CN114162791A - Method for inhibiting selenization reaction on platinum surface and controlling growth of single-layer platinum diselenide by using graphene - Google Patents
Method for inhibiting selenization reaction on platinum surface and controlling growth of single-layer platinum diselenide by using graphene Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 294
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 134
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims abstract description 59
- 239000002356 single layer Substances 0.000 title claims abstract description 52
- JTPDXCIVXNLRFP-UHFFFAOYSA-N bis(selanylidene)platinum Chemical compound [Pt](=[Se])=[Se] JTPDXCIVXNLRFP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 26
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 16
- 239000013078 crystal Substances 0.000 claims abstract description 80
- 125000003748 selenium group Chemical group *[Se]* 0.000 claims abstract description 11
- 238000000151 deposition Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims description 57
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 31
- 239000005977 Ethylene Substances 0.000 claims description 31
- 229910052799 carbon Inorganic materials 0.000 claims description 27
- 238000000137 annealing Methods 0.000 claims description 20
- 239000012535 impurity Substances 0.000 claims description 20
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 19
- 238000010884 ion-beam technique Methods 0.000 claims description 18
- 229910052711 selenium Inorganic materials 0.000 claims description 18
- 238000005336 cracking Methods 0.000 claims description 17
- 238000010894 electron beam technology Methods 0.000 claims description 17
- 239000002344 surface layer Substances 0.000 claims description 15
- 239000011669 selenium Substances 0.000 claims description 14
- 238000009830 intercalation Methods 0.000 claims description 13
- 230000002687 intercalation Effects 0.000 claims description 13
- 239000010410 layer Substances 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 238000009423 ventilation Methods 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 230000033228 biological regulation Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000005273 aeration Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000005764 inhibitory process Effects 0.000 abstract description 3
- 238000000059 patterning Methods 0.000 abstract description 2
- LFGRDRAXRZFPAB-UHFFFAOYSA-N selanylideneplatinum Chemical compound [Pt]=[Se] LFGRDRAXRZFPAB-UHFFFAOYSA-N 0.000 description 76
- 230000001276 controlling effect Effects 0.000 description 10
- 238000010586 diagram Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- 238000005262 decarbonization Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910002601 GaN Inorganic materials 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- OHKMFOAYJDGMHW-UHFFFAOYSA-N [Si].[Se] Chemical compound [Si].[Se] OHKMFOAYJDGMHW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CUYHGAIVHCHFIA-UHFFFAOYSA-N bis(selanylidene)rhenium Chemical compound [Se]=[Re]=[Se] CUYHGAIVHCHFIA-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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Abstract
The invention discloses a method for inhibiting a selenization reaction on a platinum surface by utilizing graphene and controlling the growth of single-layer platinum diselenide; in the process of growing platinum diselenide by a direct selenization method, a single layer of platinum diselenide can be epitaxially grown on the surface of platinum by depositing selenium atoms on a platinum (111) crystal face which is heated to a proper temperature in vacuum; according to the invention, the inhibition effect of the confinement effect of the graphene on the platinum (111) surface on the selenization reaction is utilized, and the inhibition on the selenization reaction can be realized by epitaxially growing the graphene on the platinum surface before selenization; the selenization reaction in a specific area can be inhibited by controlling the coverage area of the graphene, so that the morphology of the single-layer platinum diselenide is controlled; the control method for the growth of the single-layer platinum diselenide provides a new way for realizing the patterning of the two-dimensional material, and has wide potential in the aspects of related research and application of low-dimensional materials, nanoelectronics, sensing, catalysis and the like.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a method for inhibiting a selenization reaction on a platinum surface and controlling the growth of single-layer platinum diselenide by utilizing graphene.
Background
Two-dimensional transition metal dichalcogenides are considered ideal candidates for low-dimensional electronic devices due to their unique structural and electrical properties. Single layer platinum diselenide (PtSe) as a member of transition metal dichalcogenides2) Is a two-dimensional semiconductor material. Meanwhile, the material has excellent performances such as high carrier mobility, valley electron effect and the like, and the characteristics have important application prospects in the fields of electronics, spintronics, catalysis, sensors and the like. This two-dimensional material was first reported in 2015 to be prepared by a direct selenization process of platinum (111) surfaces by depositing selenium atoms onto the platinum (111) surface and heating to 270 deg.c to achieve epitaxial growth of a single layer of platinum diselenide on the platinum (111) surface. Before a two-dimensional material is subjected to device formation, the two-dimensional material is required to be molded into a specific shape and a heterostructure. Therefore, how to construct the planar structure of the two-dimensional material and connect the two-dimensional material with other two-dimensional materials is a key problem for expanding the application range of the two-dimensional material besides growing and preparing the single-layer platinum diselenide.
In order to construct fine nano-structures of platinum diselenide, an effective bottom-up method is needed to control the morphology. The reason why the bottom-up method is required is that the common top-down etching method is easy to cause the damage of the platinum diselenide structure. On the basis of growing a single-layer platinum diselenide by a direct selenization method, the selenization process of different positions of a platinum (111) substrate is further controlled, so that the method can be used as a feasible means for directly controlling the appearance from bottom to top in the growth process. On the other hand, recent studies have shown that a limited-domain Reaction (defined Reaction) regulated by a two-dimensional material interface can form a regulation on the growth process of the intercalation at the interface, thereby changing the final Reaction product. This is because the confinement effect of the interface can significantly affect the chemical behavior of the atoms and molecules bound inside, changing their chemical potential, resulting in different reactions under non-confined conditions. By utilizing the confinement reaction, people can grow the two-dimensional material with a novel structure on the interface in the layered heterostructure, for example, the two-dimensional material such as single-layer gallium nitride, rhenium diselenide, silicon selenium and the like can be grown on the interface of the graphene heterostructure.
Disclosure of Invention
The invention aims to provide a method for inhibiting a selenization reaction on the surface of platinum by utilizing graphene and controlling the growth of single-layer platinum diselenide, so as to realize the construction of a fine nano structure of platinum diselenide.
In order to solve the technical problems, the invention specifically provides the following technical scheme:
a method of suppressing a selenization reaction of a platinum surface with graphene, comprising epitaxially growing a single-layer graphene overlying a platinum (111) surface.
As a preferable scheme of the invention, the method adopts a mode of cracking ethylene at 800-1000 ℃ on the platinum (111) to cover the surface of the platinum (111) with single-layer graphene so as to realize the purpose of inhibiting the selenization reaction of the platinum (111) surface in the temperature range of 250-500 ℃.
As a preferable scheme of the present invention, the step of inhibiting the selenization reaction of the platinum (111) surface in the temperature range of 250-500 ℃ specifically comprises:
step 101, heating a platinum (111) single crystal with a polished crystal face to 800-1000 ℃ in a vacuum environment and keeping the temperature unchanged;
step 102, introducing ethylene gas into the vacuum chamber until the pressure is 1 × 10-4Pa, keeping the temperature and the air pressure unchanged to ensure that ethylene is fully cracked on the surface of the platinum (111);
stopping heating after 2mins, stopping ventilation, and epitaxially growing on the surface of platinum (111) to obtain a layer of graphene;
and 104, heating the platinum (111) single crystal covered with the graphene to 250-500 ℃ and depositing selenium atoms to form a selenium intercalation layer on the interface of the platinum (111) and the graphene.
As a preferred embodiment of the present invention, before step 101, the method further includes removing carbon impurities in the platinum (111) single crystal by a multi-round ion beam bombardment and oxygen-introducing annealing cycle to avoid interference of the carbon impurities on the controlled growth of the graphene island, specifically including:
001, heating the platinum (111) to 550 ℃ by adopting electron beam heating in an ultrahigh vacuum environment, annealing for 2mins, stopping introducing oxygen, rapidly increasing the temperature to 700 ℃, and immediately stopping heating to enable carbon impurities contained in the surface layer of the platinum (111) single crystal to seep out;
002, bombarding the surface of the platinum (111) single crystal by adopting an argon ion source and an ion beam with energy of 1.5keV for 20 minutes under an ultrahigh vacuum environment, wherein the ion beam current is 15-20 muA, so that carbon exuded from the surface layer of the platinum (111) single crystal is bombarded and removed;
step 003, circularly repeating the steps 001 and 002 for about 3-5 times so as to fully remove the carbon impurities on the surface layer of the platinum (111) single crystal;
and 004, annealing to 500 ℃ for 2mins, so that the surface of the platinum (111) single crystal after the last round of bombardment is reconstructed to form a flat crystal face again.
As a preferable scheme of the invention, in the process of cracking ethylene to grow graphene, the platinum (111) single crystal adopts an electron beam heating method to realize accurate regulation and control of ethylene cracking reaction time.
A method for controlling growth of single-layer platinum diselenide by utilizing graphene comprises the steps of covering a single-layer graphene island on the surface of platinum (111), and controlling the growth range of the platinum diselenide to be outside the coverage area of the graphene island.
As a preferable scheme of the invention, a single-layer graphene island is covered on the surface of the platinum (111) in a mode of cracking ethylene at 850 ℃ on the platinum (111) at 750 ℃ to realize the control of the morphology of the grown single-layer platinum diselenide within the temperature range of 500 ℃ at 250 ℃.
As a preferred scheme of the invention, the shape of the grown single-layer platinum diselenide is controlled within the temperature range of 250-500 ℃, and the method specifically comprises the following steps:
step 201, heating the platinum (111) single crystal with the polished crystal face to 750-850 ℃ and keeping the temperature unchanged;
step 202, introducing ethylene gas into the vacuum chamber to reach the air pressureIs 1 × 10-4Pa；
Step 203, stopping ventilation after keeping the temperature and the air pressure unchanged for 5-20s, then stopping heating, and epitaxially growing on the surface of the platinum (111) to obtain a plurality of incompletely covered graphene islands;
step 204, heating the platinum (111) single crystal covered with the graphene island to 250-500 ℃ and depositing selenium atoms, so that a single-layer selenium intercalation between the graphene and platinum (111) interface is formed in the graphene island covered area, and a single-layer platinum diselenide is formed outside the graphene island covered area.
As a preferred embodiment of the present invention, before step 201, the method further includes removing carbon impurities in the platinum (111) single crystal by a multi-round ion beam bombardment and oxygen-introducing annealing cycle to avoid interference thereof on the controlled growth of the graphene island, specifically including:
001, heating the platinum (111) to 550 ℃ by adopting electron beam heating in an ultrahigh vacuum environment, annealing for 2mins, stopping introducing oxygen, rapidly increasing the temperature to 700 ℃, and immediately stopping heating to enable carbon impurities contained in the surface layer of the platinum (111) single crystal to seep out;
step 002, bombarding the surface of the platinum (111) single crystal by adopting an argon ion source and an ion beam with energy of 1.5keV for 20 minutes under an ultrahigh vacuum environment, wherein the ion beam current is about 15-20 muA, so that carbon exuded from the surface layer of the platinum (111) single crystal is bombarded and removed;
step 003, circularly repeating the steps 001 and 002 for about 3-5 times so as to fully remove the carbon impurities on the surface layer of the platinum (111) single crystal;
and 004, annealing to 500 ℃ for 2mins, so that the surface of the platinum (111) single crystal after the last round of bombardment is reconstructed to form a flat crystal face again.
In a preferable scheme of the invention, in the process of cracking ethylene to grow graphene, the coverage degree of the graphene islands is regulated and controlled by regulating the ventilation time of ethylene.
Compared with the prior art, the invention has the following beneficial effects:
according to the method, the local inhibition of the selenization reaction on the platinum (111) surface is realized by utilizing the confinement effect of the graphene, and the control of the growth of platinum diselenide on the platinum (111) surface is realized by controlling the coverage degree of the graphene. The method provides a new way for realizing the patterning of the two-dimensional material, and has wide potential in the aspects of related research and application of low-dimensional materials, nano electronics, sensing, catalysis and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It should be apparent that the drawings in the following description are merely exemplary, and that other embodiments can be derived from the drawings provided by those of ordinary skill in the art without inventive effort.
Fig. 1 is a schematic structural view of a pallet separating and dropping device according to an embodiment of the present invention.
The reference numerals in the drawings denote the following, respectively:
fig. 1, (a) shows a schematic diagram of the present invention for suppressing the selenization reaction of a platinum (111) surface and controlling the growth of a single-layer platinum diselenide using graphene, (b) is a partially enlarged schematic diagram of fig. (a);
fig. 2, (a) shows a sectional view of a tem after depositing and annealing a pt (111) single crystal covered with full-layer graphene according to the present invention, showing the lattice periods of the se and pt (111) atoms, (b) is an intensity distribution curve along a vertical double arrow in the diagram (a), the gray arrows respectively indicating the positions and the distances of the respective atomic layers, (c) is a distribution image of the relative resistance loss spectra of the se and pt (111) elements in the diagram (a), showing the distribution positions of the two elements, and (d) is a sem image of the same sample. (e) Is an enlarged image of the corresponding area of (d) showing the honeycomb-like moire fringes produced by the stacking of selenium intercalation on the platinum (111) face;
fig. 3, (a) shows a scanning electron microscope image of a platinum (111) single crystal covered with less than one graphene island after selenium deposition and annealing in the present invention, showing two different morphologies of the graphene island boundary; (b) (c) is a partial enlarged view of the corresponding region in the graph (a), and respectively shows honeycomb-shaped molar stripes formed by selenium intercalation and platinum (111) planes in a graphene island covering region and triangular molar stripes formed by platinum diselenide and platinum (111) planes in a graphene island uncovering region; (d) and (e) is a partial enlarged view of the corresponding regions of (b) and (c), respectively.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in FIG. 1, a method for inhibiting a selenization reaction of a platinum surface by using graphene comprises the step of covering a single-layer graphene on the platinum (111) surface, wherein the covering single-layer graphene covers the single-layer graphene on the platinum (111) surface in a mode of cracking ethylene at the temperature of 800-1000 ℃ on the platinum (111) so as to realize the purpose of inhibiting the selenization reaction of the platinum (111) surface in the temperature range of 250-500 ℃.
Wherein, the step of inhibiting the selenization reaction of the platinum (111) surface in the temperature range of 250-500 ℃ specifically comprises the following steps:
step 101, heating a platinum (111) single crystal with a polished crystal face to 800-1000 ℃ in a vacuum environment and keeping the temperature unchanged;
step 102, introducing ethylene gas into the vacuum chamber until the pressure is 1 × 10-4Pa, keeping the temperature and the air pressure unchanged to ensure that ethylene is fully cracked on the surface of the platinum (111);
stopping heating after 2mins, stopping ventilation, and epitaxially growing on the surface of platinum (111) to obtain a layer of graphene;
and 104, heating the platinum (111) single crystal covered with the graphene to 250-500 ℃ and depositing selenium atoms to form a selenium intercalation layer on the interface of the platinum (111) and the graphene.
The single-layer selenium intercalation is in a single-atom-layer and planar hexagonal structure, and the lattice period is 0.37 nm.
Before the step 101, the method further comprises removing carbon impurities in the platinum (111) single crystal by a multi-round ion beam bombardment and oxygen-introducing annealing cycle method to avoid interference on the controllable growth of the graphene island, and specifically comprises the following steps:
001, heating the platinum (111) to 550 ℃ by adopting electron beam heating in an ultrahigh vacuum environment, annealing for 2mins, stopping introducing oxygen, rapidly increasing the temperature to 700 ℃, and immediately stopping heating to enable carbon impurities contained in the surface layer of the platinum (111) single crystal to seep out;
002, bombarding the surface of the platinum (111) single crystal by adopting an argon ion source and an ion beam with energy of 1.5keV for 20 minutes under an ultrahigh vacuum environment, wherein the ion beam current is 15-20 muA, so that carbon exuded from the surface layer of the platinum (111) single crystal is bombarded and removed;
step 003, circularly repeating the steps 001 and 002 for about 3-5 times so as to fully remove the carbon impurities on the surface layer of the platinum (111) single crystal;
and 004, annealing to 500 ℃ for 2mins, so that the surface of the platinum (111) single crystal after the last round of bombardment is reconstructed to form a flat crystal face again.
In the process of cracking ethylene to grow graphene, the platinum (111) single crystal adopts an electron beam heating method to realize accurate regulation and control of ethylene cracking reaction time.
Based on the above, the embodiment of the present invention provides a method for inhibiting a selenization reaction on a platinum (111) surface by using graphene, which is applied to an actual production operation, and comprises the following specific steps:
the method comprises the following steps: a finished platinum (111) single wafer with a polished crystal face of 0.5mm × 4mm × 4mm was mounted on a tantalum sample holder. Pre-pumping a sample holder filled with platinum (111) single crystal through a sample injection cavity and then transferring the sample holder into a 1 x 10 sample injection cavity-6Pa, and inserting the substrate into a heating table heated by electron beams. Heating single crystal to 550 deg.C within 30s by electron beam heating, maintaining the temperature for 30s, and introducing oxygen into vacuum chamber to 1 × 10-4Pa continuously maintains the temperature of the single crystal. After 2mins, the oxygen supply is stopped, the temperature is rapidly increased to 700 ℃, and then the heating is immediately stopped. Then bombarding the surface of the single crystal for 20mins by an argon ion beam with 1500keV energy, then heating and annealing to 500 ℃ by an electron beam, keeping for 2mins, and naturally cooling to complete a decarbonization process. Repeatedly circulating for 3-5 times to obtain platinum (111) single crystal with carbon impurities removed;
step two: at 5X 10-8Heating the platinum (111) single crystal after carbon removal to 800 ℃ by electron beam heating under an ultrahigh vacuum environment of Pa. Keeping the temperature for 30s, and introducing ethylene into the vacuum cavity to 1 multiplied by 10-4Pa is kept at the single crystal temperature, heating is stopped after 2mins, and then ventilation is stopped. Thus obtaining a platinum (111) single crystal covered with a single layer of graphene on the surface through ethylene cracking;
step three: a sample of a single crystal of platinum (111) grown with graphene was heated to 270 ℃ holding temperature. Heating the elemental selenium to 120 ℃ by a resistance type heating source to generate selenium atom beam. The selenium atom beam was deposited onto the sample at 270 ℃ for 20 mins. The deposited selenium atoms will intercalate under the graphene without reacting with the platinum (111) to form a monolayer of selenium intercalation, the atomic structure of which is shown in fig. 2.
Based on the method for inhibiting the selenization reaction on the surface of the platinum (111) by using the graphene, the invention also provides a method for controlling the growth of the single-layer platinum diselenide by using the graphene, which comprises the steps of covering a single-layer graphene island on the surface of the platinum (111) and controlling the growth range of the platinum diselenide to be outside the coverage area of the graphene island.
Specifically, a single-layer graphene island is covered on the surface of platinum (111) in a mode of cracking ethylene at the temperature of 750-850 ℃ on the platinum (111) so as to realize the control of the grown single-layer platinum diselenide appearance in the temperature range of 250-500 ℃.
Wherein, the shape of the grown single-layer platinum diselenide is controlled in the temperature range of 250-500 ℃, and the method specifically comprises the following steps:
step 201, heating the platinum (111) single crystal with the polished crystal face to 750-850 ℃ and keeping the temperature unchanged;
step 202, introducing ethylene gas into the vacuum chamber to a pressure of 1 × 10-4Pa；
Step 203, stopping ventilation after keeping the temperature and the air pressure unchanged for 5-20s, then stopping heating, and epitaxially growing on the surface of the platinum (111) to obtain a plurality of incompletely covered graphene islands;
step 204, heating the platinum (111) single crystal covered with the graphene island to 250-500 ℃ and depositing selenium atoms, so that a single-layer selenium intercalation between the graphene and platinum (111) interface is formed in the graphene island covered area, and a single-layer platinum diselenide is formed outside the graphene island covered area.
The single-layer selenium intercalation is in a single-atom-layer and planar hexagonal structure, and the lattice period is 0.37 nm.
The single-layer platinum diselenide is of a single-layer hexagonal sandwich structure (namely three-layer atoms of selenium-platinum (111) -selenium), and the lattice period is 0.37 nm.
Before step 201, the method further includes removing carbon impurities in the platinum (111) single crystal by multiple rounds of ion beam bombardment and oxygen-filling annealing cycles to avoid interference of the carbon impurities on the controlled growth of the graphene island, which has been described in step 001-004 of the previous section and will not be described herein again.
In the process of cracking ethylene to grow graphene, the platinum (111) single crystal is heated by an electron beam to rapidly stop heating, so that the ethylene cracking time is accurately controlled, meanwhile, the coverage degree of the graphene island can be regulated and controlled by adjusting the ventilation time of ethylene,
based on the above, the embodiment of the present invention provides the specific steps of using graphene to control the growth of single-layer platinum diselenide, which are applied to actual production operations:
the method comprises the following steps: a finished platinum (111) single wafer with a polished crystal face of 0.5mm × 4mm × 4mm was mounted on a tantalum sample holder. Pre-pumping a sample holder filled with platinum (111) single crystal through a sample injection cavity and then transferring the sample holder into a 1 x 10 sample injection cavity-6Pa, and inserting the substrate into a heating table heated by electron beams. Heating single crystal to 550 deg.C within 30s by electron beam heating, maintaining the temperature for 30s, and introducing oxygen into vacuum chamber to 1 × 10-4Pa continuously maintains the temperature of the single crystal. After 2mins, the oxygen supply is stopped, the temperature is rapidly increased to 700 ℃, and then the heating is immediately stopped. Then bombarding the surface of the single crystal for 20mins by an argon ion beam with 1500keV energy, then heating and annealing to 500 ℃ by an electron beam, keeping for 2mins, and naturally cooling to complete a decarbonization process. Repeatedly circulating for 2-5 times to obtain platinum (111) single crystal with carbon impurities removed;
step two: at 5X 10-8Heating the platinum (111) single crystal after carbon removal to 800 ℃ by electron beam heating under an ultrahigh vacuum environment of Pa. Health-care productAfter the temperature is 30s, ethylene is introduced into the vacuum chamber to 1 multiplied by 10-4Pa was kept at the single crystal temperature, and after 10 seconds, the aeration was stopped and then the heating was stopped. Thus, some incompletely covered graphene islands are obtained on the platinum (111) surface;
step three: a sample of a single crystal of platinum (111) grown with graphene was heated to 270 ℃ holding temperature. Heating the elemental selenium to 120 ℃ by a resistance type heating source to generate selenium atom beam. The selenium atom beam was deposited onto the sample at 270 ℃ for 20 mins. In the area covered by the graphene island, the deposited selenium atoms are intercalated below the graphene and do not react with the platinum (111) to form a single-layer selenium intercalation; in the areas not covered by the graphene islands, the selenium atoms deposited on the surface of the bare platinum (111) react with the platinum (111) to form a single layer of platinum diselenide. These two regions have significantly different moire patterns due to the different stacking patterns on the platinum (111) surface, as shown in fig. 3. Thus, the growth area of the platinum diselenide is controlled to be outside the graphene coverage area through the domain limiting effect of the graphene.
The above embodiments are only exemplary embodiments of the present application, and are not intended to limit the present application, and the protection scope of the present application is defined by the claims. Various modifications and equivalents may be made by those skilled in the art within the spirit and scope of the present application and such modifications and equivalents should also be considered to be within the scope of the present application.
Claims (10)
1. A method for inhibiting a selenization reaction on a platinum surface by utilizing graphene is characterized by comprising the step of epitaxially growing a single-layer graphene covering a platinum (111) surface.
2. The method as claimed in claim 1, wherein the method for inhibiting the selenization reaction on the platinum surface by using graphene is characterized in that a single-layer graphene is epitaxially grown on the platinum (111) surface in a manner of cracking ethylene on the platinum (111) at 800-.
3. The method as claimed in claim 2, wherein the step of inhibiting the selenization reaction on the platinum (111) surface at a temperature of 250-500 ℃ comprises:
step 101, heating a platinum (111) single crystal with a polished crystal face to 800-1000 ℃ in a vacuum environment and keeping the temperature unchanged;
step 102, introducing ethylene gas into the vacuum chamber until the pressure is 1 × 10-4Pa, keeping the temperature and the air pressure unchanged to ensure that ethylene is fully cracked on the surface of the platinum (111);
stopping heating after 2mins, stopping ventilation, and epitaxially growing on the surface of platinum (111) to obtain a layer of graphene;
and 104, heating the platinum (111) single crystal covered with the graphene to 250-500 ℃ and depositing selenium atoms to form a selenium intercalation layer on the interface of the platinum (111) and the graphene.
4. The method of claim 3, wherein before the step 101, the method further comprises removing carbon impurities in the platinum (111) single crystal by a multi-round ion beam bombardment and oxygen-introducing annealing cycle to avoid interference on the controlled growth of graphene islands, and specifically comprises:
001, heating the platinum (111) to 550 ℃ by adopting electron beam heating in an ultrahigh vacuum environment, annealing for 2mins, stopping introducing oxygen, rapidly increasing the temperature to 700 ℃, and immediately stopping heating to enable carbon impurities contained in the surface layer of the platinum (111) single crystal to seep out;
002, bombarding the surface of the platinum (111) single crystal by adopting an argon ion source and an ion beam with energy of 1.5keV for 20 minutes under an ultrahigh vacuum environment, wherein the ion beam current is 15-20 muA, so that carbon exuded from the surface layer of the platinum (111) single crystal is bombarded and removed;
step 003, circularly repeating the steps 001 and 002 for about 3-5 times so as to fully remove the carbon impurities on the surface layer of the platinum (111) single crystal;
and 004, annealing to 500 ℃ for 2mins, so that the surface of the platinum (111) single crystal after the last round of bombardment is reconstructed to form a flat crystal face again.
5. The method for inhibiting the selenization reaction on the platinum surface by using the graphene as claimed in claim 3, wherein in the process of cracking ethylene to grow the graphene, the platinum (111) single crystal is heated by an electron beam to realize precise regulation and control of the ethylene cracking reaction time.
6. A method for controlling growth of single-layer platinum diselenide by using graphene is characterized by comprising the steps of epitaxially growing and covering a single-layer graphene island on the surface of platinum (111), and controlling the growth range of the platinum diselenide to be outside the coverage area of the graphene island.
7. The method as claimed in claim 6, wherein the method for controlling the growth of single-layer platinum diselenide comprises the step of covering the surface of the platinum (111) with single-layer graphene islands by cracking ethylene on the platinum (111) at 750-850 ℃ to control the morphology of the epitaxially grown single-layer platinum diselenide within the temperature range of 250-500 ℃.
8. The method as claimed in claim 7, wherein the controlling of the morphology of the grown single-layer platinum diselenide within the temperature range of 250-500 ℃ comprises:
step 201, heating the platinum (111) single crystal with the polished crystal face to 750-850 ℃ and keeping the temperature unchanged;
step 202, introducing ethylene gas into the vacuum chamber to a pressure of 1 × 10-4Pa；
Step 203, stopping ventilation after keeping the temperature and the air pressure unchanged for 5-20s, then stopping heating, and epitaxially growing on the surface of the platinum (111) to obtain a plurality of incompletely covered graphene islands;
step 204, heating the platinum (111) single crystal covered with the graphene island to 250-500 ℃ and depositing selenium atoms, so that a single-layer selenium intercalation between the graphene and platinum (111) interface is formed in the graphene island covered area, and a single-layer platinum diselenide is formed outside the graphene island covered area.
9. The method of claim 8, wherein before step 201, the method further comprises removing carbon impurities in the platinum (111) single crystal by multiple rounds of ion beam bombardment and oxygen-introducing annealing cycles to avoid interference with the controlled growth of graphene islands, and specifically comprises:
001, heating the platinum (111) to 550 ℃ by adopting electron beam heating in an ultrahigh vacuum environment, annealing for 2mins, stopping introducing oxygen, rapidly increasing the temperature to 700 ℃, and immediately stopping heating to enable carbon impurities contained in the surface layer of the platinum (111) single crystal to seep out;
step 002, bombarding the surface of the platinum (111) single crystal by adopting an argon ion source and an ion beam with energy of 1.5keV for 20 minutes under an ultrahigh vacuum environment, wherein the ion beam current is about 15-20 muA, so that carbon exuded from the surface layer of the platinum (111) single crystal is bombarded and removed;
step 003, circularly repeating the steps 001 and 002 for about 3-5 times so as to fully remove the carbon impurities on the surface layer of the platinum (111) single crystal;
and 004, annealing to 500 ℃ for 2mins, so that the surface of the platinum (111) single crystal after the last round of bombardment is reconstructed to form a flat crystal face again.
10. The method of claim 8, wherein the coverage of the graphene islands is controlled by adjusting the aeration time of ethylene during the process of cracking ethylene to grow graphene.
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