KR20130039119A - Complex of graphene and polymer, device having complex of graphene and polymer and manufacturing method thereof - Google Patents
Complex of graphene and polymer, device having complex of graphene and polymer and manufacturing method thereof Download PDFInfo
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- KR20130039119A KR20130039119A KR1020110103590A KR20110103590A KR20130039119A KR 20130039119 A KR20130039119 A KR 20130039119A KR 1020110103590 A KR1020110103590 A KR 1020110103590A KR 20110103590 A KR20110103590 A KR 20110103590A KR 20130039119 A KR20130039119 A KR 20130039119A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
Abstract
Graphene-polymer complexes are disclosed. Graphene-polymer composite according to an embodiment of the present invention, the plate-shaped graphene; And a polymer coating layer formed by bonding a polymer to one or both sides of the graphene and forming a flexible bendable film form together with the graphene layer.
Description
The present invention relates to graphene-polymer composites, devices equipped with graphene-polymer composites and methods for their preparation.
Graphene is a material in which carbon exists in a two-dimensional hexagonal shape. It has high electron mobility and high current density, and carbon atoms are strongly connected through covalent bonds to have high Young's modulus. It has electrical, optical and mechanical properties.
Accordingly, there are various applications such as electrical, mechanical and optical sensors, actuators, and the like, and mechanical peeling from graphite, chemical peeling of graphite oxide, epitaxial growth, chemical vapor deposition (CVD, chemical vapor deposition technique).
Chemical Vapor Deposition (CVD) is a method in which high-energy plasma is applied to a gas containing chemicals so that radically reactive chemicals are deposited on the substrate. Graphene having a uniform thickness can be obtained, and a desired pattern can be processed only by a photoresist process using a mask.
According to the chemical vapor deposition (CVD), the graphene grows on the copper or nickel catalyst, and the work of separating the generated graphene from the catalyst and moving it to the next working position is involved. In general, the polymer is further bonded to the graphene, and then the copper or nickel is etched to remove the graphene suspended in the etching solution, rinsed with distilled water, and transferred to a processing position on a designated substrate. The polymer is then removed with acetone.
While chemical vapor deposition (CVD) allows the use of patterned graphene in a desired shape, its practical use has been favored, while the manufacturing process or graphene can be used as a distilled water in an etching solution, another distilled water for rinsing, and a substrate in the last distilled water. Technical problems in the course of a series of transfers to (processing locations) have resulted in graphene rupture, damage due to folds, or inhomogeneities.
Other factors that cause damage to graphene and decrease in electrical sensitivity include the process of processing the graphene into a desired shape by defects on the surface of the graphene, photolithography, and the like, which are caused by exposure to the external environment. Contamination generated, tearing due to contact with the measuring tip, and the like.
1 and 2 are 'Kanghyun Kim et.al.', “Electric Property Evolution of Structurally Defected Multilayer Graphene”, Nano Letters, LETTERS 2008 Vol. 8, No. The graph shows the results of experiments showing that the electrical properties of graphene are degraded by applying oxygen plasma to graphene.
Referring to FIGS. 1 and 2, when a defect occurs in graphene or the graphene is continuously exposed to oxygen, electrical properties (a degree of current change according to voltage change (FIG. 1) and a reaction rate (G (ms) It can be seen that () (FIG. 2) is significantly reduced.
3, 4 is' J. Scott Bunch et.al., "Electromechanical Resonators from Graphene Sheets", SCIENCE, 26 JANUARY 2007 VOL 315 ', is a photograph taken of the photoresist that is contaminated by the graphene constituting the graphene resonator.
Referring to FIGS. 3 and 4, it can be seen that a part of the graphene structure is contaminated in the photoresist (part indicated by a red circle). Only by the degree of contamination to the photoresist, the sensitivity can be significantly reduced.
Efforts have been made to reduce the damage and contamination of the graphene and graphene devices due to such physical and chemical factors, and thus the decrease in electrical sensitivity. However, the graphene bends in the manufacturing and transfer process of the graphene or graphene device. It is a situation that requires attention to reducing the degree of deformation, the contact portion of the graphene, minimizing the stress concentration.
The present invention devised to solve the problems described above, it is possible to reliably prevent and protect the damage and contamination caused by physical and chemical factors generated during the manufacture and transfer of graphene (graphene) or graphene-based device It is an object of the present invention to provide a graphene-polymer composite, a device equipped with a graphene-polymer composite, and a method for producing the same.
The present invention for achieving the above object, the plate-shaped graphene (graphene) (20a); And a
Here, the
In addition, the
In addition, the
In addition, the polymer coating layer (30a), a
In addition, the present invention, the base preparation step of preparing a base (10a) having a flat surface; A composite forming step of depositing or transferring polymer and graphene on a flat surface of the
Here, in the complex forming step, the
In the complex forming step, the
In addition, the present invention, in the graphene-based device, the substrate (10b); A
Here, the
In addition, the
In addition, the
In addition, the
In addition, the present invention, in the graphene-based device manufacturing method, by depositing or transferring a polymer (graphene) and graphene (graphene) on the substrate (10b) to be laminated to the polymer layer (30b) and the graphene layer (20b) Forming a composite layer; A pattern forming step of forming a pattern with a photoresist on the upper surface of the structure formed through the composite layer forming step; And etching the
In the complex forming step, the
In addition, an electrode layer forming step of forming an electrode layer (40a) by depositing or transferring a conductive material including the portion of the graphene-
Although graphene has a wide range of applications due to its excellent electromagnetic, mechanical, and chemical properties, it is susceptible to damage due to contact, bending and contact during manufacturing, transfer, due to the single crystal organic thin film structure, and its sensitivity even by a small amount of contamination. Is significantly lowered, and due to a naturally occurring defect (defect) over time, due to the sharply shortened life, there was a difficulty in commercialization.
According to the present invention having the above-described configuration, by the simple structure in which the polymer is bonded to one or both sides of the graphene, the void generated by the rupture of the graphene is filled with the conductive polymer to reduce the electromagnetic characteristics. The graphene may be exposed to an external pollutant such as a photoresist or oxygen in the air, thereby minimizing its performance and shortening its lifespan.
In addition, it is possible to form a protective film of the graphene by the hardness of the polymer, transfer the graphene to a specified position, or measure the mechanical properties, temperature, etc. of the graphene in a state in which the tip directly contacted the graphene. In this process, the graphene can be easily torn or broken by contact with the tip.
Conventionally, in order to solve the problem that the graphene is easily torn or ruptured by the contact with the tip, an electrode or the like is formed on the graphene, but a deposition process of a metal layer for forming the electrode, etc. should be additionally performed. The contact resistance caused by the difference in the work function (graph function) of the graphene was generated, according to an embodiment of the present invention can also solve this problem.
On the other hand, if the graphene is located close to the substrate surface, electrons passing through the graphene, which is a 2D conductor, are scattered by irregularities (molecules, atomic units) on the substrate surface. In order to compensate for this, a method of securing a distance between the graphene and the substrate by etching a part of the substrate was used, but there was a problem that the process was difficult and cumbersome.
According to the embodiment of the present invention, the simple configuration of additionally forming a non-conductive polymer layer between the substrate and the graphene reduces the influence from the substrate such that the graphene is suspended above the substrate, thereby reducing the electron scattering effect. By compensating for the degradation of the electromagnetic transfer characteristics of the graphene, it is possible to prevent the loss of power or the electrical signal through the substrate.
By the structure of the polymer graphene (Graphene) composite having a polymer layer formed on one side or both sides of the graphene as described above, physical and chemical generated in the process of manufacturing and transferring the graphene or graphene-based device It can stably prevent and protect damage and contamination by factors, making it possible to stably utilize the excellent electrical, optical and mechanical properties of graphene.
As a result, it is possible to contribute to the performance improvement and productivity of the resonator, filter, oscillator, sensor device for chemistry, bio, mass measurement, etc. which are essential for communication elements, and the compatibility of graphene. To ensure that
Figure 1-Graph showing the change in electrical properties of graphene with exposure to oxygen
Figure 2-Graph showing the change in the reaction rate of graphene as exposed to oxygen
Figure 3-Partial photo of the graphene resonator contaminated with photoresist
Figure 4-Another photograph of a graphene resonator contaminated with photoresist
5-a perspective view showing a graphene-polymer composite according to a first embodiment of the present invention
6 to 5 are schematic diagrams for explaining the structure of FIG.
7-a perspective view of a graphene-polymer composite according to a second embodiment of the present invention
8 to 7 are schematic diagrams for explaining the structure of FIG.
9-5 is a conceptual diagram illustrating an example of a process of manufacturing FIG.
10-7 is a conceptual diagram illustrating an example of a process of manufacturing FIG.
11-a perspective view of a graphene-polymer composite device according to a first embodiment of the present invention
12-a perspective view of a graphene-polymer composite device according to a second embodiment of the present invention
13 to 11 is a conceptual diagram showing an example of the process of manufacturing the graphene-polymer composite shown in FIG.
14 to 12 are conceptual views illustrating an example of a process of manufacturing the graphene-polymer composite shown in FIGS.
15 is a conceptual diagram illustrating an example of a process of forming an electrode;
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.
FIG. 5 is a perspective view illustrating a graphene-polymer composite according to the first embodiment of the present invention, and FIG. 6 is a view for explaining the structure of the graphene-polymer composite according to the first embodiment shown in FIG. It is a schematic diagram.
5 and 6, the graphene-
The
The polymer coating layer (30a), the material, the thickness is determined so as to form a flexible film form flexible together in the state bonded to the graphene (20a), flexible film form with the graphene (20a) It can be variously changed in consideration of the conditions and the like of the use of the graphene-
Generally, a polymer is a polymer which is a unit of molecular masses called a monomer, which is continuously polymerized to form one large molecule. A combination of various monomers includes various components including vinyl chloride, nylon, The composition is present.
As the material of the
When the
When the
In applying the conductive polymer material, the
The graphene-
In forming the
7 is a perspective view illustrating a graphene-
7, 8, the graphene-
The graphene-
Since the plurality of
In addition, since one surface is insulated from the
The graphene-
9 (a) to 9 (f) are conceptual views illustrating an example of a process of manufacturing the graphene-polymer composite according to the first embodiment of the present invention shown in FIG. 5, and FIGS. f) is a conceptual diagram showing an example of a process for producing a graphene-polymer composite according to a second embodiment of the present invention shown in FIG.
9 and 10, the graphene-
The base preparation step is a process of preparing a
The complex forming step is a process of depositing or transferring a polymer and graphene on the flat surface of the
In forming the
According to the order and the number of times to form the
In addition, in the case of manufacturing a graphene-polymer composite having a specific shape or arrangement other than a simple large-area flat surface, the graphene-polymer composite is etched and processed into a designated shape by a lithography process after the complex forming step. The composite processing step may be additionally roughened (see 'Pattern forming step' and 'Composite layer processing step' described below).
The base etching step, by wet-etching (wet-etching) using an etching solution (etchant), by etching part or all of the contact with the
By etching the
11 and 12 are perspective views showing graphene-polymer composite devices according to the first and second embodiments of the present invention, respectively.
11 and 12, a graphene-based device according to an embodiment of the present invention includes a
Referring to FIG. 11, in the graphene-based device according to the first embodiment of the present invention, a
In graphene-based devices, when graphene is located close to the substrate surface, electrons passing through graphene, a 2D conductor, are scattered by irregularities (molecules, atomic units) on the substrate surface, and its electromagnetic transfer characteristics. In order to compensate for this, in the past, a method of securing a distance between the graphene and the substrate by etching a part of the substrate was used, but the process was difficult and cumbersome.
According to the graphene-based device according to the first embodiment of the present invention, the graphene is formed by a simple configuration in which the
Referring to FIG. 12, in the graphene-based device according to the second embodiment of the present invention, the graphene-
Since the plurality of graphene layers 20b are electromagnetically interconnected by the
In implementing the structure in which the
Further, by forming the
The graphene-based device according to the embodiment of the present invention also, like the graphene-
In addition, when the
13A to 13F are conceptual views illustrating an example of a process of manufacturing the graphene-polymer composite device according to the first embodiment of the present invention shown in FIG. 11, and FIG. (F) is a conceptual diagram showing an example of a process of manufacturing a graphene-polymer composite device according to the second embodiment of the present invention shown in Figure 12, Figures 15 (a) to (d) is 4 is a conceptual diagram illustrating an example of a process of forming an electrode of the graphene-polymer composite device according to the first and second embodiments of the present invention.
Referring to Figures 13 to 15, the graphene-based device according to an embodiment of the present invention, may be manufactured through the composite layer forming step, pattern forming step, composite layer processing step sequentially.
The composite layer forming step is a process of depositing or transferring a polymer and graphene on the
In forming the
According to the order and the number of times the
Lithography is a process of forming a pattern of a specified shape on a desired surface of a substrate, and employing various optical technology-based processing techniques such as photolithography using a mask and electron beam lithography without a mask. it means.
The pattern forming step is a process of forming a designated pattern with a photoresist on the top surface of the graphene structure generated through the composite layer forming step, and applying a photoresist to the top surface of the graphene structure. A photosensitive agent coating step, an exposure step of irradiating light onto the photoresist by projecting a mask or a reticle using an exposure apparatus, and a developing step of selectively removing the exposed part or the non-exposed part with a developer to form a desired pattern with the photoresist. (See FIG. 13 (d) and FIG. 14 (f).)
In the composite layer processing step, the
The graphene-based device according to the first and second embodiments of the present invention has a structure in which a pair of
The electrode layer forming step may be performed by depositing or transferring a conductive material constituting the
The electrode forming step is a process of etching the
The present invention has been described with reference to preferred embodiments of the present invention, but the present invention is not limited to these embodiments, and the claims and detailed description of the present invention together with the embodiments in which the above embodiments are simply combined with existing known technologies. In the present invention, it can be seen that the technology that can be modified and used by those skilled in the art are naturally included in the technical scope of the present invention.
10a:
20: graphene-
20b:
30b: polymer layer 31: conductive polymer layer
33
40a: electrode layer PR: photoresist pattern
Claims (16)
A polymer coating layer 30a formed by coupling a polymer to one or both surfaces of the graphene 20a and forming a flexible flexible film together with the graphene layer 20b;
Graphene-polymer composite comprising a.
The polymer coating layer 30,
Graphene-polymer composite consisting of the non-conductive material capable of insulating the graphene (20a) from the outside.
The polymer coating layer 30a,
Graphene composed of a conductive polymer capable of maintaining and supplementing the electromagnetic properties of the graphene 20a by a graphene connection portion continuously connected to one or both surfaces of the graphene 20a or inserted into the graphene layer 20b. Device with a pin-polymer composite.
The graphene 20a and the polymer coating layer 30a,
A graphene-polymer composite in which a plurality of layers are alternately stacked.
The polymer coating layer 30a,
A conductive polymer layer 31 composed of a conductive polymer; And
A nonconductive polymer layer 33 formed to be spaced apart from the conductive polymer layer 31 with the graphene 20a therebetween and made of a nonconductive polymer;
Graphene-polymer composite comprising a.
A composite forming step of depositing or transferring polymer and graphene on a flat surface of the base 10a to form a polymer coating layer 30a and graphene 20a stacked thereon; And
A base etching step of etching the base (10a) to form a graphene-polymer composite (20) in the form of a film in which the polymer coating layer (30a) is bonded to the graphene (20a);
Method for producing a graphene-polymer composite comprising a.
The complex forming step,
Method for producing a graphene-polymer composite to form the polymer coating layer (30a) on one side or both sides of the graphene (20a).
The complex forming step,
The graphene (20a) and the method for producing a graphene-polymer composite to form a plurality of alternating layers of the polymer coating layer (30a) alternately.
A substrate 10b;
A graphene layer 20b formed by depositing or transferring graphene on the substrate 10b; And
A polymer layer 30b formed by bonding a polymer between the substrate 10b and the graphene layer 20b and / or on the graphene layer 20b;
Device comprising a graphene-polymer composite comprising a.
The polymer layer 30b,
Device having a graphene-polymer composite composed of a non-conductive material capable of insulating between the graphene layer (20b) and the substrate (10b).
The polymer layer 30b,
Graphene composed of a conductive polymer capable of maintaining and supplementing the electromagnetic properties of the graphene layer 20b by a graphene connection portion continuously coupled to one or both surfaces of the graphene layer 20b or inserted into the graphene layer 20b. Device with a pin-polymer composite.
The graphene layer 20b and the polymer layer 30b,
A device having a graphene-polymer composite formed of a plurality of alternating overlaps.
The polymer layer 30b,
A conductive polymer layer 31 composed of a conductive polymer; And
A nonconductive polymer layer 33 formed spaced apart from the conductive polymer layer 31 with the graphene layer 20b therebetween and made of a conductive polymer;
Device comprising a graphene-polymer composite comprising a.
A composite layer forming step of depositing or transferring polymer and graphene on the substrate 10b to stack the polymer layer 30b and the graphene layer 20b;
A pattern forming step of forming a pattern with a photoresist on the upper surface of the structure formed through the composite layer forming step; And
A composite layer processing step of etching the polymer layer 30b and the graphene layer 20b in a shape corresponding to the photoresist pattern to form a graphene-polymer composite 20 on the substrate 10b in a designated shape;
Method for producing a device having a graphene-polymer composite comprising a.
The complex forming step,
Method for manufacturing a device with a graphene-polymer composite to form the polymer coating layer (30a) on one side or both sides of the graphene layer (20b).
An electrode layer forming step of forming an electrode layer 40a by depositing or transferring a conductive material, including a portion where the graphene-polymer composite 20 is formed on the upper surface of the structure formed through the composite layer processing step; And
A part is located on the top surface of the graphene-polymer composite 20, and the other part is etched to the electrode layer 40a in a specified shape located on the substrate 10b, the graphene-polymer composite 20 An electrode forming step of forming a pair of electrodes 40 electrically connected by each other;
Graphene-polymer composite further comprising a device manufacturing method comprising a.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435036A (en) * | 2013-08-21 | 2013-12-11 | 南开大学 | Selective fixed-point transfer method for graphene |
| CN104465328A (en) * | 2014-12-11 | 2015-03-25 | 中国科学院微电子研究所 | Method for controllably removing residual optical photoresist in graphene-metal contact region |
| CN104977347A (en) * | 2014-04-04 | 2015-10-14 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene-based chemical or biological sensor and manufacture method thereof |
| KR20160136910A (en) * | 2015-05-21 | 2016-11-30 | 삼성전자주식회사 | Flexible device having flexible interconnect using 2 dimensional materials |
| US10074737B2 (en) | 2015-04-30 | 2018-09-11 | Samsung Electronics Co., Ltd. | Flexible device including two-dimensional material and method of manufacturing the same |
| CN109741859A (en) * | 2019-02-28 | 2019-05-10 | 业成科技（成都）有限公司 | Transparent conductive film substrate and preparation method thereof |
-
2011
- 2011-10-11 KR KR1020110103590A patent/KR20130039119A/en not_active Application Discontinuation
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435036A (en) * | 2013-08-21 | 2013-12-11 | 南开大学 | Selective fixed-point transfer method for graphene |
| CN103435036B (en) * | 2013-08-21 | 2015-02-04 | 南开大学 | Selective fixed-point transfer method for graphene |
| CN104977347A (en) * | 2014-04-04 | 2015-10-14 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene-based chemical or biological sensor and manufacture method thereof |
| CN104465328A (en) * | 2014-12-11 | 2015-03-25 | 中国科学院微电子研究所 | Method for controllably removing residual optical photoresist in graphene-metal contact region |
| US10074737B2 (en) | 2015-04-30 | 2018-09-11 | Samsung Electronics Co., Ltd. | Flexible device including two-dimensional material and method of manufacturing the same |
| KR20160136910A (en) * | 2015-05-21 | 2016-11-30 | 삼성전자주식회사 | Flexible device having flexible interconnect using 2 dimensional materials |
| US10134676B2 (en) | 2015-05-21 | 2018-11-20 | Samsung Electronics Co., Ltd. | Flexible device having flexible interconnect layer using two-dimensional materials |
| CN109741859A (en) * | 2019-02-28 | 2019-05-10 | 业成科技（成都）有限公司 | Transparent conductive film substrate and preparation method thereof |
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