CN115896947A - Method for growing single crystal III group nitride on ceramic substrate - Google Patents
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Abstract
The invention discloses a method for growing single crystal III-group nitride on a ceramic substrate. Firstly, depositing a filling material on the surface of a ceramic substrate, grinding and polishing to obtain a smooth surface, and/or forming an Al-O compound layer or a two-dimensional material layer on the surface; then, a nitride layer and a two-dimensional material layer are sequentially formed on the surface, and the single crystal III-nitride is regrown. A smooth surface is achieved by depositing a filler material on a ceramic substrate and grinding and polishing; forming an Al-O compound layer or a two-dimensional material layer on the surface to optimize the c-axis orientation of the nitride in the next step; the subsequent nitride layer provides a polarization field for the growth of the single crystal III-group nitride, ensures the growth orientation of the single crystal III-group nitride and promotes the nucleation in the growth process; the two-dimensional material layer provides an ordered hexagonal structure for the growth of the III-group nitride layer, and the III-group nitride with a single crystal hexagonal structure is guaranteed to grow. The method realizes epitaxial growth of single crystal III group nitride on the ceramic substrate, improves the crystal quality and the heat dissipation performance, and greatly reduces the cost.
Description
Technical Field
The invention belongs to the technical field of semiconductors, and particularly relates to a method for growing single crystal III-group nitride on a ceramic substrate.
Background
Group III nitride materials, including GaN, alN, inN and ternary and quaternary compounds of these, have important applications in power electronics, radio frequency electronics, and optoelectronic devices. However, as group III-nitride material homogeneous substrates have evolved slowly, a number of group III-nitride material and device applications have focused on heteroepitaxy, commonly used heteroepitaxial substrates including SiC, si and sapphire substrates. The SiC substrate is expensive, the Si substrate has large lattice mismatch and thermal mismatch, and the sapphire substrate has poor thermal conductivity.
Ceramic substrates are increasingly being valued for the purpose of reducing substrate cost while simultaneously addressing substrate thermal conductivity and group III nitride material epitaxial quality. At present, ceramic materials such as ceramic AlN and ceramic SiC are generally used as packaging heat dissipation substrates of electronic devices due to excellent heat conduction performance and mechanical strength, relevant industries are mature, and ceramic substrates with low cost, large size and good quality can be provided for epitaxial material growth. Meanwhile, ceramic materials such as ceramic AlN and ceramic SiC also have thermal expansion coefficients close to those of III-group nitride materials, and can reduce thermal stress in the high-temperature and low-temperature processes of epitaxial growth, so that defects in epitaxial materials are reduced, and the epitaxial quality is improved.
However, the ceramic substrate surface is not long range ordered and growing single crystal group III nitride materials on ceramic substrates is difficult.
Disclosure of Invention
In order to solve the problem of difficulty in growing single crystal group III nitride materials on ceramic substrates in the prior art, the invention aims to provide a method for growing single crystal group III nitride on a ceramic substrate.
Firstly, aiming at the problem that the surface of the ceramic substrate is not in long-range order, the invention introduces a two-dimensional material with hexagonal symmetry on the surface of the ceramic substrate to solve the problem. Secondly, studies on epitaxial growth of single-crystal group III nitride materials on the surface of two-dimensional materials have shown that difficulties in nucleation on the surface of two-dimensional materials and non-uniform in-plane orientation of epitaxial group III nitride materials are important causes of poor epitaxial quality. In this regard, the present invention addresses this problem by introducing a nitride material with a vertically oriented polarity beneath the two-dimensional material. Finally, the surface of the ceramic substrate is generally rough and cannot meet the epitaxial requirement, and a filling material can be introduced to solve the problem.
In order to realize the technical purpose, the invention adopts the following technical scheme:
a method of growing single crystal group III nitrides on ceramic substrates, comprising the steps of:
1) Selecting a ceramic substrate;
2) Depositing a filling material on the surface of the ceramic substrate, and then grinding and polishing to obtain a smooth surface; and/or forming an Al-O compound layer or a two-dimensional material layer on the surface;
3) Forming a nitride layer on the surface;
4) Forming a two-dimensional material layer on the surface;
5) Single crystal group III nitrides are grown on the surface.
The ceramic substrate selected in the step 1) can be AlN ceramic, siC ceramic or other ceramic materials.
Step 2) above, the filling material may be deposited only on the surface of the ceramic substrate, and step 3) is performed after the smooth surface is obtained by grinding and polishing; or directly forming an Al-O compound layer or a two-dimensional material layer on the surface of the ceramic substrate, and then entering the step 3); or depositing a filling material on the surface of the ceramic substrate, grinding and polishing to form an Al-O compound layer or a two-dimensional material layer on the surface, and then entering the step 3). The specific treatment method depends on the smoothness of the surface of the ceramic substrate and actual requirements.
The filling material deposited on the surface of the ceramic substrate in the step 2) can be AlN, siC, gaN, siO2, siN, al2O3 or other materials, and is preferably a material with the same element composition as the substrate.
The method of depositing the filling material of the above step 2) may be PVD (physical vapor deposition), CVD (chemical vapor deposition), MOCVD (metal organic vapor phase epitaxy), PLD (pulsed laser deposition), MBE (molecular beam epitaxy), ALD (atomic layer deposition), or HVPE (hydride vapor phase epitaxy). The thickness of the deposited filling material can be 100 to 100 000 nanometers, then grinding and polishing are carried out, the thickness is preferably reduced to 100 to 10000 nanometers, and a smooth surface is generally obtained by adopting a mechanical grinding and mechanical polishing (or mechanical polishing and chemical mechanical polishing). The treatment can solve the problems of pits, steps and the like on the surface of the ceramic substrate and optimize the orientation of the nitride layer in the subsequent step 3).
In the step 2), the material of the Al-O compound layer can be Al2O3, alpha-Al 2O3 or AlON/alpha-Al 2O3, and the thickness of the Al-O compound layer is generally 1-100 nanometers.
One preferable process for forming the Al — O compound layer on the surface in the above step 2) includes: al2O3 is formed on the surface by ALD, MBE or PVD, and then the Al2O3 is converted into alpha-Al 2O3 by high temperature treatment. The high-temperature treatment method here may be thermal annealing or laser annealing.
Another preferred process for forming an Al — O compound layer on the surface in the above step 2) includes: firstly, al2O3 is formed on the surface through ALD, MBE or PVD, then the Al2O3 is converted into alpha-Al 2O3 through high-temperature treatment in a nitrogen-containing atmosphere, and an AlON layer is formed on the surface of the AlON layer to form an AlON/alpha-Al 2O3 structure. The high-temperature treatment under the nitrogen-containing atmosphere described herein may be thermal annealing; the nitrogen-containing atmosphere may be ammonia, nitrogen, or other atmosphere containing ammonia or nitrogen.
In the step 2), the method for forming the two-dimensional material on the surface may adopt wet transfer. The two-dimensional material layer may be a combination of monoatomic or polyatomic layers selected from one or more of graphene, moS2, BN.
Preferably, in step 2) the two-dimensional material is a single-crystal material.
In the step 3), the nitride layer may be formed by PVD, CVD or MOCVD, and the nitride may be AlN, gaN or BN, preferably, an AlN layer formed by PVD. The thickness of the nitride layer is 10-500 nm.
The process of forming the nitride layer on the surface in the step 3) preferably includes: firstly, nitride is deposited on the surface, and then high-temperature treatment is carried out. The temperature of the high-temperature treatment may be 1000-1300 ℃.
The nitride layer formed in the step 3) provides a polarization field for epitaxial growth of the monocrystalline group III nitride, ensures epitaxial orientation and promotes nucleation.
In the step 4), the method for forming the two-dimensional material layer on the surface may be wet transfer, and the two-dimensional material layer may be a single atomic layer or a combination of multiple atomic layers of one or more selected from graphene, moS2, and BN.
Preferably, the two-dimensional material in step 4) is a single crystal monolayer material.
The two-dimensional material layer formed in step 4) above provides an ordered hexagonal structure for the epitaxial growth of single-crystal group III nitrides and possibly provides a polarization field.
The method for growing single-crystal group III nitride on the surface in the above step 5) may be MOCVD, CVD, MBE or HVPE. The single crystal group III nitride may be GaN, alN, alGaN, or a combination thereof.
The invention has the beneficial effects that:
in the method for growing the monocrystalline group III nitride on the ceramic substrate, the deposited filling material can cover the height difference between the pores and the crystal grains on the surface of the ceramic; grinding and polishing the filling material can realize a smooth surface on the surface of the ceramic substrate; the Al-O compound layer or the two-dimensional material layer is formed on the surface, so that the c-axis orientation of the nitride in the next step can be optimized; forming a nitride layer on the surface to provide a polarization field for the growth of the III-group nitride layer, ensuring the growth orientation of the III-group nitride layer and promoting the nucleation in the growth process; the formation of the two-dimensional material layer on the surface provides an ordered hexagonal structure for the growth of the group III nitride, ensuring the growth of the group III nitride in a single crystal hexagonal structure, and, if a two-dimensional material having a polarity is used, the two-dimensional material also provides a polarity for the growth of the group III nitride layer.
The invention breaks through the strict requirements on the single crystal substrate in the traditional epitaxial technology, realizes the epitaxial growth of the single crystal material on the ceramic substrate, greatly reduces the cost of the ceramic substrate compared with the traditional SiC, sapphire, si and GaN substrates, and can realize the large-size wafer-level manufacturing of the ceramic substrate. In addition, the ceramic substrate such as AlN ceramic has a thermal expansion coefficient very close to that of the III-nitride, has small thermal mismatch with the III-nitride, and can ensure that small thermal stress is generated in the high-low temperature process of epitaxial growth of the III-nitride, thereby reducing defects in the single-crystal III-nitride material and improving the crystal quality of the single-crystal III-nitride material. And, the ceramic substrate has a higher thermal conductivity, and is more advantageous in heat dissipation for high power applications than conventional sapphire and Si substrates.
Drawings
FIG. 1 is a flow chart illustrating a method for growing single crystal group III nitride on a ceramic substrate according to one embodiment of the present invention.
FIG. 2 is a flow chart of a method for growing single crystal group III nitride on a ceramic substrate according to a second embodiment of the present invention.
FIG. 3 is a flow chart of a method for growing single crystal group III nitride on a ceramic substrate according to a third embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
Example one
Referring to fig. 1, fig. 1 is a schematic flow chart of a method for growing single-crystal group III nitride on a ceramic substrate according to the present embodiment, the method including the following steps 11-19:
and 11, selecting a ceramic substrate. Specifically, the ceramic substrate was AlN ceramic, had a thickness of 1000 μm, and was circular in shape with a diameter of 100 mm.
And 12, depositing a filling material on the surface of the ceramic substrate. Specifically, the filling material is AlN, the deposition method is PVD, and the thickness is 5 microns.
And step 13, grinding and polishing the surface. Specifically, the method of polishing the surface is mechanical polishing. The method for polishing the surface is mechanical polishing and then chemical mechanical polishing.
And 14, forming an Al2O3 layer on the surface. Specifically, the formation method of the Al2O3 layer is ALD, and the thickness is 10 nanometers.
And step 15, carrying out high-temperature treatment on the nitrogen-containing atmosphere to form an alpha-Al 2O3 layer, and forming an AlON layer on the surface, wherein the AlON layer and the alpha-Al 2O3 layer form an AlON/alpha-Al 2O3 layer. Specifically, the high-temperature treatment is thermal annealing, and the nitrogen-containing atmosphere is nitrogen.
Step 16, an AlN layer is formed on the surface. Specifically, the AlN layer is formed by PVD with a thickness of 100 nm.
And step 17, performing high-temperature treatment to convert the AlN layer into the high-temperature treated AlN layer. Specifically, the high-temperature treatment is thermal annealing at 1200 ℃.
Step 18, forming a graphene layer on the surface. Specifically, the method for forming the graphene layer on the surface is wet transfer, the thickness of the graphene layer is a monoatomic layer, and the graphene layer is single crystal graphene.
Step 19, growing single crystal group III nitride on the surface. Specifically, the method for growing the single crystal III-nitride on the surface is MOCVD, the single crystal III-nitride material is firstly used for growing an AlN nucleating layer, and then a single crystal GaN layer is grown.
Example two
Referring to fig. 2, fig. 2 is a schematic flow chart of a method for growing single crystal group III nitride on a ceramic substrate according to the present embodiment, which includes the following steps 21-25:
step 21, selecting a ceramic substrate. Specifically, the ceramic substrate is AlN ceramic, has a thickness of 500 micrometers, and is square with a side of 100 millimeters.
Step 22, forming a graphene layer on the surface. Specifically, the method for forming the graphene layer on the surface is wet transfer, the thickness of the graphene layer is a diatomic layer, and the graphene layer is single crystal graphene.
Step 23, an AlN layer is formed on the surface. Specifically, the AlN layer is formed by PVD with a thickness of 50 nm.
And 24, forming a graphene layer on the surface. Specifically, the method for forming the graphene layer on the surface is wet transfer, the thickness of the graphene layer is a monoatomic layer, and the graphene layer is single crystal graphene.
Step 25, growing single crystal group III nitride on the surface. Specifically, the method of growing single-crystal group III nitride on the surface is MOCVD, and the single-crystal group III nitride material is AlN.
EXAMPLE III
Referring to fig. 3, fig. 3 is a schematic flow chart of a method for growing single crystal group III nitride on a ceramic substrate according to the present embodiment, which includes the following steps 31-36:
step 31, selecting a ceramic substrate. Specifically, the ceramic substrate is an AlN ceramic, has a thickness of 1000 mm, and is 4-inch wafer-shaped.
And 32, depositing a filling material on the surface of the ceramic substrate. Specifically, the filling material is AlN, the deposition method is PVD, and the thickness is 10000 nanometers.
Step 33, the surface is ground and polished. Specifically, the method of polishing the surface is mechanical polishing. The method for polishing the surface is mechanical polishing and then chemical mechanical polishing.
Step 34, an AlN layer is formed on the surface. Specifically, the AlN layer is formed by PVD with a thickness of 50 nm.
Step 35, forming a graphene layer on the surface. Specifically, the graphene layer is formed by wet transfer, the thickness of the graphene layer is a monoatomic layer, and the graphene layer is single-crystal graphene.
Step 36, growing single crystal group III nitride on the surface. Specifically, the method of growing single-crystal group III nitride on the surface is MOCVD, and the single-crystal group III nitride material is AlN.
Claims (10)
1. A method of growing single crystal group III nitride on a ceramic substrate comprising the steps of:
1) Selecting a ceramic substrate;
2) Depositing a filling material on the surface of the ceramic substrate, and then grinding and polishing to obtain a smooth surface; and/or forming an Al-O compound layer or a two-dimensional material layer on the surface;
3) Forming a nitride layer on the surface;
4) Forming a two-dimensional material layer on the surface;
5) A single crystal group III nitride is grown on the surface.
2. The method of claim 1, wherein the ceramic substrate selected in step 1) is an AlN ceramic or a SiC ceramic.
3. The method as claimed in claim 1, wherein the step 2) is to deposit the filling material on the surface of the ceramic substrate, and the step 3) is carried out after the filling material is ground and polished to obtain a smooth surface; or, step 2) directly forming an Al-O compound layer or a two-dimensional material layer on the surface of the ceramic substrate, and then entering step 3); or, step 2) firstly depositing a filling material on the surface of the ceramic substrate, grinding and polishing to form an Al-O compound layer or a two-dimensional material layer on the surface, and then entering step 3).
4. The method of claim 1, wherein the filler material deposited on the surface of the ceramic substrate in step 2) is selected from the group consisting of AlN, siC, gaN, siO 2 、SiN、Al 2 O 3 。
5. The method according to claim 1, wherein the material of the Al — O compound layer in step 2) is Al 2 O 3 、α-Al 2 O 3 Or AlON/alpha-Al 2 O 3 The thickness of the film is 1-100 nanometers.
6. The method of claim 5, wherein the forming of the Al — O compound layer on the surface in step 2) comprises: al is firstly formed on the surface by ALD, MBE or PVD 2 O 3 And then Al is treated at high temperature 2 O 3 Conversion to alpha-Al 2 O 3 (ii) a Alternatively, al is first formed on the surface by ALD, MBE or PVD 2 O 3 And then treating Al at high temperature in nitrogen-containing atmosphere 2 O 3 Conversion to alpha-Al 2 O 3 And forming an AlON layer on the surface to form AlON/alpha-Al 2 O 3 The structure of (1).
7. The method of claim 1, wherein the two-dimensional material layer in step 2) and step 4) is selected from graphene, moS 2 A monoatomic layer or a combination of polyatomic layers of one or more single crystal materials in BN.
8. The method of claim 1, wherein step 3) comprises depositing nitride by PVD, CVD or MOCVD, followed by high temperature treatment to obtain the nitride layer having a thickness of 10-500 nm.
9. The method of claim 1, wherein the nitride layer formed in step 3) is AlN, gaN, or BN.
10. The method of claim 1, wherein step 5) grows single crystal group III nitride using MOCVD, CVD, MBE or HVPE, the single crystal group III nitride being GaN, alN, alGaN or combinations thereof.
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