CN110120440B - Method for carrying out optical degeneracy doping on transition metal chalcogenide and application thereof - Google Patents
Method for carrying out optical degeneracy doping on transition metal chalcogenide and application thereof Download PDFInfo
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 26
- -1 transition metal chalcogenide Chemical class 0.000 title claims abstract description 18
- 230000003287 optical effect Effects 0.000 title abstract description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000010931 gold Substances 0.000 claims abstract description 25
- 229910052737 gold Inorganic materials 0.000 claims abstract description 25
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- 239000000758 substrate Substances 0.000 claims description 16
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- 238000000151 deposition Methods 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 8
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- 239000002052 molecular layer Substances 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 6
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 4
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- 238000001883 metal evaporation Methods 0.000 claims description 4
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- 238000010894 electron beam technology Methods 0.000 claims description 3
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- 230000008018 melting Effects 0.000 claims description 2
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- 239000000463 material Substances 0.000 abstract description 36
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
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- H—ELECTRICITY
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- H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
- H01L31/10—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors characterised by at least one potential-jump barrier or surface barrier, e.g. phototransistors
- H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
- H01L31/112—Devices sensitive to infrared, visible or ultraviolet radiation characterised by field-effect operation, e.g. junction field-effect phototransistor
- H01L31/113—Devices sensitive to infrared, visible or ultraviolet radiation characterised by field-effect operation, e.g. junction field-effect phototransistor being of the conductor-insulator-semiconductor type, e.g. metal-insulator-semiconductor field-effect transistor
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Abstract
The invention discloses a method for carrying out optical degenerated doping on transition metal chalcogenide and application thereof. Under the irradiation of ultraviolet light, electrons of the gold nanolayers overflow due to the external photoelectric effect and are injected into the semiconductor layer, and the redundant electrons form stable N-type doping on the semiconductor. After the ultraviolet irradiation is removed, the surplus electrons generated by light generation still remain in the material, so that the doping mode has long-term stability, and meanwhile, the method has universality and can be applied to various N-type TMDC materials. The novel rapid, simple, convenient, universal and stable doping method opens a new idea for the research of two-dimensional semiconductor materials.
Description
Technical Field
The invention relates to the technical field of semiconductor material modification, in particular to a method for carrying out optical degenerate doping on transition metal chalcogenide, and specifically relates to an N-type doping mode for a two-dimensional semiconductor material.
Background
With the development of moore's law, silicon-based semiconductors have been developed to the limit nodes. In recent years, semiconductor-type two-dimensional transition metal chalcogenides (TMDs) with tunable band gap have been considered as alternatives to the next generation silicon-based semiconductors due to their large carrier mobility, high field-effect on-state ratio, low subthreshold swing, and effective suppression of short channel effects. Doping of TMDs materials has received a great deal of attention in order to achieve the functionality of silicon-based semiconductors. The traditional doping methods include ion implantation, in-situ atom replacement, and the like, but for two-dimensional materials, high-energy particles brought by the ion implantation method can destroy the crystal lattice periodicity of the two-dimensional materials, and introduce vacancies, impurity energy levels, and the like, which can greatly reduce the performance of the materials, particularly the carrier mobility. Although researchers have found that in-situ atomic growth replacement can be effective in doping materials both N-type and P-type, such as in MoS2Rubidium element is introduced to replace part of molybdenum in the growth process, so that the material can be effectively doped in a P type mode, but the operation process is complex, specificity is realized, and selective area doping can not be carried out on the material.
According to the characteristics of the thickness of the atomic layer of the two-dimensional material, researchers find that the surface charge transfer mode can effectively dope the two-dimensional material in a P type and an N type, and the common surface charge transfer modes comprise surface compounds, surface quantum dots, ions, nano particles, surface adsorbed gas, surface physical deposition and the like. However, the surface charge transfer method may cause instability of the doping method and poor process repeatability due to air instability of the surface material, and the doping method of surface physical layer deposition is considered to be the most stable and efficient doping method. Surface plasma treatment of two-dimensional materials is also an effective doping method, and under the bombardment of high-energy plasma, part of ions are combined with the materials to change the electrical characteristics of the materials, but the introduced high-energy method also destroys the lattice structure of the materials to a certain extent. Therefore, the exploration of a universal and stable doping method has important significance for the modification of the two-dimensional material.
Disclosure of Invention
The present invention aims at providing one kind of optically degenerated transition metal chalcogenide doping method with simple technological process and easy operation.
Another object of the present invention is to provide an electric device prepared by the method of optically degenerately doping, which has an MIS structure formed of gold-transition metal oxide-transition metal chalcogenide with strong photo-physical interaction.
It is a further object of the invention to provide an application of said electric device and said method for ultraviolet light detection, which has the advantage of a high sensitivity of the response outside the violet light.
The technical scheme adopted for realizing the purpose of the invention is as follows:
the invention relates to a method for carrying out optical degeneracy doping on transition metal chalcogenide, which comprises the following steps:
and 3, annealing the device obtained in the step 2, heating the device to 300-400 ℃ from the room temperature of 20-25 ℃ at the speed of 5-15 ℃/min, preserving the heat for 20-40 minutes, and naturally cooling the device to the room temperature.
In the above technical solution, the thickness of the transition metal chalcogenide in step 1 is 10-50 nm.
In the above technical scheme, the thickness of the gold nanolayer in the step 2 is 3-10 nm.
In the above technical solution, the transition metal chalcogenide in step 1 is MoS2、ReS2Or MoSe2。
In the above technical solution, the transition metal chalcogenide thin sheet in step 1 is compounded on the substrate by a dry transfer method.
In the technical scheme, the gold nanolayer in the step 2 is deposited on the device obtained in the step 1 in an electron beam evaporation mode, and the specific steps are that 99.999 percent of purity gold is bombarded by electron beams in a metal evaporation instrument to reach the melting temperature, and the film deposition speed is within the range of
In the above technical solution, the substrate in the step 1 is a heavily doped silicon or silicon dioxide substrate.
In another aspect of the invention, the method for optically degenerately doping transition metal chalcogenides is used for ultraviolet light detection.
In another aspect of the present invention, the method for optically degenerately doping is used to prepare an electric device having an MIS structure formed of a gold-transition metal oxide-transition metal chalcogenide.
In another aspect of the present invention, the electric device is applied to ultraviolet light detection, after the electric device is irradiated by ultraviolet light, the current transfer characteristic curve shows stronger N-type doping characteristics than the ground state without the ultraviolet light, the off-current of the electric device is increased by two to four orders of magnitude compared with the ground state photointerruption current, and the electric device is used for detecting ultraviolet lightAfter the device is subjected to ultraviolet illumination, the grid modulation switch ratio of the device is 2-10 times of the ground state, and the surface electron concentration reaches 1013～1014Per square centimeter.
And after the electric device is completely soaked in deionized water and dried after being irradiated by ultraviolet light, the current transfer characteristic of the electric device returns to the ground state.
Compared with the prior art, the invention has the beneficial effects that:
the semiconductor type layered transition metal chalcogenide is used as a photoelectric sensitive material, the band gap of the material is between 1 eV and 2eV, the material has strong light-object interaction, and a metal-insulator-semiconductor (MIS) structure is formed on the upper layer of the material in a high-temperature annealing mode (the structure of the application is gold-transition metal oxide-transition metal chalcogenide respectively, the transition metal oxide is a small amount of oxide formed in the annealing process, and the existence of the transition metal oxide can be shown in an X-ray photoelectron spectroscopy test).
And (3) performing electron beam evaporation deposition on the surface of the two-dimensional material to obtain a gold nano layer, and forming a gold nano film with good wettability on the surface of the TMDs material after high-temperature annealing treatment. Under the irradiation of ultraviolet light, electrons of the gold nanolayers overflow due to the external photoelectric effect and are injected into the semiconductor layer, and the redundant electrons form stable N-type doping on the semiconductor. After the ultraviolet irradiation is removed, the surplus electrons generated by light generation still remain in the material, so that the doping mode has long-term stability, and meanwhile, the method has universality and can be applied to various N-type TMDs. The novel rapid, simple, convenient, universal and stable doping method opens a new idea for the research of two-dimensional semiconductor materials.
Drawings
FIG. 1 is a MoS2A scanning electron microscopy image of the device;
FIG. 2 is a MoS2Electrical test patterns of the samples;
wherein: MoS with curve 1 as ground state2A transfer characteristic curve; the curve 2 is a device transfer characteristic curve after ultraviolet illumination; and the curve 3 is a device transfer characteristic curve after illumination treatment and deionized water treatment.
FIG. 3 is ReS2A scanning electron microscopy image of the device;
FIG. 4 is ReS2Electrical test patterns of the samples;
wherein: ReS with curve 1 as ground state2A transfer characteristic curve; the curve 2 is a device transfer characteristic curve after ultraviolet illumination;
FIG. 5 is MoSe2A scanning electron microscopy image of the device;
FIG. 6 is MoSe2Electrical test patterns of (a);
wherein: MoSe with curve 1 as ground state2A transfer characteristic curve; curve 2 is the transfer characteristic curve of the device after uv illumination.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
(1) Transfer of 15 nm thick MoS on heavily doped silicon or silicon dioxide substrates by dry transfer2A sheet;
(2) using MODELLWA-650 MZ-23NPP spin coater to coat with semiconductor material MoS2The PMMA950 is spin-coated on the substrate to be used as electron beam photoresist, an FEI aspect F50 scanning electron microscope is utilized to carry out electron beam lithography to expose two ends of the material, and a Tikono metal evaporation instrument is used for depositing titanium/gold (10nm/35nm) on two sides of the exposed material to be used as a test electrode of the material;
(3) the device is placed in a Tekno metal evaporation instrument again, a 6-nanometer gold layer is deposited on the surface of the device in an electron beam evaporation mode, and at the moment, a part of the nanometer gold is deposited on MoS2On the thin sheet, a part of nano gold is directly deposited on a silicon or silicon dioxide substrate;
(4) then placing the obtained electric device in a quartz tube for annealing treatment, wherein the annealing process comprises the following steps: heating up to 350 deg.C at 10 deg.C/min for 35 min from 20 deg.C, holding for 30 min, cooling to room temperature, taking out sample, and testingSee fig. 1, wherein: curve 1 is MoS2Gold on the flakes and surfaces; curve 2 is the annealed electrode; 3 is a gold nanostructure on a silica substrate; MoS2The white part of the position is the appearance of a gold nano-layer deposited on the material after high-temperature annealing, and the dark part is exposed MoS2The nano particles on the silicon dioxide substrate are gold nano particles annealed at high temperature, and the nano particles do not participate in electric conduction.
(5) And (4) electrically testing the device obtained in the step (4) by using a B1500 semiconductor tester, wherein the substrate is heavily doped with low-resistance silicon and serves as a grid voltage application end, and the source and drain electrodes are MoS2Contact electrodes on both sides. Wherein: curve 1 in FIG. 2 is the MoS obtained in step (4)2A transfer characteristic curve; as shown in curve 1 in fig. 2, the ground state transfer characteristic curve shows a strong N-type characteristic, and when the gate voltage is increased from-80V to +80V, the current changes from picoampere level to microampere level;
(6) after the device is subjected to ultraviolet irradiation by using the handheld ultraviolet lamp, a curve 2 in fig. 2 is a transfer characteristic curve of the device after the ultraviolet irradiation; as shown in a curve 2 in FIG. 2, the current transfer characteristic curve of the transistor shows N-type doping characteristics, particularly in that the off current of the transistor is increased by four orders of magnitude compared with the ground state off current, and the grid modulation switching ratio is 104Reduced to 2, the surface electron concentration calculated from the transfer characteristic curve reached 1014Per square centimeter, which is not achievable with conventional optical doping. The surface current density in the invention is calculated by the formula: n is a radical of2D＝(IdsL)/(qWVdsu) in the formula, N2DIs the area current density, IdsIs channel current, VdsFor the channel voltage, W and L are the length and width of the channel, respectively, and u is the mobility of the channel material.
(7) And (4) completely soaking the sample irradiated by the ultraviolet light in the step (6) in deionized water, taking out the sample, drying the residual moisture on the surface of the sample by using a high-purity nitrogen gun, and performing electrical test by using B1500. Curve 3 in fig. 2 is a transfer characteristic curve of the device after being subjected to the light irradiation treatment and then being subjected to the deionized water treatment, and as shown by curve 3 in fig. 2, the electrical property of the sample is close to the ground state property when not being irradiated by the ultraviolet light.
Example 2
ReS was transferred on heavily doped silicon or silicon dioxide substrates using the same method as in example 12And (3) a scanning electron microscope image of a prepared sample is shown in figure 3, wherein the thin sheet is prepared by depositing titanium/gold on two sides of the material by using an electron beam lithography mode to be used as contact electrodes, and performing the deposition and high-temperature annealing processes of a nano gold layer. Wherein: 1 is ReS2Gold on the flakes and surfaces; 2, annealing the electrode;
when the sample is subjected to an electrical test, as shown by a curve 1 in fig. 4, a ground state transfer characteristic curve of the device shows a strong N-type characteristic, and after the device is subjected to ultraviolet illumination, a current transfer characteristic curve shows an N-type doping characteristic.
The transfer characteristic of the device after UV illumination with a handheld UV lamp is shown in FIG. 4 as curve 2. The current transfer characteristic curve shows the characteristic of N-type doping, which is particularly embodied in that the turn-off current of the transistor is increased by two orders of magnitude compared with the ground state turn-off current, and the grid modulation switching ratio is 103Reduced to 6, the surface electron concentration calculated from the transfer characteristic curve reached 1013Per square centimeter of the total volume of the suspension,
example 3
MoSe was transferred to heavily doped silicon or silicon dioxide substrates using the same method as in example 12The slice, MoSe2 slice, followed by electron beam lithography to deposit titanium/gold on both sides of the material as contact electrodes, and the deposition and high temperature annealing process of nano gold layer, the prepared sample is shown in fig. 5.
When the sample is subjected to an electrical test, as shown by a curve 1 in fig. 6, a ground state transfer characteristic curve of the device shows a strong N-type characteristic, and after the device is subjected to ultraviolet illumination, a current transfer characteristic curve shows an N-type doping characteristic.
The transfer characteristic of the device after UV illumination with a handheld UV lamp is shown in FIG. 6 as curve 2. The current transfer characteristic curve shows the characteristic of N-type doping, particularly the turning-off of the current transfer characteristic curveThe current rises three orders of magnitude compared with the ground state turn-off current, and the grid modulation switching ratio is from 104Reduced to 10, the surface electron concentration calculated from the transfer characteristic curve reached 1013Per square centimeter of the total volume of the suspension,
the foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. An electrical device prepared by a method of optically degenerate doping a transition metal sulfide, the device being prepared by the steps of:
step 1, transferring a transition metal sulfide sheet with a nanometer thickness to a substrate;
step 2, depositing a gold nano layer on the device obtained in the step 1;
step 3, annealing the device obtained in the step 2, heating the device to 300-400 ℃ from the room temperature of 20-25 ℃ at the speed of 5-15 ℃/min, preserving the temperature for 20-40 minutes, and naturally cooling the device to the room temperature;
the electric device has an MIS structure formed by gold-transition metal oxide-transition metal sulfide, and the transition metal sulfide in the step 1 is MoS2、ReS2Or MoSe2。
2. The electrical device according to claim 1, wherein the transition metal sulfide in step 1 has a thickness of 10 to 50 nm.
3. The electrical device according to claim 1, wherein the gold nanolayer of step 2 has a thickness of 3-10 nm.
4. The electrical device according to claim 1, wherein the transition metal sulfide flakes of step 1 are composited on the substrate by dry transfer.
5. The electrical device of claim 1, wherein the substrate of step 1 is a heavily doped silicon or silicon dioxide substrate.
6. The electric device according to claim 1, wherein the gold nanolayers in the step 2 are deposited on the device obtained in the step 1 by electron beam evaporation, and the method comprises the specific steps of bombarding 99.999% pure gold to a melting temperature by using electron beams in a metal evaporation instrument, wherein the deposition speed of the thin film is 0.1-0.3
。
7. The application of the electric device in ultraviolet light detection according to claim 1, wherein after the electric device is subjected to ultraviolet light irradiation, the current transfer characteristic curve shows stronger N-type doping characteristics than a ground state without the ultraviolet light irradiation, the off-current of the electric device is increased by two to four orders of magnitude compared with the ground state light interruption current, after the electric device is subjected to ultraviolet light irradiation, the grid modulation switching ratio of the electric device is 2 to 10 times of the ground state, and the surface electron concentration reaches 1013~1014Per square centimeter.
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