CN110158048B - Method for growing ultrathin high-quality oxide film on two-dimensional layered material and application thereof - Google Patents

Method for growing ultrathin high-quality oxide film on two-dimensional layered material and application thereof Download PDF

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CN110158048B
CN110158048B CN201910356258.8A CN201910356258A CN110158048B CN 110158048 B CN110158048 B CN 110158048B CN 201910356258 A CN201910356258 A CN 201910356258A CN 110158048 B CN110158048 B CN 110158048B
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CN110158048A (en
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王欣然
李卫胜
周健
于志浩
施毅
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Nanjing University
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Abstract

The invention discloses a method for growing an ultrathin high-quality oxide film on a two-dimensional layered material and application thereof, wherein the method comprises the following steps: (1) growing a single-layer organic dye molecular film on the two-dimensional layered material by adopting a van der Waals epitaxial growth technology; (2) and growing an ultrathin and uniform oxide film on the two-dimensional layered material by using an atomic layer deposition technology and taking the single-layer organic dye molecular film as a seed layer. The invention grows a single-layer organic dye molecular film on the surface of the two-dimensional layered material by Van der Waals epitaxy to be used as a seed layer, so that the two-dimensional layered material can be nearly not damaged, and the seed layer can be deposited to obtain an ultrathin, uniform and compact high-quality oxide film; meanwhile, the growth method has low cost and simple processing realization; the oxide film prepared by the method can still keep excellent uniformity and pressure resistance under the condition of thinness, and can be suitable for electronic devices in various forms.

Description

Method for growing ultrathin high-quality oxide film on two-dimensional layered material and application thereof
Technical Field
The invention relates to a method for growing an ultrathin high-quality oxide film on a two-dimensional layered material and application of the ultrathin high-quality oxide film in preparation of an electronic device, belonging to the field of two-dimensional material electronic devices.
Background
In recent decades, silicon-based electronic devices have been scaled down in feature size under the guidance of moore's law. However, as the scale approaches the quantum limit, problems including short channel effects limit further scaling of silicon-based electronic devices. The study and development of new materials is one of the main approaches to continue moore's law. Since the discovery of graphene, more and more two-dimensional layered materials have received attention due to their excellent properties in force, heat, light, electricity, and the like. The property that the two-dimensional material is bonded by covalent bonds in the plane and only by van der waals force between layers enables a single-layer two-dimensional material with atomic scale to be obtained, and the thickness of the single-layer two-dimensional material is generally below 1 nanometer. Due to the atomic-scale thickness of the two-dimensional material, the two-dimensional material can still maintain excellent performance in a short-channel device, and particularly, the preparation of a 1-nanometer gate length device shows the advantages that a silicon-based electronic device does not have.
Currently, one of the significant challenges limiting the development of two-dimensional layered material logic devices is the deposition of high quality oxide dielectric layers. Because the surface of the two-dimensional layered material has no dangling bond, the atomic layer is directly used for depositing the oxide film on the surface, the problems of large roughness, air holes, discontinuity, incompactness, unevenness and the like exist, and the development and the application of a two-dimensional layered material top gate device are inhibited. A currently common approach is to deposit metal on a two-dimensional material, which after oxidation acts as a seed layer. However, when depositing metal, the energy of high-temperature metal vapor is large, which easily damages the two-dimensional material and causes many defects, and when depositing metal as a seed layer, the required metal thickness is thick to ensure sufficient coverage of the two-dimensional material, which cannot realize ultra-thin oxide deposition. Other methods utilize gases such as plasma, ozone and the like to functionalize the surface of the two-dimensional material, increase the surface hydrophilicity of the two-dimensional material, and further deposit an oxide dielectric layer, but can generate some irreversible damage to the two-dimensional material. The methods reported in the prior publications are difficult to obtain uniform ultrathin high-quality oxide films.
Based on the above, the inventor has developed a method for growing a high-quality ultrathin uniform oxide by epitaxially growing a single-layer two-dimensional organic molecular film on a two-dimensional material as a seed layer.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems of damage to a two-dimensional material, non-uniformity, discontinuity, incompactness and the like of an oxide film grown on the two-dimensional material in the prior art, the invention provides a method for growing an ultrathin high-quality oxide film on a two-dimensional layered material, and provides an application of the method for preparing an electronic device.
The technical scheme is as follows: the method for growing the ultrathin high-quality oxide film on the two-dimensional layered material comprises the following steps of:
(1) growing a single-layer organic dye molecular film on the two-dimensional layered material by adopting a van der Waals epitaxial growth technology;
(2) and growing an ultrathin and uniform oxide film on the two-dimensional layered material by using an atomic layer deposition technology and taking the single-layer organic dye molecular film as a seed layer.
The two-dimensional layered material includes, but is not limited to, a transition metal chalcogenide such as graphene and molybdenum disulfide. The organic dye molecule film includes, but is not limited to, a film formed of any one of the following organic dye molecules: 3,4,9, 10-perylene tetracarboxylic dianhydride and derivatives thereof, 3,4,9, 10-perylene tetracarboxylic diimide and derivatives thereof, rubrene and derivatives thereof, and N, N-xylyl perylene diimide and derivatives thereof. The oxide film is any oxide film that can be grown by atomic layer deposition techniques, including but not limited to aluminum oxide film, hafnium oxide film, zirconium oxide film, titanium oxide film, lanthanum oxide film.
Preferably, in the step (1), the two-dimensional layered material is used as a substrate, organic dye molecules are used as a growth source, the two-dimensional layered material and the organic dye molecules are placed in a tube furnace at intervals, the tube furnace is vacuumized, the temperature of the furnace body to the position of the growth source is 240-260 ℃, the temperature is kept for 0.2-0.8 h, the organic dye molecules are evaporated, and a single-layer organic dye molecule film is formed on the upper surface of the two-dimensional layered material in a deposition mode. Wherein, the substrate and the growth source are preferably arranged at an interval of 2-4 cm. Before starting the tube furnace, the tube furnace can be vacuumized by a vacuum pump; after the tube furnace is started, preferably, the furnace body is heated to 220-240 ℃ within 10min, then the temperature is continuously heated to 240-260 ℃ within 5min, and the temperature is kept for 0.2-0.8 h; and after heating, naturally cooling the tube furnace to room temperature to finish growth.
Preferably, in the step (2), the two-dimensional layered material on which the single-layer organic dye molecular film grows is transferred into an atomic layer deposition cavity, vacuum pumping is performed, the temperature of the cavity is raised to 80-90 ℃, then a metal source and an oxidation source are introduced, and in-situ deposition is performed on the surface of a seed layer of the two-dimensional layered material to obtain an ultrathin and uniform oxide film; the integrity of the monolayer organic dye molecular film on the two-dimensional layered material can be ensured at a lower temperature, so that the oxide film can be ensured to be deposited on the two-dimensional layered material in an ultra-thin and uniform manner. Preferably, the temperature of the cavity is firstly increased to 70-80 ℃, and after waiting for 5-10min, the temperature of the cavity is increased to 80-90 ℃; the temperature of the cavity can be ensured to rise slowly by the temperature rise mode, so that the situation that the temperature exceeds the target temperature and influences the deposition quality of the oxide film is avoided.
The oxide film prepared by the method for growing the ultrathin high-quality oxide film on the two-dimensional layered material can still keep excellent uniformity and pressure resistance under the condition of thinness, and can be used for preparing various electronic devices, such as a field effect transistor, a tunneling transistor, a storage device and the like. Taking a field effect transistor as an example, the preparation method thereof can comprise the following steps:
(1) growing a single-layer organic dye molecular film on the two-dimensional layered material by adopting a van der Waals epitaxial growth technology;
(2) growing an ultrathin uniform oxide film on the two-dimensional layered material by using the single-layer organic dye molecular film as a seed layer by utilizing an atomic layer deposition technology to serve as a dielectric layer;
(3) and preparing a top gate electrode on the two-dimensional layered material on which the ultrathin oxide film grows to obtain the two-dimensional layered material field effect transistor device. The device comprises from bottom to top: two-dimensional layered materials, single-layer organic dye molecular films, ultrathin oxide films and metal top gate electrodes.
When the field effect transistor device is prepared, the raw material selection ranges of the two-dimensional layered material, the organic dye molecular film and the oxide film and the process control processes of the steps (1) to (2) are the same as those in the method for growing the ultrathin high-quality oxide film on the two-dimensional layered material.
Has the advantages that: compared with the prior art, the invention has the advantages that: (1) compared with the traditional methods of taking vapor plating metal as a seed layer, functionalizing the surface of the two-dimensional layered material and the like, the method has the advantages that a single-layer organic dye molecular film is grown on the surface of the two-dimensional layered material through Van der Waals epitaxy to serve as the seed layer, the two-dimensional layered material can be nearly not damaged, process control in the atomic layer deposition process is combined, and an ultrathin, uniform and compact oxide film can be deposited on the seed layer; meanwhile, the growth method of the invention has low cost and simple processing; (2) compared with the traditional evaporated metal as a seed layer, the thickness of the single-layer organic dye molecular film as the seed layer is only 0.3 nanometer, which is far lower than the thickness of the evaporated metal, and the influence on the capacitance of the whole gate dielectric is greatly reduced; (3) the oxide film prepared by the method can still keep excellent uniformity and pressure resistance under the condition of thinness, and can be suitable for electronic devices in various forms, including field effect transistors, tunneling transistors, storage devices and the like.
Drawings
Fig. 1 is atomic force microscope images of graphene before and after growth of a seed layer in example 1, in which (a) is an atomic force microscope image of graphene transferred onto a silicon wafer as a substrate, and (b) is an atomic force microscope image of graphene on which a monolayer of a 3,4,9, 10-perylenetetracarboxylic dianhydride molecular film is grown;
fig. 2 is an atomic force microscope image of graphene after growing a hafnium oxide thin film by using different methods, wherein (a) is the atomic force microscope image of graphene after completing growth of the hafnium oxide thin film in example 1, and (b) is the atomic force microscope image of directly growing the hafnium oxide thin film on a graphene substrate;
FIG. 3 is a scanning electron microscope image of the dual-gate graphene prepared after the growth of the hafnium oxide film in example 1 is completed;
fig. 4a is a transfer characteristic curve of the top gate voltage scanned by the graphene device under different back gate voltages, and fig. 4b is a top gate voltage-back gate voltage change curve drawn by extracting dirac points of graphene under different top gate voltages and back gate top gates in fig. 4 a;
fig. 5a is a breakdown characteristic curve of a graphene double gate device with different hafnium oxide thicknesses; fig. 5b shows the statistical breakdown voltage and breakdown electric field of 30 graphene double gate devices with different hafnium oxide thicknesses; fig. 5c is the area density of gate leakage current of 30 graphene dual-gate devices when the top gate voltage is equal to 1 v;
fig. 6 is an atomic force microscope image of graphene on which the growth of a zirconium oxide thin film was completed in example 2;
fig. 7 is an atomic force microscope image of graphene on which the growth of an alumina thin film was completed in example 3;
FIG. 8 is an atomic force microscope image of example 4, in which a single- layer 3,4,9, 10-perylene tetracarboxylic diimide molecular film was used as a seed layer to complete the growth of an alumina film on graphene;
fig. 9 is an atomic force microscope image of graphene before and after growing a seed layer in example 5, wherein (a) is an atomic force microscope image of molybdenum disulfide transferred onto a silicon wafer as a substrate, and (b) is an atomic force microscope image of molybdenum disulfide on which a monolayer of a 3,4,9, 10-perylenetetracarboxylic dianhydride molecular film is grown;
FIG. 10 is an atomic force microscope image of molybdenum disulfide with completed hafnium oxide growth of example 5;
fig. 11a is a transfer characteristic curve of the scanning top gate voltage of the molybdenum disulfide device prepared in example 5 under different back gate voltages, and fig. 11b is a top gate voltage-back gate voltage change curve drawn by extracting dirac points of graphene under different top gate voltages and back gate voltages in fig. 11 a.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
The method for growing the ultrathin high-quality oxide film on the two-dimensional layered material utilizes a single-layer organic dye molecular film which is subjected to Van der Waals epitaxy on the surface of the two-dimensional layered material as a seed layer, and then prepares the ultrathin high-quality oxide film on the two-dimensional layered material through atomic layer deposition. This ensures the fabrication of electronic devices based on two-dimensional layered materials, such as field effect transistor devices, creating advantages for the further application of two-dimensional layered materials in logic/analog circuits.
Example 1
1) Preparing a graphene two-dimensional layered material by using a mechanical stripping method, transferring the graphene two-dimensional layered material to a silicon wafer, and preparing upper source and drain electrodes on two sides of graphene; as in fig. 1(a), the thickness of the thin graphene layer transferred onto the silicon wafer as a substrate is 1.1 nm.
2) Putting 3,4,9, 10-perylenetetracarboxylic dianhydride powder into a quartz boat as a growth source, and putting the quartz boat into the center of a tube furnace; placing the silicon wafer transferred with the graphene on another quartz boat, and placing the quartz boat in a quartz tube, wherein the distance between the quartz boat and the quartz boat containing the 3,4,9, 10-perylenetetracarboxylic dianhydride powder is 2 cm; after the placement is finished, the quartz tube is arranged at the corresponding position of the tube furnace and is vacuumized;
3) starting the tubular furnace, heating the furnace body to 240 ℃ within 10 minutes, then heating to 260 ℃ within 5 minutes, maintaining the temperature at 260 ℃ for 0.2 hour, evaporating the 3,4,9, 10-perylene tetracarboxylic dianhydride powder growth source, and depositing the product on graphene; and after heating, naturally cooling the tube furnace to room temperature to finish growth.
4) Moving the graphene with the single- layer 3,4,9, 10-perylenetetracarboxylic dianhydride molecular film from the quartz tube to an atomic layer deposition cavity, vacuumizing the atomic layer deposition cavity, raising the temperature of the cavity to 80 ℃, and after waiting for 10min, raising the temperature of the cavity to 90 ℃;
5) after the temperature of the cavity/cavity wall reaches a rated temperature, taking tetra (dimethylamino) hafnium as a metal source for atomic layer deposition, taking water as an oxidation source, and setting the cycle times, wherein the pulse time of each pulse of the metal source and the oxidation source is respectively 250ms and 60ms, and the cleaning time between two pulses is 60 s; and growing a hafnium oxide film with the thickness of 1.5nm on the surface of the graphene.
FIG. 1(b) is an atomic force microscope image of a thin graphene sample grown with a monolayer of 3,4,9, 10-perylenetetracarboxylic dianhydride molecular film, the substrate surface graphene and monolayer molecular film having a thickness of 1.4nm, and compared to FIG. 1(a), an increase in thickness of 0.3nm, just as the thickness of the monolayer of 3,4,9, 10-perylenetetracarboxylic dianhydride molecular film, can be found; moreover, as can be seen from the surface morphology, the single- layer 3,4,9, 10-perylenetetracarboxylic dianhydride molecular film can be uniformly arranged on the graphene.
Fig. 2(a) is an atomic force microscope image of hafnium oxide grown, and fig. 2(b) is an atomic force microscope image of hafnium oxide film grown directly on a graphene substrate, and a comparison of the two images shows that a method for growing an ultrathin high-quality oxide film on a two-dimensional layered material by using a single-layer two-dimensional molecular film as a seed layer can prepare a uniform and flat hafnium oxide film on the surface of graphene.
6) And preparing a top gate electrode on the graphene sample on which the hafnium oxide film grows, and carrying out double-gate test on the device.
Fig. 3 is a scanning electron microscope image of the prepared thin-layer graphene double-gate device.
Fig. 4a is a transfer characteristic curve of the graphene device under different back gate voltages for scanning a top gate voltage. Fig. 4b is a top gate voltage-back gate voltage curve drawn by extracting a dirac point of graphene by using the transfer characteristic curve of fig. 4a, from which a ratio of top gate capacitance to back gate capacitance, a top gate permittivity, can be obtained: the capacitance of the back gate was 183, and the thickness of the equivalent oxide layer of the hafnium oxide thin film was 1.5nm since the back gate was 275nm silicon oxide.
The experimental results show that the method of using the single- layer 3,4,9, 10-perylenetetracarboxylic dianhydride molecular film as the seed layer can realize the growth of the ultrathin high-quality oxide film on the two-dimensional material.
The effect on the leakage current performance of the field effect transistor device is verified below.
Hafnium oxide films with thicknesses of 1.5nm, 4nm, 9nm and 15.6nm are respectively grown on graphene by adopting the method of the embodiment, then the graphene dual-gate device is manufactured, and leakage flow data of the graphene dual-gate device with different thicknesses of hafnium oxide is tested, as shown in fig. 5 a-5 b. Fig. 5a is a breakdown characteristic curve of a graphene dual-gate device with different hafnium oxide thicknesses; fig. 5b is a statistical graph of the breakdown voltage and the breakdown electric field of 30 graphene dual-gate devices with different hafnium oxide thicknesses, and it can be seen from the graph that the breakdown voltage increases linearly with the increase of the equivalent oxide layer thickness, and by linearly fitting the breakdown voltage, the maximum breakdown voltage of the device can be obtainedHigh carrier concentration of 6.5 × 1013cm-1(ii) a The breakdown electric field is rapidly increased along with the reduction of the thickness of the equivalent oxide layer, and the highest breakdown electric field can reach 15.5 megavolts/centimeter. FIG. 5c shows the gate-to-drain current areal density of 30 graphene double-gate devices when the top gate voltage is equal to 1V, which is from 10 as the thickness of the equivalent oxide layer is reduced-6The amperage slowly increased per square centimeter; when the equivalent oxide thickness is 1nm, the gate leakage current areal density is about 10-2The ampere/square centimeter can still meet the use requirement of low-power consumption electronic devices. The oxide film prepared by the method can still maintain excellent performance under the condition of thinness, and can be suitable for electronic devices in various forms.
Example 2
1) Preparing a graphene two-dimensional layered material by using a mechanical stripping method, and transferring the graphene two-dimensional layered material onto a silicon wafer;
2) putting 3,4,9, 10-perylenetetracarboxylic dianhydride powder into a quartz boat as a growth source, and putting the quartz boat into the center of a tube furnace; placing the silicon wafer transferred with the graphene on another quartz boat, and placing the quartz boat in a quartz tube, wherein the distance between the quartz boat and the quartz boat containing the 3,4,9, 10-perylenetetracarboxylic dianhydride powder is 2 cm; after the placement is finished, the quartz tube is arranged at the corresponding position of the tube furnace and is vacuumized;
3) starting the tubular furnace, heating the furnace body to 240 ℃ within 10 minutes, then heating to 260 ℃ within 5 minutes, maintaining the temperature at 260 ℃ for 0.8 hour, evaporating the 3,4,9, 10-perylene tetracarboxylic dianhydride powder growth source, and depositing the product on graphene; and after heating, naturally cooling the tube furnace to room temperature to finish growth.
4) Moving the graphene with the single- layer 3,4,9, 10-perylenetetracarboxylic dianhydride molecular film from the quartz tube to an atomic layer deposition cavity, vacuumizing the atomic layer deposition cavity, raising the temperature of the cavity to 70 ℃, waiting for 10min, and then raising the temperature of the cavity to 80 ℃;
5) and after the temperature of the cavity/cavity wall reaches a rated temperature, taking tetrakis (dimethylamino) zirconium as a metal source for atomic layer deposition, taking water as an oxidation source, setting the cycle number, and growing a zirconium oxide film with the thickness of 5nm on the surface of the graphene.
Fig. 6 is an atomic force microscope image of graphene with zirconia grown, and it can be seen that the method of the present invention can realize the growth of an ultrathin high-quality zirconia thin film on a two-dimensional material.
Example 3
1) Preparing a graphene two-dimensional layered material by using a mechanical stripping method, and transferring the graphene two-dimensional layered material onto a silicon wafer;
2) putting 3,4,9, 10-perylenetetracarboxylic dianhydride powder into a quartz boat as a growth source, and putting the quartz boat into the center of a tube furnace; placing the silicon wafer transferred with the graphene on another quartz boat, and placing the quartz boat in a quartz tube, wherein the distance between the quartz boat and the quartz boat containing the 3,4,9, 10-perylenetetracarboxylic dianhydride powder is 2 cm; after the placement is finished, the quartz tube is arranged at the corresponding position of the tube furnace and is vacuumized;
3) starting the tubular furnace, heating the furnace body to 240 ℃ within 10 minutes, then heating to 260 ℃ within 5 minutes, maintaining the temperature at 260 ℃ for 0.2 hour, evaporating the 3,4,9, 10-perylene tetracarboxylic dianhydride powder growth source, and depositing the product on graphene; and after heating, naturally cooling the tube furnace to room temperature to finish growth.
4) Moving the graphene with the single- layer 3,4,9, 10-perylenetetracarboxylic dianhydride molecular film from the quartz tube to an atomic layer deposition cavity, vacuumizing the atomic layer deposition cavity, raising the temperature of the cavity to 80 ℃, and after waiting for 10min, raising the temperature of the cavity to 90 ℃;
5) and after the temperature of the cavity/cavity wall reaches a rated temperature, taking trimethyl aluminum as a metal source for atomic layer deposition, taking water as an oxidation source, setting the cycle number, and growing an alumina film with the thickness of 5nm on the surface of the graphene.
Fig. 7 is an atomic force microscope image of graphene with aluminum oxide grown thereon, which illustrates that the method of the present invention can be used to grow an ultra-thin aluminum oxide film with high quality on a two-dimensional material.
Example 4
1) Preparing a graphene two-dimensional layered material by using a mechanical stripping method, and transferring the graphene two-dimensional layered material onto a silicon wafer;
2) putting 3,4,9, 10-perylene tetracarboxylic diimide powder into a quartz boat as a growth source, and putting the quartz boat into the center of a tube furnace; placing the silicon wafer transferred with the graphene on another quartz boat, and placing the quartz boat in a quartz tube, wherein the distance between the quartz boat and the quartz boat containing the 3,4,9, 10-perylene tetracarboxylic diimide powder is 4 cm; after the placement is finished, the quartz tube is arranged at the corresponding position of the tube furnace and is vacuumized;
3) starting the tubular furnace, heating the furnace body to 220 ℃ within 10 minutes, then heating to 240 ℃ within 5 minutes, maintaining the temperature at 240 ℃ for 0.8 hour, evaporating the 3,4,9, 10-perylene tetracarboxylic diimide powder growth source, and depositing the perylene tetracarboxylic diimide powder growth source on graphene; and after heating, naturally cooling the tube furnace to room temperature to finish growth.
4) Moving the graphene with the single- layer 3,4,9, 10-perylene tetracarboxylic diimide molecular film from the quartz tube to an atomic layer deposition cavity, vacuumizing the atomic layer deposition cavity, raising the temperature of the cavity to 70 ℃, and after waiting for 5min, raising the temperature of the cavity to 80 ℃;
5) and after the temperature of the cavity/cavity wall reaches a rated temperature, taking trimethyl aluminum as a metal source for atomic layer deposition, taking water as an oxidation source, setting the cycle number, and growing an aluminum oxide film with the thickness of 3nm on the surface of the graphene.
Fig. 8 is an atomic force microscope image of graphene on which alumina has grown, and it can be seen that an ultrathin high-quality oxide thin film can be grown on a two-dimensional material by using other organic dye molecular thin films such as a 3,4,9, 10-perylenetetracarboxylic diimide molecular thin film as a seed layer.
Example 5
1) Preparing a molybdenum disulfide two-dimensional layered material by using a mechanical stripping method, transferring the molybdenum disulfide two-dimensional layered material onto a silicon chip, and preparing upper source and drain electrodes on two sides of the molybdenum disulfide; as in fig. 9(a), the thickness of the thin layer of molybdenum disulfide transferred onto the silicon wafer as a substrate was 1.1 nm.
2) Putting 3,4,9, 10-perylenetetracarboxylic dianhydride powder into a quartz boat as a growth source, and putting the quartz boat into the center of a tube furnace; placing the silicon wafer transferred with the molybdenum disulfide on another quartz boat, and placing the quartz boat in a quartz tube, wherein the distance between the quartz boat and the quartz boat containing the 3,4,9, 10-perylene tetracarboxylic dianhydride powder is 2 cm; after the placement is finished, the quartz tube is arranged at the corresponding position of the tube furnace and is vacuumized;
3) starting the tubular furnace, heating the furnace body to 220 ℃ within 10 minutes, then heating to 240 ℃ within 5 minutes, maintaining the temperature at 240 ℃ for 0.8 hour, evaporating the 3,4,9, 10-perylene tetracarboxylic dianhydride powder growth source, and depositing the powder on molybdenum disulfide; and after heating, naturally cooling the tube furnace to room temperature to finish growth.
FIG. 9(b) is an atomic force microscope image of a thin layer of molybdenum disulfide sample grown with a monolayer of a 3,4,9, 10-perylenetetracarboxylic dianhydride molecular film, the substrate surface molybdenum disulfide and monolayer molecular film having a thickness of 1.4nm, and compared to FIG. 9(a), an increase in thickness of 0.3nm, just as the thickness of the monolayer of 3,4,9, 10-perylenetetracarboxylic dianhydride molecular film, can be found; as can be seen from the surface morphology, the single- layer 3,4,9, 10-perylenetetracarboxylic dianhydride molecular film can be uniformly arranged on the graphene.
4) Moving molybdenum disulfide with a single- layer 3,4,9, 10-perylenetetracarboxylic dianhydride molecular film from a quartz tube to an atomic layer deposition cavity, vacuumizing the atomic layer deposition cavity, raising the temperature of the cavity to 80 ℃, and after waiting for 5min, raising the temperature of the cavity to 90 ℃;
5) and after the temperature of the cavity/cavity wall reaches the rated temperature, taking tetra (dimethylamino) hafnium as a metal source for atomic layer deposition, taking water as an oxidation source, setting the cycle number, and growing a 1.5nm hafnium oxide film on the surface of the molybdenum disulfide.
6) And preparing a top gate electrode on the molybdenum disulfide sample after the hafnium oxide film grows, and carrying out double-gate test on the device.
Figure 10 is an atomic force microscope image of molybdenum disulfide grown with hafnium oxide. It can be seen that the method of the invention can prepare a uniform and flat hafnium oxide film on the surface of the molybdenum disulfide.
Fig. 11a is a transfer characteristic curve of the molybdenum disulfide of the device for scanning top gate voltage under different back gate voltages. Fig. 11b is a graph further obtained by using the transfer characteristic curve of fig. 11a to extract threshold voltages in the top gate transfer characteristic curve under different back gate voltages, and draw a top gate voltage-back gate voltage curve, from which a ratio of top gate capacitance to back gate capacitance, a top gate permittivity, may be obtained: the permittivity of the back gate is equal to 16.8, and since the back gate is 30nm of aluminum oxide and the dielectric constant of the aluminum oxide is 7, the equivalent oxide thickness of the hafnium oxide thin film is 1 nm. The results show that the method can realize the growth of the ultrathin high-quality oxide film on the molybdenum disulfide.

Claims (8)

1. A method for growing an ultrathin high-quality oxide film on a two-dimensional layered material is characterized by comprising the following steps of:
(1) growing a single-layer organic dye molecular film on the two-dimensional layered material by adopting a van der Waals epitaxial growth technology;
taking a two-dimensional layered material as a substrate and organic dye molecules as a growth source, placing the two-dimensional layered material in a tube furnace at intervals, vacuumizing the tube furnace, heating the furnace body to the position of the growth source to 240-260 ℃, and preserving heat for 0.2-0.8 h to evaporate the organic dye molecules, and depositing on the upper surface of the two-dimensional layered material to form a single-layer organic dye molecule film; the substrate and the growth source are placed at an interval of 2-4 cm;
(2) and growing an ultrathin and uniform oxide film on the two-dimensional layered material by using the atomic layer deposition technology and taking the single-layer organic dye molecular film as a seed layer.
2. The method of claim 1, wherein the two-dimensional layered material is graphene, black phosphorus, boron nitride or a transition metal chalcogenide.
3. The method for growing ultrathin high-quality oxide film on two-dimensional layered material as claimed in claim 1, wherein the organic dye molecular film is any one of 3,4,9, 10-perylene tetracarboxylic dianhydride and its derivatives, 3,4,9, 10-perylene tetracarboxylic diimide and its derivatives, rubrene and its derivatives, N-xylyleperylene imide and its derivatives.
4. The method of claim 1, wherein the oxide film is an aluminum oxide film, a hafnium oxide film, a zirconium oxide film, a titanium oxide film, or a lanthanum oxide film.
5. The method for growing the ultrathin high-quality oxide film on the two-dimensional layered material as claimed in claim 1, wherein in the step (2), the two-dimensional layered material on which the single-layer organic dye molecule film grows is transferred into an atomic layer deposition cavity, the cavity is vacuumized, the temperature of the cavity is raised to 80-90 ℃, then a metal source and an oxidation source are introduced, and the ultrathin uniform oxide film is obtained by in-situ deposition on the surface of a seed layer of the two-dimensional layered material.
6. The method for growing the ultrathin high-quality oxide film on the two-dimensional layered material as claimed in claim 5, wherein after vacuumizing, the temperature of the atomic layer deposition cavity is firstly raised to 70-80 ℃, and after waiting for 5-10min, the temperature of the cavity is raised to 80-90 ℃.
7. Use of the process of claim 1 for the preparation of an electronic device.
8. The use according to claim 7, wherein the electronic device is a field effect transistor and the method of manufacturing comprises the steps of:
(1) growing a single-layer organic dye molecular film on the two-dimensional layered material by adopting a van der Waals epitaxial growth technology;
(2) growing an ultrathin uniform oxide film on the two-dimensional layered material by using the single-layer organic dye molecular film as a seed layer by utilizing an atomic layer deposition technology to serve as a dielectric layer;
(3) and preparing a top gate electrode on the two-dimensional layered material on which the ultrathin oxide film grows to obtain the two-dimensional layered material field effect transistor device.
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