METHOD FOR PREPARING ULTRATHIN TWO-DIMENSIONAL NANOSHEETS AND APPLICATIONS THEREOF
20200403111 ยท 2020-12-24
Inventors
- Jie Xiong (Chengdu, CN)
- Chuanhui Gong (Chengdu, CN)
- Yang Wang (Chengdu, CN)
- Gaofeng Rao (Chengdu, CN)
- Chujun Yin (Chengdu, CN)
- Chaoyi Yan (Chengdu, CN)
- Junwei Chu (Chengdu, CN)
- Jianwen Huang (Chengdu, CN)
- Miao ZHANG (Chengdu, CN)
- Xinrui Chen (Chengdu, CN)
- Yuqing Liu (Chengdu, CN)
- Chunyang Wu (Chengdu, CN)
- Xianfu Wang (Chengdu, CN)
- Liping Dai (Chengdu, CN)
- Wanli Zhang (Chengdu, CN)
- Yanrong Li (Chengdu, CN)
Cpc classification
H01L31/032
ELECTRICITY
H01L31/09
ELECTRICITY
H01L31/036
ELECTRICITY
C23C14/16
CHEMISTRY; METALLURGY
C30B25/183
CHEMISTRY; METALLURGY
C30B25/10
CHEMISTRY; METALLURGY
International classification
H01L31/18
ELECTRICITY
C23C14/04
CHEMISTRY; METALLURGY
C30B25/10
CHEMISTRY; METALLURGY
H01L31/032
ELECTRICITY
Abstract
A method for preparing an ultrathin two-dimensional (2D) monocrystalline nanosheet, the method including: 1) placing BiX.sub.3 powder where X=I, Br, or Cl in a crucible, and putting the crucible on a first heating zone of a furnace disposed at a gas inlet of a quartz tube; placing substrates covered with metal sheets on a second heating zone of the furnace disposed at a gas outlet of the quartz tube; 2) vacuumizing the quartz tube; pumping Ar gas into the quartz tube until the air pressure is 101.325 kPa; pumping a carrier gas into the quartz tube; and 3) heating and maintaining the second heating zone; heating the first heating zone for BiX.sub.3 evaporation until producing chemical reaction between BiX.sub.3 and the metal sheets, and preparing ultrathin 2D nanosheets on the substrates simultaneously; and cooling the substrate naturally to 15-30 C.
Claims
1. A method, comprising: placing BiX.sub.3 powder where X=I, Br, or Cl in a crucible, and putting the crucible on a first heating zone of a furnace disposed at a gas inlet of a quartz tube; placing substrates covered with metal sheets on a second heating zone of the furnace disposed at a gas outlet of the quartz tube; vacuumizing the quartz tube by a mechanical pump; pumping Ar gas into the quartz tube until a gas pressure is equal to 101.325 kPa; pumping a carrier gas into the quartz tube and adjusting and maintaining a steady flow rate of the carrier gas; and heating and maintaining the second heating zone; heating the first heating zone to evaporate BiX.sub.3 until the ultrathin 2D nanosheets are formed on the substrate; and cooling the substrate naturally to 15-30 C.
2. The method of claim 1, wherein the metal sheets are unoxidized transition or naturally oxidized transition; the metal sheets and the substrates construct micro-nano scale confined space, and a gap distance between the metal sheets and the substrates is 0-100 microns.
3. The method of claim 2, wherein the transition metal sheets are copper sheets or iron sheets.
4. The method of claim 1, wherein the naturally oxidized transition metal sheets are oxidized in the air at 15-30 C. for 1-2 days.
5. The method, comprising: 1) placing BiBr.sub.3 powder in a crucible, and putting the crucible on a first heating zone of a furnace disposed at a gas inlet of a quartz tube; placing substrates covered with copper sheets on a second heating zone of the furnace disposed at a gas outlet of the quartz tube; wherein a confined spacing gap between the copper sheets and the substrates is 0-100 m; 2) vacuumizing the quartz tube to less than 0.1 Pa; pumping Ar gas into the quartz tube until an air pressure is equal to one atmosphere pressure; pumping mixed gas of Ar and H.sub.2 to the quartz tube and adjusting and maintaining a steady flow rate of the mixed gas; and 3) heating the second heating zone to a temperature of 275-325 C. and keeping the temperature for 10-60 min; heating the first heating zone to 200-275 C. for 3-20 min until producing chemical reaction between BiBr.sub.3 and metal sheets, and preparing ultrathin 2D nanosheets on the substrates simultaneously; and cooling the substrate naturally to 15-30 C., thereby yielding a two-dimensional ultrathin monocrystalline CuBr nanosheet.
6. The method of claim 5, wherein the substrates in 1) are mica or graphene substrate and a mass of the BiBr.sub.3 powder is 2-200 mg.
7. The method of claim 5, wherein the H.sub.2 in 2) is 0-10% (v/v) in the mixed gas and a flow velocity of the mixed gas is about 50-100 sccm.
8. A two-dimensional ultrathin monocrystalline CuBr nanosheet prepared according to the method of claim 5, wherein a thickness of the two-dimensional ultrathin monocrystalline CuBr nanosheet is 0.9-200 nm and a sheet size thereof is 2-150 m.
9. A method for preparing a photodetector based on the two-dimensional ultrathin monocrystalline CuBr nanosheet of claim 8, the method comprising: depositing a silver electrode with a thickness of 25-100 nm using a copper mesh as a mask on the two-dimensional ultrathin monocrystalline CuBr nanosheet.
10. A method, comprising: 1) placing BiI.sub.3 powder in a crucible, and putting the crucible on a first heating zone of a furnace disposed at a gas inlet of a quartz tube; placing substrates covered with naturally oxidized iron sheets on a second heating zone of the furnace disposed at a gas outlet of the quartz tube; 2) vacuumizing the quartz tube to less than 1 Pa; pumping Ar gas into the quartz tube until an air pressure is equal to one atmosphere pressure; continuously pumping the Ar gas to the quartz tube with a flow velocity of 10-75 sccm; and 3) heating the second heating zone to a temperature of 370-450 C. and keeping the temperature for 10-60 min; heating the first heating zone to 450-520 C. for 5-20 min until producing chemical reaction between BiI.sub.3 and metal sheets, and preparing ultrathin 2D nanosheets on the substrates simultaneously; and cooling the substrate naturally to 15-30 C., thereby yielding a two-dimensional ultrathin monocrystalline Fe.sub.3O.sub.4 nanosheet.
11. The method of claim 10, wherein a mass of the BiI.sub.3 powder in 1) is 1-20 mg and the substrates are mica.
12. The method of claim 10, wherein the naturally oxidized iron sheets in 1) is obtained by placing iron sheets in the air with 15-30 C. for 1 to 2 days.
13. A two-dimensional ultrathin monocrystalline Fe.sub.3O.sub.4 nanosheet prepared according to the method of claim 10, wherein a thickness of the two-dimensional ultrathin monocrystalline Fe.sub.3O.sub.4 nanosheet is 1.95-100 nm and a sheet size thereof is 1-20 nm.
14. A method for preparing the two-dimensional ultrathin monocrystalline Fe.sub.3O.sub.4 nanosheet of claim 13, the method comprising: transferring the Fe.sub.3O.sub.4 nanosheet from a mica substrate to an Si/SiO.sub.2 substrate; depositing an electrode by electron beam exposure and thermal evaporation, the electrode comprising a Cr with a thickness of 1-10 nm and an Au with a thickness of 10-100 nm.
15. A method, comprising: 1) placing BiBr.sub.3 powder in a crucible, and putting the crucible on a first heating zone of a furnace disposed at a gas inlet of a quartz tube; placing substrates covered with naturally oxidized copper sheets on a second heating zone of the furnace disposed at a gas outlet of the quartz tube; 2) vacuumizing the quartz tube to less than 0.1 Pa; pumping Ar gas into the quartz tube until an air pressure is equal to one atmosphere pressure; continuously pumping the Ar gas to the quartz tube with a flow velocity of 25-50 sccm; and 3) heating the second heating zone to a temperature of 380-400 C. and keeping the temperature for 1-60 min; heating the first heating zone to 220-275 C. for 5-30 min until producing chemical reaction between BiI.sub.3 and metal sheets, and preparing ultrathin 2D nanosheets on the substrates simultaneously; and cooling the substrate naturally to 15-30 C., thereby yielding a two-dimensional ultrathin monocrystalline BiOBr nanosheet.
16. The method of claim 15, wherein a mass of the BiBr.sub.3 powder in 1) is 2-50 mg.
17. The method of claim 15, wherein the naturally oxidized copper sheets in 1) is obtained by placing the copper sheets in the air with 15-30 C. for 1 to 2 days.
18. The method of claim 15, wherein the cooling in 3) is natural cooling or rapid cooling, and a rate of the rapid cooling is over 50 C./min.
19. A two-dimensional ultrathin monocrystalline BiOBr nanosheet prepared according to the method of claim 15, wherein a growth crystal surface of the two-dimensional ultrathin monocrystalline BiOBr nanosheet is (001), a thickness is 0.57-200 nm, and a sheet size is 0.5-70 nm.
20. A method for preparing a photodetector based on the two-dimensional ultrathin monocrystalline BiOBr nanosheet of claim 19, the method comprising: transferring the BiOBr nanosheet with a thickness of 0.57 nm-20 nm onto a silicon substrate using a wet method, and manufacturing an electrode by electron beam lithography and thermal evaporation.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION
[0065] To further illustrate the invention, embodiments detailing a method to space-confined synthesis of ultrathin two-dimensional nanosheets are described below. It should be noted that the following embodiments are intended to describe and not to limit the disclosure.
Example 1
[0066] A method for preparing ultrathin 2D monocrystalline CuBr nanosheets, the method comprises:
[0067] 1) placing 10 mg of BiBr.sub.3 powder in an Al.sub.2O.sub.3 crucible; putting the Al.sub.2O.sub.3 crucible in the middle of the first heating zone of a furnace with a quartz tube, which is locating at the gas inlet of the quartz tube; placing a mica substrate covered with copper sheets in the middle of the second heating zone of the quartz tube, which is locating at the gas outlet of the quartz tube; the confined spacing gap between the copper sheets and the substrate is 50 m;
[0068] 2) vacuumizing the quartz tube to less than 0.1 Pa; pumping the Ar gas at 500 sccm into the quartz tube to remove the residual air in the tube, until the air pressure is equal to atmosphere pressure; pumping the Ar/H.sub.2 mixture gas, which takes up 5% of H.sub.2 volume, and the flow velocity of the mixture gas is 50 sccm;
[0069] 3) heating the second heating zone to 325 C. within 15 min and keeping the temperature for 15 min; heating the first heating zone to 200 C. within 10 min and keeping the temperature for 5 min; evaporating the BiBr.sub.3 powder until ultrathin 2D monocrystalline CuBr nanosheets are formed on the substrate; and cooling the substrate naturally to 30 C.
[0070] The method for preparing a photodetector comprising the nanocrystalline CuBr nanosheets, comprising the following steps of: covering a 600-mesh nickel grid on the ultrathin 2D nanocrystalline CuBr nanosheets, and depositing Ag electrodes with thickness of 50 nm on the surface of the ultrathin 2D nanocrystalline CuBr sheets by hot evaporation.
[0071] The optical micrograph of the ultrathin 2D monocrystalline CuBr nanosheet prepared by Example 1 is shown in
Example 2
[0072] A method for preparing ultrathin 2D monocrystalline CuBr nanosheets, the method comprises:
[0073] 1) placing 10 mg of BiBr.sub.3 powder in an Al.sub.2O.sub.3 crucible; putting the Al.sub.2O.sub.3 crucible in the middle of the first heating zone of a furnace with a quartz tube, which is locating at the gas inlet of the quartz tube; placing a mica substrate covered with copper sheets in the middle of the second heating zone of the quartz tube, which is locating at the gas outlet of the quartz tube; the confined spacing gap between the copper sheets and the substrate is 0 m;
[0074] 2) vacuumizing the quartz tube to less than 0.1 Pa; pumping the Ar gas at 500 sccm into the quartz tube to remove the residual air in the tube, until the air pressure is equal to atmosphere pressure; pumping the Ar/H.sub.2 mixture gas, which takes up 5% of H.sub.2 volume, and the flow velocity of the mixture gas is 50 sccm;
[0075] 3) heating the second heating zone to 325 C. within 15 min and keeping the temperature for 15 min; then heating the first heating zone to 220 C. within 10 min and keeping the temperature for 5 min; evaporating the BiBr.sub.3 powder until ultrathin 2D monocrystalline CuBr nanosheets are formed on the substrate; and cooling the substrate naturally to 30 C.
[0076] The AFM scanning diagram of monocrystalline CuBr nanosheets according to Example 2 is shown in
Example 3
[0077] A method for preparing ultrathin 2D monocrystalline CuBr nanosheets, the method comprises:
[0078] 1) placing 50 mg of BiBr.sub.3 powder in an Al.sub.2O.sub.3 crucible, then putting the Al.sub.2O.sub.3 crucible in the middle of the first heating zone of a furnace with a quartz tube, which is locating at the gas inlet of the quartz tube; placing a mica substrate covered with copper sheets in the middle of the second heating zone of the quartz tube, which is locating at the gas outlet of the quartz tube; the confined spacing gap between the copper sheets and the substrate is 25 m;
[0079] 2) vacuumizing the quartz tube to less than 0.1 Pa; pumping the Ar gas at 500 sccm into the quartz tube to remove the residual air in the tube, until the air pressure is equal to atmosphere pressure; pumping the Ar/H.sub.2 mixture gas, which takes up 5% of H.sub.2 volume, and the flow velocity of the mixture gas is 75 sccm;
[0080] 3) heating the second heating zone to 305 C. within 15 min and keeping the temperature for 15 min; heating the first heating zone to 275 C. within 10 min and keeping the temperature for 5 min; evaporating the BiBr.sub.3 powder until ultrathin 2D monocrystalline nanosheets on the substrates simultaneously; and cooling the substrate naturally to 30 C.
Example 4
[0081] Ultrathin 2D monocrystalline CuBr nanosheets were prepared in accordance with the method of Example 2, except that the spacing between the copper sheets and the mica substrate in 1) was adjusted to 100 m while remaining unchanged in other steps.
[0082] The thickness of monocrystalline CuBr nanosheets prepared in Example 4 is up to 200 nm.
Example 5
[0083] A method for preparing ultrathin 2D monocrystalline Fe.sub.3O.sub.4 nanosheets, the method comprises:
[0084] 1) placing 10 mg of BiI.sub.3 powder in an Al.sub.2O.sub.3 crucible, then putting the Al.sub.2O.sub.3 crucible in the middle of the first heating zone of a furnace with a quartz tube, which is locating at the gas inlet of the quartz tube; placing a mica substrate covered with naturally oxidized iron sheets in the middle of the second heating zone of the quartz tube, which is locating at the gas outlet of the quartz tube;
[0085] 2) vacuumizing the quartz tube to less than 1 Pa; pumping the Ar gas into the quartz tube until the air pressure is equal to atmosphere pressure; after that, pumping the Ar gas as a current-carrying gas with a flow rate of 50 sccm;
[0086] 3) heating the second heating zone to 400 C. and keeping the temperature for 20 min; heating the first heating zone to 470 C. for 10 min, and evaporating the BiI.sub.3 powder until ultrathin 2D nanosheets are formed on the mica substrate; and cooling the substrate naturally to 15 C.
[0087] The method for preparing a photodetector comprising the ultrathin 2D monocrystalline Fe.sub.3O.sub.4 nanosheets, comprising: transferring the Fe.sub.3O.sub.4 monocrystalline nanosheets from the mica substrate onto a Si/SiO.sub.2 substrate, and depositing a Cr electrode with a thickness of 5 nm and an Au electrode with a thickness of 50 nm by electron beam exposure and thermal evaporation.
[0088] The optical micrograph of monocrystalline Fe.sub.3O.sub.4 nanosheets prepared by this Example is shown in
Example 6
[0089] The ultrathin 2D monocrystalline Fe.sub.3O.sub.4 nanosheets were prepared in accordance with Example 5. The temperature in the first heating zone and the second heating zone in 3) was only adjusted to 520 C. and 420 C., respectively, and kept for 1 hour, while remaining unchanged in other steps.
[0090] The AFM scanning diagram of monocrystalline Fe.sub.3O.sub.4 nanosheets prepared by Example 6 is shown in
Example 7
[0091] A method for preparing ultrathin 2D monocrystalline Fe.sub.3O.sub.4 nanosheets, the method comprises:
[0092] 1) placing 10 mg of BiI.sub.3 powder in an Al.sub.2O.sub.3 crucible; putting the Al.sub.2O.sub.3 crucible in the middle of the first heating zone of a furnace with a quartz tube, which is locating at the gas inlet of the quartz tube; placing a mica substrate covered with naturally oxidized iron sheets in the middle of the second heating zone of the quartz tube, which is locating at the gas outlet of the quartz tube;
[0093] 2) vacuumizing the quartz tube to less than 1 Pa; pumping Ar gas at a flow rate of 500 sccm into the quartz tube until the air pressure is equal to atmosphere pressure; and pumping the Ar gas as a current-carrying gas with a flow rate of 75 sccm;
[0094] 3) heating the second heating zone to 390 C. and keeping the temperature for 20 min; heating the first heating zone to 460 C. for 20 min; evaporating the BiI.sub.3 powder until ultrathin 2D monocrystalline Fe.sub.3O.sub.4 nanosheets are formed on the substrates; and cooling the substrate naturally to 15 C.
[0095] The ultrathin 2D monocrystalline Fe.sub.3O.sub.4 nanosheets prepared by this Example has a thickness up to 100 nm.
Comparison Example 1
[0096] The 2D ultrathin monocrystalline Fe.sub.3O.sub.4 nanosheets were prepared in accordance with Example 5, but not placing BiI.sub.3 powder in 1), and other steps remained unchanged.
[0097] The contrast Example 1 shows that the ultrathin 2D monocrystalline Fe.sub.3O.sub.4 nanosheets fail to grow on the mica substrate.
Comparison Example 2
[0098] The ultrathin 2D monocrystalline Fe.sub.3O.sub.4 nanosheets were prepared in accordance with Example 7. In 3), the temperatures of the first heating zone and the second heating zone were respectively adjusted to 400 C. and 500 C., while remaining unchanged in other steps.
[0099] The Contrast Example 2 shows that the ultrathin 2D monocrystalline Fe.sub.3O.sub.4 nanosheets fail to grow on the mica substrate.
[0100] Fe.sub.2O.sub.3 is formed when the iron sheets are exposed to oxygen and moisture to generate the naturally oxidized iron sheets. In a high vacuum tube furnace, Ar carrier gas is used to purge oxygen and create a high-temperature environment during the heating process. The ultrathin 2D monocrystalline Fe.sub.3O.sub.4 nanosheets grows in an interlayer space confined between the naturally oxidized iron sheets and the mica substrate. BiI.sub.3, as a passivator, inhibits growth of the non-layered nanosheets along the c-axis by inhibiting the unsaturated suspension bond on the surface of the nanosheets.
Example 8
[0101] A method for preparing ultrathin 2D monocrystalline BiOBr nanosheets, the method comprises:
[0102] 1) placing 10 mg of BiBr.sub.3 powder in an Al.sub.2O.sub.3 crucible; putting the Al.sub.2O.sub.3 crucible in the middle of the first heating zone of a furnace with a quartz tube, which is locating at the gas inlet of the quartz tube; placing a mica substrate covered with naturally oxidized copper sheets in the middle of the second heating zone of the quartz tube, which is locating at the gas outlet of the quartz tube;
[0103] 2) vacuumizing the quartz tube to less than 0.1 Pa; pumping Ar gas into the quartz tube until the air pressure is equal to atmosphere pressure; and pumping Ar gas as a carrier gas, with the flow velocity of 25 sccm;
[0104] 3) heating the second heating zone to 385 C. and keeping the temperature for 10 min; heating the first heating zone to 220 C. for 30 min; evaporating the BiBr.sub.3 powder until ultrathin 2D monocrystalline BiOBr nanosheets are formed on the mica substrates; and cooling the substrate to room temperature at a cooling rate of 50 C./min.
[0105] The dark field optical micrograph of the ultrathin 2D monocrystalline BiOBr nanosheets prepared by this embodiment is shown in
Example 9
[0106] A method for preparing ultrathin 2D monocrystalline BiOBr nanosheets, the method comprises:
[0107] 1) placing 50 mg of BiBr.sub.3 powder in an Al.sub.2O.sub.3 crucible; putting the Al.sub.2O.sub.3 crucible on the first heating zone of a furnace with a quartz tube, which is locating at the gas inlet of the quartz tube; placing a mica substrate covered with naturally oxidized copper sheets on the second heating zone of the quartz tube, which is locating at the gas outlet of the quartz tube;
[0108] 2) vacuumizing the quartz tube to less than 0.1 Pa; pumping Ar gas into the quartz tube until the air pressure is equal to atmosphere pressure; after that, pumping Ar gas as a carrier gas, with the flow velocity of 50 sccm;
[0109] 3) heating the second heating zone to 385 C. and keeping the temperature for 30 min; heating the first heating zone to 275 C. for 30 min; evaporating the BiBr.sub.3 powder until ultrathin 2D nanosheets are formed on the mica substrate; and the cover of the CVD furnace was opened to rapidly cool the quartz tube to room temperature.
[0110] The TEM image of the ultrathin 2D monocrystalline BiOBr nanosheets prepared by Example 9 is shown in
Example 10
[0111] A method for preparing ultrathin 2D monocrystalline BiOBr nanosheets, the method comprises:
[0112] 1) placing 10 mg of BiBr.sub.3 powder in an Al.sub.2O.sub.3 crucible, then putting the Al.sub.2O.sub.3 crucible in the middle of the first heating zone of a furnace with a quartz tube, which is locating at the gas inlet of the quartz tube; placing a mica substrate covered with naturally oxidized copper sheets in the middle of the second heating zone of the quartz tube, which is locating at the gas outlet of the quartz tube;
[0113] 2) vacuumizing the quartz tube to less than 0.1 Pa; pumping Ar gas into the quartz tube until the air pressure is equal to atmosphere pressure; after that, pumping Ar gas as a carrier gas, with the flow velocity of 37 sccm;
[0114] 3) heating the second heating zone to 385 C. and keeping the temperature for 30 min; heating the first heating zone to 250 C. for 30 min; evaporating the BiBr.sub.3 powder until ultrathin 2D nanosheets are formed on the substrates; and cooling the mica substrate to room temperature at a cooling rate of 80 C./min.
[0115] A method for preparing a UV photodetector comprising the ultrathin 2D monocrystalline BiOBr nanosheets, comprising: transferring the ultrathin 2D BiOBr nanosheets with thickness of 0.57-5 nm from the mica substrate onto a silicon substrate by wet transfer method; spinning a layer of primary polymethyl methacrylate (PMMA) photoresist onto the silicon substrate; etching a designed pattern on the layer of the PMMA resist by electron beam lithography; depositing a Cr/Au electrode on the silicon substrate (i.e., a Cr electrode with a thickness of 10 nm and an Au electrode with a thickness of 50 nm) by evaporation; soaking the silicon substrate in acetone solution to remove photoresist, thereby obtaining a UV photodetector comprising the ultrathin 2D monocrystalline BiOBr nanosheets.
[0116] The SEM diagram of ultrathin 2D monocrystalline BiOBr nanosheets prepared by Example 10 is shown in
[0117] The BiOBr materials prepared by Example 10 have the high-performance UV detection capability due to high light gain, which can be ascribed to the photogating effect existing in the low dimension material. The trap state constrained the photoproduction minority carrier, prolong the lifetime of majority carrier, so as to improve the value of photocurrent, which makes the photoelectric detector based on the material preparation in the deep ultraviolet high responsibility, high external quantum efficiency and high detectivity.
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[0121] It will be obvious to those skilled in the art that changes and modifications may be made, and therefore, the aim in the appended claims is to cover all such changes and modifications.