STM-induced growth of single atomic layer nitride

Abstract

The present invention discloses a method for STM-induced growth of a single atomic layer of nitride, comprising: selecting an organic molecular precursor containing at least a group IIIA metal and a molecular precursor containing at least a group IIIA metal halide, injecting an electron beam into them through the needle tip of an STM, causing the organic molecular precursor and the molecular precursor to break bonds to obtain the organic molecular precursor and the required groups in the molecular precursor; applying voltage through the needle tip of the STM to guide the organic molecular precursor and the required groups in the molecular precursor to polymerize to generate a single atomic layer of nitride. The method for STM-induced growth of a single atomic layer of nitride of the present invention can use the tip of a probe to precisely manipulate atoms or molecules, induce molecules containing group IIIA metals and group IIIA metal halides to couple and recombine, and realize the growth of a single layer of nitride.

Description

Technical Field

[0001] The invention relates to the technical field of semiconductor growth, in particular to a method for an SPM probe to induce the growth of a single atomic layer III-V group wide bandgap two-dimensional nitride semiconductor. Background Art

[0002] Nitride semiconductors are an important family of third-generation semiconductors. They have ultra-wide bandgap, high temperature resistance, and excellent radiation resistance, and are suitable for high-frequency and high-power devices. With the in-depth study of single-atomic-layer two-dimensional nitrides, compared with traditional bulk nitrides, single-atomic-layer two-dimensional nitrides have more excellent properties: wider bandgap, excellent mechanical strain capacity, extremely strong optical transmittance, and ultra-low thermal conductivity.

[0003] The method of inducing growth using STM probe technology has a long history. As early as 1990, IBM successfully used 35 xenon atoms to spell out the three letters "IBM" on a Ni crystal, achieving the rearrangement of a single atom for the first time. Later, it was successfully achieved in an ultra-high vacuum environment, using probes to induce molecular organic precursors to complete a series of reactions such as Ullmann reaction, Schiff base reaction, and boric acid condensation reaction to prepare a two-dimensional network on a substrate, thereby preparing a single atomic layer compound. When applying voltage to the needle tip to extract, drag, and drop a single atom or molecule, the sample surface can also be scanned in constant current mode or constant height mode to obtain morphological information. The combination of the two can understand the effect of tip-induced growth in situ.

[0004] The information disclosed in this background technology section is only intended to enhance the understanding of the overall background of the invention and should not be regarded as an acknowledgment or any form of suggestion that the information constitutes the prior art already known to a person skilled in the art. Summary of the invention

[0005] The purpose of the present invention is to provide a method for STM-induced growth of a single atomic layer of nitride, which can use the probe tip to accurately manipulate atoms or molecules, induce molecules containing IIIA group metals and IIIA group metal halides to couple and recombine, and realize the growth of a single layer of nitride.

[0006] To achieve the above-mentioned purpose, an embodiment of the present invention provides a method for STM-induced growth of a single atomic layer of nitride, comprising: selecting an organic molecular precursor containing at least a Group IIIA metal and a molecular precursor containing at least a Group IIIA metal halide, injecting an electron beam into them through the needle tip of an STM to break bonds between the organic molecular precursor and the molecular precursor to obtain the organic molecular precursor and the desired groups within the molecular precursor; applying voltage through the needle tip of the STM to guide the organic molecular precursor and the desired groups within the molecular precursor to polymerize to generate a single atomic layer of nitride.

[0007] In one or more embodiments of the present invention, the energy of the electron beam injected to break the bond between the organic molecular precursor and the molecular precursor is 10 eV-100 eV.

[0008] In one or more embodiments of the present invention, the step of applying voltage through the needle tip of the STM to guide the organic molecular precursor and the desired groups in the molecular precursor to polymerize includes: applying voltage to the needle tip of the STM so that the needle tip adsorbs the organic molecular precursor and / or the desired groups in the molecular precursor and drags them closer to each other; injecting an electron beam into the organic molecular precursor and the desired groups in the molecular precursor through the needle tip of the STM to couple and connect them to each other.

[0009] In one or more embodiments of the present invention, the step of applying voltage to the tip of the STM so that the tip adsorbs the organic molecular precursor and / or the desired groups within the molecular precursor and drags them close to each other includes: applying voltage to the tip of the STM so that the tip extracts, drags and drops a single desired group so that the organic molecular precursor and / or the desired groups within the molecular precursor are close to each other.

[0010] In one or more embodiments of the present invention, the applied voltage is in a range of less than or equal to 10V.

[0011] In one or more embodiments of the present invention, the energy of the electron beam injected to couple the organic molecular precursor and the molecular precursor to each other is 500 eV-3000 eV.

[0012] In one or more embodiments of the present invention, before selecting an organic molecular precursor containing at least a Group IIIA metal and a molecular precursor containing at least a Group IIIA metal halide, and injecting an electron beam into it through the tip of an STM, the step also includes: configuring the organic molecular precursor containing a Group IIIA metal and the molecular precursor containing a Group IIIA metal halide into a solution, and adsorbing the solution on the surface of a substrate.

[0013] In one or more embodiments of the present invention, the substrate comprises a metal single crystal.

[0014] In one or more embodiments of the present invention, before the step of adsorbing the solution onto the surface of the substrate, the method further includes: cleaning the substrate.

[0015] In one or more embodiments of the present invention, the method of STM-induced growth of single atomic layer nitride further includes: obtaining morphological information of the polymerized group by scanning with the tip of the STM in a constant current mode or a constant height mode.

[0016] In one or more embodiments of the present invention, the organic molecular precursor and the bond breaking of the molecular precursor, and the polymerization of the desired groups in the organic molecular precursor and the molecular precursor are carried out in an ultra-high vacuum environment. -8 mbar-10 -12 mbar.

[0017] In one or more embodiments of the present invention, the organic molecular precursor containing a Group IIIA metal includes: trimethylaminogallium, trimethylaminoaluminum, monoethylgallium chloride, monoethylaluminum chloride, diethylgallium chloride, diethylaluminum chloride;

[0018] The molecular precursor containing group IIIA metal halides includes: gallium iodide, gallium bromide, aluminum iodide, and aluminum bromide.

[0019] In one or more embodiments of the present invention, the method for STM-induced single atomic layer nitride growth comprises: selecting C 6 H 18 GaN 3 Organic molecular precursors and GaI 3 Molecular precursor; through the tip of the STM to C 6 H 18 GaN 3 Organic molecular precursors and GaI 3 The molecular precursor is injected with an electron beam to break the bond and obtain C 5 H 15 GaN 3 and GaI 2 ; By applying voltage to the tip of the STM, the tip adsorbs GaI 2 or C 5 H 15 GaN 3 One of them is dragged close to the other; the tip of the STM is directed to the GaI 2 and C 5 H 15 GaN 3 Inject electron beam to make GaI 2 and C 5 H 15 GaN 3 They are coupled to each other to form a single atomic layer of nitride.

[0020] Compared with the prior art, the method of STM-induced single atomic layer nitride growth according to the embodiment of the present invention is a new method based on scanning tunneling probe microscopy (STM), which uses the probe tip to precisely manipulate atoms or molecules to induce the coupling and recombination of molecules containing Group IIIA metals and Group IIIA metal halides to achieve the growth of a single layer of nitride.

[0021] The STM-induced single atomic layer nitride growth method according to the embodiment of the present invention, combined with the characteristic of extremely slow STM tip-induced atomic recombination, can well achieve single-layer growth of nitride on a substrate and prepare a single atomic layer nitride.

[0022] According to the STM-induced single-atomic-layer nitride growth method of the embodiment of the present invention, suitable organic molecular precursors and molecular precursors are innovatively selected to assemble and grow a single-atomic-layer two-dimensional nitride, and during the growth process, the adsorption, movement, desorption and recombination of atoms or molecules are completed by applying a suitable voltage at the needle tip.

[0023] According to the STM-induced single-atomic-layer nitride growth method of the embodiment of the present invention, two suitable molecular precursors are deposited on the surface of the substrate through the needle tip induction, and a large amount of electron beams are injected into them to break up unnecessary groups; then a voltage is applied to the needle tip so that the needle tip can adsorb the groups that need to react and drag them closer to each other; finally, a large amount of electron beams are injected into the groups that need to react through the needle tip again to provide the current required for the reaction, thereby generating a single-atomic-layer two-dimensional nitride.

[0024] According to the method for STM-induced growth of single atomic layer nitrides of the embodiment of the present invention, the prepared nitrides include a series of III-V group nitrides such as GaN, AlN, InN, etc. The entire growth method utilizes the tunneling effect of quantum mechanics and three-dimensional scanning to achieve atomic-level printing growth. By utilizing the inverse correlation between the distance between the needle tip and the sample surface and the tunneling current generated between them, when the distance between the needle tip and the sample surface is close enough, each time the distance is reduced a little, the tunneling current will increase sharply, thereby providing sufficient energy to break and recombine chemical bonds; by applying voltage to the needle tip to achieve the three-step operation of extracting, moving and placing single atoms or molecules, the growth of single atomic layer nitride induced by the needle tip is completed. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 is a process flow chart of a method for STM-induced single atomic layer nitride growth according to an embodiment of the present invention;

[0026] Figure 2 It is the coupling reaction formula of one molecule of trimethylaminogallium and one molecule of gallium iodide;

[0027] Figure 3 yes Figure 2 The metal organic molecular framework produced in the reaction is then coupled with a gallium iodide molecule;

[0028] Figure 4 yes Figure 3 The metal organic molecular framework produced in Figure 2 The metal organic molecular framework coupling reaction formula produced in the process;

[0029] Figure 5 This is a schematic diagram of the entire process of implementing the growth of a single atomic layer of nitride using an STM tip inducing growth of a single atomic layer of nitride according to the STM-induced growth of a single atomic layer of nitride according to Example 1 of the present invention. DETAILED DESCRIPTION

[0030] The specific implementation modes of the present invention are described in detail below in conjunction with the accompanying drawings, but it should be understood that the protection scope of the present invention is not limited by the specific implementation modes.

[0031] Unless explicitly stated otherwise, throughout the specification and claims, the term “comprise” or variations such as “include” or “comprising”, etc., will be understood to include the stated elements or components but not to exclude other elements or components.

[0032] like Figure 1 As shown, the method for STM-induced growth of a single atomic layer of nitride according to one embodiment of the present invention comprises: s1, preparing an organic molecular precursor containing a group IIIA metal and a molecular precursor containing a group IIIA metal halide into a solution, and adsorbing the solution on the surface of a substrate. s2, selecting an organic molecular precursor containing at least a group IIIA metal and a molecular precursor containing at least a group IIIA metal halide, injecting an electron beam into them through the tip of the STM, causing the organic molecular precursor and the molecular precursor to break bonds to obtain the organic molecular precursor and the desired groups in the molecular precursor; s3, applying a voltage through the tip of the STM, guiding the organic molecular precursor and the desired groups in the molecular precursor to polymerize, and generating a single atomic layer of nitride.

[0033] In step s1, the substrate is first cleaned. Then, suitable organic molecular precursors containing group IIIA metals and molecular precursors containing group IIIA metal halides are selected to form a solution, which is then dropped onto the surface of the cleaned substrate to allow the solution to adsorb onto the surface of the substrate. In order to grow a single atomic layer of two-dimensional nitride, suitable organic molecular precursors include but are not limited to the following: trimethylaminogallium (C 6 H 18 GaN 3 ), trimethylamine aluminum (C 6 H 18 AlN 3 ), ethyl gallium monochloride, ethyl aluminum monochloride, ethyl gallium dichloride, ethyl aluminum dichloride, etc. Suitable molecular precursors include but are not limited to the following: gallium iodide, gallium bromide, aluminum iodide, aluminum bromide, etc. At the same time, in order to make the experiment go smoothly, the selection of the substrate is also crucial. Generally, a metal single crystal is selected as the substrate. The electron gas on the surface of the metal single crystal can provide a large number of free electrons for the entire process of STM-induced growth.

[0034] In step s2, in an ultra-high vacuum environment (the vacuum degree range of the ultra-high vacuum environment is 10 -8 mbar-10 - 12 mbar), use the STM needle tip to locate the position of the organic molecular precursor and the molecular precursor that are close to each other, and inject electron beams into the organic molecular precursor and the molecular precursor through the STM needle tip, respectively, so that the organic molecular precursor and the molecular precursor are respectively broken, so as to break the unwanted groups and obtain the required groups in the organic molecular precursor and the molecular precursor. Exemplarily, the STM needle tip is located at the position of one of the organic molecular precursors, and constantly approaches the organic molecular precursor. When the two are close to a suitable distance, for example, the distance is less than 1nm, the current is injected 50pA-300pA, and the electron beam is 10pA-500pA at this time. The closer the distance, the greater the electron beam intensity, the tunneling current surges, and a large amount of electron injection is generated to provide enough energy for chemical bonds to break, and the bond breaking is completed. Then, the STM needle tip is located at the position of another molecular precursor, and constantly approaches the molecular precursor. When the two are close to a suitable distance, for example, the distance is less than 1nm, the tunneling current surges, and a large amount of electron injection is generated to provide enough energy for chemical bonds to break, and the bond breaking is completed.

[0035] In step s3, in an ultra-high vacuum environment, by applying voltage to the tip of the STM, the tip adsorbs the organic molecular precursor and / or the required group in the molecular precursor, and drags them close to each other; then, the electron beam is injected into the organic molecular precursor and the required group in the molecular precursor through the tip of the STM to couple and connect them to each other. Exemplarily, by applying voltage to the tip of the STM, the tip can adsorb the molecular precursor (required group) required after the bond is broken, and the single required group is extracted, dragged and dropped to make the organic molecular precursor and the required group in the molecular precursor close to each other. Among them, the extraction voltage is 2V-10V, the drag voltage is 10mV-10V, and the drop voltage is less than 10mV. Then, a certain voltage is applied to the tip of the STM, the voltage is about 500eV-3000eV, and it is maintained for a period of time, which is about not less than 10s, so that the two required groups are coupled and connected. Reapply voltage to the STM tip to drag the connected groups to check whether they are coupled. If not, reapply electron beam for coupling. Then, repeat the above process to continuously grow single atomic layer nitride.

[0036] Compared with the prior art, the method of STM-induced single atomic layer nitride growth according to the embodiment of the present invention is a new method based on scanning tunneling probe microscopy (STM), which uses the probe tip to precisely manipulate atoms or molecules to induce the coupling and recombination of molecules containing Group IIIA metals and Group IIIA metal halides to achieve the growth of a single layer of nitride.

[0037] The STM-induced single atomic layer nitride growth method according to the embodiment of the present invention, combined with the characteristic of extremely slow STM tip-induced atomic recombination, can well achieve single-layer growth of nitride on a substrate and prepare a single atomic layer nitride.

[0038] According to the STM-induced single-atomic-layer nitride growth method of the embodiment of the present invention, suitable organic molecular precursors and molecular precursors are innovatively selected to assemble and grow a single-atomic-layer two-dimensional nitride, and during the growth process, the adsorption, movement, desorption and recombination of atoms or molecules are completed by applying a suitable voltage at the needle tip.

[0039] According to the STM-induced single-atomic-layer nitride growth method of the embodiment of the present invention, two suitable molecular precursors are deposited on the surface of the substrate through the needle tip induction, and a large amount of electron beams are injected into them to break up unnecessary groups; then a voltage is applied to the needle tip so that the needle tip can adsorb the groups that need to react and drag them closer to each other; finally, a large amount of electron beams are injected into the groups that need to react through the needle tip again to provide the current required for the reaction, thereby generating a single-atomic-layer two-dimensional nitride.

[0040] According to the method for STM-induced growth of single atomic layer nitrides of the embodiment of the present invention, the prepared nitrides include a series of III-V group nitrides such as GaN, AlN, InN, etc. The entire growth method utilizes the tunneling effect of quantum mechanics and three-dimensional scanning to achieve atomic-level printing growth. By utilizing the inverse correlation between the distance between the needle tip and the sample surface and the tunneling current generated between them, when the distance between the needle tip and the sample surface is close enough, each time the distance is reduced a little, the tunneling current will increase sharply, thereby providing sufficient energy to break and recombine chemical bonds; by applying voltage to the needle tip to achieve the three-step operation of extracting, moving and placing single atoms or molecules, the growth of single atomic layer nitride induced by the needle tip is completed.

[0041] Embodiment 1:

[0042] Select trimethylaminogallium (C 6 H 18 GaN 3 ) and gallium chloride (GaCl 3 ) as suitable organic molecular precursors containing Group IIIA metals and molecular precursors containing Group IIIA metal halides.

[0043] The specific implementation method of achieving single atomic layer nitride growth by STM tip induction is as follows:

[0044] (a) Clean the metal single crystal substrate.

[0045] (b) Trimethylaminogallium (C 6 H18 GaN 3 ) and gallium chloride (GaCl 3 ) The two molecular precursors are prepared into a solution and dropped onto the surface of a cleaned metal single crystal substrate to complete the adsorption.

[0046] (c) In an ultra-high vacuum environment, the STM tip is used to locate the positions of two different molecular precursors that are close to each other.

[0047] (d) Tip positioning GaCl 3 The electron beam is injected into the position of the needle tip, and the needle tip is lowered to a suitable distance, such as less than 1nm, so that the tunneling current surges and a large amount of electron injection is generated, such as 50pA-300pA, to provide enough energy to break the chemical bond Cl-Ga bond and convert the GaCl on the metal single crystal substrate into 3 One chlorine atom is separated from the GaCl 2 and Cl atoms.

[0048] (e) Needle tip positioning C 6 H 18 GaN 3 The tip of the needle is used to inject an electron beam, and the tip is lowered to a suitable distance, such as less than 1 nm. A 50 eV electron beam is injected to break a methyl group in the trimethylaminogallium. The C 5 H 15 GaN 3 and CH 3 .

[0049] (f) By applying voltage to the needle tip, the needle tip can adsorb the molecular precursor after the bond is broken, such as GaCl 2 , and then drag it horizontally to the vicinity of another group after the bond is broken, such as C 5 H 15 GaN 3 , and then make it fall. The extraction voltage is 2V-10V, the drag voltage is 10mV-10V, and the drop voltage is less than 10mV.

[0050] (g) A certain voltage of about 500eV-3000eV is applied to the needle tip for a period of time, which is not less than 10s, to make the two-dimensional coupling connection occur, thereby connecting GaCl 2 Connect to C 5 H 15 GaN 3 In the coupling reaction between one molecule of trimethylaminogallium and one molecule of gallium chloride, the gallium in the gallium chloride will be connected to the metal organic molecular framework, and methyl chloride will be produced as a by-product.

[0051] (h) Use the needle tip to drag the connected sample to check whether it is connected. If not, reapply voltage for coupling connection. The drag voltage and coupling voltage are consistent with the voltages in steps (f) and (g).

[0052] (i) Repeat the above process continuously to make the metal (new GaCl 2 ) continuously to the metal organic molecular precursor (C 5 H 15 GaN 3 ) or metal organic molecular framework (coupled groups), so that the single atomic layer two-dimensional nitride continues to grow. Through the above reaction, the C atoms in the original metal organic molecular framework are removed one by one, and Ga atoms are added one by one, forming a six-membered ring structure of nitrogen atomic layer two-dimensional GaN.

[0053] Embodiment 2:

[0054] Select trimethylaminogallium (C 6 H 18 GaN 3 ) and gallium bromide (GaBr 3 ) as suitable organic molecular precursors containing Group IIIA metals and molecular precursors containing Group IIIA metal halides.

[0055] The specific implementation method of achieving single atomic layer nitride growth by STM tip induction is as follows:

[0056] (a) Clean the metal single crystal substrate.

[0057] (b) Trimethylaminogallium (C 6 H 18 GaN 3 ) and gallium bromide (GaBr 3 ) The two molecular precursors are prepared into a solution and dropped onto the surface of a cleaned metal single crystal substrate to complete the adsorption.

[0058] (c) In an ultra-high vacuum environment, the STM tip is used to locate the positions of two different molecular precursors that are close to each other.

[0059] (d) Tip positioning GaBr 3 The electron beam is injected into the position of the metal single crystal substrate by using the needle tip, and the needle tip is lowered to a suitable distance, such as less than 1nm, so that the tunneling current surges and a large amount of electron injection is generated, such as 50pA-300pA, to provide enough energy to break the chemical bond Br-Ga bond and convert the GaBr on the metal single crystal substrate into 3 One bromine atom is separated from the GaBr 2 and Br atoms.

[0060] (e) Needle tip positioning C6 H 18 GaN 3 The tip of the needle is used to inject an electron beam, and the tip is lowered to a suitable distance, such as less than 1 nm. A 50 eV electron beam is injected to break a methyl group in the trimethylaminogallium. The C 5 H 15 GaN 3 and CH 3 .

[0061] (f) By applying voltage to the needle tip, the needle tip can adsorb the molecular precursor after bond breaking, such as GaBr 2 , and then drag it horizontally to the vicinity of another group after the bond is broken, such as C 5 H 15 GaN 3 , and then make it fall. Among them, the extraction voltage is 2V-10V, the drag voltage is 10mV-10V, and the drop voltage is less than 10mV.

[0062] (g) A certain voltage of about 500eV-3000eV is applied to the needle tip for a period of time, which is not less than 10s, to make the two-dimensional coupling connection occur, thereby connecting GaBr 2 Connect to C 5 H 15 GaN 3 In the coupling reaction between one molecule of trimethylaminogallium and one molecule of gallium bromide, the gallium in the gallium bromide will be connected to the metal organic molecular framework, and methyl bromide will be produced as a by-product.

[0063] (h) Use the needle tip to drag the connected sample to check whether it is connected. If not, reapply voltage for coupling connection. The drag voltage and coupling voltage are consistent with the voltages in steps (f) and (g).

[0064] (i) Repeat the above process to make the metal (new GaBr 2 ) continuously to the metal organic molecular precursor (C 5 H 15 GaN 3 ) or metal organic molecular framework (coupled groups), so that the single atomic layer two-dimensional nitride continues to grow. Through the above reaction, the C atoms in the original metal organic molecular framework are removed one by one, and Ga atoms are added one by one, forming a six-membered ring structure of nitrogen atomic layer two-dimensional GaN.

[0065] Embodiment 3:

[0066] Select trimethylaminogallium (C 6 H 18 GaN 3) and gallium iodide (GaI 3 ) as suitable organic molecular precursors containing Group IIIA metals and molecular precursors containing Group IIIA metal halides.

[0067] The specific implementation method of achieving single atomic layer nitride growth by STM tip induction is as follows:

[0068] (a) Clean the metal single crystal substrate.

[0069] (b) Trimethylaminogallium (C 6 H 18 GaN 3 ) and gallium iodide (GaI 3 ) The two molecular precursors are prepared into a solution and dropped onto the surface of a cleaned metal single crystal substrate to complete the adsorption.

[0070] (c) In an ultra-high vacuum environment, the STM tip is used to locate the positions of two different molecular precursors that are close to each other.

[0071] (d) Tip positioning GaI 3 location, such as Figure 5 As shown in a, the electron beam is injected by the needle tip and the needle tip is lowered to a suitable distance, such as less than 1nm, so that the tunneling current surges and a large amount of electron injection is generated, such as 50pA-300pA, to provide enough energy to break the chemical bond I-Ga bond and convert the GaI on the metal single crystal substrate into 3 One iodine atom is separated from the GaI to complete the bond breaking; the GaI 2 and I atoms, such as Figure 5 As shown in b.

[0072] (e) Needle tip positioning C 6 H 18 GaN 3 location, such as Figure 5 As shown in c, the electron beam is injected by the needle tip, and the needle tip is lowered to a suitable distance, such as less than 1nm, and a methyl group of trimethylaminogallium is broken by 50eV electron beam injection; the C 5 H 15 GaN 3 and CH 3 ,like Figure 5 As shown in middle d.

[0073] (f) By applying voltage to the needle tip, the needle tip can adsorb the molecular precursor after the bond is broken, such as GaI 2 , and then drag it horizontally to the vicinity of another group after the bond is broken, such as C 5 H 15 GaN 3 , and then make it fall, as Figure 5As shown in e, the extraction voltage is 2V-10V, the drag voltage is 10mV-10V, and the drop voltage is less than 10mV.

[0074] (g) A certain voltage of about 500eV-3000eV is applied to the needle tip for a period of time, which is not less than 10s, to make the two-dimensional coupling connection occur, thereby connecting the GaI 2 Connect to C 5 H 15 GaN 3 In Figure 5 As shown in f. Figure 2 As shown, one molecule of trimethylaminogallium and one molecule of gallium iodide react to form Figure 2 In the structure shown on the right, the gallium in gallium iodide is connected to the metal organic molecular framework, and methyl iodide is produced as a byproduct.

[0075] (h) Use the needle tip to drag the connected sample to check whether it is connected. If not, reapply voltage for coupling connection. The drag voltage and coupling voltage are consistent with the voltages in steps (f) and (g).

[0076] (i) Repeat the above process to make the metal (new GaI 2 ) continuously to the metal organic molecular precursor (C 5 H 15 GaN 3 ) or metal organic molecular framework (coupled groups), such as Figure 3 , Figure 4 As shown, the single atomic layer of two-dimensional nitride continues to grow. Figure 3 Shown is Figure 2 The metal organic molecular framework in the structure is then coupled with a gallium iodide molecule, and then a Ga atom is connected to the structure on the metal organic molecular framework to produce an iodomethane. Figure 4 Shown is the Figure 3 The metal organic molecular framework produced in Figure 2 Through the above reaction, the C atoms in the original metal organic molecular framework are removed one by one, and Ga atoms are added one by one, forming a six-membered ring structure of nitrogen atomic layer two-dimensional GaN.

[0077] Embodiment 4:

[0078] Trimethylaluminum amide and aluminum chloride are selected as suitable organic molecular precursors containing Group IIIA metals and molecular precursors containing Group IIIA metal halides.

[0079] The specific implementation method of achieving single atomic layer nitride growth by STM tip induction is as follows:

[0080] (a) Clean the metal single crystal substrate.

[0081] (b) A solution of two molecular precursors, trimethylamine aluminum and aluminum chloride, is prepared and dropped onto the surface of a cleaned metal single crystal substrate to complete adsorption.

[0082] (c) In an ultra-high vacuum environment, the STM tip is used to locate the positions of two different molecular precursors that are close to each other.

[0083] (d) The tip locates the position of aluminum chloride, injects an electron beam using the tip, and lowers the tip to a suitable distance, such as less than 1 nm, so that the tunneling current surges and a large amount of electron injection is generated, such as 50pA-300pA, to provide enough energy to break the chemical bond and convert the AlCl 3 One of the Cl atoms in the solution is separated, completing the bond breaking; after separation, AlCl 2 and Cl atoms.

[0084] (e) The needle tip locates the position of trimethylaluminum, injects an electron beam using the needle tip, and lowers the needle tip to a suitable distance, such as less than 1 nm, and injects a 50 eV electron beam to break a methyl group in the trimethylaluminum; after separation, C 5 H 15 AlN 3 and CH 3 .

[0085] (f) By applying voltage to the needle tip, the needle tip can adsorb the molecular precursor after bond breaking, such as AlCl 2 , and then drag it horizontally to the vicinity of another group after the bond is broken, such as C 5 H 15 AlN 3 , and then make it fall. Among them, the extraction voltage is 2V-10V, the drag voltage is 10mV-10V, and the drop voltage is less than 10mV.

[0086] (g) A certain voltage of about 500eV-3000eV is applied to the needle tip for a period of time, which is not less than 10s, to make the two-dimensional coupling connection occur, thereby 2 Connect to C 5 H 15 AlN 3 middle.

[0087] (h) Use the needle tip to drag the connected sample to check whether it is connected. If not, reapply voltage for coupling connection. The drag voltage and coupling voltage are consistent with the voltages in steps (f) and (g).

[0088] (i) Repeat the above process continuously to make the metal (new AlCl 2 ) continuously to the metal organic molecular precursor (C 5 H 15 AlN 3 ) or metal-organic molecular skeletons (coupled groups), allowing the single atomic layer of two-dimensional nitride to continue to grow.

[0089] Embodiment 5:

[0090] Trimethylaluminum amide and aluminum bromide are selected as suitable organic molecular precursors containing Group IIIA metals and molecular precursors containing Group IIIA metal halides.

[0091] The specific implementation method of achieving single atomic layer nitride growth by STM tip induction is as follows:

[0092] (a) Clean the metal single crystal substrate.

[0093] (b) A solution of two molecular precursors, trimethylamine aluminum and aluminum bromide, is prepared and dropped onto the surface of a cleaned metal single crystal substrate to complete adsorption.

[0094] (c) In an ultra-high vacuum environment, the STM tip is used to locate the positions of two different molecular precursors that are close to each other.

[0095] (d) The tip locates the position of aluminum bromide, injects an electron beam using the tip, and lowers the tip to a suitable distance, such as less than 1 nm, so that the tunneling current surges and a large amount of electron injection is generated, such as 50pA-300pA, to provide enough energy to break the chemical bonds and convert the AlBr on the metal single crystal substrate into 3 One Br atom in the Br is separated, completing the bond breaking; after separation, AlBr 2 and Br atoms.

[0096] (e) The needle tip locates the position of trimethylaluminum, injects an electron beam using the needle tip, and lowers the needle tip to a suitable distance, such as less than 1 nm, injects an electron beam at 50 eV to break a methyl group in the trimethylaluminum; after separation, C 5 H 15 AlN 3 and CH 3 .

[0097] (f) By applying voltage to the needle tip, the needle tip can adsorb the molecular precursor after bond breaking, such as AlBr 2 , and then drag it horizontally to the vicinity of another group after the bond is broken, such as C 5 H 15 AlN 3, and then make it fall. Among them, the extraction voltage is 2V-10V, the drag voltage is 10mV-10V, and the drop voltage is less than 10mV.

[0098] (g) A certain voltage of about 500eV-3000eV is applied to the needle tip for a period of time, which is not less than 10s, to make the two-dimensional coupling connection occur, thereby 2 Connect to C 5 H 15 AlN 3 middle.

[0099] (h) Use the needle tip to drag the connected sample to check whether it is connected. If not, reapply voltage for coupling connection. The drag voltage and coupling voltage are consistent with the voltages in steps (f) and (g).

[0100] (i) Repeat the above process to make the metal (new AlBr 2 ) continuously to the metal organic molecular precursor (C 5 H 15 AlN 3 ) or metal-organic molecular skeletons (coupled groups), allowing the single atomic layer of two-dimensional nitride to continue to grow.

[0101] Embodiment 6:

[0102] Trimethylaluminum amide and aluminum iodide are selected as suitable organic molecular precursors containing Group IIIA metals and molecular precursors containing Group IIIA metal halides.

[0103] The specific implementation method of achieving single atomic layer nitride growth by STM tip induction is as follows:

[0104] (a) Clean the metal single crystal substrate.

[0105] (b) A solution of two molecular precursors, trimethylamine aluminum and aluminum iodide, is prepared and dropped onto the surface of a cleaned metal single crystal substrate to complete adsorption.

[0106] (c) In an ultra-high vacuum environment, the STM tip is used to locate the positions of two different molecular precursors that are close to each other.

[0107] (d) The tip locates the position of aluminum iodide, injects an electron beam using the tip, and lowers the tip to a suitable distance, causing a surge in tunneling current and generating a large amount of electron injection to provide enough energy to break chemical bonds, thus converting the AlI on the metal single crystal substrate into a quartz crystal. 3 One I atom is separated from the bond, and the bond is broken; after separation, AlI is formed 2 .

[0108] (e) The needle tip locates the position of trimethylaluminum, injects an electron beam using the needle tip, and lowers the needle tip to a suitable distance, so that a methyl group in the trimethylaluminum is broken by the electron beam injection; after separation, C 5 H 15 AlN 3 and CH 3 .

[0109] (f) By applying voltage to the needle tip, the needle tip can adsorb the molecular precursor after bond breaking, such as AlI 2 , and then drag it horizontally to the vicinity of another group after the bond is broken, such as C 5 H 15 AlN 3 , and then let it fall.

[0110] (g) A certain voltage of about 500eV-3000eV is applied to the needle tip for a period of time, which is not less than 10s, to make the two-dimensional coupling connection occur, thereby connecting the AlI 2 Connect to C 5 H 15 AlN 3 middle.

[0111] (h) Use the needle tip to drag the connected sample to check whether it is connected. If not, it is necessary to reapply voltage for coupling connection.

[0112] (i) Repeat the above process continuously to make the metal (new AlI 2 ) continuously to the metal organic molecular precursor (C 5 H 15 AlN 3 ) or metal-organic molecular skeletons (coupled groups), allowing the single atomic layer of two-dimensional nitride to continue to grow.

[0113] Comparative Example

[0114] The parameters such as organic molecular precursor, applied voltage, coupling duration, substrate, etc. were changed. Other experimental conditions were the same as those in Example 1. The effects are compared in Table 1 below.

[0115] Table 1

[0116]

[0117] It can be seen from Comparative Example 1 that the nitride generated by using organic molecular precursors of non-Group IIIA metals will grow in an island-like manner. During the process of island merging, a large number of dislocations and grain boundaries will be generated. The macroscopic manifestation is the generation of nano-scale V-pits, which will cause leakage, life attenuation and other problems during the use of the device.

[0118] From Comparative Examples 2 and 3, it can be seen that the height of the STM needle tip from the organic molecular precursor and the applied voltage have the following effects on the growth of single atomic layer nitride: when the distance is too large, the tunneling current will be too small, and the slow growth rate will cause the crystal structure to be distorted and incomplete, as well as the generation of grain boundaries and dislocations during the merging of nucleation sites. If the applied voltage is too large, the growth rate will be accelerated, but too fast will cause three-dimensional island growth and increase the number of surface defects. If the applied voltage is too large, an ionization effect may also occur, reducing the coupling effect.

[0119] From Comparative Examples 4 and 5, it can be seen that the duration of coupling has the following effects on the growth of monoatomic layer nitride: if the intermolecular coupling time is short, the structure of the adsorbed molecule may be unstable and difficult to form chemical bonds, resulting in a slow growth rate of the nitride. On the other hand, if the intermolecular coupling time is long, the structure of the adsorbed molecule may be too stable, resulting in an excessively fast reaction rate, which may form surface defects and non-ideal nitride structures.

[0120] As can be seen from Comparative Example 6, on a metal substrate, STM can induce the growth of nitrides by electronic excitation, thermal annealing, etc. In this case, STM can provide highly customized control to achieve high-quality nitride growth. On an insulating substrate, the induction effect of STM will be limited. This is because STM cannot induce the growth of nitrides by electronic excitation or thermal annealing on an insulating substrate.

[0121] In summary, the STM-induced single-atomic-layer nitride growth method of the embodiment of the present invention innovatively selects suitable organic molecular precursors and molecular precursors to assemble and grow a single-atomic-layer two-dimensional nitride, and injects a large amount of electron beams into two suitable molecular precursors deposited on the surface of the substrate through the needle tip to break up unnecessary groups; then, a voltage is applied to the needle tip so that the needle tip can adsorb the groups that need to react and drag them closer to each other; finally, a large amount of electron beams are injected into the groups that need to react through the needle tip again to provide the current required for the reaction and generate a single-atomic-layer two-dimensional nitride.

[0122] The foregoing description of specific exemplary embodiments of the present invention is for the purpose of illustration and demonstration. These descriptions are not intended to limit the present invention to the precise form disclosed, and it is clear that many changes and variations can be made based on the above teachings. The purpose of selecting and describing the exemplary embodiments is to explain the specific principles of the present invention and its practical application, so that those skilled in the art can realize and utilize various different exemplary embodiments of the present invention and various different selections and changes. The scope of the present invention is intended to be limited by the claims and their equivalents.

Claims

1. A method for STM-induced single atomic layer nitride growth, characterized in that: include: Selecting an organic molecular precursor containing at least a Group IIIA metal and a molecular precursor containing at least a Group IIIA metal halide; An organic molecular precursor containing a Group IIIA metal and a molecular precursor containing a Group IIIA metal halide are configured into a solution, and the solution is adsorbed on a surface of a substrate, wherein the substrate comprises a metal single crystal; Injecting electron beams into the organic molecular precursor and the molecular precursor through the needle tip of the STM to break bonds of the organic molecular precursor and the molecular precursor respectively to obtain the desired groups in the organic molecular precursor and the molecular precursor; By applying voltage to the tip of the STM, the tip adsorbs the organic molecular precursor and / or the desired group in the molecular precursor and drags them closer to each other; An electron beam is injected into the organic molecular precursor and the desired groups in the molecular precursor through the needle tip of the STM so as to couple and connect them to each other and generate a single atomic layer of nitride.

2. The method for STM-induced single atomic layer nitride growth according to claim 1, characterized in that: The energy of the electron beam injected to break the bond between the organic molecular precursor and the molecular precursor is 10eV-100eV.

3. The method for STM-induced single atomic layer nitride growth according to claim 1, characterized in that: The step of applying voltage to the tip of the STM so that the tip adsorbs the organic molecular precursor and / or the desired group in the molecular precursor and drags them closer to each other comprises: By applying voltage to the tip of the STM, the tip is made to extract, drag and drop a single desired group, so that the organic molecular precursor and / or the desired groups in the molecular precursor are brought close to each other.

4. The method for STM-induced single atomic layer nitride growth according to claim 1, characterized in that: The applied voltage range is less than or equal to 10V.

5. The method for STM-induced single atomic layer nitride growth according to claim 1, characterized in that: The energy of the electron beam injected to couple the organic molecular precursor and the molecular precursor to each other is 500eV-3000eV.

6. The method for STM-induced single atomic layer nitride growth according to claim 1, characterized in that: Before the step of adsorbing the solution onto the surface of the substrate, the method further comprises: The step of cleaning the substrate.

7. The method for STM-induced single atomic layer nitride growth according to claim 1, characterized in that: Also includes: The morphological information of the polymerized group can be obtained by scanning with the STM tip in constant current mode or constant height mode.

8. The method for STM-induced single atomic layer nitride growth as claimed in claim 1, characterized in that: The organic molecular precursor and the bond breaking of the molecular precursor, and the polymerization of the desired groups in the organic molecular precursor and the molecular precursor are carried out in an ultra-high vacuum environment.

9. The method for STM-induced single atomic layer nitride growth according to claim 1, characterized in that: The organic molecular precursor containing Group IIIA metals includes: trimethylaminogallium, trimethylaminoaluminum, monoethylgallium chloride, monoethylaluminum chloride, diethylgallium chloride, and diethylaluminum chloride; The molecular precursor containing group IIIA metal halides includes: gallium iodide, gallium bromide, aluminum iodide, and aluminum bromide.

10. The method for STM-induced single atomic layer nitride growth according to claim 1, characterized in that: Select C6H 18 GaN3 organic molecular precursor and GaI3 molecular precursor; The tip of the STM needle was directed to C6H 18 The GaN3 organic molecular precursor and the GaI3 molecular precursor are injected with electron beams to break the bonds and obtain C5H 15 GaN3 and GaI2; By applying voltage to the tip of the STM, the tip adsorbs GaI2 or C5H 15 One of the GaN3, drag it close to the other; The tip of the STM probe was used to 15 GaN3 is injected with electron beam to make GaI2 and C5H 15 The GaN3 are coupled to each other to form a single atomic layer of nitride.

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