CN115028145B - Transition metal doped metal selenide two-dimensional material, preparation and application thereof - Google Patents
Transition metal doped metal selenide two-dimensional material, preparation and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of two-dimensional material preparation, and particularly discloses a transition metal N-doped MSe 2 Preparation method of two-dimensional materialCarrying out hydrophilic surface modification treatment on a substrate, then coating a homogeneous aqueous solution in which a transition metal N source, a water-soluble hydroxide and a metal M source are dissolved on the surface of the substrate, and then annealing the substrate at 780-850 ℃ to obtain a precursor substrate; volatilizing selenium source and performing chemical deposition on the surface of the precursor substrate to obtain the transition metal N-doped MSe 2 A two-dimensional material; the carrier gas in the chemical deposition process comprises protective atmosphere and hydrogen, wherein the flow rate of the protective atmosphere is 60-120sccm; the flow rate of the hydrogen is preferably 1-5sccm; the temperature of the chemical deposition is 780-850 ℃. The invention also comprises the two-dimensional material prepared by the preparation method and application thereof. The invention can successfully realize doping and is beneficial to improving the doping capacity of metal; moreover, the vertical stacking growth can be avoided, and the novel material with atomic-level thickness and excellent crystallinity, morphology and performance can be obtained.
Description
Technical Field
The invention belongs to the field of nano materials, and particularly relates to the field of vapor deposition of two-dimensional materials.
Technical Field
Two-dimensional Transition Metal Dihalides (TMDs) are receiving attention for their new generation of technical applications such as photodetectors, optical modulators, spintronics and wearable devices 1-5 . Diluted Magnetic Semiconductors (DMSs), TMDs doped with magnetic elements, materials with both ferromagnetic and semiconducting properties, have great development potential in spintronics applications 6-8 。
In the last few years, primary 2D TMDs have been modulated and functionalized by 9,10 Such as doping with foreign atoms, has made considerable progress in improving device performance. In situ substitution doping can form stable bond bonds compared to poorly controlled and unstable interstitial doping and is therefore considered a more promising doping engineering. In many reports, some foreign transition metal elements are added to the TMDs crystals to modulate the electrical and magnetic properties of the TMDs. V (V) 12,13 ，Nb 14 And Zn 15 Atomic doped MoS 2 Nanoplatelets exhibit p-type conductivity, while Re and Fe doped MoS 2 The nanoplatelets exhibit n-type conductivity 16-18 . Nb-doped WSe 2 Exhibiting low potential barrier and excellent electrical properties. In addition, some theoretical and experimental researches show that the doping of the transition metal elements such as Co, mn, fe, V in the intrinsic non-ferromagnetic TMDs can realize ferromagnetism 20,21 . It is reported that Fe is doped with SnS 2 Exhibit ferromagnetic behavior, curieTemperature (T) C ) Is 31K 22 . Cr-doped Td-WTE 2 Has a Curie temperature of 283K and a saturation magnetization of 4.20emu g -1 And Cr-doped H-MoTe 2 Single crystals exhibit large out-of-plane magnetic anisotropy 23,24 . However, the method of obtaining doped TMDs nanoplatelets by mechanical exfoliation in these reports is not scalable. To solve this problem, it was subsequently reported that Fe-doped MoS was controlled by chemical vapor deposition 2 Obtaining Gu Saiman split 25 . Doping MoS by Co 2 Amplitude of valley splitting is designed 26 . Conventional CVD growth typically involves high melting point precursor powders, following a gas-solid (VSS) growth mechanism, which has the disadvantages of low reaction vapor pressure, random distribution over the substrate, poor repeatability, and poor scalability. Another method for obtaining ferromagnetism at room temperature is to prepare a well-pretreated deposition substrate or sol-gel precursor, which requires a complicated experimental process and a long period. Clearly, the controlled synthesis of atomic thin TMDs instead of magnetic transition metal doping remains a challenge.
Reference to the literature
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Disclosure of Invention
To fill the technical gap that the metal selenide is not doped in the industry, a first aim of the invention is to provide a method for realizing N doping MSe of transition metal 2 The invention discloses a preparation method of a two-dimensional material (also called as a transition metal doped metal selenide two-dimensional material), which aims to successfully realize the doping of transition metal to metal selenide and improve the morphology and performance of a prepared product.
A second object of the present invention is to provide a transition metal N-doped MSe obtained by the above-mentioned method 2 Two-dimensional materials and their use in optical, electrical, magnetic and other fields.
A third object of the present invention is to provide a semiconductor device comprising the transition metal N-doped MSe 2 Optical, electrical, magnetic, etc. devices of two-dimensional materials.
There is no related technology in the industry for doping two-dimensional materials of metal selenide, mainly because the reactivity of metal selenide is not high, metal alloying is easy to exist in the metal doping process, metal doping is difficult to realize, the metal doping capacity is not ideal, and the morphology, crystallinity and performance of the obtained material are also not ideal. Aiming at the problem that metal selenide is difficult to dope with metal, the invention provides the following preparation method:
MSe doped with transition metal N 2 Preparation method of two-dimensional material comprises modifying hydrophilic surface of substratePerforming sex treatment, coating a homogeneous aqueous solution in which a transition metal N source, a water-soluble hydroxide and a metal M source are dissolved on the surface of the substrate, and annealing the substrate at 780-850 ℃ to obtain a precursor substrate;
volatilizing selenium source and performing chemical deposition on the surface of the precursor substrate to obtain the transition metal N-doped MSe 2 A two-dimensional material;
the carrier gas in the chemical deposition process comprises protective atmosphere and hydrogen, wherein the flow rate of the protective atmosphere is 60-120sccm; the flow of the hydrogen is 1-5sccm;
the temperature of the chemical deposition is 780-850 ℃.
In order to fill the technical blank of doping metal to metal selenide, the invention successfully realizes the doping of metal element to metal selenide, and researches find that the hydrophilic treatment is innovatively carried out on a substrate, then the surface coating and annealing treatment are carried out by adopting the homogeneous solution of the components, and the subsequent combined control of the processes of carrier gas, temperature and the like of chemical vapor deposition is further matched, so that alloying of doping elements and selenide can be avoided, the doping can be successfully realized, and the doping capacity of metal can be improved; moreover, the vertical stacking growth can be avoided, and the novel material with atomic-level thickness and excellent crystallinity, morphology and performance can be obtained.
The research of the invention discovers that the surface treatment of the substrate, the control of the morphology and the components of the homogeneous solution, the control of the annealing process and the combined control of the atmosphere and the temperature in the deposition process are key to cooperatively realizing the successful doping of metal, improving the crystallinity and the morphology, reducing the vertical stacking, obtaining the atomic-level thickness and giving consideration to new materials with excellent properties.
In the present invention, the surface hydrophilic treatment can be performed by conventional means.
Preferably, the hydrophilic surface modification treatment is an oxygen plasma treatment. In the whole technical scheme of the invention, the oxygen plasma treatment is adopted, so that the doping of metal to the metal selenide two-dimensional material is improved cooperatively, and the doping effect and the material performance are improved.
Preferably, the oxygen plasma treatment time is not less than 30s; more preferably 1 to 5 minutes.
The substrate of the invention is a substrate material known in the industry, such as SiO 2 Si substrate, pure silicon substrate, silicon nitride substrate, glass substrate or sapphire substrate, etc.; further preferably SiO 2 A Si substrate or a sapphire substrate.
The method is theoretically suitable for doping various transition metals into the metal selenide two-dimensional material.
For example, the element of the transition metal N is preferably at least one of Fe, co, ni, V, cr. In the invention, when the elements of the transition metal N are Fe, co and Ni, the magnetically doped two-dimensional selenide material can be obtained. For example, the prepared material shows room temperature ferromagnetism through PPMS test.
The transition metal N source is preferably a water-soluble component of the transition metal N, and more preferably at least one of chloride, sulfate and nitrate of each element;
preferably, the water-soluble hydroxide is a substance capable of ionizing OH-in water, preferably at least one of NaOH, KOH;
preferably, the element of the metal M is at least one of Mo and W;
preferably, the metal M source is a water-soluble compound of the respective element, more preferably a polyoxometalate of the respective element, further preferably (NH) 4 ) 2 MoO 4 、Na 2 MoO 4 、(NH 4 ) 6 Mo 7 O 24 、(NH 4 ) 2 WO 4 、Na 2 WO 4 、(NH 4 ) 6 W 7 O 24 At least one of them.
The research of the invention finds that the joint synergy of the coating and other processes by adopting a homogeneous solution in which the transition metal N source, the hydroxide and the transition metal M are dissolved is one of the keys for successfully preparing the material. In the invention, the solution coprecipitation is reduced by the combined control of components, proportion and concentration, thus being beneficial to reducing the adverse effect of metal doping on the preparation of the two-dimensional selenide, avoiding the subsequent vertical nucleation deposition and being beneficial to preparing the material with thick atomic scale and good crystallinity, morphology and performance.
The research shows that the control of the proportion of each component in the homogeneous solution is beneficial to regulating and controlling the nucleation mode and morphology, and is beneficial to obtaining the material with high crystallinity and good morphology uniformity. For example, taking N as iron, the shape is gradually changed from a triangle to a sawtooth-like truncated triangle.
Preferably, in the homogeneous aqueous solution, the molar ratio of the transition metal N to the metal M is 0.05-0.3: 1, more preferably 0.2 to 0.25:1.
The mole ratio of the water-soluble hydroxide and the transition metal M is 0.1-0.3: 1, more preferably 0.2 to 0.25:1;
the molar concentration of the alkali metal hydroxide is 1 to 4mM, more preferably 2 to 4mM.
Preferably, the coating mode is spin coating; the spin-coating speed is, for example, 1000 to 3000r/30s (1000 to 3000 rpm for 30 seconds), more preferably 2000 to 2500r/30s, and the number of repetitions is, for example, 1 to 5, more preferably 2 to 4.
According to the invention, annealing treatment is further innovatively carried out, so that the problem of doping of the transition metal to the metal selenide can be solved unexpectedly, the preparation of the material can be facilitated, and the morphology, crystallinity and performance of the material are facilitated.
In the invention, the atmosphere in the annealing stage is protective atmosphere and hydrogen; preferably, the atmosphere and flow rate of the annealing stage are the same as the carrier gas and flow rate of the subsequent deposition process.
Preferably, the annealing temperature is 800-850 ℃. Further preferably, the annealing temperature may be the same as the deposition temperature.
Preferably, the annealing time is 2 to 8 minutes, more preferably 4 to 6 minutes.
In the invention, the selenium source is subjected to vapor deposition reaction on the surface of the annealed substrate, so that the preparation of the metal-doped two-dimensional selenium compound material is facilitated, and the preparation of a single-layer material with excellent crystallinity and excellent performance is facilitated.
In the invention, the protective gas in the carrier gas is at least one of nitrogen and inert gas.
According to the invention, the deposition conditions can be further finely controlled according to different doping elements, so that the preparation effect can be unexpectedly further improved; is beneficial to preparing ultrathin, high-crystallization and good-morphology uniformity two-dimensional materials.
Preferably, the volatilization of the selenium source is performed at 360 to 450 ℃, more preferably at 380 to 400 ℃.
Preferably, the flow rate of the protective atmosphere in the carrier gas is 70-90 sccm; the flow rate of the hydrogen is 2-4 sccm.
Preferably, the temperature of the chemical deposition is 800-850 ℃; the preferred deposition time is 5 to 20 minutes.
Preferably, M is Mo and N is Fe, the deposition temperature is 800-840 ℃, preferably 815-825 ℃, and the deposition time is 10-15min. Preferably, M is Mo and N is Co, the deposition temperature is 800-830 ℃, more preferably 810-820 ℃, and the deposition time is 10-15min. Preferably, M is Mo and N is Ni, the deposition temperature is 800-820 ℃, and the deposition time is preferably 10-15min.
The invention provides a preferable Fe doped MoSe 2 The preparation method of the two-dimensional material comprises the following steps: naOH, na 2 MoO 4 ,FeCl 3 ·6H 2 O mixed salt precursor solution (homogeneous solution) is spin-coated on SiO 2 Annealing on Si substrate at 815-825 deg.C, and vapor depositing with carrier gas containing protective gas and hydrogen gas at flow rate of 70-90sccm and hydrogen gas at flow rate of 2-4sccm to obtain atomic-scale thin doped Fe MoSe 2 A nano-sheet. The temperature of the chemical vapor deposition is 815-825 ℃; the volatilization temperature of the selenium powder is preferably 380-400 ℃; the preferred deposition time is 10-15min.
The invention provides a preferable Co-doped MoSe 2 The preparation method of the nano-sheet comprises the following steps: naOH, na 2 MoO 4 ,CoCl 2 ·6H 2 O mixed salt precursor solution (homogeneous solution) is spin-coated on a sapphire substrate at 810-Annealing at 820 ℃, then carrying out chemical vapor deposition growth with the volatilized selenium powder raw material under the condition that the carrier gas component is in a mixed gas atmosphere of protective gas and hydrogen, wherein the flow rate of the protective gas is 70-90sccm and the flow rate of the hydrogen is 2-4sccm to obtain the atomic-level thin Co-doped MoSe 2 A nano-sheet. The temperature of vapor deposition is 810-820 ℃; the volatilization temperature of the selenium powder is preferably 380-400 ℃; the preferred deposition time is 10-15min.
The invention provides a Ni-doped MoSe 2 The preparation method of the nano-sheet comprises the following steps: naOH, na 2 MoO 4 ,NiCl 2 Spin-coating the mixed salt precursor solution (homogeneous solution) on a sapphire substrate, annealing at 800-820 ℃, and then growing with the volatilized selenium powder raw material in a mixed gas atmosphere of protective gas and hydrogen gas, wherein the protective gas flow is 70-90sccm, and the hydrogen gas flow is 2-4sccm to obtain atomic-level thin Ni-doped MoSe 2 A nano-sheet. The vapor deposition temperature is 800-820 ℃; the volatilization temperature of the selenium powder is preferably 380-400 ℃; the preferred deposition time is 10-15min.
The invention also provides the transition metal N-doped MSe prepared by the preparation method 2 Two-dimensional material.
The new material of the invention passes through the transition metal N pair MSe 2 Doping is performed and the thickness is atomic. The preferable doping amount is 0.9 to 6.5at.%.
The invention further proves that Fe is substituted and doped into MoSe through high-angle annular dark field scanning transmission electron microscope test 2 In the crystal lattice. The transmission electron microscope result shows that the MoSe doped with Fe/Co/Ni 2 Still in hexagonal phase and good in crystal quality, and the X-ray energy spectrum analysis result also shows doped MoSe 2 The Fe/Co/Ni, mo and Se elements in the alloy are uniformly distributed.
The research of the invention discovers that the preparation method can endow the product with special microstructure and crystallization characteristics, is a brand new material, and the new material has better performance.
The invention also provides the transition metal N-doped MSe prepared by the preparation method 2 The application of the two-dimensional material for preparing at least one device in optics, electricity and magnetism;
preferably, at least one photoelectric device of a field effect transistor, a Hall device and a photoelectric detector is prepared.
In the invention, the transition metal N-doped MSe of the invention can be based on the prior theory and equipment 2 The two-dimensional material prepares any desired device.
For example, the single layer prepared by the invention is doped with Fe 2 The preparation method comprises the following steps of:
MoSe doped with Fe in single layer 2 The surface of the nano sheet is marked with a sample by electron beam exposure, and then metal is deposited on the surface of the nano sheet to obtain the field effect transistor. Preferably, the single layer of Fe doped MoSe is coated with Fe by a vacuum coater 2 Depositing metal on the surface. Preferably, the metal is Au, which is used for the preparation of electrical devices. The method has simple operation process and good repeatability.
For another example, the Fe-doped MoSe prepared by the invention 2 The preparation method of the Hall device comprises the following steps: moSe doped with Fe in multiple layers 2 The surface of the nano sheet is marked with a sample by electron beam exposure, and then metal is deposited on the surface of the nano sheet to obtain a field effect transistor; preferably, the Fe-doped MoSe is coated on multiple layers by a vacuum coating machine 2 Depositing a metal on the surface; preferably, the metal is Au, which is applied to the preparation of Hall devices;
in addition, the Fe-doped MoSe prepared by the invention can also be prepared by adopting the known technology 2 Nanosheets, co doped MoSe 2 Nanosheets, ni doped MoSe 2 The nano-sheet is used for preparing a magnetic device.
The invention also provides a device which comprises the transition metal N-doped MSe prepared by the preparation method 2 Two-dimensional material. The device according to the present invention is, for example, at least one of an optical device, an electrical device, a magnetic device, and the like.
Advantageous effects
1. The invention provides a new material for doping a metal selenide two-dimensional material by adopting transition metal.
2. The invention carries out hydrophilic treatment on the substrate, then adopts the homogeneous solution of the components to carry out surface coating and annealing treatment, and is further matched with the combined control of the processes of carrier gas, temperature and the like of the subsequent chemical vapor deposition, thereby being capable of accidentally avoiding alloying of doping elements and the substrate, successfully realizing doping and being beneficial to improving the doping capacity of metal; moreover, the vertical stacking growth can be avoided, and the novel material with atomic-level thickness and excellent crystallinity, morphology and performance can be obtained.
3. The material prepared by the invention has good crystallinity, doping amount and morphology and excellent performance.
For example, the material prepared by the method provides a basis for the study of electricity and magnetism of two-dimensional dimensions, and is expected to be applied to the fields of spintronics, nanoelectronics and the like. The preparation process of the invention has no complex operation steps and the use of expensive raw materials, simple equipment, simple and easy operation and good reproducibility.
Drawings
FIG. 1 is a schematic diagram of an atmospheric pressure chemical vapor deposition apparatus for preparing molybdenum selenide doped with different magnetic transition metal elements;
FIG. 2 is a schematic diagram of a reaction process for preparing molybdenum selenide doped with different magnetic transition metal elements;
FIG. 3 is a Fe-doped MoSe of example 1-1 2 A nanosheet-related characterization map;
FIG. 4 shows MoSe doped with different Fe concentrations in examples 1-2 2 Nanosheet correlation characterization map
FIG. 5 is a schematic diagram showing the preparation of Fe-doped MoSe at different annealing times in examples 1-3 2 A nanosheet-related characterization map;
FIG. 6 is a schematic diagram of the preparation of Fe-doped MoSe by different deposition processes in examples 1-4 2 An optical schematic of the nanoplatelets;
FIG. 7 is a schematic illustration of the preparation of Fe-doped MoSe without plasma treatment of the substrate of comparative example 1-1 2 Nanosheet optical schematic
FIG. 8 is a graph of comparative examples 1-2 where no additive was usedPreparation of Fe doped MoSe by adding sodium hydroxide with required content 2 Nanosheet optical schematic
FIG. 9 is a schematic diagram of the preparation of Fe-doped MoSe using a heterogeneous solution in comparative examples 1-3 2 Nanosheet optical schematic
FIG. 10 is a schematic diagram of the preparation of Fe-doped MoSe without annealing treatment in comparative examples 1-4 2 Nanosheet optical schematic
FIG. 11 is a schematic diagram of a process for preparing Fe-doped MoSe without adding hydrogen to the carrier gas in comparative examples 1-5 2 Nanosheet optical schematic
FIG. 12 is a Co-doped MoSe of example 2-1 2 Correlation characterization map of nanoplatelets
FIG. 13 is a Ni-doped MoSe of example 3-1 2 Correlation characterization map of nanoplatelets
FIG. 14 is a Fe-doped MoSe of example 4-1 2 A field effect transistor output profile (a) and a transfer profile (b);
FIG. 15 is a Fe-doped MoSe of example 5-1 2 Temperature dependence of Hall device longitudinal resistance (R xx ) Graph (a) and resistance graph (b) measured at 3K for different magnetic fields;
FIG. 16 is a Fe/Co/Ni doped MoSe of example 6-1 2 Magnetic field dependent magnetization profile of nanoplatelets at room temperature (a-c);
the specific implementation method comprises the following steps:
the present invention will be further described by way of examples, but the content of the present invention is not limited to the following.
The experimental set-up is shown in figure 1. The whole reaction process is schematically shown in figure 2.
1. Fe doped MoSe 2 Preparation of nanosheets:
example 1-1
SiO is made of 2 The Si substrate was treated with oxygen plasma for 2min, and a 25mM NaOH solution and 5mM FeCl solution were prepared 3 Solution, 20mM concentration Na 2 MoO 4 Solution, at 0.2:1:1 (volume ratio) to prepare a homogeneous mixed solution, and the solution is prepared at the present time. Spin coating the precursor solution on the pretreated SiO at the rate of 2000r/30s 2 on/Si substrateRepeated 3 times.
SiO loaded with 0.3g selenium powder and spin-coating Fe doped precursor solution is prepared by adopting a Chemical Vapor Deposition (CVD) method 2 Two porcelain boats of the/Si substrate are respectively placed in a constant temperature zone 1 and a constant temperature zone 2 of the tube furnace. Before heating, the air in the quartz tube is discharged and cleaned by argon with larger flow, and then H is introduced 2 -a carrier gas of Ar and controlling the temperature of the constant temperature zones 1 and 2, annealing the substrate at 820 ℃ for 5min, controlling the temperature of the constant temperature zone 1 in the annealing stage, and raising the temperature of the constant temperature zone 1 to 380 ℃ when the annealing is completed, maintaining the temperature of the constant temperature zones 1 and 2, and carrying volatilized selenium to the surface of the annealed substrate under the carrier gas for chemical deposition; in the carrier gas, the argon flow is 80sccm, the hydrogen flow is 2sccm, and the chemical deposition time is 10min. And after the reaction is finished, naturally cooling the inside of the furnace. In SiO 2 The Si substrate has Fe doped MoSe 2 Generating the nano-sheet.
FIG. 3a is a schematic diagram of a prepared Fe-doped MoSe 2 Optical schematic of nanoplatelets, fe doped MoSe obtained under this condition 2 The nanoplatelets have good crystallinity, and figure b shows a thickness of about 0.7nm and a size of about 40 μm. Fig. 3c shows good crystallinity of the product and fig. 3d shows a doping level of about 3.48%.
The difference compared with the method of example 1-1 is that pure silicon, silicon nitride, glass, sapphire substrate is used for SiO 2 the/Si substitution is performed and other operations and parameters are the same. The optical schematic of the resulting products from the different substrates are shown in FIGS. 3e-h, respectively.
Examples 1 to 2
Compared with the embodiment 1-1, the difference is only that the volume ratio of the spin-coating homogeneous solution is controlled, and the volume ratio is respectively: group (a) volume ratio: naOH/FeCl 3 :Na 2 MoO 4 =0.2: 0.2: group (B): naOH/FeCl 3 :Na 2 MoO 4 Volume ratio = 0.2:1.2:1.
optical pictures of the resulting products are shown in fig. 4a-b, respectively, and fig. 4c-d show that a minimum doping level of about 0.93% and a maximum doping level of about 6.1% is obtained.
Examples 1 to 3
The difference from example 1-1 is that the annealing time is 2min and 8min; the optical photographs of the products obtained are shown in FIGS. 5a-b, respectively.
Examples 1 to 4
The difference compared with example 1-1 is only that spin coating at 2000r/30s, repeated 1 and 5 times, the optical photographs of the products obtained are shown in FIGS. 6a-b, respectively.
Comparative examples 1 to 1
The difference compared to example 1-1 is only that the substrate was not plasma treated. The optical photograph of the prepared product is shown in fig. 7, and the target product is not successfully prepared.
Comparative examples 1 to 2
The only difference compared to example 1-1 is that the desired amount of sodium hydroxide is not added to the precursor solution. The optical photograph of the prepared product is shown in fig. 8, and the nano-sheets are unevenly grown.
Comparative examples 1 to 3
The difference compared with example 1-1 is that, in the precursor solution, naOH solution and FeCl solution 3 Solution, na 2 MoO 4 The volume ratio of the solution is 1:1:1 (volume ratio) NaOH is too much in composition to form a heterogeneous solution. As shown in FIG. 9, good products were not obtained by affecting the reaction.
Comparative examples 1 to 4
The difference compared with example 1-1 is only that no annealing treatment was performed. As shown in fig. 10, the product was prepared unevenly.
Comparative examples 1 to 5
The difference compared with example 1-1 is that no hydrogen was added to the carrier gas, and the reaction was insufficient as shown in FIG. 11, and the obtained product was small.
2. Co-doped MoSe 2 Preparation of nanosheets:
example 2-1
The sapphire substrate was treated with oxygen plasma for 2min, and 25mM NaOH solution and 5mM CoCl solution were prepared 2 Solution, 20mM concentration Na 2 MoO 4 Solution, at 0.2:1:1 are prepared into mixed solution according to the corresponding proportion, and the mixed solution is prepared at present. Will be carried out at a rate of 2000r/30sThe precursor solution was spin coated on the pretreated sapphire substrate and repeated 3 times. Two porcelain boats of a sapphire substrate loaded with 0.3g of selenium powder and spin-coating Co-doped precursor solution were placed in a constant temperature zone 1 and a constant temperature zone 2 of a tube furnace, respectively, using a Chemical Vapor Deposition (CVD) method. Before heating, the air in the quartz tube is discharged and cleaned by argon with larger flow, and then H is introduced 2 The carrier gas of Ar and controlling the temperature of the constant temperature areas 1 and 2, the temperature of the constant temperature area 2 is controlled at 815 ℃ to anneal the substrate for 5min, the temperature of the constant temperature area 1 is controlled in the annealing stage, the temperature of the constant temperature area 1 is raised by 380 ℃ when the annealing is finished, the temperatures of the constant temperature areas 1 and 2 are kept, and volatile selenium is carried to the surface of the annealed substrate under the carrier gas to carry out chemical deposition; in the carrier gas, the flow rate of argon is 80sccm, the flow rate of hydrogen is 1sccm, and the growth is carried out for 10min at constant temperature. And after the reaction is finished, naturally cooling the inside of the furnace. There will be Co doped MoSe on the sapphire substrate 2 Generating the nano-sheet.
FIG. 12a is a Co-doped MoSe prepared 2 The optically schematic size of the nanoplatelets is about 12 μm. Co-doped MoSe obtained under the conditions 2 The nanoplatelets have good crystallinity as shown in fig. 12b.
3. Ni doped MoSe 2 Preparation of nanosheets
Example 3-1
Treating sapphire substrate with oxygen plasma for 2min, preparing 25mM NaOH solution and 5mM NiCl solution 2 Solution, 20mM concentration Na 2 MoO 4 Solution, at 0.2:1:1 are prepared into mixed solution according to the corresponding proportion, and the mixed solution is prepared at present. The precursor solution was spin coated on the pretreated sapphire substrate at a rate of 2000r/30s, and repeated 3 times. Two porcelain boats of a sapphire substrate loaded with 0.3g of selenium powder and spin-coating Ni-doped precursor solution were placed in a constant temperature zone 1 and a constant temperature zone 2 of a tube furnace, respectively, using a Chemical Vapor Deposition (CVD) method. Before heating, the air in the quartz tube is discharged and cleaned by argon with larger flow, and then H is introduced 2 Ar carrier gas and temperature control of the constant temperature zone 1 and 2, annealing the substrate at 800 ℃ for 5min, temperature control of the constant temperature zone 1 during the annealing stage, and raising the temperature of the constant temperature zone 1 to 380 ℃ when annealing is completedMaintaining the temperature of the constant temperature areas 1 and 2, and carrying volatilized selenium to the surface of the annealed substrate under carrier gas for chemical deposition; in the carrier gas, the flow rate of argon is 80sccm, the flow rate of hydrogen is 2.5sccm, and the growth is carried out for 10min at constant temperature. And after the reaction is finished, naturally cooling the inside of the furnace. There will be Ni doped MoSe on the sapphire substrate 2 Generating the nano-sheet.
FIG. 13a is a Ni-doped MoSe prepared 2 The optical schematic of the nanoplatelets is about 18 μm in size. The Ni-doped MoSe obtained under the condition 2 The nanoplatelets have good crystallinity as shown in fig. 13b.
4. Preparation of field effect transistor
Example 4-1
Fe doped MoSe 2 Preparation method of field effect transistor and Fe doped MoSe prepared by CVD method 2 Depositing metal Au (60 nm) on the nanoplatelets (example 1-1) by electron beam exposure to obtain Au-contact Fe-doped MoSe 2 A field effect transistor. The prepared Fe doped MoSe 2 A picture of the field effect transistor is shown in the inset of fig. 14 a.
FIG. 14a is a schematic diagram of Fe-doped MoSe 2 A field effect transistor output characteristic curve; FIG. 14b is a Fe-doped MoSe 2 Transfer characteristic of field effect transistor. All prove that the Fe doped MoSe prepared by the invention 2 The nanoplatelets are n-type semiconductors.
5. Preparation of Hall device
Example 5-1
Fe doped MoSe 2 Preparation method of Hall device, fe doped MoSe prepared by CVD method 2 Depositing metal Au (60 nm) on the multilayer nanoplatelets (example 1-1) by electron beam exposure to obtain Au contact Fe doped MoSe 2 A Hall device. The prepared Fe doped MoSe 2 A picture of the hall device is shown in the inset of fig. 15 a.
FIG. 15a is a schematic diagram of Fe-doped MoSe 2 Temperature dependence of Hall device longitudinal resistance (R xx ) A curve; FIG. 15b is a Fe-doped MoSe 2 Resistance curves measured at 3K under different magnetic fields of the hall device. All prove that the Fe doped MoSe prepared by the invention 2 Nanoplatelets are n-type semiconductors and exhibit magnetic behavior.
6. Preparation of nanoplatelets required for measuring magnetism:
example 6-1
The same as other growth conditions in example 1-1, and the growth time was prolonged to 30min to obtain large-area single crystal Fe-doped MoSe 2 The nanoplatelets were generated and tested to give a magnetic field dependent magnetization curve at room temperature as shown in fig. 16a. The same as other growth conditions in example 2-1, and the growth time was prolonged to 30min to obtain large-area single crystal Co-doped MoSe 2 The nanoplatelets were generated and tested to give a magnetic field dependent magnetization curve at room temperature as shown in fig. 16b. The same as other growth conditions in example 3-1, and the growth time was prolonged to 30min to obtain large-area single-crystal Ni-doped MoSe 2 The nanoplatelets were generated and tested to give a magnetic field dependent magnetization curve at room temperature as shown in fig. 16c.
Claims (27)
1. MSe doped with transition metal N 2 The preparation method of the two-dimensional material is characterized by comprising the steps of carrying out hydrophilic surface modification treatment on a substrate, then coating a homogeneous aqueous solution which is dissolved with a transition metal N source, a water-soluble hydroxide and a metal M source on the surface of the substrate, and then annealing at 780-850 ℃ to obtain a precursor substrate;
volatilizing selenium source and performing chemical deposition on the surface of the precursor substrate to obtain the transition metal N-doped MSe 2 A two-dimensional material;
the carrier gas in the chemical deposition process comprises protective atmosphere and hydrogen, wherein the flow rate of the protective atmosphere is 60-120sccm; the flow of the hydrogen is 1-5sccm;
the chemical deposition temperature is 780-850 ℃;
the hydrophilic surface modification treatment is oxygen plasma treatment;
the element of the transition metal N is at least one of Fe, co, ni, V, cr;
the element of the metal M is Mo;
in the homogeneous aqueous solution, the molar ratio of the transition metal N to the metal M is 0.05-0.3: 1, a step of;
the molar ratio of the water-soluble hydroxide to the metal M is 0.1-0.3: 1.
2. the transition metal N-doped MSe of claim 1 2 The preparation method of the two-dimensional material is characterized in that the oxygen plasma treatment time is not less than 30 s.
3. The transition metal N-doped MSe of claim 2 2 The preparation method of the two-dimensional material is characterized in that the oxygen plasma treatment time is 1-5 min.
4. The transition metal N-doped MSe of claim 1 2 The preparation method of the two-dimensional material is characterized in that the transition metal N source is a water-soluble component of the transition metal N.
5. The transition metal N-doped MSe of claim 4 2 The preparation method of the two-dimensional material is characterized in that the transition metal N source is at least one of chloride, sulfate and nitrate of the transition metal N.
6. The transition metal N-doped MSe of claim 1 2 The preparation method of the two-dimensional material is characterized in that the water-soluble hydroxide is a substance capable of ionizing OH-in water.
7. The transition metal N-doped MSe of claim 6 2 The preparation method of the two-dimensional material is characterized in that the water-soluble hydroxide is at least one of NaOH and KOH.
8. The transition metal N-doped MSe of claim 1 2 The preparation method of the two-dimensional material is characterized in that the metal M source is (NH) 4 ) 2 MoO 4 、Na 2 MoO 4 、(NH 4 ) 6 Mo 7 O 24 At least one of them.
9. The method for preparing a transition metal N-doped MSe two-dimensional material according to claim 1, wherein the molar ratio of the transition metal N to the metal M in the homogeneous aqueous solution is 0.2-0.25:1; the molar ratio of the water-soluble hydroxide to the metal M is 0.2-0.25:1;
the molar concentration of the alkali metal hydroxide is 1-4 mM.
10. The method for preparing the transition metal N-doped MSe2 two-dimensional material according to claim 1, wherein the coating mode is spin coating.
11. The method for preparing a transition metal N-doped MSe2 two-dimensional material according to claim 10, wherein the spin-coating speed is 1000-3000 r/30s and the number of repetitions is 1-5.
12. The transition metal N-doped MSe of claim 1 2 The preparation method of the two-dimensional material is characterized in that the atmosphere in the annealing stage is protective atmosphere and hydrogen.
13. The transition metal N-doped MSe of claim 1 2 The preparation method of the two-dimensional material is characterized in that the annealing temperature is 800-850 ℃.
14. The transition metal N-doped MSe of claim 1 2 The preparation method of the two-dimensional material is characterized in that the annealing temperature is 800-820 ℃.
15. The transition metal N-doped MSe of claim 1 2 The preparation method of the two-dimensional material is characterized in that the annealing time is 2-8 min.
16. The transition metal N-doped MSe of claim 1 2 The preparation method of the two-dimensional material is characterized in that the volatilization temperature of the selenium source is 360-450 ℃.
17. The transition metal N-doped according to claim 1MSe 2 The preparation method of the two-dimensional material is characterized in that the chemical deposition temperature is 800-850 ℃.
18. The transition metal N-doped MSe of claim 1 2 The preparation method of the two-dimensional material is characterized in that the chemical deposition time is 5-20 min.
19. The transition metal N-doped MSe of claim 1 2 The preparation method of the two-dimensional material is characterized in that M is Mo, N is Fe, the deposition temperature is 800-840 ℃, and the deposition time is 10-15min.
20. The transition metal N-doped MSe of claim 19 2 The preparation method of the two-dimensional material is characterized in that the deposition temperature is 815-825 ℃.
21. The transition metal N-doped MSe of claim 1 2 The preparation method of the two-dimensional material is characterized in that M is Mo, N is Co, the deposition temperature is 800-830 ℃, and the deposition time is 10-15min.
22. The transition metal N-doped MSe of claim 21 2 The preparation method of the two-dimensional material is characterized in that the deposition temperature is 810-820 ℃.
23. The transition metal N-doped MSe of claim 1 2 The preparation method of the two-dimensional material is characterized in that M is Mo, N is Ni, the deposition temperature is 800-820 ℃, and the deposition time is 10-15min.
24. A transition metal N-doped MSe prepared by the method of any one of claims 1 to 23 2 Two-dimensional material.
25. A transition metal N-doped MSe prepared by the method of any one of claims 1 to 23 2 Of two-dimensional materialUse, characterized in that it is used for the preparation of at least one device of optical, electrical and magnetic.
26. Use according to claim 25, characterized in that it is used for the preparation of at least one optoelectronic device of the group consisting of field effect transistors, hall devices, photodetectors.
27. A device comprising a transition metal N-doped MSe prepared by the method of any one of claims 1 to 23 2 Two-dimensional material.
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