CN113716555B - Structural design of two-dimensional semiconductor material based on graphene - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 84
- 239000000463 material Substances 0.000 title claims abstract description 28
- 238000013461 design Methods 0.000 title claims abstract description 27
- 239000004065 semiconductor Substances 0.000 title claims abstract description 24
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 239000002356 single layer Substances 0.000 claims description 18
- 238000001179 sorption measurement Methods 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 12
- 125000004429 atom Chemical group 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 238000009396 hybridization Methods 0.000 claims description 9
- 230000002687 intercalation Effects 0.000 claims description 9
- 238000009830 intercalation Methods 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 8
- 230000033228 biological regulation Effects 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 230000005684 electric field Effects 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 230000010287 polarization Effects 0.000 claims description 6
- 229920000997 Graphane Polymers 0.000 claims description 5
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- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004299 exfoliation Methods 0.000 description 2
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Abstract
The invention discloses a structural design of a two-dimensional semiconductor material based on graphene, which comprises the following steps: the invention has the characteristics of simple structure, convenient operation, easy processing and controllable energy gap, can be applied to photovoltaic, energy sources and microelectronic devices, and has very wide application prospect.
Description
Technical Field
The invention relates to the field of dielectric material application, in particular to a structural design of a two-dimensional semiconductor material based on graphene.
Background
Graphene is a hexagonal honeycomb-like two-dimensional material composed of a single layer of carbon atoms. The physicist Andre Geim and Konstantin Novoselov, university of manchester, united kingdom, successfully exfoliated graphene from graphite in 2004. From this point forward, the study of graphene reached an unprecedented climax. The birth of graphene is undoubtedly an important milestone of condensed physics. Graphene has many excellent properties including ultra-high electrical conductivity, excellent thermal conductivity, superhydrophobicity, and mechanical properties due to its special structure. These properties make graphene a promising new generation of electronic devices. With the continuous deep research of researchers on graphene, more and more fields have opened the door to graphene. However, the pure graphene has no energy gap, which limits the application of the pure graphene in the field of semiconductor electronics. Semiconductor materials currently have a wide market value, who dominates the semiconductor technology, and who can go on the front of technology. On this basis, researchers are trying to change a semi-metallic material, which is graphene, having excellent properties into a semiconductor material that can be used for applications.
The valence band and conduction band of the intrinsic graphene are in conical contact in the center of the Brillouin zone, and the intrinsic graphene has semi-metallic property. There are many methods for exfoliation of graphene from graphite, including micro-mechanical exfoliation, chemical Vapor Deposition (CVD), epitaxy, epitaxial growth of silicon carbide surfaces, and reduction of graphene oxide. Graphene itself is zero band gap, if graphene is to be applied to semiconductor materials, a band gap of a certain size must be opened for the graphene, and the currently proposed method for opening the band gap of graphene mainly comprises the following steps:
1. breaking the lattice or chemical structure of graphene opens the bandgap. The energy band structure of graphene is mainly due to orbital hybridization of the free pi bond and sp 2. When the symmetrical structure of the graphene is broken, the chemical structure is broken, the energy band structure is changed, and then the graphene energy band is opened;
2. the graphene energy band is opened by doping atoms. Doping other atoms to cause orbital hybridization destruction of carbon-carbon bonds; a new chemical bond is formed. The energy band structure of the graphene can be changed as well;
3. the graphene band gap is opened by the adsorbed atoms. Hydrogenated graphene is a hybrid in which a sp3 orbital is formed by chemisorption to bond with a carbon atom. Saturated hydrogenated graphene has a band gap of 3.4eV by calculation;
4. the graphene band gap is opened by introducing periodic defects. Due to the loss of the periodic structure, the sp2 orbital hybridization between carbon and carbon is broken. The energy band structure of the graphene is changed, so that the energy gap is opened;
5. applying strain causes the graphene bandgap to open. By increasing the strain, the space inversion symmetry structure of the graphene is broken; adding strain to the different axes lengthens the carbon-carbon bonds. Thereby forming a Landolt energy level to open the band gap;
6. the application of the external field causes the energy bands of the graphene. Applying an external field to break the space or time inversion symmetry of the graphene structure, thereby opening the band gap;
7. opening the bandgap by increasing the substrate; after the substrate is added, the contact surface of the substrate and the graphene has energy difference, and a potential is formed, and the potential can change the energy band structure of the graphene.
Disclosure of Invention
The invention aims to solve the problems, and provides a structure and a method for opening a graphene energy gap and enabling the graphene energy gap to be a two-dimensional semiconductor with adjustable energy gap.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
a structural design of a two-dimensional semiconductor material based on graphene implementation, the design comprising the steps of:
step one, selecting a substrate
In order to meet the design requirements of low dimension and small dimension of the nano multifunctional semiconductor device, graphene oxide with a two-dimensional monolayer is selected as a base material, but the graphene oxide has no energy gap, and Fe atoms are selected as an intercalation material;
step two, bonding design:
c in the graphene oxide forms a hexagonal honeycomb structure, and C in a plane is covalently bonded through sp2 hybridization; adjacent pz orbit electrons are bonded through a large pi bond, after graphene is oxidized, the large pi bond is destroyed, O is bonded with C at the upper and lower positions of C atoms, and as with hydrogenated graphene, O and C form chemical adsorption, C atoms are bonded through sp3 orbit hybridization, so that a large fold exists on the plane of the C atoms; such that the O-plane is symmetrically distributed about the C-atom layer, i.e. the C-atom of the next nearest neighbor forms a covalent bond with O on the same side;
step three, fe atomic intercalation structure design:
simulating and constructing an Fe intercalated graphene oxide crystal structure by utilizing material Studio 2019 and VESTA visual structure drawing software, performing preliminary structural optimization after intercalation by utilizing a VASP software program package, and calculating to obtain an optimal adsorption position of Fe, wherein due to the charge transfer between Fe and O, the physical adsorption of Fe in the graphene oxide is finally converted into chemical adsorption to form a chemical unit of C2O2Fe, fe ions are-2 valence, and the crystal belongs to a crystal film with coexisting ionic bonds and covalent bonds, so that the energy gap is opened;
step four, strain:
and fixing the Fe intercalated graphene oxide single-layer film on a lattice matched substrate, and applying strain to the graphene oxide single-layer film by applying two-dimensional biaxial mechanical stress to the substrate.
Further, in the second step, the optimal adsorption position of Fe: the Fe ion is located between the center of the C six ring and the center of three O atoms adjacent in the plane.
Further, in the fourth step, two-dimensional biaxial strain is applied to the Fe-intercalated graphene oxide single-layer film, that is, tensile strain or compressive strain is applied simultaneously in the orthogonal x and y directions in the plane, and the elastic strain range of the film is detected.
Further, in the fourth step, the energy gap is calculated to decrease with increasing biaxial tensile strain, and increases with increasing compressive strain; the size of the energy gap can be varied with the change in biaxial strain, and therefore, the strain to be applied to the film is determined according to the size of the band gap required for microelectronic device applications.
Furthermore, although the regulation of the strain to the energy gap is obtained, in practical application, various external factors have influence, and an error is necessarily present between the external factors and a theoretical curve, wherein the strain of the film is regulated and controlled by applying the strain to the film substrate, and the energy gap of the film is detected, so that the practical regulation and control relation between the film sample and the external strain is specifically determined.
Further, according to theoretical calculation, the band gap of the structure reaches 1.66eV under the condition of no strain; under 30% strain, the structure has an energy gap of about 0.45eV, the energy gap can be further increased when biaxial compressive strain is applied, and the adjustable range of the energy gap can be about 0-3 eV through the applied strain.
Further, in the fourth step, biaxial tensile strain is applied to the single-layer film, the strain is as large as possible in the elastic range, then the electric field is gradually increased in the direction perpendicular to the surface of the film, and the polarization intensity of the film is measured in situ in real time until the polarization intensity of the film along the direction of the electric field is no longer increased.
The invention provides a structural design of a two-dimensional semiconductor material based on graphene, which has the following effects:
(1) The structure of the Fe intercalated graphene oxide film is simpler;
(2) The energy gap of the single-layer graphene can be effectively regulated and controlled by externally adding biaxial strain to the single-layer graphene, and the adjustable range of the energy gap is wide; according to theoretical calculation, the band gap of the structure under the condition of no strain reaches 1.66eV; the structure has a gap of about 0.45 and eV under 30% strain, and the gap can be further increased when biaxial compressive strain is applied. The adjustable range of the energy gap can be about 0-3 eV through the additional strain.
(3) The invention has the characteristics of simple structure, convenient operation, easy processing and controllable energy gap, can be applied to photovoltaic and energy sources, is also suitable for microelectronic devices, and has very wide application prospect.
Drawings
FIG. 1 is a block diagram of different sides of Fe intercalated graphene oxide, wherein a is a top view, b is a side view;
fig. 2 is a graph of band gap as a function of strain.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
A structural design of a two-dimensional semiconductor material based on graphene implementation, the design comprising the steps of:
step one, selecting a substrate
In order to meet the design requirements of low dimension and small dimension of the nano multifunctional semiconductor device, graphene oxide with a two-dimensional monolayer is selected as a base material, but the graphene oxide has no energy gap, and Fe atoms are selected as an intercalation material;
step two, bonding design:
c in the graphene oxide forms a hexagonal honeycomb structure, and C in a plane is covalently bonded through sp2 hybridization; adjacent pz orbit electrons are bonded through a large pi bond, after graphene is oxidized, the large pi bond is destroyed, O is bonded with C at the upper and lower positions of C atoms, and as with hydrogenated graphene, O and C form chemical adsorption, C atoms are bonded through sp3 orbit hybridization, so that a large fold exists on the plane of the C atoms; such that the O-plane is symmetrically distributed about the C-atom layer, i.e. the C-atom of the next nearest neighbor forms a covalent bond with O on the same side;
step three, fe atomic intercalation structure design:
simulating and constructing an Fe intercalated graphene oxide crystal structure by utilizing material Studio 2019 and VESTA visual structure drawing software, performing preliminary structural optimization after intercalation by utilizing a VASP software program package, and calculating to obtain an optimal adsorption position of Fe, wherein due to the charge transfer between Fe and O, the physical adsorption of Fe in the graphene oxide is finally converted into chemical adsorption to form a chemical unit of C2O2Fe, fe ions are-2 valence, and the crystal belongs to a crystal film with coexisting ionic bonds and covalent bonds, so that the energy gap is opened;
step four, strain:
and fixing the Fe intercalated graphene oxide single-layer film on a lattice matched substrate, and applying strain to the graphene oxide single-layer film by applying two-dimensional biaxial mechanical stress to the substrate.
Further in this example, the best adsorption position of Fe in step two: the Fe ion is located between the center of the C six ring and the center of three O atoms adjacent in the plane.
In this example, further, in the fourth step, a two-dimensional biaxial strain is applied to the Fe-intercalated graphene oxide single-layer film, that is, tensile strain or compressive strain is applied simultaneously in the orthogonal x and y directions in the plane, and the elastic strain range of the film is detected.
Further in this example, in the fourth step, the energy gap is calculated to decrease with increasing biaxial tensile strain, and to increase with increasing compressive strain; the size of the energy gap can be varied with the change in biaxial strain, and therefore, the strain to be applied to the film is determined according to the size of the band gap required for microelectronic device applications.
Further, in this example, although the regulation of the strain to the energy gap is obtained, there are various external factors in practical application, and there must be an error with the theoretical curve, where the actual regulation relationship between the film sample and the applied strain is specifically determined by applying strain to the film substrate, regulating the strain to which the film is subjected, and detecting the energy gap of the film.
Further in this example, according to theoretical calculation, the band gap of the structure reaches 1.66eV under no strain; under 30% strain, the structure has an energy gap of about 0.45eV, the energy gap can be further increased when biaxial compressive strain is applied, and the adjustable range of the energy gap can be about 0-3 eV through the applied strain.
In this example, further, in the fourth step, biaxial tensile strain is applied to the single-layer film, the strain is as large as possible in the elastic range, then the electric field is gradually increased in the direction perpendicular to the surface of the film, and the polarization intensity of the film is measured in situ in real time until the polarization intensity of the film along the direction of the electric field is no longer increased.
Fig. 1 is a schematic diagram showing different sides of Fe intercalated graphene oxide. In the figure, the atoms with particle diameters are O atoms, the atoms with small particle diameters are C atoms, and the atoms with large particle diameters are Fe atoms. In the figure, in the C six ring, one O above each C atom of the next neighbor coordinates with the C atom to form a covalent bond, O forms a planar regular triangle lattice, and the other three C atoms of the next neighbor are left to coordinate with O atoms below the C atom of the next neighbor, and the lower O also forms the planar regular triangle lattice. All Fe ions are located above (or below) the center of the C six ring and below (or above) the center of the upper (or lower) O-ion regular triangle lattice. The figure shows the case where the Fe ion insertion is all located on the same side of the C six ring.
According to theoretical calculation results, the band gap of the Fe intercalated graphene oxide is about 1.66 and eV when no external strain is applied, and the band gap is relatively close to the optimal band gap for absorbing visible light of the solar photovoltaic effect, so that the Fe intercalated graphene oxide can be used as a photovoltaic film material. By applying strain, as can be seen in fig. 2, energy band modulation over a wide range can be achieved, which provides a carrier and basis for miniaturized, integrated nanoscale semiconductor device-based circuit designs. In the design process, the Fe intercalated graphene oxide film can be subjected to strain regulation and control according to the energy gap required by a specific circuit, so that the required energy gap requirement is met.
While the embodiments and effects of the present invention have been shown and described, it should be noted that it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations should and are intended to be comprehended within the scope of the invention.
Claims (7)
1. The structural design of the two-dimensional semiconductor material based on graphene is characterized in that: the design scheme comprises the following steps:
step one, selecting a substrate
In order to meet the design requirements of low dimension and small dimension of the nano multifunctional semiconductor device, graphene oxide with a two-dimensional monolayer is selected as a base material, but the graphene oxide has no energy gap, and Fe atoms are selected as an intercalation material;
step two, bonding design:
c in the graphene oxide forms a hexagonal honeycomb structure, and C in a plane is covalently bonded through sp2 hybridization; adjacent pz orbit electrons are bonded through a large pi bond, after graphene is oxidized, the large pi bond is destroyed, O is bonded with C at the upper and lower positions of C atoms, and as with hydrogenated graphene, O and C form chemical adsorption, C atoms are bonded through sp3 orbit hybridization, so that a large fold exists on the plane of the C atoms; such that the O-plane is symmetrically distributed about the C-atom layer, i.e. the C-atom of the next nearest neighbor forms a covalent bond with O on the same side;
step three, fe atomic intercalation structure design:
simulating and constructing an Fe intercalated graphene oxide crystal structure by utilizing material Studio 2019 and VESTA visual structure drawing software, performing preliminary structural optimization after intercalation by utilizing a VASP software program package, and calculating to obtain an optimal adsorption position of Fe, wherein due to the charge transfer between Fe and O, the physical adsorption of Fe in the graphene oxide is finally converted into chemical adsorption to form a chemical unit of C2O2Fe, fe ions are-2 valence, and the crystal belongs to a crystal film with coexisting ionic bonds and covalent bonds, so that the energy gap is opened;
step four, strain:
and fixing the Fe intercalated graphene oxide single-layer film on a lattice matched substrate, and applying strain to the graphene oxide single-layer film by applying two-dimensional biaxial mechanical stress to the substrate.
2. The structural design of a graphene-based two-dimensional semiconductor material of claim 1, wherein: optimal adsorption position of Fe in the second step: the Fe ion is located between the center of the C six ring and the center of three O atoms adjacent in the plane.
3. The structural design of a graphene-based two-dimensional semiconductor material of claim 1, wherein: and step four, applying two-dimensional biaxial strain to the Fe intercalated graphene oxide single-layer film, namely applying tensile strain or compressive strain simultaneously in the orthogonal x and y directions in a plane, and detecting the elastic strain range of the film.
4. The structural design of a graphene-based two-dimensional semiconductor material of claim 1, wherein: in the fourth step, the energy gap is calculated to be reduced along with the increase of the biaxial tensile strain, and the energy gap is increased along with the increase of the compressive strain; the size of the energy gap can be varied with the change in biaxial strain, and therefore, the strain to be applied to the film is determined according to the size of the band gap required for microelectronic device applications.
5. The structural design of a graphene-based two-dimensional semiconductor material of claim 4, wherein: although the regulation of the strain to the energy gap is obtained, various external factors have influence in practical application, and errors necessarily exist between the strain and a theoretical curve, wherein the strain of the film is regulated and controlled by applying the strain to the film substrate, and the energy gap of the film is detected, so that the practical regulation and control relation between the film sample and the applied strain is specifically determined.
6. The structural design of a graphene-based two-dimensional semiconductor material of claim 4, wherein: according to theoretical calculation, the band gap of the structure reaches 1.66eV under the condition of no strain; under 30% strain, the structure has an energy gap of 0.45eV, the energy gap can be further increased when biaxial compressive strain is added, and the adjustable range of the energy gap can be between 0 and 3eV through the added strain.
7. The structural design of a graphene-based two-dimensional semiconductor material of claim 1, wherein: and in the fourth step, biaxial tensile strain is applied to the single-layer film, the strain is as large as possible in the elastic range, then the electric field is gradually increased in the direction vertical to the surface of the film, and the polarization intensity of the film is measured in situ in real time until the polarization intensity of the film along the direction of the electric field is not increased any more.
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CN105088350A (en) * | 2015-08-17 | 2015-11-25 | 山东建筑大学 | Method for regulating electronic band gap in SiC-based epitaxial graphene |
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CN103025655A (en) * | 2010-06-25 | 2013-04-03 | 新加坡国立大学 | Methods of forming graphene by graphite exfoliation |
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