CN115896947B - Method for growing single crystal III-nitride on ceramic substrate - Google Patents
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Abstract
A method for growing single crystal group III nitrides on ceramic substrates is disclosed. 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 forming a nitride layer and a two-dimensional material layer on the surface in turn, and regrowing single crystal III-nitride. A smooth surface is achieved by depositing a filler material on the 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 single crystal III-nitride, ensures the growth orientation thereof, and promotes the nucleation in the growth process; the two-dimensional material layer provides an orderly hexagonal structure for the growth of the III-nitride layer, and ensures that the III-nitride with a single crystal hexagonal structure grows. The method realizes epitaxial growth of single crystal III-nitride on ceramic substrate, improves crystal quality and heat dissipation performance, and greatly reduces cost.
Description
Technical Field
The invention belongs to the technical field of semiconductors, and particularly relates to a method for growing monocrystalline group III nitride on a ceramic substrate.
Background
Group III nitride materials, including GaN, alN, inN and ternary and quaternary compounds of their composition, find important applications in power electronics, radio frequency electronics, and optoelectronic devices. However, since group III nitride material homosubstrates are slowly evolving, a large number of group III nitride materials and device applications are focused on heteroepitaxy, and commonly used heteroepitaxial substrates include SiC substrates, si substrates, and sapphire substrates. Among them, siC substrates are expensive, si substrates have large lattice mismatch and thermal mismatch, and sapphire substrates have poor thermal conductivity.
Ceramic substrates are increasingly gaining attention in order to reduce substrate cost while simultaneously compromising substrate thermal conductivity and group III nitride material epitaxial quality. At present, ceramic materials such as ceramic AlN, ceramic SiC and the like are generally used as packaging heat dissipation substrates of electronic devices due to excellent heat conduction performance and mechanical strength, related industries are mature, and a ceramic substrate 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-nitride materials, and thermal stress in high and low temperature processes of epitaxial growth can be reduced, so that defects in the epitaxial materials are reduced, and epitaxial quality is improved.
However, the ceramic substrate surface is not in long range order and the difficulty of growing single crystal group III nitride materials on the ceramic substrate is great.
Disclosure of Invention
In order to solve the problem of the prior art that the single crystal group III nitride material is difficult to grow on a ceramic substrate, the present 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. Second, studies on epitaxial growth of single-crystal group III nitride materials on the surface of two-dimensional materials have shown that difficulty in nucleation of the surface of two-dimensional materials and inconsistent in-plane orientation of the epitaxial group III nitride materials are important causes of poor epitaxial quality. In this regard, the present invention solves this problem by introducing a nitride material with a polarity in the vertical direction under the two-dimensional material. Finally, the ceramic substrate surface is generally rough and cannot meet the requirement of epitaxy, and a filling material can be introduced to solve the problem.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a method of growing a 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 a 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 nitride is 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, can only deposit the filler material on the surface of the ceramic substrate, go to step 3) after grinding and polishing to obtain the smooth surface; 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 firstly, depositing filling materials on the surface of the ceramic substrate, grinding and polishing, then forming 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 the actual requirements.
The filler material deposited on the surface of the ceramic substrate in step 2) above may be AlN, siC, gaN, siO, siN, al2O3 or other material, preferably a material having the same elemental composition as the substrate.
The method of depositing the filling material in 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 100-100 nm, and then the filling material is ground and polished, preferably thinned to 100-10000 nm, and a smooth surface is generally obtained by adopting a method of 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 may be Al2O3, alpha-Al 2O3 or AlON/alpha-Al 2O3, and the thickness thereof is generally 1-100 nm.
In the above step 2), a preferable process of forming the al—o compound layer on the surface includes: al2O3 is formed on the surface by ALD, MBE or PVD, and then the Al2O3 is converted to alpha-Al 2O3 by high temperature treatment. The high temperature treatment method herein may be thermal annealing or laser annealing.
In the above step 2), another preferable process of forming the al—o compound layer on the surface includes: al2O3 is formed on the surface by ALD, MBE or PVD, then Al2O3 is converted into alpha-Al 2O3 by high-temperature treatment under nitrogen-containing atmosphere, and an AlON layer is formed on the surface to form the AlON/alpha-Al 2O3 structure. The high temperature treatment under the nitrogen-containing atmosphere may be thermal annealing; the nitrogen-containing atmosphere may be ammonia, nitrogen, or other atmospheres containing ammonia or nitrogen.
In the step 2), the method of forming the two-dimensional material on the surface may use wet transfer. The two-dimensional material layer may be a monoatomic layer or a combination of 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 above 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 depositing nitride on the surface, and then performing high-temperature treatment. The temperature of the high temperature treatment may be 1000-1300 degrees celsius.
The nitride layer formed in step 3) provides a polarizing field for epitaxial growth of single crystal group III nitride, ensuring epitaxial orientation while promoting nucleation.
In the step 4), a method of forming a 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 selected from one or more of graphene, moS2, 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 epitaxial growth of single crystal group III nitride and possibly provides a polarizing field.
In the above step 5), the method of growing the single crystal group III nitride on the surface 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 of the pores and grains on the ceramic surface; grinding and polishing the filler material can achieve a smooth surface on the ceramic substrate surface; forming an al—o compound layer or a two-dimensional material layer on the surface helps to optimize the c-axis orientation of the nitride in the next step; forming a nitride layer on the surface to provide a polarization field for the growth of the III-nitride layer, ensuring the growth orientation of the III-nitride layer and promoting the nucleation in the growth process; the formation of the two-dimensional material layer on the surface provides an orderly hexagonal structure for the growth of the group III nitride, ensures the growth of the group III nitride with a single crystal hexagonal structure, and provides polarity for the growth of the group III nitride layer if a two-dimensional material with polarity is used.
The invention breaks through the strict requirement on the monocrystalline substrate in the traditional epitaxial technology, realizes the epitaxial growth of monocrystalline materials on the ceramic substrate, greatly reduces the cost compared with the traditional SiC, sapphire, si and GaN substrates, and can also 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 smaller thermal mismatch with the III nitride, and can ensure that smaller 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, which is more advantageous in terms of heat dissipation for high power applications than conventional sapphire and Si substrates.
Drawings
FIG. 1 is a schematic flow chart of a method for growing single crystal III-nitride on a ceramic substrate according to an embodiment of the present invention.
FIG. 2 is a schematic 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 schematic 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 embodiments of the present invention are not limited thereto.
Example 1
Referring to fig. 1, fig. 1 is a flow chart showing a method for growing a single crystal group III nitride on a ceramic substrate, which includes the following steps 11 to 19:
and 11, selecting a ceramic substrate. Specifically, the ceramic substrate is AlN ceramic, has a thickness of 1000 micrometers and is round with a diameter of 100 millimeters.
And step 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 micrometers.
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 that mechanical polishing is performed first and then chemical mechanical polishing is performed later.
And 14, forming an Al2O3 layer on the surface. Specifically, the Al2O3 layer is formed by ALD and has a thickness of 10 nanometers.
And 15, performing high-temperature treatment in a 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.
And step 16, forming an AlN layer on the surface. Specifically, the AlN layer is formed by PVD, and the thickness is 100 nanometers.
And step 17, performing high-temperature treatment to convert the AlN layer into the AlN layer subjected to the high-temperature treatment. Specifically, the high temperature treatment is thermal annealing at 1200 ℃.
And 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 monocrystalline graphene.
Step 19, growing single crystal III nitride on the surface. Specifically, the method for growing the monocrystalline group III nitride on the surface is MOCVD, the monocrystalline group III nitride material is a growth AlN nucleation layer, and a monocrystalline GaN layer is grown again.
Example two
Referring to fig. 2, fig. 2 is a flow chart showing a method for growing a single crystal group III nitride on a ceramic substrate, which includes the following steps 21 to 25:
and 21, selecting a ceramic substrate. Specifically, the ceramic substrate is AlN ceramic, has a thickness of 500 micrometers and is square with a side length of 100 millimeters.
In step 22, a graphene layer is formed 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 double-atomic layer, and the graphene layer is monocrystalline graphene.
In step 23, an AlN layer is formed on the surface. Specifically, the AlN layer is formed by PVD, and the thickness is 50 nm.
And step 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 monocrystalline 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 flow chart showing a method for growing a single crystal group III nitride on a ceramic substrate, which includes the following steps 31-36:
and 31, selecting a ceramic substrate. Specifically, the ceramic substrate is AlN ceramic, has a thickness of 1000 mm and is in the shape of a 4-inch wafer.
And step 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, grinding and polishing the surface. Specifically, the method of polishing the surface is mechanical polishing. The method for polishing the surface is that mechanical polishing is performed first and then chemical mechanical polishing is performed later.
In step 34, an AlN layer is formed on the surface. Specifically, the AlN layer is formed by PVD, and the thickness is 50 nm.
And 35, forming a graphene layer on the surface. Specifically, the formation method of the graphene layer is wet transfer, the thickness of the graphene layer is a monoatomic layer, and the graphene layer is monocrystalline 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 (8)
1. A method of growing a 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, grinding and polishing to obtain a smooth surface, and then entering the step 3); 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, firstly, depositing filling material on the surface of the ceramic substrate and grindingForming an Al-O compound layer or a two-dimensional material layer on the surface after grinding and polishing, and then entering a step 3); wherein the filler material deposited on the surface of the ceramic substrate is selected from AlN, siC, gaN, siO 2 、SiN、Al 2 O 3 The material of the Al-O compound layer is alpha-Al 2 O 3 Or AlON/alpha-Al 2 O 3 ；
3) Forming a nitride layer on the surface;
4) Forming a two-dimensional material layer on the surface;
5) Growing a single crystal group III nitride on the surface, the single crystal group III nitride being GaN, alN, alGaN or a combination thereof.
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 of claim 1, wherein the Al-O compound layer in step 2) has a thickness of 1 to 100 nm.
4. The method of claim 1, wherein the forming of the Al-O compound layer on the surface in step 2) includes: al is formed on the surface by ALD, MBE or PVD 2 O 3 Then, al is treated at high temperature 2 O 3 Conversion to alpha-Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Alternatively, al is first formed on the surface by ALD, MBE, or PVD 2 O 3 Then, al is treated at high temperature in a nitrogen-containing atmosphere 2 O 3 Conversion to alpha-Al 2 O 3 Forming AlON layer on the surface to form AlON/alpha-Al 2 O 3 Is a structure of (a).
5. The method of claim 1, wherein the two-dimensional material layer in step 2) and step 4) is selected from the group consisting of graphene, moS 2 Single atomic layers or combinations of multiple atomic layers of one or more single crystal materials in BN.
6. The method of claim 1, wherein step 3) comprises depositing nitride by PVD, CVD or MOCVD, and then treating at high temperature to obtain the nitride layer having a thickness of 10-500 nm.
7. The method of claim 1, wherein the nitride layer formed in step 3) is AlN, gaN, or BN.
8. The method of claim 1, wherein step 5) grows single crystal group III nitride using MOCVD, CVD, MBE or HVPE.
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