CN116555724A - Method for preparing monoatomic layer nitride - Google Patents

Method for preparing monoatomic layer nitride Download PDF

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CN116555724A
CN116555724A CN202310535984.2A CN202310535984A CN116555724A CN 116555724 A CN116555724 A CN 116555724A CN 202310535984 A CN202310535984 A CN 202310535984A CN 116555724 A CN116555724 A CN 116555724A
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metal
single crystal
monoatomic layer
monocrystal
preparing
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李春晓
宋文涛
吴伟汉
陈科蓓
韩厦
徐科
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Priority to CN202410583633.3A priority patent/CN118422163A/en
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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    • C23C16/301—AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi
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Abstract

The invention discloses a method for preparing monoatomic layer nitride, which comprises the following steps: providing a metal monocrystal as a substrate; selecting a metal organic matter as an evaporation source to be adsorbed on the surface of the metal single crystal; and heating the substrate to 350-450 ℃, and decomposing metal organic matters on the surface of the substrate and carrying out surface on-site chemical reaction to generate monoatomic layer nitride. The method for preparing the monoatomic layer nitride can realize the controllable growth of the monoatomic layer nitride, and the grown single-layer sub-layer nitride crystal has good crystallinity and high flatness, thereby laying a good foundation for preparing a highly integrated gallium nitride device.

Description

Method for preparing monoatomic layer nitride
Technical Field
The invention relates to the technical field of semiconductor material growth, in particular to a method for growing monoatomic layer nitride on the surface of a metal organic matter through in-situ chemical reaction.
Background
The third generation semiconductor has progressed rapidly after entering twenty-first century, and nitride semiconductor is one of the star products. Nitride semiconductors offer a number of advantages over conventional silicon material semiconductors, including: high electron mobility, wide forbidden bandwidth, high electron saturation drift velocity, high energy electron beam irradiation and stability in high temperature environment. The wurtzite structure of the nitride semiconductor is a direct band gap semiconductor and is a mainstream material of novel display devices, electronic power devices, solar inverters, communication equipment and radar systems at present. However, group III-V nitrides are sp3 orbital hybrids, are prone to longitudinal bonding during growth, and are difficult to obtain by conventional vapor phase growth or mechanical lift-off methods. Theoretical calculation shows that when the atomic layer of the nitride material is reduced by 5 layers, thermodynamic properties tend to be stable, and the phenomena of lattice constant increase, band gap blue shift and the like can occur. Due to its ultra-thin thickness, monoatomic nitrides exhibit strong quantum confinement effects and visible light transmittance, which results in some new electronic, optical and phonon properties, such as modulation of the energy-efficient structure, confinement of electron transport, enhancement of optical absorption, blue-shift of luminescence, etc., which make them of great application potential in optoelectronics, transparent electronic devices and optoelectronic devices.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention aims to provide a method for preparing monoatomic layer nitride, which can realize the controllable growth of monoatomic layer nitride, and the grown single-layer sub-layer nitride crystal has good crystallinity and high flatness, thereby laying a good foundation for preparing a highly integrated gallium nitride device.
To achieve the above object, an embodiment of the present invention provides a method of preparing a monoatomic layer nitride, including: providing a metal monocrystal as a substrate; selecting a metal organic matter as an evaporation source to be adsorbed on the surface of the metal single crystal; and heating the substrate to 350-450 ℃, and decomposing metal organic matters on the surface of the substrate and carrying out surface on-site chemical reaction to generate monoatomic layer nitride.
In one or more embodiments of the present invention, the metalorganic includes one or more of trimethylaminogallium, trimethylaminoindium, and trimethylaminoaluminum.
In one or more embodiments of the present invention, the metal single crystal includes one of Au, ag, cu.
In one or more embodiments of the present invention, before the step of adsorbing the metal organic to the surface of the metal single crystal, the method further includes: and (3) cleaning, degassing and annealing the metal single crystal.
In one or more embodiments of the present invention, the step of performing a cleaning process on the metal single crystal includes: soaking the metal monocrystal in an organic solvent, and performing ultrasonic treatment to remove organic matters on the surface of the metal monocrystal; immersing the metal monocrystal in deionized water or pure water, and adding a reducing agent to remove oxides on the surface of the metal monocrystal; immersing the metal monocrystal in an acidic solution to remove residual oxide and impurities on the surface of the metal monocrystal; immersing the metal monocrystal in an alkaline solution to neutralize acidic substances on the surface of the metal monocrystal, and cleaning the surface of the metal monocrystal; the metal single crystal is immersed in deionized water or pure water for surface rinsing, and dried using nitrogen gas or under vacuum.
In one or more embodiments of the invention, the organic solvent includes ethanol, acetone.
In one or more embodiments of the invention, the reducing agent comprises hydrofluoric acid, ferrous chloride.
In one or more embodiments of the invention, the acidic solution comprises nitric acid, sulfuric acid.
In one or more embodiments of the invention, the alkaline solution comprises sodium hydroxide, ammonia.
In one or more embodiments of the present invention, the step of degassing and annealing the metal single crystal includes: bombarding the surface of the metal monocrystal with argon ion with energy of 0.7-1.5eV for 15-20min, heating the metal monocrystal to 700-800 ℃ at 10-15 ℃/min, cooling to 380-400 ℃ at 10-15 ℃/min, and preserving heat for 18-22min; repeating the above steps until the metal single crystal surface is detected by STM to have no impurity adsorption and contain more than 100nm 2 To the mesa of the display panel.
In one or more embodiments of the present invention, the step of selecting a metal organic as an evaporation source to be adsorbed on the surface of the metal single crystal includes: providing MBE equipment, analyzing the beam current of metal organic source introduced into the interior of MBE growth chamber by using beam current detector equipped in MBE chamber, and making the beam current of metal organic source be 1×10 -6 Torr-1×10 -5 Between Torr; and (3) placing the metal single crystal into an MBE growth chamber, opening a metal organic source baffle plate to enable the metal organic to be adsorbed on the surface of the metal single crystal, and closing the metal organic source baffle plate after the metal organic is deposited for 10-30 seconds.
In one or more embodiments of the invention, the substrate is heated at a heating rate of 10 ℃/min to 15 ℃/min, and the reaction time of the in-situ chemical reaction of the metal-organic surface is 10 to 30s.
In one or more embodiments of the present invention, the preparation environment is an ultra-high vacuum environment in which the vacuum degree is not less than 1×10 -5 Torr。
In one or more embodiments of the invention, the metalorganic has a purity of greater than or equal to 99.999%.
Compared with the prior art, the method for preparing the monoatomic layer nitride according to the embodiment of the invention has the advantages that in an ultra-high vacuum chamber (the vacuum degree is not less than 1 x 10 -5 Torr), taking metal organic as a metal source and nitrogen source, firstly degassing a metal single crystal in a vacuum chamber, and then annealingAnd then introducing metal organic matters into the cavity, heating the metal single crystal by physical adsorption to the surface of the metal single crystal, desorbing the metal organic matters by methyl at a proper temperature, causing a metal organic matter system to become unstable, carrying out atomic rearrangement on original metal organic matter molecules, and reassembling the molecules, thereby realizing the preparation of monoatomic layer nitride by in-situ chemical reaction.
According to the method for preparing the monoatomic layer nitride, disclosed by the embodiment of the invention, a metal organic matter (trimethyl aminogallium, trimethyl aminoindium and trimethyl amino aluminum) with a metal source and a nitrogen source is used as a reaction precursor, a metal monocrystal is used as a substrate (Au, ag, cu and the like), methyl desorption in the metal organic matter is realized by controlling the temperature in the growth process, and the rest Ga-N system energy is unstable, so that the inside of molecules can be promoted to be reassembled, and the monoatomic layer nitride is formed.
According to the method for preparing the monoatomic layer nitride, the nitride growth rate is controlled by controlling the beam flow of the metal organic precursor, the transition of the nitride growth mode from the layer island combination to the two-dimensional lamellar mode is successfully realized, and the monoatomic layer nitride is grown, so that the self-supporting monoatomic layer nitride material with high crystallinity and high flatness is obtained, and the method is expected to pave the way for preparing deep ultraviolet photoelectric and power electronic devices.
Drawings
FIG. 1 is a process flow diagram of a method of preparing monoatomic layer nitrides according to an embodiment of the invention;
FIG. 2 is a detailed process flow diagram of a method of preparing monoatomic layer nitrides according to an embodiment of the invention;
FIG. 3 is an in-situ chemical reaction of a trimethyl aminogallium synthesized GaN surface;
FIG. 4 is a scanning electron microscope image of the surface morphology of monoatomic layer gallium nitride prepared according to the method of preparing monoatomic layer nitride of example 1 of the present invention;
fig. 5a is an auger electron spectrum (corresponding to position 1 in fig. 4) of monoatomic layer gallium nitride prepared according to the method of preparing monoatomic layer nitride of example 1 of the present invention;
fig. 5b is an auger electron spectrum (corresponding to position 2 in fig. 4) of monoatomic layer gallium nitride prepared according to the method of preparing monoatomic layer nitride of example 1 of the present invention;
FIG. 6 is an atomic force microscope image of a surface topography of monoatomic layer gallium nitride prepared according to the method of preparing monoatomic layer nitride of example 1 of the present invention;
fig. 7 is a cathode fluorescence spectrum of monoatomic layer gallium nitride prepared according to the method of preparing monoatomic layer nitride of example 1 of the present invention.
Detailed Description
The following detailed description of embodiments of the invention is, therefore, to be taken in conjunction with the accompanying drawings, and it is to be understood that the scope of the invention is not limited to the specific embodiments.
Throughout the specification and claims, unless explicitly stated otherwise, the term "comprise" or variations thereof such as "comprises" or "comprising", etc. will be understood to include the stated element or component without excluding other elements or components.
As described in the background art, the monoatomic layer nitride semiconductor has important application potential in optoelectronics, transparent electronic devices and optoelectronic devices because of its special properties, but monoatomic layer nitride is sp3 orbital hybridization, is easy to bond longitudinally during growth, and is difficult to obtain by conventional vapor phase growth or mechanical lift-off methods.
In order to solve the technical problems, the application creatively provides a method for preparing monoatomic layer nitride, the monoatomic layer nitride grows on the surface of a metal organic precursor through in-situ chemical reaction, the preparable nitride comprises three III-V nitrides of GaN, alN, inN, and the grown monoatomic layer nitride crystal is good in crystallinity and highly flat, so that a good foundation is laid for preparing a highly integrated gallium nitride device.
As shown in fig. 1, a method of preparing a monoatomic layer nitride according to an embodiment of the present invention includes: s1 provides a metal single crystal as a substrate. And s2, cleaning, degassing and annealing the metal single crystal. s3, selecting a metal organic matter as an evaporation source to be adsorbed on the surface of the metal single crystal. And s4, heating the substrate to 350-450 ℃, decomposing metal organic matters on the surface of the substrate, and carrying out surface in-situ chemical reaction to generate monoatomic layer nitride.
Wherein in step s1 and step s2, the metal single crystal includes one of Au, ag, cu. Referring to fig. 2, the cleaning process of the metal single crystal includes the steps of: s201, removing organic matters on the surface of the metal monocrystal: soaking the metal monocrystal in organic solvent, and ultrasonic treatment to eliminate organic matter on the surface of the metal monocrystal, wherein the organic solvent includes ethanol and acetone. s202 removing oxide on the surface of the metal monocrystal: soaking metal monocrystal in deionized water or pure water, adding reducing agent to remove oxide on surface of metal monocrystal, wherein the reducing agent comprises hydrofluoric acid (HF) and ferrous chloride (FeCl) 2 ). s203 acid washing: immersing the metal single crystal in an acidic solution comprising concentrated nitric acid (HNO) to remove residual oxides and impurities on the surface of the metal single crystal 3 ) Concentrated sulfuric acid (H) 2 SO 4 ). s204 alkali washing: immersing the metal single crystal in an alkaline solution to neutralize acidic substances remaining on the surface of the metal single crystal and to clean the surface of the metal single crystal, the alkaline solution including sodium hydroxide (NaOH), ammonia (NH) 3 ·H 2 O). s205 flushing: the metal single crystal is soaked in deionized water or pure water to carry out surface flushing for a plurality of times, so that no residual chemical substances are ensured on the surface of the metal single crystal. And S206, drying: the metal single crystal is dried using nitrogen blow-drying or under vacuum.
In step s2, the step of degassing and annealing the metal single crystal includes: providing MBE equipment, fixing a metal single crystal on a support, then moving and placing the metal single crystal in a sample injection cavity of the MBE, and keeping the sample injection cavity in an ultra-high vacuum environment, wherein the vacuum degree in the ultra-high vacuum environment is not lower than 1 x 10 -5 Torr. Bombarding the surface of the metal monocrystal with argon ion with energy of 0.7-1.5eV for 15-20min, heating the metal monocrystal to 700-800 ℃ at 10-15 ℃/min, cooling to 380-400 ℃ at 10-15 ℃/min, and preserving the temperature for 18-22min, preferably 20min; STM is used for detecting whether the surface of the metal monocrystal is flat or not, and when the surface of the metal monocrystal is not flatAdsorption of impurities and their content exceeding 100nm 2 The table top of the metal monocrystal is proved to be cleaned; otherwise, continuing to use the argon ion and the high-temperature annealing process until the surface of the metal single crystal is detected by STM to be free of impurity adsorption and contain more than 100nm 2 To the mesa of the display panel.
In step s3, a step of selecting a metal organic as an evaporation source to be adsorbed on the surface of the metal single crystal, comprising: providing MEB equipment, analyzing the beam current of the metal organic source introduced into the MBE growth chamber by using a beam current detector arranged in the MBE chamber, and controlling the beam current of the metal organic source to be 1 multiplied by 10 by controlling the temperature of the top and the bottom of a metal organic crucible in the MBE -6 Torr-1×10 -5 Between Torr; placing metal monocrystal into MBE growth chamber, maintaining the growth chamber in ultrahigh vacuum environment with vacuum degree not lower than 1 x 10 -5 And (3) Torr, opening the metal organic source baffle, adsorbing the metal organic on the surface of the metal single crystal, and closing the metal organic source baffle after depositing the metal organic for 10-30 seconds. Wherein the metal organic is one or more of trimethyl amino gallium, trimethyl amino indium and trimethyl amino aluminum, and the purity of the metal organic is more than or equal to 99.999%.
In step s4, the substrate is heated to 350-450 ℃ at a heating rate of 10-15 ℃/min. At this temperature, the metal organic on the substrate surface is decomposed, the methyl groups in the metal organic are desorbed, and monoatomic layer nitrides are formed by in-situ chemical reaction, as shown in fig. 3. Wherein the reaction time of the in-situ chemical reaction is 10-30 s.
In the technical scheme, the method for preparing the monoatomic layer nitride uses metal organic matters (trimethyl amino gallium, trimethyl amino indium and trimethyl amino aluminum) with a metal source and a nitrogen source as reaction precursors, uses metal single crystals as substrates (Au, ag, cu and the like), realizes methyl desorption in the metal organic matters by controlling the temperature in the growth process, and causes the rest Ga-N system energy to be unstable, so that the inside of molecules can be promoted to be reassembled, and the monoatomic layer nitride is formed.
According to the method for preparing the monoatomic layer nitride, disclosed by the embodiment of the invention, the nitride growth rate is controlled by controlling the beam flow of the metal organic precursor, the transition of the nitride growth mode from the layer island combination to the two-dimensional lamellar mode is successfully realized, and the monoatomic layer nitride is grown, so that the self-supporting monoatomic layer nitride material with high crystallinity and high flatness is obtained, and the method is expected to pave the way for preparing deep ultraviolet photoelectric and power electronic devices.
Example 1
Au is adopted as the metal monocrystal, and trimethyl aminogallium is adopted as the metal organic matter.
The beaker was cleaned. Ultrasonic cleaning is carried out on deionized water in a beaker, ultrasonic cleaning is carried out on acetone, and the process is repeated for several times.
And (5) cleaning the metal monocrystal Au. 1. Removing surface organic matters: the Au single crystal is soaked in an organic solvent, such as ethanol or acetone, and more organic matters are removed by ultrasonic treatment. 2. Removing surface oxide: soaking Au single crystal in deionized water or pure water, adding hydrofluoric acid (HF) or ferrous chloride (FeCl) 2 ) And reducing agent to remove oxide on the surface. 3. Acid washing: soaking Au single crystal in acidic solution such as concentrated nitric acid (HNO) 3 ) Or concentrated sulfuric acid (H) 2 SO 4 ) And removing the oxide and other impurities remained on the surface. 4. Alkali washing: soaking Au single crystal in alkaline solution such as sodium hydroxide (NaOH) or ammonia water (NH) 3 ·H 2 O) can neutralize the acidic material remaining from the acidic solution and clean the surface. 5. Washing with deionized water again: the Au single crystal is soaked in deionized water or pure water and washed clean for a plurality of times to ensure that the surface is free of residual chemical substances. 6. The Au single crystal was blow-dried using nitrogen or dried under vacuum.
The metal single crystal Au was fixed to a holder and then transferred to the MBE sample introduction chamber.
In order to further remove impurities on the surface of the metal monocrystal Au and enlarge the surface table top, the metal monocrystal Au is bombarded with argon ions with the energy of 0.7-1.5eV for 15-20min, the temperature of the metal monocrystal Au is increased to 700-800 ℃ at 10-15 ℃/min, and then the temperature of the metal monocrystal Au is increased to 10-1 °cCooling to 380-400 deg.c at 5 deg.c/min, maintaining the temperature for 18-22min, preferably 20min, and STM to detect whether the metal monocrystal Au is smooth or not, and when the surface of the metal monocrystal Au has no magazine adsorption and contains more than 100nm 2 And (3) cleaning, and if the table top is not up to the standard, continuing to use argon ions and high-temperature goods returning process steps.
Analysis of the metalorganic Source Beam, here Triaminogallium, introduced into the MBE growth Chamber Using Beam Detector in the MBE Chamber, the beam control of the Triaminogallium Source was controlled at 1×10 by controlling the temperature at the top and bottom of the metalorganic crucible in the MBE -6 Torr-1×10 -5 Between Torr.
And (3) placing the treated metal monocrystal Au into an MBE growth chamber, opening a metal organic evaporation source baffle, adsorbing trimethyl aminogallium on the surface of the metal monocrystal Au, and closing the metal organic evaporation source baffle after depositing for 10-30 s. Heating metal monocrystal Au to 350-450 ℃ at a heating rate of 10-15 ℃ per minute, decomposing trimethyl aminogallium on the surface of the metal monocrystal Au, desorbing methyl in the trimethyl aminogallium, and forming monoatomic layer nitride through in-situ chemical reaction; wherein, the purity of the trimethyl aminogallium reaches 99.999 percent, and the reaction time of the in-situ chemical reaction is 10-30 s.
After the reaction is completed, the tray is transferred to the growth chamber.
Sealing the sample in a vacuum bag, taking out and carrying out subsequent characterization test of crystal quality to obtain characterization results in fig. 4, 5a, 5b, 6 and 7. The grown sample material can be judged to be single atomic layer gallium nitride by a scanning electron microscope, an Auger electron spectrum, an atomic force microscope image and a cathode fluorescence spectrum.
Example 2:
au is adopted as the metal monocrystal, and trimethyl amino indium is adopted as the metal organic matter.
The beaker was cleaned. Ultrasonic cleaning is carried out on deionized water in a beaker, ultrasonic cleaning is carried out on acetone, and the process is repeated for several times.
And (5) cleaning the metal monocrystal Au. 1. Removing surface organic matters: soaking Au single crystal in organic solvent such as ethanol or acetone, and ultrasonic treatingExcept for more organics. 2. Removing surface oxide: soaking Au single crystal in deionized water or pure water, adding hydrofluoric acid (HF) or ferrous chloride (FeCl) 2 ) And reducing agent to remove oxide on the surface. 3. Acid washing: soaking Au single crystal in acidic solution such as concentrated nitric acid (HNO) 3 ) Or concentrated sulfuric acid (H) 2 SO 4 ) And removing the oxide and other impurities remained on the surface. 4. Alkali washing: soaking Au single crystal in alkaline solution such as sodium hydroxide (NaOH) or ammonia water (NH) 3 ·H 2 O) can neutralize the acidic material remaining from the acidic solution and clean the surface. 5. Washing with deionized water again: the Au single crystal is soaked in deionized water or pure water and washed clean for a plurality of times to ensure that the surface is free of residual chemical substances. 6. The Au single crystal was blow-dried using nitrogen or dried under vacuum.
The metal single crystal Au was fixed to a holder and then transferred to the MBE sample introduction chamber.
In order to further remove impurities on the surface of the metal single crystal Au and enlarge the surface table top, the metal single crystal Au is bombarded by argon ions with the energy of 0.7-1.5eV for 15-20min, the metal single crystal is heated to 700-800 ℃ at 10-15 ℃/min, then is cooled to 380-400 ℃ at 10-15 ℃/min, and is kept for 18-22min, preferably 20min, and STM is used for detecting whether the metal single crystal Au is flat or not when the surface of the metal single crystal Au is not adsorbed by magazines and contains more than 100nm 2 And (3) cleaning, and if the table top is not up to the standard, continuing to use argon ions and high-temperature goods returning process steps.
Analysis of the beam of the metalorganic Source introduced into the interior of the MBE growth Chamber, here, trimethylaminoindium, by means of a beam detector equipped in the chamber of the MBE, the beam of the trimethylaminoindium source was controlled at 1X 10 by controlling the temperature of the top and bottom of the metalorganic crucible in the MBE -6 Torr-1×10 -5 Between Torr.
And (3) placing the treated metal monocrystal Au into an MBE growth chamber, opening a metal organic evaporation source baffle, adsorbing trimethyl amino indium on the surface of the metal monocrystal Au, and closing the metal organic evaporation source baffle after depositing for 10-30 s. Heating metal monocrystal Au to 350-450 ℃ at a heating rate of 10-15 ℃ per minute, decomposing trimethyl amino indium on the surface of the metal monocrystal Au, desorbing methyl in the trimethyl amino indium, and forming monoatomic layer nitride through in-situ chemical reaction; wherein, the purity of the trimethyl amino indium reaches 99.999 percent, and the reaction time of the in-situ chemical reaction is 10 to 30 seconds.
After the reaction is completed, the tray is transferred to the growth chamber.
Sealing the sample in a vacuum bag, taking out the sample, and performing subsequent characterization test of crystal quality, wherein the grown sample material can be judged to be monoatomic layer indium nitride through a scanning electron microscope, an atomic force microscope image, an Auger electron spectrum and a cathode fluorescence spectrum.
Example 3:
au is adopted as the metal monocrystal, and trimethylaluminum amide is adopted as the metal organic matter.
The beaker was cleaned. Ultrasonic cleaning is carried out on deionized water in a beaker, ultrasonic cleaning is carried out on acetone, and the process is repeated for several times.
And (5) cleaning the metal monocrystal Au. 1. Removing surface organic matters: the Au single crystal is soaked in an organic solvent, such as ethanol or acetone, and more organic matters are removed by ultrasonic treatment. 2. Removing surface oxide: soaking Au single crystal in deionized water or pure water, adding hydrofluoric acid (HF) or ferrous chloride (FeCl) 2 ) And reducing agent to remove oxide on the surface. 3. Acid washing: soaking Au single crystal in acidic solution such as concentrated nitric acid (HNO) 3 ) Or concentrated sulfuric acid (H) 2 SO 4 ) And removing the oxide and other impurities remained on the surface. 4. Alkali washing: soaking Au single crystal in alkaline solution such as sodium hydroxide (NaOH) or ammonia water (NH) 3 ·H 2 O) can neutralize the acidic material remaining from the acidic solution and clean the surface. 5. Washing with deionized water again: the Au single crystal is soaked in deionized water or pure water and washed clean for a plurality of times to ensure that the surface is free of residual chemical substances. 6. The Au single crystal was blow-dried using nitrogen or dried under vacuum.
The metal single crystal Au was fixed to a holder and then transferred to the MBE sample introduction chamber.
To further remove the metal single crystal Au surfaceImpurity and enlarging surface table surface, bombarding metal monocrystal Au with argon ion with energy of 0.7-1.5eV for 15-20min, heating metal monocrystal Au to 700-800 deg.C at 10-15 deg.C/min, cooling to 380-400 deg.C at 10-15 deg.C/min, maintaining for 18-22min, preferably 20min, and detecting whether metal monocrystal Au is flat or not by STM when metal monocrystal Au has no magazine adsorption and contains more than 100nm 2 And (3) cleaning, and if the table top is not up to the standard, continuing to use argon ions and high-temperature goods returning process steps.
Analysis of the beam of the metallorganic source, here trimethylammonium, introduced into the MBE growth chamber by means of a beam detector provided in the chamber of the MBE, the beam of the trimethylammonium source was controlled at 1X 10 by controlling the temperature of the top and bottom of the metallorganic crucible in the MBE -6 Torr-1×10 -5 Between Torr.
And (3) placing the treated metal monocrystal Au into an MBE growth chamber, opening a metal organic evaporation source baffle, adsorbing trimethyl aluminum amino on the surface of the metal monocrystal Au, and closing the metal organic evaporation source baffle after depositing for 10-30 s. Heating metal monocrystal Au to 350-450 ℃ at a heating rate of 10-15 ℃ per minute, decomposing trimethyl aluminum on the surface of the metal monocrystal Au, desorbing methyl in the trimethyl aluminum, and forming monoatomic layer nitride through in-situ chemical reaction; wherein the purity of the trimethyl aluminum amide reaches 99.999 percent, and the reaction time of the in-situ chemical reaction is 10 to 30 seconds.
After the reaction is completed, the tray is transferred to the growth chamber.
Sealing the sample in a vacuum bag, taking out the sample, and performing subsequent characterization test of crystal quality, wherein the grown sample material can be judged to be monoatomic layer aluminum nitride through a scanning electron microscope, an atomic force microscope image, an Auger electron spectrum and a cathode fluorescence spectrum.
Comparative example:
the beam flux of the metal organic source, the metal organic deposition time, the substrate temperature rise rate, the substrate temperature rise height, the in-situ chemical reaction time and other parameters were changed, and other experimental conditions were the same as in example 1, and the effects were compared with those of the following table 1.
TABLE 1
From comparative examples 1 and 2, it can be seen that the beam flux and deposition time of the metal-organic source have the following effect on the preparation of monoatomic layer nitrides: the beam flux and the deposition time jointly determine the amount of metal organic matters deposited on the substrate, and the same time, too large beam flux and too much metal organic matters can cause metal organic aggregation and then form gallium nitride islands. Too small an amount of metal-organic material at too small a beam flux results in too small a size of gallium nitride formed to form a film.
From comparative examples 3 and 4, it can be seen that the substrate temperature increase rate has the following effect on the preparation of monoatomic layer nitrides: the faster the temperature rising speed is, the less uniform the methyl desorption of the metal organic molecules is caused, the self-assembly process is started without completely desorbing the methyl, and the sample is not pure enough; the temperature rising speed is too slow, so that after methyl desorption, part of methyl is adsorbed again by the surface of the sample, and the sample is not pure enough.
From comparative examples 5 and 6, it is understood that the substrate temperature elevation has the following effect on the preparation of monoatomic layer nitrides: too low a substrate temperature results in reaction failure and methyl desorption failure. Too high a temperature of the lining may cause the reaction to occur too quickly, and the assembled partial structure may become disordered.
From comparative examples 7 and 8, it can be seen that the length of the in-situ chemical reaction time has the following effect on the preparation of monoatomic layer nitrides: too short a reaction time may result in incomplete and unstable nitride layers. Too long a time may result in excessive crystallization with defects and impurities.
In summary, according to the method for preparing a monoatomic layer nitride according to the embodiment of the present invention, a metal organic (trimethyl aminogallium, trimethyl aminoindium, trimethyl amino aluminum) having both a metal source and a nitrogen source is used as a reaction precursor, a metal single crystal is used as a substrate (Au, ag, cu, etc.), methyl desorption in the metal organic is achieved by controlling the temperature during growth, and the remaining ga—n system energy is unstable, which may promote reassembly inside molecules, to form the monoatomic layer nitride.
According to the method for preparing the monoatomic layer nitride, the nitride growth rate is controlled by controlling the beam flow of the metal organic precursor, the transition of the nitride growth mode from the layer island combination to the two-dimensional lamellar mode is successfully realized, and the monoatomic layer nitride is grown, so that the self-supporting monoatomic layer nitride material with high crystallinity and high flatness is obtained, and the method is expected to pave the way for preparing deep ultraviolet photoelectric and power electronic devices.
The foregoing descriptions of specific exemplary embodiments of the present invention are presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.

Claims (10)

1. A method of preparing a monoatomic layer nitride comprising:
providing a metal monocrystal as a substrate;
selecting a metal organic matter as an evaporation source to be adsorbed on the surface of the metal single crystal;
and heating the substrate to 350-450 ℃, and decomposing metal organic matters on the surface of the substrate and carrying out surface on-site chemical reaction to generate monoatomic layer nitride.
2. The method of preparing a monoatomic layer nitride according to claim 1, wherein the metalorganic comprises one or more of trimethylaminogallium, trimethylaminoindium, and trimethylaminoaluminum.
3. The method of preparing a monoatomic layer nitride according to claim 1, wherein the single metal crystal comprises one of Au, ag, cu.
4. The method of preparing a monoatomic layer nitride according to claim 1, wherein prior to the step of adsorbing the metal organics to the surface of the metal single crystal, further comprising: and (3) cleaning, degassing and annealing the metal single crystal.
5. The method for preparing monoatomic layer nitride according to claim 4, wherein the step of cleaning the metal single crystal comprises:
soaking the metal monocrystal in an organic solvent, and performing ultrasonic treatment to remove organic matters on the surface of the metal monocrystal;
immersing the metal monocrystal in deionized water or pure water, and adding a reducing agent to remove oxides on the surface of the metal monocrystal;
immersing the metal monocrystal in an acidic solution to remove residual oxide and impurities on the surface of the metal monocrystal;
immersing the metal monocrystal in an alkaline solution to neutralize acidic substances on the surface of the metal monocrystal, and cleaning the surface of the metal monocrystal;
the metal single crystal is immersed in deionized water or pure water for surface rinsing, and dried using nitrogen gas or under vacuum.
6. The method for preparing monoatomic layer nitride according to claim 5, wherein the organic solvent comprises ethanol, acetone; and/or
The reducing agent comprises hydrofluoric acid and ferrous chloride; and/or
The acidic solution comprises nitric acid and sulfuric acid; and/or
The alkaline solution comprises sodium hydroxide and ammonia water.
7. The method for preparing monoatomic layer nitride according to claim 4, wherein the step of degassing and annealing the single crystal metal comprises:
bombarding the surface of the metal monocrystal with argon ion with energy of 0.7-1.5eV for 15-20min, heating the metal monocrystal to 700-800 ℃ at 10-15 ℃/min, cooling to 380-400 ℃ at 10-15 ℃/min, and preserving heat for 18-22min;
repeating the above steps until the metal single crystal surface is detected by STM to have no impurity adsorption and contain more than 100nm 2 To the mesa of the display panel.
8. The method of preparing a monoatomic layer nitride according to claim 1, wherein the step of selecting a metal organic as an evaporation source to be adsorbed on the surface of the metal single crystal comprises:
providing MBE equipment, analyzing the beam current of metal organic source introduced into the interior of MBE growth chamber by using beam current detector equipped in MBE chamber, and making the beam current of metal organic source be 1×10 -6 Torr-1×10 -5 Between Torr;
and (3) placing the metal single crystal into an MBE growth chamber, opening a metal organic source baffle plate to enable the metal organic to be adsorbed on the surface of the metal single crystal, and closing the metal organic source baffle plate after the metal organic is deposited for 10-30 seconds.
9. The method of preparing a monoatomic layer nitride according to claim 1, wherein the substrate is heated at a heating rate of 10 ℃/min to 15 ℃/min and the reaction time of the metal-organic surface in-situ chemical reaction is 10 to 30s.
10. The method for producing a monoatomic layer nitride according to claim 1, wherein the production environment is an ultra-high vacuum environment in which the degree of vacuum is not less than 1 x10 -5 Torr; and/or the number of the groups of groups,
the purity of the metal organic matters is more than or equal to 99.999 percent.
CN202310535984.2A 2023-05-12 2023-05-12 Method for preparing monoatomic layer nitride Pending CN116555724A (en)

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