CN104651777A - Method for printing type fixed point growth of two-dimensional sulfur group crystals - Google Patents
Method for printing type fixed point growth of two-dimensional sulfur group crystals Download PDFInfo
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- CN104651777A CN104651777A CN201510072662.4A CN201510072662A CN104651777A CN 104651777 A CN104651777 A CN 104651777A CN 201510072662 A CN201510072662 A CN 201510072662A CN 104651777 A CN104651777 A CN 104651777A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/04—Coating on selected surface areas, e.g. using masks
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
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Abstract
The invention discloses a method for printing type fixed point growth of two-dimensional sulfur group crystals. The method comprises the following steps: (1) soaking an elastic stamp in a volatile solvent, taking out the elastic stamp, stamping the elastic stamp on the surface of a substrate, and peeling off the substrate from the elastic stamp when the volatile solvent is volatilized to obtain a patterning modified substrate; and (2) sequentially placing the patterning modified substrate and a sulfur group material to perform physical vapor deposition in a non-oxidizing atmosphere according to a sequence from downstream to upstream of a gas path, and cooling after deposition to obtain the two-dimensional sulfur group crystals. The invention develops a universal method for controlling the growth of two-dimensional sulfur group atomic crystals; and by adopting the method, the two-dimensional sulfur group atomic crystals with large areas, high-quality shapes and controllable nucleation sites, orientation and thicknesses can be obtained. A two-dimensional sulfur group atomic crystal array prepared by the method can be transferred to any other substrate, and has an important potential application in the fields of photoelectric detection and the like.
Description
Technical field
The present invention relates to a kind of printing-type fixed point growth method of two-dimentional sulfur family crystal.
Background technology
Two-dimensional atomic crystal refers to mainly with the New Two Dimensional crystalline material of the single or a few atomic thickness of covalent bonds formation.Two dimension sulfur family atomic crystal is that one of them is of a great variety, the colourful family of character, and composition all contains one or more in sulfur family element sulphur, selenium, tellurium.Structurally, two-dimentional sulfur family atomic crystal is all made up of several atomic shell many times of Rotating fields unit formed that are alternately arranged.Connected by strong covalent linkage in many times of layers, interlayer is then connected by weak Van der Waals force, the anisotropic structure of height of formation.Two dimension sulfur family atomic crystal is quantitatively more than 60 kinds, and its body material character is very abundant, covers and comprises metalloid as NbS
2, semi-metal is as WTe
2, semi-conductor is as In
2se
3, clasp Y insulation Y body is as HfS
2, topological insulator is as Bi
2se
3etc. scope can be with, for we providing wide Material selec-tion space.Enrich except character except inheriting figure's material, two-dimentional sulfur family atomic crystal also presents the much novel character different from body material.As the band gap variation caused due to quantum confined effect, large specific surface area highlights the contribution of surface state, has certain flexibility and the transparency etc.The character of these uniquenesses impels that two-dimentional this quantity of sulfur family atomic crystal is various, the colourful extended familys of character develop into a frontier got most of the attention.
The same with other any materials, in order to realize constructing of integrated, high-level efficiency device, very crucial to the fixed point growth of the big area of material, high crystalline.At present, for the preparation of two-dimentional sulfur family material, people have developed the multiple methods such as micromechanics stripping, liquid phase synthesis, molecular beam epitaxy, vapour deposition.These methods respectively have oneself advantage, but be all difficult to the control of nucleation site, shape, orientation and the thickness etc. simultaneously realized high quality two dimension sulfur family atomic crystal, in order to construct integrated device, the regulation and control to these parameters must be realized simultaneously, realizing fixed point growth.
Summary of the invention
The object of this invention is to provide a kind of printing-type fixed point growth method of two-dimentional sulfur family crystal.
The method of the two-dimentional sulfur family crystal of preparation provided by the invention, comprises the steps:
1) elastomeric stamp is first soaked in volatile solvent, then takes out described elastomeric stamp and be stamped in substrate surface, after described volatile solvent evaporates, described substrate is peeled off from described elastomeric stamp, obtain the substrate that patterning is modified;
2) in non-oxidizing atmosphere, according to gas routing downstream to the order of upstream, successively place step 1) gained patterning modify substrate and sulfur family material, physical vapor deposition is carried out by after room temperature, lower the temperature after deposition, in the substrate of the modification of described patterning, namely obtain described two-dimentional sulfur family crystal.
The step 1 of aforesaid method) in, the material forming described elastomeric stamp is polydimethylsiloxane (PDMS); Elastomeric stamp can carry out design preparation as required, and the pattern on this elastomeric stamp can be circular or linear; As being circle, then the diameter of circular pattern is at least 30nm; As for linear, then the line thickness of linear pattern is at least 30nm;
On described elastomeric stamp, the shape of pattern is circle, trilateral, square, hexagon, volution or continuous grids shape;
The material forming described substrate is selected from least one in white mica, fluorophlogopite, intrinsic silicon, silicon-dioxide-silicon, sapphire, Graphene, boron nitride, strontium titanate and silicon carbide;
The thickness of described substrate is 0.1 millimeter-2 millimeters;
Elastomeric stamp is soaked in after in volatile solvent, PDMS oligomer can stripping under the effect of volatile solvent, thus ink is formed in elastomeric stamp surface and solvent, therefore when this elastomeric stamp is stamped in substrate surface, can under the effect of ink by the imprint patterns on elastomeric stamp in substrate.
At least one in described volatile solvent selected from ethanol, acetone and water;
The process of described volatilization can be naturally volatilize in an atmosphere, also can be to heat to impel to evaporate in thermal station, and the mode that also vacuum can be adopted to drain impels volatilization, and this process often needs 3-10 minute.
Described method also comprises the steps: in described step 1) before patterning modification step, surface cleaning is carried out in described substrate.
Various conventional method for cleaning surface is all applicable, as mechanically peel method or carry out the method for ultrasonic cleaning with solvent.Specifically, for white mica or fluorophlogopite, the method for mechanically peel can be used to be removed by the mica layer on substrate surface, obtain the surface of fresh clean; And for intrinsic silicon or silicon-dioxide-silicon base, ultrasonic cleaning can be carried out with water, ethanol and acetone successively.
Described step 2) in, described sulfur family material is selected from In
2se, Bi
2te
3, at least one in GaS and SnSe; Its mode of appearance can be block or powder;
The gas mixture that gas in described nonoxidizing atmosphere is rare gas element or is made up of reducing gas and rare gas element;
Wherein, described rare gas element is selected from least one in nitrogen and argon gas;
Described reducing gas is specially hydrogen;
In the described gas mixture be made up of reducing gas and rare gas element, the volume parts of hydrogen specifically can be 5%;
In described non-oxidizing atmosphere, the flow of gas is 20 to 1000 cubic centimetres per minute, specifically can be 100,200 cubic centimetres per minute.
Described step 2) in physical vapor deposition step, the temperature 50-250 DEG C lower than the temperature of described sulfur family material of the substrate that described patterning is modified; For making step 1) depositing temperature of substrate modified of gained patterning meets this temperature requirement, the substrate that described patterning is modified can be placed in the position of the downstream direction 7cm-16cm of described sulfur family material;
The pressure of deposition is 1.3 Qian Pa – 27 kPas, specifically can be 2.7 kPas, 6.7 kPas;
The depositing temperature of described sulfur family material is the temperature of the fusing point 100 DEG C-200 DEG C lower than described sulfur family material, specifically can be 450 DEG C, 500 DEG C, 510 DEG C, 550 DEG C, 650 DEG C, 750 DEG C, 850 DEG C; According to the needs of the thickness to required two-dimensional material, can also regulate this temperature, temperature is higher, and the two-dimentional sulfur family crystal obtained when other conditions are identical is thicker.
The time of deposition is 2min-10h, specifically can be 2min, 5min, 60min, 2h, 10h.When other conditions are identical, the time is longer, and the thickness of two-dimentional sulfur family crystal is larger.
In described cooling, the mode of cooling is naturally cooling cooling.
In addition, described method also comprises the steps: in described step 1) after patterning modification step, in described step 2) before deposition step, to step 2) deposit pipeline used and clean; Various conventional purging method tool is suitable for.As cleaned in accordance with the following steps: start vacuum mechanical pump, system pressure to be deposited is down to after below 0.13 kPa, close vacuum mechanical pump, pass into gas to normal atmosphere, and then close intake valve, open vacuum mechanical pump, repeatedly this process 3-5 time.
In addition, described method also can comprise the steps:
In step 2) after, with medium transfer polymethyl methacrylate (PMMA) by gained two dimension sulfur family crystal by substrate being transferred in other arbitrary target substrates.These target substrate, except can being previously mentioned substrate, can also be other flexibility or non-flexible substrates, as glass, polyethylene terephthalate (PET), polydimethylsiloxane (PDMS), plastics etc.
PMMA solution used can be the PMMA photoresist material series of commercial PMMA photoresist material as MicroChem company, also can be the ethyl lactate solution of massfraction at the PPMA of 3%-6% of the commercial PMMA solid particulate preparation utilizing weight-average molecular weight to be 950K.
Concrete steps are as follows:
PMMA solution is dropped in step 2) the two-dimentional sulfur family plane of crystal that obtains, with the even glue of the speed of 1000-4000 rpm 20 seconds to 60 seconds.Then toast to 180 degrees Celsius at 140 degrees Celsius, baking time is 2 to 10 minutes.Subsequently substrate is etched, the etching agent different according to the different choice of substrate and etching time.As for mica, the etching that the hydrofluoric acid solution of massfraction 1-10% carries out 30 minutes to 10 hours can be selected.To be etched complete after, two-dimentional sulfur family crystal has been transferred on PMMA film, utilizes deionized water to clean this film.Be fitted in subsequently and target substrate dry and can dissolve the solvent removing PMMA layer of PMMA with acetone etc., two-dimentional sulfur family crystal has just been transferred in target substrate.
In addition, the two-dimentional sulfur family crystal that aforesaid method prepares and this application of two-dimentional sulfur family crystal in Photoelectric Detection, also belong to protection scope of the present invention.
The present invention utilizes elastomeric stamp to carry out patterning modification to growth substrate, coring and increment process in two-dimentional sulfur family atomic crystal growth is regulated and controled, develop the method that a set of pervasive two-dimentional sulfur family atomic crystal controls growth, the two-dimentional sulfur family atomic crystal that big area, high-quality shape, nucleation site, orientation and thickness are controlled can have been obtained.The two-dimentional sulfur family atomic crystal array that this method prepares can be transferred to other any substrate, and has important potential application in fields such as Photoelectric Detection.
Accompanying drawing explanation
The device schematic diagram that the granule surface contral growth method that Fig. 1 is two-dimentional sulfur family material provided by the invention adopts.
Fig. 2 is the experiment flow figure of the granule surface contral growth method of two-dimentional sulfur family material provided by the invention.
Fig. 3 is the optical imagery of array type PDMS elastomeric stamp used in embodiment 1.
Fig. 4 be in embodiment 1 thickness main body at the Bi of 2 nanometer to 4 nanometers
2se
3the big area optical microscope image of array.
Fig. 5 be in embodiment 1 thickness main body at the Bi of 2 nanometer to 4 nanometers
2se
3the optical microscope image of array.
Fig. 6 be in embodiment 1 thickness at the Bi of 20 nanometer to 300 nanometers
2se
3the optical microscope image of array.
Fig. 7 is the Bi shown in Fig. 6 in embodiment 1
2se
3the statistical Butut of the hexagonal margin orientation of array.
Fig. 8 is the two-dimentional In obtained in embodiment 1
2se
3the optical microscope image of array.
Fig. 9 is the two-dimentional Bi obtained in embodiment 1
2te
3the optical microscope image of array.
Figure 10 is the optical microscope image of the two-dimentional GaSe array obtained in embodiment 1.
Figure 11 is the optical microscope image of the two-dimentional SnSe array obtained in embodiment 1.
Figure 12 is the Bi shown in Fig. 5 in embodiment 1
2se
3the atomic force microscope images of array and height map thereof.
Figure 13 is the experiment flow figure that the two-dimentional sulfur family atomic crystal obtained control growth in embodiment 1 shifts.
Figure 14 is for utilizing method shown in Figure 12 by the Bi shown in Fig. 6 in embodiment 1
2se
3array is transferred to the low Resolution Transmission Electron MIcrosope image on transmission micro-grid copper mesh.
Figure 15 is Bi shown in Figure 14 in embodiment 1
2se
3the high resolution transmission electron microscope image of array.
Figure 16 is by In in embodiment 1
2se
3array is transferred to SiO
2the optical microscope image of field-effect transistor/Si substrate utilizing electronics art exposure technique make and the transfer characteristic curve under different bias voltage thereof.
Figure 17 is the Bi measured by angle resolved photoelectron spectroscope
2se
3array energy band structure figure.
Figure 18 is Bi
2se
3the mobility of array and the temperature variant graph of a relation of two-dimentional carrier concentration, embedded figure is the optical photograph of hall device.
Figure 19 is having the In controlling growth and obtain in embodiment 1
2se
3the mica substrate of array directly utilizes seven In of photolithographic exposure fabrication techniques
2se
3the optical microscope image of photoelectric device in parallel.
Figure 20 is the photoelectric response performance of 2 to No. 4 devices in Figure 19 in embodiment 1.
Figure 21 is the optical microscope image of the latticed PDMS elastomeric stamp of continuous print in embodiment 2.
Figure 22 grows for utilizing seal shown in Figure 21 in embodiment 2 the latticed continuous print Bi obtained
2se
3the optical microscope image of two dimensional crystal.
Figure 23 grows for utilizing seal shown in Figure 21 in embodiment 2 the latticed continuous print In obtained
2se
3the optical microscope image of two dimensional crystal.
Figure 24 has trilateral, square, hexagon and round-shaped PDMS elastomeric stamp in embodiment 2.
Figure 25 has trilateral, square, hexagon and round-shaped Bi for what utilize the growth of seal shown in Figure 24 to obtain in embodiment 2
2se
3the optical microscope image of two dimensional crystal.
Figure 26 has trilateral, square, hexagon and round-shaped In for what utilize the growth of seal shown in Figure 24 to obtain in embodiment 2
2se
3the optical microscope image of two dimensional crystal.
Figure 27 is the optical microscope image of the PDMS elastomeric stamp in embodiment 2 with helicoidal structure.
Figure 28 grows for utilizing seal shown in Figure 27 in embodiment 2 Bi with helicoidal structure obtained
2se
3the optical microscope image of two dimensional crystal.
Figure 29 is the optical microscope image of the PDMS elastomeric stamp in embodiment 2 with dumbbell shape.
Figure 30 grows for utilizing seal shown in Figure 29 in embodiment 2 Bi with dumbbell shape obtained
2se
3the optical microscope image of two dimensional crystal.
Embodiment
Below in conjunction with specific embodiment, the present invention will be described, but the present invention is not limited thereto.
Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
In following embodiment, mica substrate used is fluorophlogopite, buys from Changchun Tai Yuan fluorophlogopite company limited.Before use, all adopt the method for mechanically peel to peel off and obtain thickness at the unsalted surface of 20 to 50 μm.
The device schematic diagram that the granule surface contral growth method of two-dimentional sulfur family material provided by the present invention adopts as shown in Figure 1.
The experiment flow figure of the granule surface contral growth method of two-dimentional sulfur family material provided by the present invention as shown in Figure 2.Wherein, numbering 1 is elastomeric stamp, is PDMS elastomeric stamp in present case.Numbering 2 is substrate, is fluorophlogopite substrate in present case, and numbering 3 is control to grow the two-dimentional sulfur family atomic crystal material obtained in substrate.Steps A is taken out for being soaked in by elastomeric stamp after in volatile solvent, then impress in substrate, step B is for waiting until that volatile solvent evaporates is complete, and step C is the physical vapor deposition growth utilizing the substrate of modifying through patterning to carry out two-dimentional sulfur family atomic crystal.
The controlled synthesis of embodiment 1, two-dimentional sulfur family atomic crystal array
1) be soaked in ethanol liquid by array type PDMS elastomeric stamp as shown in Figure 3, the stripping of PDMS oligomer forms ink, and the thickness directly impressed subsequently in fresh stripping is the fluorophlogopite substrate surface of 2mm.Draining process by heating or vacuum makes ethanol volatilize completely, obtains the fluorophlogopite substrate of modifying through patterning.
2) by source (sulfur family material In
2se
3, Bi
2se
3, SnSe or GaSe) pulverizing lastly is placed in semicircle quartz boat, be placed in silica tube central authorities, by 1) gained patterning modify fluorophlogopite substrate be placed in the silica tube of air flow line downstream far from source 7 to 16 centimeters, make step 1) the depositing temperature 50-250 DEG C lower than the depositing temperature of sulfur family material of fluorophlogopite substrate that modify of gained patterning, by silica tube central authorities and tube furnace central alignment, in the device system of access shown in Fig. 1.
Start vacuum mechanical pump, be down to after below 0.13 kPa until system pressure, close vacuum mechanical pump, close argon inlet valve after passing into high-purity argon gas to normal atmosphere, open vacuum mechanical pump, this process is cleaned device system for 3-5 time repeatedly.
Subsequently, pass into the high-purity argon gas of certain flow, its flow is generally at 20 to 1000 sccm.The pressure of the hierarchy of control is certain value simultaneously, generally between 1.3 kPas to 27 kPas.
Control tube furnace subsequently and be warming up to certain temperature, be incubated and carried out physical vapor deposition by 10 hours in 2 minutes, after deposition, naturally cool to room temperature, namely obtain the two-dimentional sulfur family crystal of corresponding sulfur family material provided by the invention.
Below as non-specifically is pointed out, high-purity argon gas flow is 200 cubic centimetres per minute, and system pressure is 6.7 kPas.
Fig. 4 and Fig. 5 carries out within 2 to 60 minutes, growing the thickness main body that the obtains Bi in 2 to 4 nanometers at 450 degrees Celsius to 500 degrees Celsius
2se
3the optical microscope image of array.Wherein Fig. 4 is big area optical microscope image, illustrates that the method can realize the growth of large-area fixed point.
Fig. 6 carries out growth in 2 to 60 minutes or at the Bi of 480 to 510 degrees Celsius of thickness carrying out obtaining to 10 hours growth for 60 minutes in 20 nanometer to 300 nanometers at 500 to 550 degrees Celsius
2se
3the optical microscope image of array.
Fig. 7 is the Bi shown in Fig. 6
2se
3the statistical Butut of the hexagonal margin orientation of array, illustrates that we achieve the control of the orientation to two-dimentional sulfur family atomic crystal.
The present invention has universality, can be used in the fixed point growth of all kinds of chalcogenide.
Fig. 8 is the two-dimentional In carrying out obtaining to 2 hours growth for 5 minutes at 650 degrees Celsius to 750 degrees Celsius
2se
3the optical microscope image of array.High-purity argon gas flow is 100 sccm, and system pressure is 2.7 kPas.
Fig. 9 is the Bi carrying out obtaining to 2 hours growth for 5 minutes at 450 degrees Celsius to 500 degrees Celsius
2te
3the optical microscope image of array.
Figure 10 is the optical microscope image of carrying out the two-dimentional GaSe array that 5 minutes obtain to 2 hours growth at 750 degrees Celsius to 850 degrees Celsius.High-purity argon gas flow is 100 sccm, and system pressure is 2.7 kPas.
Figure 11 is the optical microscope image of carrying out the two-dimentional SnSe array that 5 minutes obtain to 2 hours growth at 550 degrees Celsius to 650 degrees Celsius.High-purity argon gas flow is 100 sccm, and system pressure is 6.7 kPas.
Figure 12 is the Bi shown in Fig. 5
2se
3the atomic force microscope images of array and height map thereof, illustrate the thickness that two-dimentional sulfur family atomic crystal that the method obtains is homogeneous.
In addition, the control of gained is grown the two-dimentional sulfur family crystal obtained and is transferred in other substrates by the method that PMMA can also be utilized to assist.Its step schematic diagram as shown in figure 13, wherein numbering 1 is the mica with two-dimentional sulfur family crystal array, numbering 2 is the PMMA film with two-dimentional sulfur family atomic crystal array, numbering 3 is sandwiched between PMMA and target substrate for two-dimentional sulfur family crystal array, and numbering 4 is that two-dimentional sulfur family crystal array is in target substrate.Steps A is spin coating PMMA, step B is hf etching, and step C is by film adhered in target substrate for the PMMA with two-dimentional sulfur family crystal array, and step D removes PMMA for utilizing acetone solution.
Meanwhile, the present invention fixes a point to grow gained two dimensional crystal, has the crystallinity of height, and shows electronic structure and electricity, the photoelectric characteristic of two-dimentional sulfur family crystal uniqueness.
Figure 14 utilizes method shown in Figure 13 by the Bi shown in Fig. 6
2se
3array is transferred to the low Resolution Transmission Electron MIcrosope image on transmission micro-grid copper mesh.
Figure 15 is Bi shown in Figure 14
2se
3the high resolution transmission electron microscopy image of array, illustrates good crystalline quality.
Figure 16 is by In
2se
3array is transferred to SiO
2after in/Si substrate, the transfer characteristic curve under the optical microscope image of the field-effect transistor utilizing electronics art exposure technique to make and different bias voltage, illustrates and grows with random nucleation the In obtained
2se
3similar performance.Transfer characteristic curve uses Keithley SCS-4200 semi-conductor test instrument to measure on Micromanipulator 6200 probe station, by changing the transfer characteristic curve under bias voltage acquisition corresponding conditions.
Figure 17 is the Bi measured by angle resolved photoelectron spectroscope
2se
3array energy band structure figure, has showed and has bored by single dirac the surface state formed, and proves the Bi fixing a point to grow
2se
3what crystal had a canonical topology isolator can be with feature.
Figure 18 is Bi
2se
3the mobility of array and the temperature variant graph of a relation of two-dimentional carrier concentration, embedded figure is the optical photograph of hall device, proves the Bi fixing a point to grow
2se
3crystal has the electrical properties of single crystal-like.
Figure 19 is having the In controlling growth and obtain
2se
3the mica substrate of array directly utilizes seven In of photolithographic exposure fabrication techniques
2se
3the optical microscope image of photoelectric device in parallel.
Figure 20 is the photoelectric response performance curve of 2 to No. 4 devices in Figure 19.This curve uses KeithleySCS-4200 semi-conductor test instrument to measure on Micromanipulator 6200 probe station, measures electric current to illumination response in time by switching light sources.
The controlled shape preparation of embodiment 2, two-dimentional sulfur family atomic crystal
The present embodiment is identical with the concrete operation step of embodiment 1, and difference is to use variform PDMS elastomeric stamp to grow, and obtains the two-dimentional sulfur family atomic crystal that shape is identical with seal.This illustrates that the present invention can prepare the two-dimentional sulfur family atomic crystal of controlled shape.In the present embodiment, high-purity argon gas flow is 200 sccm, and system pressure is 6.7 kPas.In physical vapor deposition, under the condition of 490 degrees Celsius, all carry out the growth of 10 minutes.
Figure 21 is the optical microscope image of the latticed PDMS elastomeric stamp of continuous print.
Figure 22 utilizes seal shown in Figure 21 to grow the latticed continuous print Bi obtained
2se
3the optical microscope image of two-dimensional atomic crystal.
Figure 23 utilizes seal shown in Figure 21 to grow the latticed continuous print In obtained
2se
3the optical microscope image of two-dimensional atomic crystal.
Figure 24 is the optical microscope image with trilateral, square, hexagon and round-shaped PDMS elastomeric stamp.
Figure 25 be utilize seal shown in Figure 24 grow obtain there is trilateral, square, hexagon and round-shaped Bi
2se
3the optical microscope image of two dimensional crystal.
Figure 26 is that to utilize seal shown in Figure 24 to grow what obtain be have trilateral, square, hexagon and round-shaped In
2se
3the optical microscope image of two dimensional crystal.
Figure 27 is the optical microscope image of the PDMS elastomeric stamp with helicoidal structure.
Figure 28 utilizes seal shown in Figure 27 to grow the Bi with helicoidal structure obtained
2se
3the optical microscope image of two dimensional crystal.
Figure 29 is the optical microscope image of the PDMS elastomeric stamp with dumbbell shape.
Figure 30 utilizes seal shown in Figure 29 to grow the Bi with dumbbell shape obtained
2se
3the optical microscope image of two dimensional crystal.
Other character are similar to Example 1, do not repeat them here.
Claims (7)
1. prepare a method for two-dimentional sulfur family crystal, comprise the steps:
1) elastomeric stamp is first soaked in volatile solvent, then takes out described elastomeric stamp and be stamped in substrate surface, after described volatile solvent evaporates, described substrate is peeled off from described elastomeric stamp, obtain the substrate that patterning is modified;
2) in non-oxidizing atmosphere, according to gas routing downstream to the order of upstream, successively place step 1) gained patterning modify substrate and sulfur family material, physical vapor deposition is carried out by after room temperature, lower the temperature after deposition, in the substrate of the modification of described patterning, namely obtain described two-dimentional sulfur family crystal.
2. method according to claim 1, is characterized in that: described step 1) in, the material forming described elastomeric stamp is polydimethylsiloxane;
The material forming described substrate is selected from least one in white mica, fluorophlogopite, intrinsic silicon, silicon-dioxide-silicon, sapphire, Graphene, boron nitride, strontium titanate and silicon carbide;
The thickness of described substrate is 0.1 millimeter 2 millimeters;
At least one in described volatile solvent selected from ethanol, acetone and water.
3. method according to claim 1 and 2, is characterized in that: described step 2) in, described sulfur family material is selected from In
2se, Bi
2te
3, at least one in GaS and SnSe;
The gas mixture that gas in described nonoxidizing atmosphere is rare gas element or is made up of reducing gas and rare gas element;
Wherein, described rare gas element is selected from least one in nitrogen and argon gas;
Described reducing gas is specially hydrogen;
In described non-oxidizing atmosphere, the flow of gas is 20 to 1000 cubic centimetres per minute.
4., according to described method arbitrary in claim 1-3, it is characterized in that: described step 2) in physical vapor deposition step, the temperature 50-250 DEG C lower than the temperature of described sulfur family material of the substrate that described patterning is modified;
The pressure of deposition is 1.3 Qian Pa – 27 kPas;
The depositing temperature of described sulfur family material is the temperature of the fusing point 100 DEG C-200 DEG C lower than described sulfur family material;
The time of deposition is 2min-10h.
5., according to described method arbitrary in claim 1-4, it is characterized in that: described step 2) in cooling step, the mode of cooling is naturally cooling cooling.
6. the two-dimentional sulfur family crystal that in claim 1-5, arbitrary described method prepares.
7. the application of two-dimentional sulfur family crystal in Photoelectric Detection described in claim 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510072662.4A CN104651777B (en) | 2015-02-11 | 2015-02-11 | The printing-type fixed point growing method of two-dimentional sulfur family crystal |
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| CN108531981A (en) * | 2018-03-09 | 2018-09-14 | 广东工业大学 | A method of preparing two-dimentional indium trisulfide monocrystalline in mica substrate |
| CN110335809A (en) * | 2019-07-03 | 2019-10-15 | 电子科技大学 | A method of growing monocrystalline γ phase indium selenide film in mica substrate |
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| CN110117769A (en) * | 2019-05-20 | 2019-08-13 | 陕西科技大学 | A kind of preparation method of selenizing tin thin film |
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| CN103413594A (en) * | 2013-08-12 | 2013-11-27 | 北京大学 | Flexible transparent conductive material of topological insulator and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108531981A (en) * | 2018-03-09 | 2018-09-14 | 广东工业大学 | A method of preparing two-dimentional indium trisulfide monocrystalline in mica substrate |
| CN110335809A (en) * | 2019-07-03 | 2019-10-15 | 电子科技大学 | A method of growing monocrystalline γ phase indium selenide film in mica substrate |
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