the external stimulus, and the magnitude of the electrical signal measured is quantitatively related to the change in the microchemical structure.

In a preferred embodiment, the microchemical structural change comprises at least one of a polymer chain conformational change and isomerization.

In a preferred embodiment, coulombic confinement vibration occurs in the composite material through the change in the polymer chain shape.

In a preferred embodiment, the coulol blocking vibration is controlled by controlling the polymerization degree of the amphiphilic block copolymer.

In addition, the present invention provides an application product comprising any one of the above-mentioned conductive layer/non-conductive polymer layer laminated composite material.

In a preferred embodiment, the application is a sensor or coulomb block based transistor.

In a preferred embodiment, the sensor performs at least one of an electrical signal conversion mechanism, an electronic signal conversion mechanism, and an electrochemical signal conversion mechanism.

First, the conductive layer/non-conductive polymer layer laminated composite material of the present invention is formed in a laminate structure in which a non-conductive polymer is inserted between conductors using a laminate structure having conductor properties that can be peeled into a two-dimensional structure and a non-conductive polymer. Electrical properties can be imparted to non-conductive polymers.

In addition, since the composite material manufacturing method of the present invention can manufacture a composite material having a laminate structure in which a non-conductive polymer layer is inserted between conductors through a simple process, the molecular weight of the non-conductive polymer layer can be controlled in a desired manner, etc. Through this, the microchemical structure change can be easily observed.

In addition, the electrical property observation method for the amphiphilic block copolymer of the present invention electrically senses an external stimulus through a composite material formed by inserting a non-conductive polymer to observe the electrical properties between the conductor layers, and Through post-processing, changes in the microchemical structure of the non-conductive polymer can be confirmed by measuring the electrical signal by analyzing the movement occurring inside the complex. It is possible to control, in particular, to generate and control Coulomb-blocking vibration, and it is possible to provide various application products that can utilize these electrical characteristics, including sensors.

These technical effects of the present invention are not limited only to the above-mentioned range, and even if not explicitly mentioned, the effect of the invention that can be recognized by a person of ordinary skill in the art from the description of the specific content for the implementation of the invention to be described later is also of course included.

Figure 1a shows the synthesis process of the photoreactive, amphiphilic block copolymer used in the composite material of the present invention, Figure 1b is a PEO- b -PVBA block copolymer according to Figure 1a using a PVBA block having a different molecular weight It is a graph as a result of analyzing the conversion rate and molecular weight increase by nuclear magnetic resonance spectroscopy while synthesizing, and FIG. 1c is a 1H NMR spectrum of _{PEO 113} -b -PVBA ₂₅ (red) and PEO ₁₁₃ -b -PVBO _{25 (blue).} 1d shows the photo-induced isomerization between PEO-b- PVBO(Z) and PEO-b- PVBO(E) under alternating UV and visible light irradiation, and FIG. 1e shows the theoretical B3LYP/6 Energy density mapping of isomers calculated at the -311+G (d, p) level is shown.
In Figure 2 (a) is _{a photograph showing the color change of P n} GNH dispersions (n = 25, 40 and 50) under visible light and ultraviolet light, (b) is n = 25, (c) is n = 40, _{and (d) is an SEM image of P n} GNH with n = 50 and (e) a control (graphene sheet alone). (scale bar is 200 nm)
3a and 3b, respectively PEO ₁₁₃ - UV UV-visible absorption spectrum upon irradiation for 90 min for the aqueous dispersions and the aqueous dispersion of the P _n GNH _{b -PVBO n (0, 5,} 10, 20, 30, 60 and 90 min), and FIGS. 3c and 3d show the molar extinction coefficient at 400 nm as a function of irradiation time for _{PEO 113} -b -PVBO _n and P _{n GNH, respectively.} 3e and 3f show _{the relative absorbance [A(t)/A 0} ] of the main peak at 400 nm as a function of irradiation time for _{PEO 113} - b -PVBO _n and P _n GNH, respectively (absorbance A is set to the initial value A _{value divided by 0} ), and FIG. 3G shows the calculated rate constants (including standard deviation) for different DPs.
4 is a schematic diagram for observing the electrical reaction of the non-conductive polymer included in the composite material using the composite material of the present invention.
5a to 5d are observations of the electrical reaction of the PGNH electrode periodically exposed to visible light (white region) and UV (gray region) light containing the composite material according to the first to third embodiments of the present invention. As a result, FIG. 5A shows a plot of current density change over time (ΔI), FIG. 5B shows a plot of d(ΔI)/dt versus time, and FIG. 5C shows FFT analysis data from the plot of FIG. 5B. (Inset: enlarged data view at 0.25 to 0.80 Hz), and Fig. 5d is the amplitude and average amplitude at the fundamental frequency peak f1 (5 mHz) and the fundamental frequency band f2 (174 ㅁ 25 mHz), and Fig. 5c their harmonics obtained from FIG. 5e shows the types of two Coulomb oscillations found by examining the periodicity and amplitude of the Coulomb containment oscillations in the electrode including the composite material according to the first embodiment of the present invention.
6A and 6B are graphs of results obtained by extracting Coulomb vibrations by Fourier transform signal processing from the electrode including the composite material according to the first embodiment of the present invention.
7A and 7B are graphs of results obtained by extracting Coulomb vibrations by Fourier transform signal processing from an electrode including a composite material according to a fourth embodiment of the present invention.
8A and 8B are graphs of results obtained by extracting Coulomb vibrations by Fourier transform signal processing from an electrode including a composite material according to a fifth embodiment of the present invention.

The terms used in the present invention are only used to describe specific embodiments, and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present application, terms such as “comprise” or “have” are intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the specification is present, and includes one or more other features or It should be understood that the existence or addition of numbers, steps, operations, components, parts, or combinations thereof does not preclude the possibility of addition.

Terms such as first, second, etc. may be used to describe various elements, but the elements should not be limited by the terms. The above terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, a first component may be referred to as a second component, and similarly, a second component may also be referred to as a first component.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present invention. does not

In the case of a description of a temporal relationship, for example, if the temporal relationship is described as 'after', 'following', 'after', 'before', etc., 'immediately' or 'directly' This includes cases that are not continuous unless ' is used.

Hereinafter, the technical configuration of the present invention will be described in detail with reference to the accompanying drawings and preferred embodiments.

However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Like reference numbers used to describe the invention throughout the specification refer to like elements.

A technical feature of the present invention is that a non-conductive polymer is inserted between a laminated structure having conductor characteristics that can be peeled into a two-dimensional structure and a non-conductive polymer material as a starting material, and the conductor layer/non-conductive polymer layer is formed in a laminated structure. An external stimulus is electrically sensed through a composite material to which electrical properties are imparted to a non-conductive polymer, a manufacturing method thereof, and a non-conductive polymer to be observed electrical properties are inserted between the conductive layers, and after the obtained signal We provide a method for observing electrical properties of amphiphilic block copolymers that can check the changes in the microchemical structure of non-conductive polymers by measuring electrical signals by analyzing the movement occurring inside the composite through processing, and application products containing the composite material. is in doing

That is, since most non-conductive polymers including block copolymers have electrical insulating properties, it is impossible to analyze electronic, electrical, or electrochemical properties, so the electronic/electrical properties of the block copolymer cannot be observed, but the composite material of the present invention This is because electrical properties can be imparted to the block copolymer in a structure in which a block copolymer having electrical insulating properties is intercalated into a conductor such as graphene. If necessary, in addition to electrical properties, other properties may be imparted by attaching functional groups reactive to changes in environmental parameters such as pH, temperature, humidity, pressure and light.

Accordingly, the conductive layer/non-conductive polymer layer laminated composite material of the present invention has a laminate structure consisting of a conductive layer made of a conductive material and a non-conductive polymer layer made of an amphiphilic non-conductive polymer copolymer formed on the conductive layer. More than one is included sequentially. As an embodiment, the non-conductive polymer layer and the conductive layer constituting the laminated structure each have a nano-scale thickness, the conductive layer may have a thickness of 0.3 to 10 nm, and the non-conductive polymer layer is the distance between the conductive layer and the conductive layer. It may have a thickness corresponding to , and may be 50 nm or less depending on the applied product, and in particular may be implemented to be less than 10 nm.

The conductor material forming the conductor layer is derived from a laminated structure having conductor properties made up of a peelable two-dimensional structure, and a laminated structure having conductor characteristics is not limited as long as it has conductor characteristics and has physical characteristics that can be peeled into a two-dimensional structure. However, it may be at least one selected from the group consisting of graphite, graphene, black phosphorus, molybdenum-based compounds, and metal chalcogen-based compounds. Here, the conductive material may be formed of a single layer or multiple layers. For example, when the conductive material is a multilayer, the conductive material and the laminated structure may be the same.

The non-conductive polymer layer is made of an amphiphilic non-conductive polymer copolymer, which is not limited as long as it has excellent dispersibility in a solvent, is non-conductive, and can be well combined with the conductive material forming the conductive layer. The copolymer may be an amphiphilic block copolymer in which a hydrophilic polymer and a hydrophobic polymer form a block through a copolymerization reaction, respectively. If necessary, the polymer constituting the amphiphilic block copolymer may include any one or more of a photoreactive functional group, a temperature responsive functional group, a moisture responsive functional group, and a pH responsive functional group to add various desired stimuli reactivity to the non-conductive polymer.

Here, the photoreactive functional group may be any one selected from the group consisting of cis-azobenzene, trans-azobenzene diarylethene, spiropyran, merocyanine, oxazolidine, oxazine, o-nitrobenzyl ester, fulgide, and spiroxazine. The pH-reactive functional group may be any one selected from the group consisting of carboxyl, pyridine, sulfonic, phosphate, and tertiary amines. Polymers with temperature-reactive functional groups are poly(N-isopropylacrylamide), poly(N-(2-hydroxypropyl)methacrylamide), poly(N,N-diethylacrylamide), poly (methylvinylether), poly(N-vinylcaprolactam), poly(ethylene oxide) and poly(propylene oxide), poly(N,N-dimethylaminoethyl methacrylate), poly(3-dimethyl(methacryloyloxyethyl)ammonium propane sulfonate), poly(2-hydroxyethyl methacrylate), poly(methacrylamide), poly It may be any one selected from the group consisting of (N-acryloyl asparagine amide), poly(N-acryloyl glycinamide), and poly(6-(acryloyloxymethyl)uracil).

On the other hand, the conductive layer/non-conductive polymer layer laminated composite material of the present invention exhibits Coulomb blockade oscillation when a current is applied to an external stimulus or a current is generated by an external stimulus. It can be controlled by controlling the degree of polymerization of the amphiphilic non-conductive polymer copolymer constituting the layer.

In particular, as an embodiment of the composite material of the present invention, the conductive layer is made of any one of graphene, molybdenum compound, or black phosphorus, and the non-conductive polymer layer is poly[(ethylene oxide) -b -poly[(3-vinylbenzyl ideneoxazolone) )] (PEO- b -PVBO) may be formed of any one of graphene, a molybdenum compound, or black phosphorus. As such, when the non-conductive polymer layer is made of PEO-b- PVBO, since photoreactive functional groups are attached to the PVBO block, the degree of polymerization can be controlled to control the photoreactivity and Coulombic block vibration of PEO- b-PVBO.

Next, the method for manufacturing a multilayer composite material of the present invention comprises the steps of synthesizing an amphiphilic block copolymer constituting a non-conductive polymer layer; obtaining an amphiphilic stimulus-responsive block copolymer by introducing a stimulus-responsive functional group into the amphiphilic block copolymer; obtaining a dispersion solution in which the conductor material is dispersed by adding a conductor material forming a conductor layer to a dispersion solvent and then physically treating the conductor material so that the conductor material is peeled off as separate layers or a predetermined space is formed between each layer; adding the amphiphilic stimulus-responsive block copolymer to the dispersion solution; The amphiphilic stimulus-responsive block copolymer surrounds a separate layer of the dispersed conductor material, or the amphiphilic stimulus-reactive block copolymer is inserted in a predetermined space formed between each layer of the conductor material, so that the conductive material and the amphiphilic a bonding step in which the block copolymer is combined to form a laminated precursor; and a lamination step in which two or more laminated precursors dispersed in the solvent are laminated to form a laminated structure. Here, the physically treating step may be performed by any one of ultrasonication treatment, agitator treatment, centrifugal separator treatment, and ball milling treatment, and the lamination step may be performed by removing the solvent to the lower side of the reactor.

Next, the method for observing electrical properties for the amphiphilic block copolymer of the present invention comprises the steps of preparing the composite material of any one of claims 3 to 11 in which the amphiphilic block copolymer to be analyzed is inserted; measuring an electrical signal inside the composite material while applying an external stimulus to the composite material; and monitoring the change of the block copolymer by analyzing the measured electrical signal.

Here, the change in the block copolymer is a change in the microchemical structure at the molecular level with respect to the external stimulus, and the magnitude of the measured electrical signal is quantitatively related to the change in the microchemical structure. chain conformational change) and isomerization (isomerization). In particular, coulombic confinement vibration occurs in composite materials through polymer chain conformation change, and the current change range during coulombic confinement vibration is 10 nA or less, which can appear as small as several picoA.

Examples 1-3

1. Obtaining a PEO- b- PVBO block copolymer, which is an amphiphilic photoreactive block copolymer that forms a non-conductive polymer layer

As shown in FIG. 1a, the PEO-b- PVBA block copolymer was polymerized by performing the steps described below, and then a photoreactive PEO-b- PVBO block copolymer was prepared through a synthesis process in which a photoreactive functional group was substituted.

(1) synthesizing an amphiphilic block copolymer, PEO- b -PVBA block copolymer

To prepare PEO-b- PVBA, 2.287 mL of 3-VBA, 0.9 g of PEO-Br, 37.58 μL of PMDETA and 5.0 mL of anisole were added to a Schlenk flask, and the mixture was stirred with a magnetic stirrer. In three freeze-pump-thaw cycles, oxygen inside the flask was removed, and 25.82 mg of CuBr was added in an argon environment, followed by polymerization at 110 °C. A sample was extracted using a syringe at regular intervals every 2, 4, and 6 hours, and the extracted solution was passed through a neutral alumina column to remove the catalyst. The catalyst-free solution was added to cold diethyl ether to precipitate a polymer sample, and the product was dried at room temperature under vacuum for 12 hours. As a result, PEO-b-PVBA in which the DP of the PVBA block was controlled to 25, 40 and 50 was obtained.

(2) obtaining an amphiphilic stimulus-responsive block copolymer, PEO-b-PVBO block copolymer

0.85 g of PEO-b- PVBA, 1.99 g of hippuric acid, 0.911 g of sodium acetate and 15.0 mL of acetic anhydride were added to a round bottom flask and heated at 120°C for 4 hours. After stirring, the mixture was stirred at room temperature for 12 hours. Acetic anhydride was removed by evaporation under vacuum, and the remaining mixture was precipitated in cold diethyl ether. The resulting polymer was dried at room temperature under vacuum for 12 hours to PEO- b -PVBO (PEO ₁₁₃ - b -PVBO ₂₅ , PEO ₁₁₃ - b -PVBO ₄₀ , PEO ₁₁₃ - b -PVBO ₅₀ ) got

2. Step of obtaining a dispersion solution in which the conductor material is dispersed

An acidic solution was used to exfoliate the graphite. Phosphorus pentoxide and potassium persulfate were dissolved in a sulfuric acid solution, and graphite flakes having a reagent-to-graphite weight ratio of 5:1 were mixed with the solution and stirred at 80° C. for 40 minutes. The exfoliated graphite (EG) was washed with distilled water and heat-treated at 1000° C. for 90 minutes under a nitrogen atmosphere. EG was sonicated to disperse EG and distilled water in a weight ratio of 1:2000 to obtain an EG dispersion solution.

3. Adding the amphiphilic stimulus-responsive block copolymer to the dispersion solution

Prepared PEO- b -PVBO (PEO ₁₁₃ - b -PVBO ₂₅ , PEO ₁₁₃ - b -PVBO ₄₀ , PEO ₁₁₃ - b -PVBO ₅₀ ) was added to the EG dispersion solution at a PEO- b -PVBO/EG weight ratio of 2:1, respectively. added.

4. Bonding step to form a laminated precursor

A bonding step was performed to form a stacked precursor by sonicating the PEO- b-PVBO/EG dispersion to promote the insertion of the block copolymer into graphene.

5. Lamination step

_{Composites 1 to 3 (P 25} GNH, P ₄₀ GNH, P ₅₀ GNH) were prepared by removing the solvent to the lower side of the reactor in which the laminated precursor was formed, thereby stacking two or more laminated precursors to form a laminated structure.

Example 4

_{Composite material 4 (P 25} 1T-MoS ₂ ) in the same manner as in Example 1 except that the _{1T-MoS 2} dispersion obtained by performing the step of obtaining a dispersion solution in which the conductor material is dispersed was used instead of the EG dispersion got

1T-MoS ₂ exfoliation step

Bulk 1T-MoS ₂ was physically peeled off as follows. Powder 1T-MoS ₂ and methylpyrrolidone (N- Methyl-2-pyrrolidone) having a weight ratio of 2000 times were prepared and sonicated. At this time, it was treated with 43 Watts for 60 minutes to obtain _{a 1T-MoS 2 dispersion.}

Example 5

_{Composite material 5 (P 25} black phosphorus) was obtained in the same manner as in Example 1, except that the black phosphorus dispersion obtained by performing the step of obtaining a dispersion solution in which the conductive material was dispersed was used instead of the EG dispersion.

peeling of black phosphorus

The bulk black phosphorus was physically exfoliated as follows. Powdered black phosphorus and 2000 times the weight ratio of methylpyrrolidone ( N- Methyl-2-pyrrolidone) were prepared and sonicated. At this time, it was treated with 43 Watts for 60 minutes to obtain a black phosphorus dispersion.

Experimental Example 1

Example 1 A parent prepared in stimulation reactive block copolymer PEO- b periodically, in the polymerization process of -PVBO (2 times) to extract the sample block the other PVBA molecular weight _{(PEO 113 - b - PVBO 25} , PEO 113 - b -PVBO ₄₀ , PEO ₁₁₃ -b -PVBO ₅₀ ) was obtained, and properties such as conversion and molecular weight increase were observed, and the results are shown in FIGS. 1b to 1e.

First, poly [(ethylene oxide) - b -poly [(3-vinylbenzaldehyde)] (PEO- b -PVBA) block copolymer gel permeation chromatography (GPC) using a sulfated dimethyl (DMSO) -d ₆ as a solvent and ^{1B analyzed by 1} H nuclear magnetic resonance (NMR) spectroscopy showed that the GPC traces shifted continuously towards high molecular weight throughout the polymerization, showing well-controlled block bonding.

The DP of the PEO-b- PVBA block copolymer was also experimentally obtained from ¹ H NMR spectra (DP n , NMR) by calculating the integration region of the PEO monomer signal at 3.5 ppm and the aldehyde signal of the PVBA block at 9.9 ppm. The calculated DPs of the PVBA blocks were 25, 40 and 50. Then, by reacting with hippuric acid in the presence of sodium acetate, the aldehyde group of PEO-b- PVBA is converted to BO and poly[(ethylene oxide) -b -poly[(3-vinylbenzyl ideneoxazolone)] (PEO- b -PVBO) was created. ¹ H NMR spectrum provided quantitative evidence of modification after polymerization because the aldehyde peak of VBA completely disappeared at 9.9 ppm (Fig. 1c).

The chromophore BO has a unique light-switching behavior based on geometrical heterogeneity upon irradiation with UV and visible light. The introduction of BO into the block segment enabled the intrinsic chain conformational change of PEO- b- PVBO by geometric isomerization under different wavelengths (365 and 650 nm) irradiation. The emission reduction behavior of PEO-b- PVBO also depended on the DP of the PVBO block). Figure 1d shows the Z??E isomerization of PEO-b-PVBO induced by ultraviolet and visible light. The different geometries of the E and Z isomers result in different chain conformational structures of the block copolymer. Furthermore, the ester moiety of the E isomer is close to the adjacent benzene ring, whereas the ester moiety of the Z isomer is relatively free from steric hindrance. The oxygen atom in the ester ring of BO has a pair of electrons. Therefore, isomerization by light can further change important properties of PEO-b-PVBO, such as chemical reactivity and electron density distribution.

Density functional theory was used to calculate the electronic structure of the isomer (Fig. 1e). The electron density distributions of the two isomers are clearly different. Surprisingly, the red region representing the C=O group of the E isomer overlaps the blue region representing the proton of the adjacent benzene ring, indicating that the C=O group is bound to the proton of benzene through a physical bond. In contrast, no intermolecular interactions were observed inside the Z isomer. These calculated data confirm that photoisomerization triggered by different light sources can induce significant changes in the chemical and electronic properties of PEO-b-PVBO as well as the geometry.

Experimental Example 2

_{As in Examples 1 to 3, P n} GNH dispersions (n = 25, 40 and 50) under visible light and ultraviolet light in the process of preparing composite materials 1 to 3 (P ₂₅ GNH, P ₄₀ GNH, P _{50 GNH)} The color change was observed, and _{an SEM image of P n} GNH was taken, and the results are shown in FIG. 2 .

As shown in Figure 2, PGNHs showed good colloidal stability in aqueous solution, which was in contrast to the poor colloidal stability of the exfoliated graphene sheet used as a control. Graphene itself is inherently hydrophobic. Therefore, the stable aqueous phase dispersion of PGNHs indicates that the amphiphilic PEO-b- PVBO is adsorbed onto the graphene sheet, which improves the colloidal stability. Figure 2 (a) shows the water-soluble colloidal distribution of PGNHs under visible light and ultraviolet irradiation. Under visible light illumination, the aqueous PGNH dispersion appeared black. In contrast, under UV illumination, the dispersion turned dark yellow, and the color intensity was dependent on the DP of the PVBO block. The yellow color appeared more intense as the DP of the PVBO block in PEO-b- PVBO increased, indicating that the PVBO block intercalated between graphene sheets functions as a chromophore. b??e of FIG. 2 shows a scanning electron microscope (SEM) image of PGNH and a control image (only graphene sheets exist). In all PGNHs, PEO- b- PVBO was well embedded in graphene sheets. Further, the form of PEO- b -PVBO liver PEO- b -PVBO intercalation is notable that the viscosity depends on the DP of PVBO block. The PEO block is hydrophilic and the PVBO block is hydrophobic. Therefore, as the DP of the PVBO block increases, the hydrophilic-hydrophobic balance decreases. P ₂₅ GNH was relatively hydrophobic because it was found to be adsorbed on graphene in the form of a rather atypical and rough film. Conversely, particulate PEO-b- PVBO was observed between graphene sheets of PVBO blocks with higher DP. In particular, almost spherical nanoparticles (diameter of about 50 nm) were found in _{P 50 GNH, indicating that the PEO 113} -b -PVBO ₅₀ block copolymer is hydrophobic enough to self-assemble into spheres due to the high interfacial tension in the water system. indicates that there is That is, it can be seen that the shape of the PEO-b- PVBO block composite inserted between the graphene sheets in aqueous solution evolved from the film to fine particles as the DP of the PVBO block increased.

Experimental Example 3

The amphiphilic stimulus-responsive block copolymer PEO- b -PVBO (PEO ₁₁₃ - b -PVBO ₂₅ , PEO ₁₁₃ - b -PVBO ₄₀ , PEO ₁₁₃ - b -PVBO ₅₀ ) prepared in Examples 1 to 3 and the composite material in aqueous solution The photoisomerization behavior of 1 to 3 (P ₂₅ GNH, P ₄₀ GNH, P ₅₀ GNH) was examined using an ultraviolet-visible spectrophotometer, and the results are shown in FIGS. 3A to 3E . After the absorption spectrum of the block copolymer and the graphene sheet intercalated with the block copolymer reached an equilibrium state under visible light, their absorption change under UV was monitored for 90 minutes.

As shown in Figures 3a and 3b, PEO ₁₁₃ -b -PVBO ₂₅ under visible light illumination showed only an unclear and weak absorbance at 370 ~ 420 nm. On the other hand, PEO ₁₁₃ -b -PVBO ₄₀ and PEO ₁₁₃ -b -PVBO ₅₀ revealed three major absorption peaks at about 356, 376 and 400 nm. PEO ₁₁₃ - 2 peak of b -PVBO ₅₀ PEO ₁₁₃ - was more intense than b -PVBO _40. The dependence of the absorption intensity on the DP of the PVBO block under visible light confirms that the BO portion of the PVBO block works well as a chromophore of the block copolymer.

After that, the absorption peak gradually decreased under UV irradiation, indicating that the color behavior of the BO portion of the PVBO block was masked through the conformational change of the chain upon photoisomerization. The same trend was observed in the absorption spectrum of PGNHs. Graphene sheets are considered to interfere with the absorption of block composites). Therefore, the level of change is slightly lower when compared to the block composite alone. The dependence of the photoisomerization rate on the DP of the PVBO block was investigated by dynamic quantification of the absorbance change. As a representative absorption peak, the absorbance at 400 nm is plotted as a function of time in FIGS. 3c and 3d . The Z??E photosynthesis rate can be explained by a first-order reaction as shown in Equation 1 below.

(Equation 1)

[ Z ( t )]/[ Z ] ₀ = e ^{?? kt}

where Z and k represent the Z isomer and rate constant of PEO- b-PVBO, respectively. The absorbance is the sum of the absorbances of the individual components (PVBO block, PEO block and graphene). Considering that the absorbance of the PEO block and graphene is kept constant during photoisomerization, the absorbance A can be correlated with the concentration of the Z isomer using the following equation (Equation 2).

(Equation 2)

A ( t )/ A ₀ = β + αe ^{?? kt}

where α and β are constants, and the relative absorbance curve is calculated using Eq. 2 is applied to calculate the ratio constant.

As shown in Fig. 3e, as the DP of the PVBO block with or without graphene increased, the photoreactivity rate constant increased. The ratio constant of PGNHs was 34.56% lower than that of PEO- b-PVBO. However, the ability of PEO-b- PVBO to exhibit photoisomerization was well maintained even after intercalation in the space between graphene sheets.

Experimental Example 4

Using the composite materials 1 to 3 (P ₂₅ GNH, P ₄₀ GNH, P ₅₀ GNH) obtained in Examples 1 to 3, the electrode schematically shown in FIG. 4 was prepared as follows, and the The photoisomerization behavior was electrically monitored by measuring the current as a function, and the results are shown in FIGS. 5A to 5D . A circular pattern of a block copolymer/graphene sheet was deposited on a glass substrate between two gold electrodes using a polydimethylsiloxane (PDMS) mask. At this time, a configuration such as a series connection of small PEO-b- PVBO/graphene pieces was formed on the gap between the gold electrodes to amplify the change in the current flowing through the electrodes.

As shown in FIG. 5a , PGNH showed photoreactivity when periodically exposed to visible light/UV. The chain conformational change of intercalated PEO-b- PVBO due to photoreactivity not only changes the main properties of the block copolymer, but can also cause physical perturbation in the narrow space between graphene sheets. The current change (ΔI = I - I ₀ , where I ₀ and I are initial current and real-time current, respectively) was positive in visible light but negative in ultraviolet light. That is, the resistance of the PGNH electrode increased due to UV illumination, indicating that the chain conformational change of PEO- b-PVBO by Z??E photoisomerization affected the current flow through the electrode. The rate of change of current depends on the DP of the PVBO block. The first derivative model of the change in current as a function of time, d(ΔI)/dt, clearly indicated that the current increased under visible light, whereas the current decreased under UV illumination (Fig. 5b). The rate of current change was also proportional to the DP of the PVBO block. Therefore, it should be noted that the electrical signal is quantitatively correlated with the chain conformational change of the block copolymer that occurs at the molecular level. This type of photoswitching action also allows the direct application of PGNH electrodes to UV sensors. Considering that PGNH electrodes are very easy and cost-effective to fabricate, while most UV sensors require sophisticated materials and sophisticated device systems, the usefulness of the composite material of the present invention can be seen.

As shown in Fig. 5b, a Coulomb-blocking vibration phenomenon was observed in the current passing through the PGNH electrode using the composite material of the present invention. The current oscillated at the level of several nanoamperes in both visible and UV illumination, as shown in Fig. 5b, where the oscillation behavior appeared to depend on the DP of the PVBO block. Photosynthesis of chains of block binders trapped between graphene sheets caused large periodic square changes in the current. In addition, continuous current oscillations were observed on small scales under visible or UV illumination. PEO-b- PVBO is a resistive material, which allows only tunneling between geometrically separated graphene sheets when embedded in conductive graphene sheets. Tunneling can be affected by photosynthesis of PEO- b- PVBO, which accompanies changes in the compatibility of graphene sheets in the limited ultrasound space. Specifically, in a limited space, physical perturbation caused by changes in the polymer chain conformation of PEO- b-PVBO may affect tunneling. Also, as shown in Fig. 1e, the isomers had different (localized) electron density distributions, which could also change tunneling through changes in Coulomb interactions. Therefore, it can be predicted that changes in the chemical/electronic properties of the tunnel junction due to the physical rearrangement of the blocks will affect the tunneling. In addition, a configuration such as a series connection of intercalated PEO- b- PVBO resistors was formed when voltage was applied vertically to the stacked graphene sheets. Here, what is important is that the series combination of resistors along the z-axis of the stacked graphene sheet will contribute to electrically amplifying the response of the intercalated block copolymer.

Fast Fourier transform (FFT) analysis was applied to the first derivative of the time-dependent current to investigate the periodicity and amplitude of the Coulomb blockade oscillation as shown in FIG. 5c. In the frequency domain, two types of vibrations were detected ( FIGS. 5D and 7 ). First, a high amplitude frequency peak was found at 5 mHz (f1), followed by odd harmonic frequency peaks (eg 3f1, 5f1, 7f1). These types of frequency peaks can be attributed to large square oscillations in the time domain due to photoisomerization. Next, a frequency band covering the ㅁ25 mHz range was found centered at 174 mHz (f2) in the low-frequency region periodically repeated at intervals of 50 mHz. The block copolymer is randomly inserted between the graphene sheets so that the frequency band includes a specific range of frequencies. A frequency band that is a positive integer multiple of the original frequency band centered at 174 mHz was observed, indicating the occurrence of sawtooth coulombic cutoff oscillations. The coulombic sequestration oscillation amplitude also depends on the DP of the PVBO block, indicating that PVBO contributed significantly to the coulombic sequestration transport.

Experimental Example 5

_{An electrode including the composite material 1 (P 25} GNH) prepared in Example 1 was prepared, and an ultraviolet sensing experiment and signal analysis were performed as follows, and the results are shown in FIGS. 6A and 6B .

1. Electrical sensing of ultraviolet light

A Keithley 2636A source meter was used to measure the real-time change in current by chronoamperometry. The electrodes were periodically exposed to UV and visible light, and the current was measured by applying a voltage of 0.1 V. The wavelengths of UV and visible light were 365 and 650 nm, respectively, at an irradiation power of 3 mW. When the conductive two-dimensional material (graphene) has a thickness of about 0.3 to 5 nm with 1 to 5 layers, resistance as shown in FIG. An increase in the value was observed, which led to a sharp change in the current signal (dΔI/dt), i.e. from positive to negative.

2. Detection signal processing

Through the same process as in FIGS. 6A and 6B, the first derivative of the current change result obtained through the electrical sensing experiment was obtained; In the first derivative, it could be easily confirmed that the sign of the current change value with time was changed according to the light source. In addition, it was confirmed that there is a regular change at the level of 5 nA in the current flow, and Fast Fourier transform (FFT) was performed on the first derivative graph.

The discrete signal observed in the low-frequency region as shown in FIGS. 6A and 6B means that the first derivative of the current change graph changes to a rectangular shape, as shown in FIG. 5E . This is due to a change in the current signal (dΔI/dt) due to a change in resistance caused by a change in the visible light/ultraviolet light source.

On the other hand, the continuous signal band observed in the entire region as seen in Fig. 5e is related to the change occurring at the level of 5 nA in the first derivative of the current change graph, and such a regular change of the Sawtooth type is the insulating block air in graphene. This was due to the coulombic oscillations caused by the coulombic shielding phenomenon occurring in the coalescence.

Experimental Example 6

An electrode including the composite material 4 (stimulus P ₂₅ 1T-MoS ₂ ) prepared in Example 4 was prepared, and UV sensing experiments and signal analysis were performed as follows, and the results are shown in FIGS. 7A and 7B .

1. Electrical sensing of ultraviolet light

It was made in the same manner as in Experimental Example 5, and when the conductive two-dimensional material (1T-MoS ₂ ) had a thickness of about 0.7 to 8 nm with 1 to 10 layers, a stimulus-responsive block inserted into a gap of up to 50 nm or less A change in the signal of the same type as in FIGS. 7A and 7B was observed due to the change occurring in the copolymer.

2. Detection signal processing

As a result of the same treatment as in Experimental Example 5, it was confirmed that there was a regular change at the level of 2 nA in the current flow along with a sharp change in the current signal (dΔI/dt) according to the light source.

3. Coulomb vibration control

As for the observed coulombic blocking vibration, it is expected that the average amplitude of the coulombic vibration will change when the polymerization degree of the block copolymer is changed similarly to Experimental Example 5, so it will be possible to control the coulombic vibration by controlling the polymerization degree of the block copolymer.

Experimental Example 7

_{An electrode including the composite material 5 (P 25} black phosphorus) prepared in Example 5 was prepared, and UV sensing experiments and signal analysis were performed as follows, and the results are shown in FIGS. 8A and 8B .

1. Electrical sensing of ultraviolet light

It was made in the same manner as in Experimental Example 5, and when the conductive two-dimensional material (black phosphorus) had a thickness of 0.5 to 6.5 nm in 1 to 8 layers, it occurred in the stimulus-responsive block copolymer intercalated in the gap of up to 50 nm A change in the signal of the same type as in FIGS. 8A and 8B was observed by the change.

2. Detection signal processing

As a result of the same processing as in Experimental Example 5, it was confirmed that there was a regular change at the level of 4 nA in the current flow along with a sharp change in the current signal (dΔI/dt) according to the light source.

3. Coulomb vibration control

As for the observed coulombic blocking vibration, it is expected that the average amplitude of the coulombic vibration will change when the polymerization degree of the block copolymer is changed similarly to Experimental Example 5, so it will be possible to control the coulombic vibration by controlling the polymerization degree of the block copolymer.

From the above experimental results, the composite material of the present invention can impart electrical properties to the non-conductive polymer layer through a structure in which two or more laminated structures composed of a non-conductive polymer layer and a conductor layer are sequentially stacked. Various industrial uses are possible. In particular, the current change of PGNH upon irradiation with visible/UV light was sensitive to the DP of the PVBO block, and more interestingly, time vs. The first derivative of the current also clearly revealed the coulombic blocking oscillations of the current flow that depended on the DP of the PVBO block. FFT analysis showed that the current flowing through the PGNH as a function of time exhibiting sawtooth oscillations. The change in current of PGNH by visible light/UV light irradiation can be directly applied to the ammeter UV sensor. It will also be possible that block co-copolymer-mediated coulombic sequestration transport of conductor layers provides an easy route to various coulombic sequestration applications such as coulombic block-based transistors and thermometers.

Although the present invention has been illustrated and described with reference to preferred embodiments as described above, it is not limited to the above-described embodiments, and those of ordinary skill in the art to which the invention pertains within the scope not departing from the spirit of the present invention Various changes and modifications will be possible.

Claims (22)

A conductive layer/non-conductive polymer layer laminated composite material comprising at least two or more sequentially laminated structures comprising a conductive layer made of a conductive material and a non-conductive polymer layer made of an amphiphilic non-conductive polymer copolymer formed on the conductive layer .
The method of claim 1,
The conductive material is derived from a laminated structure having conductor characteristics consisting of a peelable two-dimensional structure, and the laminated structure having conductor characteristics is selected from the group consisting of graphite, graphene, black phosphorus, molybdenum-based compounds, and metal chalcogen-based compounds. Conductive layer / non-conductive polymer layer laminated composite material, characterized in that at least one that is.
The method of claim 1,
The amphiphilic non-conductive polymer copolymer is an amphiphilic block copolymer in which a hydrophilic polymer and a hydrophobic polymer form a block through a copolymerization reaction, respectively.
4. The method of claim 3,
The polymer constituting the amphiphilic block copolymer comprises at least one of a photoreactive functional group, a temperature-reactive functional group, a moisture-reactive functional group, and a pH-reactive functional group.
5. The method of claim 4,
The photoreactive functional group is cis-azobenzene, trans-azobenzene diarylethene, spiropyran, merocyanine, oxazolidine, oxazine, o-nitrobenzyl ester, fulgide, conductive layer / non-conductive polymer layer, characterized in that any one selected from the group consisting of spiroxazine laminated composites.
5. The method of claim 4,
The pH-reactive functional group is a conductive layer / non-conductive polymer layer laminated type, characterized in that any one selected from the group consisting of a carboxyl group, a pyridine, a sulfonic group, a phosphate, and a tertiary amine composite material.
5. The method of claim 4,
The polymer having the temperature-reactive functional group is poly(N-isopropylacrylamide), poly(N-(2-hydroxypropyl)methacrylamide), poly(N,N-diethylacrylamide), poly (methylvinylether), poly(N-vinylcaprolactam), poly( ethylene oxide) and poly(propylene oxide) block copolymer, poly(N,N-dimethylaminoethyl methacrylate), poly(3-dimethyl(methacryloyloxyethyl)ammonium propane sulfonate), poly(2-hydroxyethyl methacrylate), poly(methacrylamide), Conductor layer / non-conductive polymer layer laminated composite material, characterized in that any one selected from the group consisting of poly(N-acryloyl asparagine amide), poly(N-acryloyl glycinamide), and poly(6-(acryloyloxymethyl)uracil).
8. The method according to any one of claims 1 to 7,
The laminated structure formed in two or more sequentially is a conductive layer/non-conductive polymer layer laminated composite material, characterized in that it exhibits Coulomb blockade oscillation when an external stimulus is applied.
9. The method of claim 8,
The Coulomb-blocking vibration is a conductive layer/non-conductive polymer layer laminated composite material, characterized in that it is controlled by controlling the polymerization degree of the amphiphilic non-conductive polymer copolymer constituting the non-conductive polymer layer.
9. The method of claim 8,
The conductive layer is made of any one of graphene, a molybdenum compound, or black phosphorus, and the non-conductive polymer layer is made of poly[(ethylene oxide) -b -poly[(3-vinylbenzyl ideneoxazolone)] (PEO- b- PVBO). Conductive layer / non-conductive polymer layer laminated composite material, characterized in that.
11. The method of claim 10
In the PEO-b- PVBO, when the polymerization degree of the PVBO block is controlled, the photoreactivity and Coulomb-blocking vibration of the PEO- b-PVBO are controlled.
The method for manufacturing the composite material of any one of claims 4 to 7,
synthesizing an amphiphilic block copolymer constituting a non-conductive polymer layer;
obtaining an amphiphilic stimulus-responsive block copolymer by introducing a stimulus-responsive functional group into the amphiphilic block copolymer;
obtaining a dispersion solution in which the conductor material is dispersed by adding a conductor material forming a conductor layer to a dispersion solvent and then physically treating the conductor material so that the conductor material is peeled off as separate layers or a predetermined space is formed between each layer;
adding the amphiphilic stimulus-responsive block copolymer to the dispersion solution;
The amphiphilic stimulus-responsive block copolymer surrounds a separate layer of the dispersed conductor material, or the amphiphilic block copolymer is inserted in a predetermined space formed between each layer of the conductor material, so that the conductor material and the amphiphilic block copolymer a bonding step of coalescing to form a laminated precursor; and
A method for manufacturing a laminated composite material comprising a; a lamination step in which two or more laminated precursors dispersed in the solvent are laminated to form a laminated structure.
13. The method of claim 12,
The physically treating step is a method for manufacturing a conductive layer/non-conductive polymer layer laminated composite material, characterized in that any one of ultrasonic treatment, stirrer treatment, centrifugal separator treatment, and ball milling treatment is performed.
13. The method of claim 12,
The lamination step is a method for manufacturing a conductive layer/non-conductive polymer layer laminated composite material, characterized in that it is performed by removing the solvent to the lower side of the reactor.
Preparing the composite material of any one of claims 3 to 11, wherein the amphiphilic block copolymer to be analyzed is inserted;
measuring an electrical signal inside the composite material while applying an external stimulus to the composite material; and
Monitoring the change of the block copolymer by analyzing the measured electrical signal; Electrical property observation method for the amphiphilic block copolymer comprising a.
16. The method of claim 15,
The change in the block copolymer is a change in the microchemical structure at the molecular level with respect to the external stimulus, and the magnitude of the electrical signal measured is quantitatively related to the change in the microchemical structure. Characteristic observation method.
17. The method of claim 16,
The microchemical structural change is a polymer chain conformational change (chain conformational change) and isomerization (isomerization) method for observing electrical properties for an amphiphilic block copolymer, characterized in that it includes at least one.
18. The method of claim 17,
A method for observing electrical properties for an amphiphilic block copolymer, characterized in that Coulomb blocking vibration occurs in the composite material through the change in the polymer chain shape.
19. The method of claim 18,
The coulol blocking vibration is a method for observing electrical properties for an amphiphilic block copolymer, characterized in that it is controlled by controlling the polymerization degree of the amphiphilic block copolymer.
An application product comprising the conductive layer/non-conductive polymer layer laminated composite material according to any one of claims 1 to 11.
21. The method of claim 20,
The application product, characterized in that the sensor or coulomb block-based transistor.
22. The method of claim 21,
The sensor performs at least one of an electrical signal conversion mechanism, an electronic signal conversion mechanism, and an electrochemical signal conversion mechanism.

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