KR101736972B1 - Structure of graphene and inorganic material, and electrical device comprising the same - Google Patents
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Abstract
Graphen and an inorganic material-containing structure are provided. By stacking an inorganic material in parallel with the (0001) plane of graphene, the charge transfer between the graphene and the inorganic material is smooth, and the electrical characteristics of the device can be improved.
Description
The present invention relates to a laminated structure of graphene and an inorganic material and an electric device having the laminated structure of the graphene and the inorganic material, .
Generally, graphite is a structure in which a plate-like two-dimensional graphene sheet in which carbon atoms are connected in a hexagonal shape is laminated. Recently, graphenes were peeled off from the graphite layer or the aqueous layer, and the characteristics of the sheet were investigated. As a result, very useful properties different from those of conventional materials were found.
In the case of the graphen, the electrical characteristics change depending on the crystal orientation of the graphene of a given thickness, so that electrical characteristics can be expressed in the selection direction. The characteristics of such graphenes can be applied to carbon-based electric devices or carbon-based electromagnetic devices in the future.
However, when a device is manufactured by laminating a material to the graphene, the interface structure between the graphene and the stacked material greatly affects the characteristics of the device. Also, when charge transfer between the graphene and the deposited material is accompanied, the interface defect acts as interfacial resistance between the graphene and the deposited material. Therefore, in order to effectively utilize the excellent conductivity characteristics of graphene, it is necessary to develop a structure in which the interface defects are minimized.
Accordingly, a technical problem to be solved in one embodiment is to provide a laminated structure of graphene and an inorganic material which is minimized in interfacial defects and has a reduced interfacial resistance and is excellent in economy.
Another technical problem to be solved in one embodiment is to provide various electric elements employing the above laminated structure.
According to one aspect, the graphene and inorganic-
Graphene; And an inorganic material having a crystal system,
At least one crystal plane of the inorganic material may be oriented parallel to the (0001) reference plane of the graphene.
According to one embodiment, the structure may further comprise a substrate on the graphene.
According to one embodiment, the crystal plane of the inorganic material may have a hexagonal, pentagonal, or rectangular atomic arrangement.
According to one embodiment, the crystal system of the inorganic material may be a cubic system, a tetragonal system, a hexagonal system, an orthorhomic system, a trigonal system, a monoclinic system, system, or a triclinic system.
According to one embodiment, the inorganic material is Ge, Si, Sn, SiC, AlAs, AlP, AlSb, Al 2 O 3, BP, GaAs, GaN, GaP, GaSb, GaNO, InN, InNO, InAs, InP, InSb, CdSe, CdTe, ZnO, ZnS, ZnSe, ZnTe, PbS, PbTe, AlN, BN, BNO, MgS, MgSe, or MgTe.
According to one embodiment, the inorganic material may be ZnO, GaN, Al 2 O 3, or a combination thereof.
According to one embodiment, the length between the two atoms located at
According to one embodiment, the minor axis of the hexagonal atomic arrangement of the inorganic material and the major axis of the graphene may be oriented in the same direction.
According to one embodiment, the inorganic material may be deposited on the graphene in an epitaxial form.
According to one embodiment, the graphene may have an area of at least 1 mm 2 in sheet form.
According to one aspect, the structure can be employed in various electric devices.
The structure according to one aspect,
A substrate having a surface; 1. An inorganic material having a crystal system, wherein at least one crystal plane of the crystal system is oriented parallel to a surface of the substrate; And graphen located between the surface of the substrate and the inorganic material.
Since the graphenes and the inorganic material-containing structure minimize the interfacial defects and reduce the interfacial resistance, it is possible to increase the charge transfer efficiency and use the graphene which is excellent in economical efficiency. Therefore, various electric devices such as LED, Power devices.
Fig. 1 is a schematic view showing the number of planes of the hexagonal system.
2A and 2B are schematic views showing the interface orientation state of graphene and an inorganic material.
3A and 3B are schematic diagrams showing the axial lengths of the hexagonal units of graphene and inorganic materials.
Fig. 4 is a schematic view showing an atomic state in which graphene and an inorganic material are stacked. Fig.
5 is a SEM photograph showing the nanorods of ZnO grown vertically on the surface of the graphene obtained in Example 1. Fig.
6 shows the result of TEM analysis of the interface between the ZnO nanorod and the graphene obtained in Example 1. FIG.
Fig. 7 shows the results of evaluating the characteristics of the nano-power device obtained in Example 2
According to one aspect of the present invention, graphene and an inorganic material-containing structure are graphenes; And an inorganic material having a crystal system, wherein at least one crystal plane of the inorganic material is oriented parallel to the (0001) reference plane of the graphene.
As used herein, the term "graphene" refers to a molecule in which a plurality of carbon atoms are linked together by a covalent bond to form a polycyclic aromatic molecule, wherein the carbon atoms linked by the covalent bond form a 6-membered ring as the basic repeat unit, It is also possible to further include a 5-membered ring and / or a 7-membered ring. As a result, the graphene appears as a single layer of covalently bonded carbon atoms (usually sp 2 bonds). The graphene may be composed of a single layer, but they may be stacked to form a plurality of layers, and a thickness of up to 100 nm may be formed.
The basic unit of the graphene is a six-membered ring having six carbon atoms, and the six-membered ring is connected to each other in a plate form, and then has a laminated structure. Since the six-membered ring structure is similar to a hexagonal prism structure, the same surface index and orientation index can be applied. As shown in FIG. 1, the unit table of the hexagonal column has a 1 , a 2 , a 3 axes intersecting at 120 degrees in the same plane and a c axis perpendicular to the plane. Thus, the surface and orientation indices have four indices corresponding to these four axes, and can be defined, for example, by the Miller index. For example, the reference plane of the six-membered ring of the graphen which is a plate-like two-dimensional structure is a shadow-treated plane in FIG. 1 and has an index of (0001).
Similarly, in the case of an inorganic material such as a metal or a metal oxide, it is possible to have various crystal systems, for example, a cubic system, a tetragonal system, a hexagonal system, an orthorhomic system ), A trigonal system, a monoclinic system, or a triclinic system. The crystal system may include crystal faces defined by the Miller index. The crystal plane of the inorganic material may have various atomic arrangements of hexagon, pentagon, or quadrangle as a unit structure.
In one embodiment, at least one of the crystal planes of the inorganic material having a variety of crystal systems can be oriented parallel to the (0001) reference plane of the graphene so that a given layer of inorganic material is substantially parallel to the (0001) plane of the graphene Lt; / RTI >
Examples of such a structure are shown in Figs. 2A and 2B. 2A shows an example in which a sheet-shaped inorganic material is laminated on a graphene, and it can be seen that the inorganic material is arranged parallel to the (0001) plane which is the reference plane of the graphene on the interface. In the case of FIG. 2B, which is stacked in the form of a rod, it can be seen that the interface of the inorganic material is grown parallel to the reference plane (0001) plane of the graphene on the interface. In one embodiment, the graphene may have an epitaxial structure, so that the crystal structure of the inorganic rod and the graphene may have substantially the same or similar orientation. 2A and 2B, an inorganic material can be formed (grown) in such a manner that a single crystal plane of the inorganic material is directly oriented parallel to the (0001) plane of the graphene.
In order to orient the inorganic substance such that a predetermined crystal plane is parallel to the (0001) plane of the graphene, the crystal structure of the gummy substance may have a hexagonal, pentagonal, or rectangular atomic arrangement as a unit structure.
Of the inorganic non-limiting examples include Ge, Si, Sn, SiC, AlAs, AlP, AlSb, Al 2 O 3, BN, BP, GaAs, GaN, GaP, GaSb, GaNO, InN, InNO, InAs, InP, InSb, CdS , CdSe, CdTe, ZnO, ZnS, ZnSe, ZnTe, PbS, PbTe, AlN, BNO, MgS, MgSe, and MgTe.
As described above, the inorganic material is oriented parallel to the reference plane on the c-axis of the graphene, and in such an orientation, the inorganic material is grown, for example, in an epitaxy structure. The epitaxial structure refers to a structure in which the long axis of the graphene and the short axis of the inorganic material are arranged so as to be adjacent to each other, and the definitions of the long axis of the graphene and the short axis of the inorganic material are shown in FIGS. 3A and 3B. Figure 3a shows a six-membered ring unit of graphene, wherein the length between C1 and C4 is defined as the long axis of the graphene, which corresponds roughly to 2.852 angstroms. FIG. 3B shows crystal structure units of ZnO, for example, among inorganic substances, wherein the length between the oxygen atoms located at
Therefore, when the graphene and the inorganic material are stacked, the short axis of the inorganic material is aligned so as to be adjacent to the long axis of the graphene, and thus the inorganic material has a plate-like structure parallel to the graphene having a plate- .
The difference in length between the graphene and the short axis of the long axis and the short axis of the inorganic material may be in the range of -20% to 20% based on the long axis length of the graphene. Within this range, it may be possible to orient the long axis of the graphen and the short axis of the inorganic substance to be aligned adjacent to each other.
An example of such a lamination is shown in Fig. In FIG. 4, the circle indicates a portion where the long axis of the graphene aligns with the short axis of the inorganic material, and the parallel orientation of the inorganic material can be achieved according to the interaction. As shown in Fig. 4, it is not necessary that all the long axes of the graphenes align with the short axis of the inorganic matter, or all the short axes of the inorganic matter must align with the long axis of the graphene, It is possible.
According to the structure in which the graphenes and the inorganic materials are parallel to each other, the possibility that the orientation properties of the graphenes and the inorganic materials have a certain direction becomes high, and thus the defects existing between the graphenes and the inorganic material interface can be minimized. That is, when an inorganic material is laminated on the graphene, the possibility that the predetermined crystal face of the inorganic material grows in a direction perpendicular or oblique to each other is not parallel to the (0001) plane of the reference plane of the graphene, .
In this structure, the inorganic material can be laminated in the range of from 1 atomic layer to 10 cm. The structure can be formed in the form of a rod, a wire, a thin film, and a bulk, and examples thereof include a nano rod, Nano thin film, and bulk.
As the interface defects are minimized, when the charge transfer occurs along the interface, the charge transfer efficiency at the interface increases and the interface resistance decreases accordingly. The reduced interfacial resistance increases the efficiency of various electrical devices such as light emitting diodes (LEDs), solar cells, and power devices employing the graphene and the inorganic material-containing structure.
The graphene and the inorganic material-containing structure can be formed on various substrates, and a metal substrate, a non-metal substrate, or a laminated substrate thereof can be used. The non-metallic substrate may be an inorganic substrate, for example, an Si substrate, a glass substrate, a GaN substrate, a silica substrate, an ITO substrate, or the like, which may be laminated and used as a silicon layer / silica layer. As the non-metallic substrate, an organic substrate may be a plastic substrate or the like. The metal substrate may be at least one selected from the group consisting of a nickel substrate, a copper substrate, and a tungsten substrate.
The above-described graphene and inorganic material-containing structures can be prepared as follows.
First, graphene can be prepared according to a conventionally known method, for example, the method described in Korean Patent Publication No. 2009-0043418. The graphene may have an area of 1 mm 2 or more, for example, an area of 1 mm 2 to 100 m 2 or an area of 1 mm 2 to 25 m 2 . Also, the graphenes are present in an area of 99% to 99.999% per 1 mm 2 of unit area, for example, graphenes exist in an area of 99% or more per 1 mm 2 of unit area. In such an existing range, the graphenes can exist homogeneously, and thus can exhibit homogeneous electrical characteristics and the like.
The graphen may be immersed in a solution containing an inorganic substance to perform solution growth of the inorganic substance on the graphene. As a result of such in-solution growth, the inorganic material can be grown by aligning a single crystal plane of the inorganic material parallel to the (0001) plane of the reference plane of the graphene.
The solvent which can be used in the inorganic substance-containing solution is not particularly limited as long as it can disperse or dissolve the inorganic substance. Ethanol, methanol, acetone, water and the like can be used and the concentration thereof is in the range of 0.001 M to 1.0 M Lt; / RTI >
The growth of the inorganic material can be carried out at a temperature ranging from 50 to 100 DEG C for 10 minutes to 4 hours.
The graphene may be formed on a variety of substrates as described above, and then an inorganic material may be laminated thereon.
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
Example 1
In this study, a 0.01 M solution of Zinc acetate [(C 2 H 3 O 2 ) 2 Zn] powder was dissolved in ethanol, and then graphene (2 cm in length, 2 cm in width) was spin coated or dip- A ZnO seed layer is formed on a coated plastic substrate (PET) substrate. The graphene-coated plastic substrate on which seeds are formed is immersed in a solution for ZnO growth to form ZnO nanorods.
Figure 5 shows the nanorods of ZnO grown vertically on the surface of the graphene.
The results of TEM analysis of the interface between the ZnO nano-rod and graphene are shown in Fig. From FIG. 6, it can be seen that the ZnO (0001) plane and the (0001) plane of the graphene are aligned parallel to each other at the interface. 6, the left drawing shows that the graphene crystal surface on the Si substrate and the atomic crystal surface of the ZnO nano-rods are sequentially stacked, and the portion indicated by the rectangle shows a part of the stacked product in order to more accurately analyze the interface between the graphene and the ZnO nano- ≪ / RTI > to TEM analysis; The upper part of the central drawing shows ZnO nanorod atomic crystal faces, and the lower part shows graphene atomic crystal faces. The right drawing shows the electron diffraction pattern, the upper drawing shows the electron diffraction pattern of the ZnO nanorod, and the lower drawing shows the electron diffraction pattern of the graphene, which are sequentially and regularly stacked.
Example 2
ZnO nanorods are grown using the same process shown in Example 1 using a substrate on which ITO is coated with a thickness of about 100 nm on a PET substrate. The length and diameter of the grown ZnO nanorods are the same as those of ZnO nanorods grown on a PET substrate coated with graphene. The ITO substrate has a sheet resistance of about 70 ohm / sq and the graphene substrate has a sheet resistance of about 200 ohm / sq. A nano-power device is fabricated using each substrate. The method of fabricating the nano-power device is as follows. A sample on which ZnO nanorods are grown on a PET substrate coated with ITO is used as a lower plate, and a substrate on which ITO is coated is used as a top plate on a PET substrate. The obtained upper and lower plates are stacked to form a nano-power device, and the current generated in the nano-power device is measured by connecting ITO electrodes of the upper and lower plates. A nano-power device using graphene is also manufactured by the same method as described above. A sample in which ZnO nano-rods are grown on a graphene-coated PET substrate is used as a lower plate, and a substrate coated with graphene on a PET substrate is used as a top plate do. The obtained upper and lower plates are stacked to form a nanopower device, and the current generated in the nanopower device is measured by connecting the graphenes of the upper and lower plates to the electrodes. The left graph of FIG. 7 shows the results of an ITO coated nanofiber device and the right graph shows the results of a graphene coated nanofiber device. When pressed, the nano-power device with a force of 0.9 kgf can be seen that about 1 (approximately 2 (current occurs in A / cm 2 for the generation, and the graphene current A / cm 2 for ITO. Graphene (0001m / sq.), The electric power generated is doubled even though the sheet resistance is about three times higher than that of ITO (70 ohm / sq.). This is because the graphene (0001) (0001) planes are stacked in parallel, which means that the interface defects are reduced and the charge movement is efficiently performed.
Claims (18)
1. An inorganic material having a crystal system, wherein at least one crystal plane of the crystal system is oriented parallel to a surface of the substrate; And
And graphen located between the surface of the substrate and the inorganic material,
Wherein at least one crystal plane of the inorganic material is oriented parallel to the (0001) reference plane of the graphene.
Wherein the crystal plane of the inorganic material has an atomic arrangement of hexagonal, pentagonal, and quadrangular.
The crystal of the inorganic material may be selected from the group consisting of a cubic system, a tetragonal system, a hexagonal system, an orthorhomic system, a trigonal system, a monoclinic system, gt; and / or < / RTI > the triclinic system.
Wherein the inorganic Ge, Si, Sn, SiC, AlAs, AlP, AlSb, Al 2 O 3, BP, GaAs, GaN, GaP, GaSb, GaNO, InN, InNO, InAs, InP, InSb, CdS, CdSe, CdTe, Wherein the graphene is at least one selected from the group consisting of ZnO, ZnS, ZnSe, ZnTe, PbS, PbTe, AlN, BN, BNO, MgS, MgSe, and MgTe.
The inorganic material is ZnO, GaN, Al 2 O 3 or the graphene and mineral-containing structure that is water a combination of the two.
The length between the two atoms located at positions 1 and 3 in the hexagonal atomic arrangement of the inorganic material ranges from -20% to 20% of the length between the carbon atoms located at positions 1 and 4 of the hexagonal unit constituting the graphene ≪ / RTI >
Wherein the minor axis of the hexagonal atomic arrangement of the inorganic material and the major axis of the graphenes are oriented in the same direction.
Wherein the inorganic material is laminated on the graphene in an epitaxial form.
Wherein the graphene has an area of at least 1 mm 2 in sheet form.
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| GB201211038D0 (en) | 2012-06-21 | 2012-08-01 | Norwegian Univ Sci & Tech Ntnu | Solar cells |
| GB201311101D0 (en) * | 2013-06-21 | 2013-08-07 | Norwegian Univ Sci & Tech Ntnu | Semiconducting Films |
| KR101517551B1 (en) * | 2013-11-14 | 2015-05-06 | 포항공과대학교 산학협력단 | Method for manufacturing light emitting device and light emitting device manufactured thereby |
| TWI772266B (en) | 2015-07-13 | 2022-08-01 | 挪威商卡亞奈米公司 | Light emitting diode device and photodetector device |
| WO2017021380A1 (en) | 2015-07-31 | 2017-02-09 | Crayonano As | Process for growing nanowires or nanopyramids on graphitic substrates |
| GB201705755D0 (en) | 2017-04-10 | 2017-05-24 | Norwegian Univ Of Science And Tech (Ntnu) | Nanostructure |
| KR102557754B1 (en) * | 2018-08-03 | 2023-07-20 | 삼성디스플레이 주식회사 | Light emitting element, Method of manufacturing the same and Display device comprising the Light emitting element |
| CN111604064A (en) * | 2020-05-12 | 2020-09-01 | 河南大学 | Pollution-free hydrothermal synthesis method of zinc selenide microspheres and synthesis method of composite material thereof |
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| JP2006216874A (en) | 2005-02-07 | 2006-08-17 | Toshiba Ceramics Co Ltd | Hexagonal boron nitride single crystal substrate and its manufacturing method |
| US20080261116A1 (en) | 2007-04-23 | 2008-10-23 | Burton David J | Method of depositing silicon on carbon materials and forming an anode for use in lithium ion batteries |
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| JP2006216874A (en) | 2005-02-07 | 2006-08-17 | Toshiba Ceramics Co Ltd | Hexagonal boron nitride single crystal substrate and its manufacturing method |
| US20080261116A1 (en) | 2007-04-23 | 2008-10-23 | Burton David J | Method of depositing silicon on carbon materials and forming an anode for use in lithium ion batteries |
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