CN113186599A - Preparation method of ultrathin two-dimensional germanium (110) single crystal with high crystallization quality - Google Patents
Preparation method of ultrathin two-dimensional germanium (110) single crystal with high crystallization quality Download PDFInfo
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- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 79
- 239000013078 crystal Substances 0.000 title claims abstract description 72
- 238000002425 crystallisation Methods 0.000 title claims abstract description 34
- 230000008025 crystallization Effects 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 60
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- 238000002844 melting Methods 0.000 claims abstract description 21
- 230000008018 melting Effects 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 17
- 239000000956 alloy Substances 0.000 claims abstract description 17
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 22
- 229910052721 tungsten Inorganic materials 0.000 claims description 22
- 239000010937 tungsten Substances 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 18
- 229910052733 gallium Inorganic materials 0.000 claims description 18
- 229910052786 argon Inorganic materials 0.000 claims description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 238000005229 chemical vapour deposition Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 9
- 229910052738 indium Inorganic materials 0.000 claims description 8
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 8
- 239000012498 ultrapure water Substances 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 1
- 239000004065 semiconductor Substances 0.000 abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 36
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 36
- 239000004926 polymethyl methacrylate Substances 0.000 description 36
- 229910052710 silicon Inorganic materials 0.000 description 36
- 239000010703 silicon Substances 0.000 description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- 238000005530 etching Methods 0.000 description 7
- 238000004528 spin coating Methods 0.000 description 7
- 238000007664 blowing Methods 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
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- 230000001681 protective effect Effects 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910000846 In alloy Inorganic materials 0.000 description 2
- 229910001128 Sn alloy Inorganic materials 0.000 description 2
- YZZNJYQZJKSEER-UHFFFAOYSA-N gallium tin Chemical compound [Ga].[Sn] YZZNJYQZJKSEER-UHFFFAOYSA-N 0.000 description 2
- -1 germanium alkene Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 1
- RZJQYRCNDBMIAG-UHFFFAOYSA-N [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn] Chemical class [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn] RZJQYRCNDBMIAG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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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
- C30B29/02—Elements
- C30B29/08—Germanium
-
- 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
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
-
- 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
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/64—Flat crystals, e.g. plates, strips or discs
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
The invention discloses a preparation method of an ultrathin two-dimensional germanium (110) single crystal with high crystallization quality, which comprises the following steps: (1) taking metal with a higher melting point as a supporting substrate, and pretreating the supporting substrate; (2) placing a lower melting point metal or alloy on a pretreated support substrate, introducing a germanium source at H2Heating in an/Ar atmosphere to obtain a metal or alloy substrate with low melting point and flat atomic level; (3) growing an ultrathin two-dimensional germanium (110) single crystal with high crystallization quality on a metal or alloy substrate; (4) and transferring to obtain the ultrathin two-dimensional germanium (110) single crystal with high crystallization quality. The preparation method has the advantages of simple preparation process and easily controlled conditions, and the prepared two-dimensional germanium (110) single crystal has high crystal quality, is ultrathin, realizes two-dimension and has a wide tunable band gap. The prepared two-dimensional germanium (110) single crystal is in the fields of semiconductors, nonlinear optics and the likeGreat application potential.
Description
Technical Field
The invention belongs to the technical field of semiconductor materials, and particularly relates to a preparation method of an ultrathin two-dimensional germanium (110) single crystal with high crystallization quality, which is mainly applied to the fields of semiconductor electronic devices, nonlinear optics and the like.
Background
Germanium is the earliest semiconductor applied, and has the excellent performances of narrow band gap, high carrier mobility, high near infrared light absorption performance and the like. Therefore, germanium-based materials are widely used in the fields of semiconductors, solid-state electronics, biomedicine, light detection, and the like. The preparation method thereof has made great progress at present. However, the currently prepared germanium alkene only contains a (111) crystal plane, and other crystal planes with high crystallinity are rarely reported, so that the further application of the germanium alkene in the field of semiconductors is limited. Theoretical calculation predicts that the two-dimensional structure of the germanium (110) plane has a wide tunable band gap and has outstanding potential application value in the application field of electronic devices, but the realization of controllable preparation of the germanium (110) plane is still a great challenge. There is a need for a method of preparing a two-dimensional germanium (110) single crystal having high crystal quality.
Disclosure of Invention
Based on the problems, the invention provides a preparation method of an ultrathin two-dimensional germanium (110) single crystal with high crystallization quality. The two-dimensional germanium (110) single crystal is successfully prepared by a Chemical Vapor Deposition (CVD) method, has high crystallization quality, and shows important application prospects in the fields of semiconductor electronic devices, nonlinear optics and the like.
The technical scheme provided by the invention is as follows:
a preparation method of an ultrathin two-dimensional germanium (110) single crystal with high crystallization quality comprises the following steps:
(1) taking metal with a higher melting point as a supporting substrate, and pretreating the supporting substrate;
(2) placing a lower melting point metal or alloy on a supporting substrate, introducing a germanium source in H2Heating the alloy in an/Ar atmosphere at a temperature higher than the melting temperature of the metal or alloy with a lower melting point to obtain an atomic-level flat metal substrate of the metal or alloy with the lower melting point;
(3) growing a two-dimensional germanium crystal on an atomic-level flat metal substrate to obtain an ultrathin two-dimensional germanium (110) single crystal with high crystallization quality;
(4) ultra-thin, high crystalline quality two-dimensional germanium (110) single crystals are transferred to a target substrate.
Further, the metal with higher melting point in the step (1) is selected from one of molybdenum, tungsten, titanium, vanadium, chromium, ruthenium, rhodium, palladium, platinum and iridium foil.
Still further, the higher melting point metal in step (1) is selected from molybdenum or tungsten.
Further, the pretreatment method in the step (1) comprises the following steps: the support substrate was sequentially placed in acetone, ethanol and ultrapure water for ultrasonic treatment. The size of the support substrate is preferably 1X 1cm2. The sonication time is preferably 30 min.
Further, the metal with lower melting point in the step (2) is selected from gallium, indium or tin, and the alloy is selected from an alloy consisting of two or three of gallium, indium and tin.
Further, the adding amount of the metal or the alloy with the lower melting point in the step (2) is 10-30 mg.
Further, the germanium source is germanium powder dispersed by an organic solvent, and the organic solvent is one or two of methanol, ethanol, isopropanol and acetone; the dosage of the organic solvent is 0.1-0.5 ml. Preferably, the organic solvent is selected from two of methanol, ethanol, isopropanol and acetone in a volume ratio of 1: 2-1: 10.
Further, in the step (2), if argon is introduced, the flow rate is 100-500 sccm; if hydrogen is introduced, the flow rate is 10-200 sccm.
Further, in the step (3), the method for growing the two-dimensional germanium crystal is a chemical vapor deposition method, and the deposition conditions are as follows: the method comprises the following steps of hydrogen and inert atmosphere, wherein the flow rate of the hydrogen is 10-300 sccm, the flow rate of inert gas flow is 20-500 sccm, the heating temperature is 500-1200 ℃, the temperature rise time is 20-55 min, the high-temperature heat preservation time is 0-60 min, and the growth time is 10-120 min.
Furthermore, in the step (3), the inert gas is one or two of argon and nitrogen, the flow rate of the hydrogen is 20-50 sccm, the flow rate of the inert gas is 150-600 sccm, the heating temperature is 800-1100 ℃, the temperature rise time is 25-55 min, the high-temperature heat preservation time is 0-15 min, and the growth time is 5-20 min.
Further, the specific steps of the step (3) are as follows: and (3) in hydrogen and argon or nitrogen in inert atmosphere, wherein the flow rate of the hydrogen is 20-50 sccm, the flow rate of the inert gas is 150-600 sccm, the growth substrate in the step (2) is kept at the growth temperature (500-1200 ℃) for 5-55 min, and the liquid phase gallium, indium and tin or the liquid phase alloy of the two of the gallium, the indium and the tin in the metal substrate is spontaneously converted into 110 surfaces at high temperature of germanium. After growing for 10-40 min, quickly cooling to 500 ℃, opening the cover, cooling to about 100 ℃, and collecting the ultrathin two-dimensional germanium (110) single crystal with high crystallization quality to perform the next transfer. The hydrogen and inert atmosphere in the temperature reduction stage are the same as in the temperature rise stage, and the gas flow is also the same.
Further, the target substrate is one of a silicon wafer, silicon dioxide, a quartz plate, a plastic film, a mica plate, a hafnium oxide plate or beryllium oxide.
Further, the specific steps of the step (4) are as follows: spin-coating polymethyl methacrylate (PMMA) on a two-dimensional germanium (110) single crystal under the conditions of 1500-2500 r/min and 60s, placing for 8-12H, and etching with hydrochloric acid (HCl) (HCl: H)2The volume ratio of O is 1: 1-1: 5) for 8-12 h, the PMMA film with the sample falls off from the substrate, the PMMA film is supported by a clean silicon wafer, then the silicon wafer with the PMMA film is heated on a heating table at 50-100 ℃ for 30min, the silicon wafer is placed into micro-boiling acetone to be soaked for 5min to remove PMMA, the silicon wafer is taken out from the acetone and dried by blowing with nitrogen, and the ultrathin two-dimensional germanium (110) single crystal with high crystallization quality can be obtained.
The invention has the following beneficial effects:
1. the synthesis process is simple, and the conditions are easy to control;
2. the prepared two-dimensional germanium (110) single crystal has high crystallization quality;
3. provides an ultrathin two-dimensional germanium (110) single crystal with high crystallization quality, and has important application prospect in the fields of semiconductor electronic devices, nonlinear optics and the like;
4. the invention provides a new idea for preparing the two-dimensional germanium (110) single crystal with high crystallization quality and has higher reference value.
Drawings
FIG. 1 is a schematic diagram of a process for synthesizing an ultra-thin, high crystalline quality two-dimensional germanium (110) single crystal;
FIG. 2 is an OM diagram of an ultra-thin, high crystalline quality two-dimensional germanium (110) single crystal;
FIG. 3 is SEM and mapping of an ultra-thin, high crystalline quality two-dimensional germanium (110) single crystal;
fig. 4 is a Raman diagram of a prepared ultra-thin, high crystalline quality two-dimensional germanium (110) single crystal.
Detailed Description
The following description will be made for the embodiments of the present invention, which are implemented on the premise of the present invention as a technical solution, but the scope of the present invention is not limited to the following embodiments.
Example 1
Preparation of two-dimensional germanium (110) single crystal
The method comprises the following steps:
1) selecting the thickness of 50 μm and the size of 1 × 1cm2The tungsten foil is used as a supporting substrate, and ultrasonic treatment is carried out for 30min in acetone, ethanol and ultra-pure water in sequence.
2) 20mg of gallium was placed on a tungsten plate and allowed to adhere thereto under heating at 40 ℃.
3) 2 drops of organic methanol solution with fully dispersed germanium powder are added dropwise.
4) Heating the tungsten substrate adhered with the gallium dropwise organic methanol solution fully dispersed with germanium powder obtained in the step 3) to a growth temperature of 1080 ℃ from room temperature through 45min in a CVD reaction furnace under the conditions of hydrogen (the flow rate is 20sccm) and argon (the flow rate is 200sccm), then keeping the temperature at a high temperature for 5min so as to form an atomic-level flat metal substrate of the gallium, quickly cooling after 10min of heat preservation reaction, opening a cover to cool when the temperature is 500 ℃, closing the hydrogen when the temperature is reduced to 100 ℃, closing a protective gas argon when the temperature is lower than 100 ℃, taking out a sample, and obtaining the ultrathin two-dimensional germanium (110) single crystal with high crystallization quality on the growth substrate obtained in the step 3). The process of preparing the ultra-thin high-crystalline-quality two-dimensional germanium (110) single crystal is shown in fig. 1, fig. 2 is an OM image of the ultra-thin high-crystalline-quality two-dimensional germanium (110) single crystal, and fig. 3 is SEM and mapping images of the ultra-thin high-crystalline-quality two-dimensional germanium (110) single crystal. Fig. 4 is a Raman diagram of a prepared ultra-thin, high crystalline quality two-dimensional germanium (110) single crystal. The Raman image of the two-dimensional germanium (110) single crystal has extremely narrow main peak width, which shows that the synthesized two-dimensional germanium (110) single crystal has very high crystal quality.
5) Transferring the ultrathin two-dimensional germanium (110) single crystal with high crystallization quality prepared in the step 3) to a target silicon substrate, and specifically comprises the following steps: spin-coating polymethyl methacrylate (PMMA) on a two-dimensional germanium (110) single crystal under the conditions of 2000r/min and 60s, standing for 8-12H, and etching with hydrochloric acid (HCl: H)2The volume ratio of O is 1:3) for 12h, the PMMA film with the sample falls off from the substrate, a clean silicon wafer is used for bearing, then the silicon wafer with the PMMA film is heated on a hot table at 80 ℃ for 30min, the silicon wafer is placed into micro-boiling acetone for soaking for 5min to remove PMMA, the silicon wafer is taken out from the acetone and dried by blowing with nitrogen, and the ultrathin two-dimensional germanium (110) single crystal with high crystallization quality can be obtained.
Example 2
Preparation of two-dimensional germanium (110) single crystal
The method comprises the following steps:
1) selecting the thickness of 50 μm and the size of 1 × 1cm2The tungsten foil is used as a supporting substrate, and ultrasonic treatment is carried out for 30min in acetone, ethanol and ultra-pure water in sequence.
2) 20mg of gallium-indium alloy was placed on a tungsten plate and allowed to adhere thereto under heating at 40 ℃.
3)1 drop of organic methanol solution with fully dispersed germanium powder is added dropwise.
4) Heating the tungsten substrate adhered with the gallium-indium alloy dropwise with the organic methanol solution fully dispersed with germanium powder obtained in the step 3) to a growth temperature of 1080 ℃ from room temperature through 45min in a CVD reaction furnace under the conditions of hydrogen (the flow rate is 10sccm) and argon (the flow rate is 300sccm), then keeping the temperature at a high temperature for 5min so as to form an atomic-level flat metal substrate of gallium, quickly cooling after 10min of heat preservation reaction, closing the hydrogen when the temperature is reduced to 100 ℃, protecting argon, taking out a sample, and obtaining the ultrathin two-dimensional germanium (110) single crystal with high crystallization quality on the growth substrate obtained in the step 3).
5) Transferring the ultrathin two-dimensional germanium (110) single crystal with high crystallization quality prepared in the step 3) to a target silicon substrate, and specifically comprises the following steps: spin-coating polymethyl methacrylate (PMMA) on a two-dimensional germanium (110) single crystal under the conditions of 2000r/min and 60s, standing for 8-12H, and etching with hydrochloric acid (HCl: H)2The volume ratio of O is 1:3) for 12h, the PMMA film with the sample falls off from the substrate, a clean silicon wafer is used for bearing, then the silicon wafer with the PMMA film is heated on a hot table at 80 ℃ for 30min, the silicon wafer is placed into micro-boiling acetone for soaking for 5min to remove PMMA, the silicon wafer is taken out from the acetone and dried by blowing with nitrogen, and the ultrathin two-dimensional germanium (110) single crystal with high crystallization quality can be obtained.
Example 3
Preparation of two-dimensional germanium (110) single crystal
The method comprises the following steps:
1) selecting the thickness of 50 μm and the size of 1 × 1cm2The tungsten foil is used as a supporting substrate, and ultrasonic treatment is carried out for 30min in acetone, ethanol and ultra-pure water in sequence.
2) 10mg of gallium was placed on a tungsten plate and allowed to adhere thereto under heating at 40 ℃.
3) 2 drops of organic methanol solution with fully dispersed germanium powder are added dropwise.
4) Heating the tungsten substrate adhered with the gallium dropwise organic methanol solution fully dispersed with germanium powder obtained in the step 3) to a growth temperature of 1080 ℃ from room temperature through 55min in a CVD reaction furnace under the conditions of hydrogen (the flow rate is 30sccm) and argon (the flow rate is 100sccm), then keeping the temperature at a high temperature for 5min so as to form an atomic-level flat metal substrate of the gallium, quickly cooling after carrying out heat preservation reaction for 15min, opening a cover to cool when the temperature is reduced to 500 ℃, closing the hydrogen when the temperature is reduced to 200 ℃, closing a protective gas argon when the temperature is lower than 100 ℃, taking out a sample, namely obtaining the ultrathin two-dimensional germanium (110) single crystal with high crystallization quality on the growth substrate obtained in the step 3).
5) Transferring the ultrathin two-dimensional germanium (110) single crystal with high crystallization quality prepared in the step 3) to a target silicon substrate, and specifically comprises the following steps: spin-coating polymethyl methacrylate (PMMA) on a two-dimensional germanium (110) single crystal under the conditions of 1500r/min and 60s, standing for 8-12H, and etching with hydrochloric acid (HCl: H)2Volume of OThe ratio is 1:2) and 8h, the PMMA film with the sample falls off from the substrate, a clean silicon wafer is used for bearing, then the silicon wafer with the PMMA film is heated on a hot table at 80 ℃ for 30min, the silicon wafer is placed into micro-boiling acetone to be soaked for 8min to remove PMMA, the silicon wafer is taken out from the acetone and is dried by blowing with nitrogen, and the ultrathin two-dimensional germanium (110) single crystal with high crystallization quality can be obtained.
Example 4
Preparation of two-dimensional germanium (110) single crystal
The method comprises the following steps:
1) selecting the thickness of 50 μm and the size of 1 × 1cm2The tungsten foil is used as a supporting substrate, and ultrasonic treatment is carried out for 30min in acetone, ethanol and ultra-pure water in sequence.
2) 20mg of indium was placed on a tungsten plate and allowed to adhere thereto under heating at 340 ℃.
3) 2 drops of organic isopropanol solution with fully dispersed germanium powder are added dropwise.
4) Heating the tungsten substrate adhered with the indium drop organic methanol solution fully dispersed with germanium powder obtained in the step 3) to a growth temperature of 1080 ℃ from room temperature through 45min in a CVD reaction furnace under the conditions of hydrogen (the flow rate is 20sccm) and argon (the flow rate is 200sccm), then keeping the high temperature for 5min so as to form an atomic-level flat metal substrate of gallium, quickly cooling after 10min of heat preservation reaction, opening a cover to cool when the temperature is reduced to 500 ℃, closing the hydrogen when the temperature is reduced to 100 ℃, closing a protective gas argon when the temperature is lower than 100 ℃, taking out a sample, and obtaining the ultrathin two-dimensional germanium (110) single crystal with high crystallization quality on the growth substrate obtained in the step 3).
5) Transferring the ultrathin two-dimensional germanium (110) single crystal with high crystallization quality prepared in the step 3) to a target silicon substrate, and specifically comprises the following steps: spin-coating polymethyl methacrylate (PMMA) on a two-dimensional germanium (110) single crystal under the conditions of 2000r/min and 60s, standing for 8-12H, and etching with hydrochloric acid (HCl: H)2The volume ratio of O is 1:4) for 12h, the PMMA film with the sample falls off from the substrate, a clean silicon wafer is used for bearing, then the silicon wafer with the PMMA film is heated on a hot table at 80 ℃ for 30min, the silicon wafer is placed into micro-boiling acetone for soaking for 5min to remove PMMA, the silicon wafer is taken out from the acetone and dried by nitrogen, and the ultrathin high-crystalline substance silicon wafer can be obtainedA quantity of a two-dimensional germanium (110) single crystal.
Example 5
Preparation of two-dimensional germanium (110) single crystal
The method comprises the following steps:
1) selecting the thickness of 50 μm and the size of 1 × 1cm2The tungsten foil is used as a supporting substrate, and ultrasonic treatment is carried out for 30min in acetone, ethanol and ultra-pure water in sequence.
2) 20mg of gallium-tin alloy was placed on a tungsten plate and allowed to adhere thereto under heating at 40 ℃.
3)1 drop of organic methanol solution with fully dispersed germanium powder is added dropwise.
4) Heating the tungsten substrate adhered with the gallium-tin alloy dropwise with the organic methanol solution fully dispersed with germanium powder obtained in the step 3) to a growth temperature of 1080 ℃ from room temperature through 45min in a CVD reaction furnace under the conditions of hydrogen (the flow rate is 30sccm) and argon (the flow rate is 300sccm), then keeping the temperature at a high temperature for 5min so as to form an atomic-level flat metal substrate of gallium, quickly cooling after 10min of heat preservation reaction, opening a cover to cool when the temperature is 500 ℃, closing the hydrogen when the temperature is reduced to 200 ℃, closing a protective gas argon when the temperature is lower than 100 ℃, taking out a sample, namely obtaining the ultrathin two-dimensional germanium (110) single crystal with high crystallization quality on the growth substrate obtained in the step 3).
5) Transferring the ultrathin two-dimensional germanium (110) single crystal with high crystallization quality prepared in the step 3) to a target silicon substrate, and specifically comprises the following steps: spin-coating polymethyl methacrylate (PMMA) on a two-dimensional germanium (110) single crystal under the conditions of 2000r/min and 60s, standing for 8-12H, and etching with hydrochloric acid (HCl: H)2The volume ratio of O is 1:3) for 12h, the PMMA film with the sample falls off from the substrate, a clean silicon wafer is used for bearing, then the silicon wafer with the PMMA film is heated on a hot table at 80 ℃ for 30min, the silicon wafer is placed into micro-boiling acetone for soaking for 5min to remove PMMA, the silicon wafer is taken out from the acetone and dried by blowing with nitrogen, and the ultrathin two-dimensional germanium (110) single crystal with high crystallization quality can be obtained.
Example 6
Preparation of two-dimensional germanium (110) single crystal
The method comprises the following steps:
1) the thickness of the material is 50 μm and the size is selected to be1*1cm2The tungsten foil is used as a supporting substrate, and ultrasonic treatment is carried out for 30min in acetone, ethanol and ultra-pure water in sequence.
2) 20mg of gallium was placed on a tungsten plate and allowed to adhere thereto under heating at 40 ℃.
3) 2 drops of an organic solution in which germanium powder was sufficiently dispersed (methanol: isopropanol 10: 1).
4) Heating the tungsten substrate adhered with the gallium organic solution with fully dispersed germanium powder obtained in the step 3) to a growth temperature of 1080 ℃ from room temperature through 45min under the conditions of hydrogen (the flow rate is 20sccm) and argon (the flow rate is 200sccm) in a CVD reaction furnace, then keeping the high temperature for 5min so as to form an atomic-level flat metal substrate of the gallium, carrying out heat preservation reaction for 10min, then rapidly cooling to 500 ℃, opening a cover to cool, closing the hydrogen when the temperature is reduced to 200 ℃, closing a protective gas argon when the temperature is lower than 100 ℃, taking out a sample, namely obtaining the ultrathin two-dimensional germanium (110) single crystal with high crystallization quality on the growth substrate obtained in the step 3)
5) Transferring the ultrathin two-dimensional germanium (110) single crystal with high crystallization quality prepared in the step 3) to a target silicon substrate, and specifically comprises the following steps: spin-coating polymethyl methacrylate (PMMA) on a two-dimensional germanium (110) single crystal under the conditions of 2000r/min and 60s, standing for 8-12H, and etching with hydrochloric acid (HCl: H)2The volume ratio of O is 1:3) for 12h, the PMMA film with the sample falls off from the substrate, a clean silicon wafer is used for bearing, then the silicon wafer with the PMMA film is heated on a hot table at 80 ℃ for 30min, the silicon wafer is placed into micro-boiling acetone for soaking for 5min to remove PMMA, the silicon wafer is taken out from the acetone and dried by blowing with nitrogen, and the ultrathin two-dimensional germanium (110) single crystal with high crystallization quality can be obtained.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made by those skilled in the art within the technical scope of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of an ultrathin two-dimensional germanium (110) single crystal with high crystallization quality is characterized by comprising the following steps:
(1) taking metal with a higher melting point as a supporting substrate, and pretreating the supporting substrate;
(2) placing a lower melting point metal or alloy on a supporting substrate, introducing a germanium source in H2Heating the alloy in an/Ar atmosphere at a temperature higher than the melting temperature of the metal or alloy with a lower melting point to obtain an atomic-level flat metal substrate of the metal or alloy with the lower melting point;
(3) growing a two-dimensional germanium crystal on an atomic-level flat metal substrate to obtain an ultrathin two-dimensional germanium (110) single crystal with high crystallization quality;
(4) ultra-thin, high crystalline quality two-dimensional germanium (110) single crystals are transferred to a target substrate.
2. The method of claim 1, wherein: the metal with higher melting point in the step (1) is selected from one of molybdenum, tungsten, titanium, vanadium, chromium, ruthenium, rhodium, palladium, platinum and iridium foil.
3. The method of claim 2, wherein the higher melting point metal of step (1) is selected from molybdenum or tungsten.
4. The method according to claim 1, wherein the pretreatment in step (1) comprises: the support substrate was sequentially placed in acetone, ethanol and ultrapure water for ultrasonic treatment.
5. The method of claim 1, wherein the lower melting point metal in step (2) is selected from gallium, indium or tin, and the alloy is selected from alloys of two or three of gallium, indium and tin.
6. The method according to claim 1, wherein the lower melting point metal or alloy is added in the step (2) in an amount of 10 to 30 mg.
7. The method according to claim 1, wherein the germanium source is germanium powder dispersed by an organic solvent selected from one or two of methanol, ethanol, isopropanol and acetone; the dosage of the organic solvent is 0.1-0.5 ml.
8. The method as claimed in claim 1, wherein in the step (2), if argon is introduced, the flow rate is 100-500 sccm; if hydrogen is introduced, the flow rate is 10-200 sccm.
9. The method according to claim 1, wherein in the step (3), the method for growing the two-dimensional germanium crystal is a chemical vapor deposition method, and the deposition conditions are as follows: the method comprises the following steps of hydrogen and inert atmosphere, wherein the flow rate of the hydrogen is 10-300 sccm, the flow rate of inert gas flow is 20-500 sccm, the heating temperature is 500-1200 ℃, the temperature rise time is 20-55 min, the high-temperature heat preservation time is 0-60 min, and the growth time is 10-120 min.
10. The method as claimed in claim 9, wherein in the step (3), the inert gas is one or two of argon and nitrogen, the flow rate of hydrogen is 20 to 50sccm, the flow rate of the inert gas is 150 to 600sccm, the heating temperature is 800 to 1100 ℃, the temperature rising time is 25 to 55min, the high-temperature holding time is 0 to 15min, and the growth time is 5 to 20 min.
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