CN-122002874-A - Nano semiconductor composite material and preparation method and application thereof

CN122002874ACN 122002874 ACN122002874 ACN 122002874ACN-122002874-A

Abstract

The invention relates to the technical field of semiconductor composite materials, and discloses a nano semiconductor composite material, a preparation method and application thereof, wherein the nano semiconductor composite material comprises a substrate, a transition metal nitride buffer layer and a co-doped aluminum nitride single crystal film; the invention provides a method for preparing a nano semiconductor composite material, which comprises the steps of depositing a transition metal nitride buffer layer on one side surface of a substrate, growing a co-doped aluminum nitride single crystal film on one side of the transition metal nitride buffer layer far away from the substrate, and realizing breakthrough of the nano semiconductor composite material in multiple performance dimensions by the synergistic effect of component design and process steps. The combination of the transition metal nitride buffer layer and the co-doped structure solves the problem that the crystallization quality and the electrical property of the traditional AlN-based material are difficult to be compatible, and the substrate pretreatment and the accurate regulation and control of the growth process of each layer effectively relieve the defect problem caused by interface mismatch and improve the overall stability of the material.

Inventors

WEI WENWANG
Xu Xiuning
ZHANG YUCHEN
Liao jiaxin
LIN FANGYU

Assignees

贺州学院

Dates

Publication Date: 20260508
Application Date: 20260209

Claims (10)

1. The nano semiconductor composite material is characterized by comprising a substrate, a transition metal nitride buffer layer and a co-doped aluminum nitride single crystal film, wherein the transition metal nitride buffer layer is deposited on one side surface of the substrate, and the co-doped aluminum nitride single crystal film grows on one side of the transition metal nitride buffer layer far away from the substrate; The co-doped aluminum nitride single crystal film is of an AlN-Si-M co-doped structure, wherein M is at least one of Ge and Sn; the transition metal nitride buffer layer is at least one of TiN and ZrN; The transition metal nitride buffer layer accounts for 5-15% of the total mass percent, and the co-doped aluminum nitride single crystal film accounts for 85-95%; In the co-doped aluminum nitride single crystal film, the doping concentration of Si is 1 multiplied by 10 18 -5×10 19 cm -3 , the doping concentration of M is 5 multiplied by 10 17 -2×10 18 cm -3 , and the balance is AlN.
2. The nano semiconductor composite material according to claim 1, wherein the substrate is a sapphire substrate or a SiC substrate, the thickness of the substrate is 200-500 μm, and the surface roughness Ra is less than or equal to 1nm.
3. The nano-semiconductor composite according to claim 1, wherein the thickness of the transition metal nitride buffer layer is 50-200nm.
4. The nano-semiconductor composite according to claim 1, wherein the thickness of the co-doped aluminum nitride single crystal thin film is 1-5 μm.
5. A method of preparing the nano-semiconductor composite of any one of claims 1-4, comprising the steps of: The method comprises the steps of S1, substrate pretreatment, namely selecting a sapphire substrate or a SiC substrate, sequentially carrying out ultrasonic cleaning, plasma etching and hydroxylation modification, wherein the ultrasonic cleaning adopts a mixed solution of ethanol and deionized water, the plasma etching adopts Ar/O 2 mixed gas, the volume ratio of Ar to O 2 is 4-6:1, the etching power is 80-120W, the etching time is 5-15min, the hydroxylation modification adopts a mixed aqueous solution of concentrated H 2 SO 4 /H 2 O 2 for soaking at 60-80 ℃ for 20-40min, the deionized water is adopted for cleaning after the modification, and the deionized water is dried by nitrogen for standby, wherein the mass fraction of the concentrated H 2 SO 4 is 80%, and the mass fraction of H 2 O 2 is 10%; S2, preparing a transition metal nitride buffer layer, namely depositing the transition metal nitride buffer layer on the surface of the pretreated substrate by adopting a magnetron sputtering process, wherein a sputtering target is a Ti pure target or a Zr pure target, sputtering gas is Ar/N 2 mixed gas, wherein the volume fraction of N 2 is 20-40%, the sputtering temperature is 200-300 ℃, the sputtering power is 150-250W, and the deposition thickness is 50-200nm; S3, growing a co-doped aluminum nitride single crystal film, namely placing a substrate deposited with a transition metal nitride buffer layer in an MOCVD reaction cavity, firstly constructing a preset step structure with the width of 20-50nm on the surface of the buffer layer through plasma etching, then introducing an aluminum source, a nitrogen source, a silicon source and a germanium source/tin source for low-temperature epitaxial growth, wherein the aluminum source is trimethylaluminum, the nitrogen source is ammonia, the silicon source is silane, the germanium source is germane and the tin source is tetramethyltin, the growth temperature is 900-1000 ℃, the growth pressure is 50-100Torr, the flow rate of the aluminum source is 50-150sccm, the flow rate of the nitrogen source is 500-1500sccm, the flow rate of the silicon source is 10-50sccm, the flow rate of the germanium source/tin source is 5-20sccm, and the growth time is 1-4h, so as to obtain the co-doped aluminum nitride single crystal film with the thickness of 1-5 mu m; And S4, post-treatment optimization, namely performing plasma auxiliary annealing on a sample growing the co-doped aluminum nitride single crystal film, wherein the annealing temperature is 500-600 ℃, the heat preservation time is 20-40min, the plasma power is 50-100W, the annealing atmosphere is N 2 /H 2 mixed gas, and the volume fraction of N 2 is 70-90%, so that the nano semiconductor composite material is obtained.
6. The preparation method of claim 5, wherein in step S1, the volume ratio of the ethanol to deionized water is 1:2, the ultrasonic power is 100-150W, the ultrasonic time is 15-25min, and nitrogen is adopted for drying after ultrasonic treatment.
7. The method according to claim 5, wherein in step S2, the annealing treatment is performed after the deposition is completed, the annealing temperature is 400-500 ℃, the holding time is 30-60min, and the annealing atmosphere is nitrogen or argon.
8. The method of claim 5, wherein in step S3, the plasma etching parameters are Ar/O 2 mixed gas, wherein the volume ratio of Ar to O 2 is 3-5:1, the etching power is 50-80W, and the etching time is 2-5min.
9. The method according to claim 5, wherein in step S4, the flow rate of the N 2 /H 2 mixed gas is 200-300sccm, and a radio frequency plasma with a frequency of 13.56MHz is used.
10. Use of the nano-semiconductor composite material according to any one of claims 1-4 in deep ultraviolet light emitting diodes, deep ultraviolet detectors or high frequency power devices.

Description

Nano semiconductor composite material and preparation method and application thereof Technical Field The invention relates to the technical field of semiconductor composite materials, in particular to a nano semiconductor composite material, a preparation method and application thereof. Background The rapid development of deep ultraviolet photoelectronic devices, high frequency power devices and other fields puts higher and higher requirements on the performance of core semiconductor materials. Aluminum nitride (AlN) is used as a wide forbidden band semiconductor material, has excellent thermal stability, chemical stability and high breakdown electric field strength, and has wide application prospect in the scenes of deep ultraviolet light emission, high-frequency signal transmission and the like. However, pure AlN materials have poor intrinsic conductivity, and carrier concentration and mobility are difficult to meet the practical requirements of the device. At present, alN is often modified in a doping mode in the industry, but the AlN has various problems, for example, when single element doping is carried out, the activation efficiency of doping elements is low, carrier concentration is difficult to effectively improve, or material lattice distortion is serious, crystallization quality is influenced, and the balance of optical performance and electrical performance is further deteriorated. On the other hand, the AlN material and the common substrate (such as sapphire and SiC) have larger lattice mismatch and thermal expansion coefficient difference, a large number of defects (such as dislocation and cracks) are easy to generate in the film growth process, the crystallization integrity of the material is reduced, the carrier transmission efficiency is obviously affected, and the device reliability is reduced. Therefore, developing a nano semiconductor composite material which can synergistically optimize crystallization quality, electrical property and optical property and can alleviate the problem of interface mismatch between a substrate and a film and a preparation method thereof becomes a technical problem to be solved in the current industry. Disclosure of Invention Aiming at the problems in the prior art, the invention provides a nano semiconductor composite material. The technical scheme adopted for solving the technical problems is that the nano semiconductor composite material comprises a substrate, a transition metal nitride buffer layer and a co-doped aluminum nitride single crystal film, wherein the transition metal nitride buffer layer is deposited on one side surface of the substrate, and the co-doped aluminum nitride single crystal film grows on one side of the transition metal nitride buffer layer far away from the substrate; The co-doped aluminum nitride single crystal film is of an AlN-Si-M co-doped structure, wherein M is at least one of Ge and Sn, and the co-doped structure can inhibit DX transition of Si and improve the conductivity of the film; The transition metal nitride buffer layer is at least one of TiN and ZrN, and can reduce the lattice mismatch degree of the substrate and the co-doped aluminum nitride single crystal film and strengthen the binding force; The transition metal nitride buffer layer accounts for 5-15% of the total mass percent, and the co-doped aluminum nitride single crystal film accounts for 85-95%; In the co-doped aluminum nitride single crystal film, the doping concentration of Si is 1 multiplied by 10 18-5×1019cm-3, the doping concentration of M is 5 multiplied by 10 17-2×1018cm-3, and the balance is AlN. As a further technical scheme, the substrate is a sapphire substrate or a SiC substrate, the thickness of the substrate is 200-500 mu m, and the surface roughness Ra is less than or equal to 1nm. As a further technical scheme, the thickness of the transition metal nitride buffer layer is 50-200nm. As a further technical scheme, the thickness of the co-doped aluminum nitride single crystal film is 1-5 mu m. A method of nanosemiconductor composite material comprising the steps of: The method comprises the steps of S1, substrate pretreatment, namely selecting a sapphire substrate or a SiC substrate, sequentially carrying out ultrasonic cleaning, plasma etching and hydroxylation modification, wherein the ultrasonic cleaning adopts a mixed solution of ethanol and deionized water, the plasma etching adopts Ar/O 2 mixed gas, the volume ratio of Ar to O 2 is 4-6:1, the etching power is 80-120W, the etching time is 5-15min, the hydroxylation modification adopts a mixed aqueous solution of concentrated H 2SO4/H2O2 for soaking at 60-80 ℃ for 20-40min, the deionized water is adopted for cleaning after the modification, and the deionized water is dried by nitrogen for standby, wherein the mass fraction of the concentrated H 2SO4 is 80%, and the mass fraction of H 2O2 is 10%; S2, preparing a transition metal nitride buffer layer, namely depositing the transition metal n