CN115012040A - Method for preparing large-size nitride object single crystal by using single crystal two-dimensional material - Google Patents
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Abstract
The invention discloses a method for preparing a large-size nitride object single crystal by using a single crystal two-dimensional material. According to the invention, a carrier nitride substrate is obtained by splicing polycrystalline nitride primitives, a single crystal expansion layer and a single crystal cut-off layer are prepared on a two-dimensional material transferred from the upper surface and the lower surface of the carrier nitride substrate, a single crystal body single crystal with a large size of centimeter-level thickness and a diameter of more than hundred micrometers can be prepared by constructing a single crystallization process from a single crystal AlN inducer to the whole nitride structure by inducing a high-temperature high-pressure temperature gradient field, different nitride body single crystals such as GaN or AlN are prepared, and the ultra-high quality single crystal AlN inducer induces recrystallization, so that the nitride body single crystal with extremely high crystal quality can be obtained, the process difficulty is small, and the method is suitable for batch production; the invention is suitable for the preparation industry of nitride semiconductor single crystal substrates, and after the nitride object single crystal is cut, the nitride object single crystal can be used as a substrate for manufacturing high-performance light-emitting devices and electronic devices, and has important application in the fields of laser illumination, radio frequency communication and the like.
Description
Technical Field
The invention relates to a compound semiconductor single crystal preparation technology, in particular to a method for preparing a large-size nitride object single crystal by using a single crystal two-dimensional material.
Background
Wurtzite structure nitrides represented by aluminum nitride (AlN) and gallium nitride (GaN) have characteristics of large forbidden bandwidth, high thermal conductivity, high breakdown field strength, high sound wave propagation speed, and the like, are optimal substrate materials for preparing semiconductor ultraviolet light emitting devices, high-frequency and high-power electronic devices, and have important applications in the fields of ultraviolet killing, 5G communication, fine processing, high-density storage, and the like.
GaN and AlN have high melting point temperatures and high decomposition pressures and can only be prepared manually under non-equilibrium or high pressure conditions. At present, two technical schemes of hydride vapor deposition or physical vapor transport are mainly adopted in the industry for preparing the nitride single crystal for the substrate. Wherein, the hydride vapor deposition technical proposal mainly adopts a micron-thick monocrystal GaN film deposited on a monocrystal sapphire substrate as a template, then epitaxially prepares and strips a hundred-micron-thick monocrystal GaN film, and after grinding and polishing processing, a single-piece GaN monocrystal substrate is obtained, the typical size of which is about 50 mm, and the typical dislocation density of which is more than 1 multiplied by 10 6 cm -2 The problems of small size, poor quality, low yield, high cost and the like exist; the physical gas phase transport technical proposal mainly adopts small-size AlN crystals or AlN single crystal substrates obtained by spontaneous nucleation growth as seed crystals, grows the seed crystals by crystal expansion to obtain single crystal AlN blocks with millimeter or centimeter thickness, and obtains a plurality of AlN single crystal substrates with typical size about60 mm with a typical dislocation density of about 5X 10 4 cm -2 The problems of small size, low yield, large process difficulty, high equipment requirement and the like exist.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a method for preparing a large-size nitride object single crystal by using a single crystal two-dimensional material.
The method for preparing the large-size nitride object single crystal by using the single crystal two-dimensional material comprises the following steps of:
1) preparing a carrier nitride substrate:
a) providing a carrier substrate and a plurality of hexagonal prism-shaped polycrystalline nitride elements with the same size, and closely arranging the plurality of polycrystalline nitride elements on the carrier substrate;
b) filling boron-oxygen-nitrogen powder in gaps between the side walls of the adjacent polycrystalline nitride elements, wherein the filling height is consistent with the height of the polycrystalline nitride elements, heating to form boron-oxygen-nitrogen compounds, so that the adjacent polycrystalline nitride elements are tightly connected through the boron-oxygen-nitrogen compounds, and a plurality of tightly arranged polycrystalline nitride elements are spliced on the bearing substrate to form a whole;
c) removing the bearing substrate to obtain a polycrystalline nitride substrate formed by splicing a plurality of polycrystalline nitride elements into a whole, respectively depositing an upper nitride cover layer and a lower nitride cover layer on the upper surface and the lower surface of the polycrystalline nitride substrate, covering the upper surface and the lower surface of the polycrystalline nitride substrate, and depositing a side wall nitride cover layer on the side wall of the polycrystalline nitride substrate to obtain a carrier nitride substrate;
2) preparing a single crystal expansion layer:
a) sequentially transferring a first single crystal h-BN thin layer with a hexagonal layered structure, a first single crystal BAlN thin layer with a wurtzite structure and a first single crystal AlN thin layer with a wurtzite structure on an upper nitride cover layer of a carrier nitride substrate;
b) high-temperature annealing is carried out, so that the first single crystal h-BN thin layer is connected with the upper surface of the carrier nitride substrate by Van der Waals force at the interface, the first single crystal h-BN thin layer is connected with the first single crystal BAlN thin layer by mixed Van der Waals force and covalent bonds at the interface, and the first single crystal BAlN thin layer is connected with the first single crystal AlN thin layer by covalent bonds at the interface, so that interlayer fastening combination of the upper surface of the carrier nitride substrate, the first single crystal h-BN thin layer, the first single crystal BAlN thin layer and the first single crystal AlN thin layer is realized;
c) growing a first monocrystal AlN induction layer on the first monocrystal AlN thin layer, wherein the first monocrystal h-BN thin layer, the first monocrystal BAlN thin layer, the first monocrystal AlN thin layer and the first monocrystal AlN induction layer form a monocrystal expansion layer;
3) preparing a reconstructed carrier nitride substrate:
a) removing boron-oxygen nitride compounds in gaps between the lower nitride cap layer and the adjacent polycrystalline nitride elements by adopting an ultraviolet laser etching technology;
b) filling polycrystalline nitride powder with the same components as the polycrystalline nitride elements again at the gaps of the adjacent polycrystalline nitride elements, fusing the adjacent polycrystalline nitride elements by melting and condensing the polycrystalline nitride powder, fusing the polycrystalline nitride elements into a whole by fusing the polycrystalline nitride powder to obtain a reconstructed carrier nitride substrate, and grinding and polishing the lower surface to enable the lower surface to be flat, compact, continuous and uniform;
4) preparing a single crystal cut-off layer:
a) sequentially aligning and transferring a second single crystal h-BN thin layer with a hexagonal layered structure, a second single crystal BAlN thin layer with a wurtzite structure and a second single crystal AlN thin layer with the wurtzite structure on the lower surface of the reconstructed carrier nitride substrate;
b) high-temperature annealing is carried out, so that the second single crystal h-BN thin layer is connected with the lower surface of the reconstructed carrier nitride substrate by Van der Waals force at the interface, the second single crystal h-BN thin layer is connected with the second single crystal BAlN thin layer by mixed Van der Waals force and covalent bonds at the interface, and the second single crystal BAlN thin layer is connected with the second single crystal AlN thin layer by covalent bonds at the interface, and interlayer fastening combination of the lower surface of the reconstructed carrier nitride substrate, the second single crystal h-BN thin layer, the second single crystal BAlN thin layer and the second single crystal AlN thin layer is realized;
c) growing a second monocrystal AlN induction layer on the second monocrystal AlN thin layer, wherein the second monocrystal h-BN thin layer, the second monocrystal BALN thin layer, the second monocrystal AlN thin layer and the second monocrystal AlN induction layer form a monocrystal cut-off layer;
5) obtaining a nitride object single crystal:
a) splicing and welding the single crystal AlN inducer at the center of the upper surface of the first single crystal AlN inducer;
b) and constructing a high-temperature high-pressure temperature gradient field, and driving recrystallization from the single crystal AlN inducer to the direction of the single crystal cut-off layer, so that the whole nitride structure from the single crystal expansion layer to the single crystal cut-off layer has the same lattice arrangement as the single crystal AlN inducer, and the nitride object single crystal is obtained.
In the step 1), in a), the material of the bearing substrate is one of titanium, nickel, copper and iron; the polycrystalline nitride element is made of AlN, GaN, AlGaN, BN, BALN, BGaN or ScAlN, and in order to be compatibly expanded to a large size, the side length of a hexagon at the bottom surface of a hexagonal prism of the polycrystalline nitride element is more than 20 mm, and the thickness of the hexagonal side is more than 1 mm; each of the poly-nitride elements is aligned with a respective sidewall of an adjacent poly-nitride element, with a spacing between adjacent sidewalls of less than 0.2 mm. The area of the carrier substrate is larger than the total area of the plurality of polycrystalline nitride elements arranged in a close-packed manner.
In the step 1) b), the boron-oxygen-nitrogen powder is a mixed powder of boron nitride and boron oxide, the molar ratio of the boron nitride to the boron oxide is 1: 2-2: 1, the boron-oxygen-nitrogen compound is formed by heating at a temperature range of 500-800 ℃, the boron-oxygen-nitrogen compound is connected with adjacent polycrystalline nitride elements to form a whole, namely the boron-oxygen-nitrogen compound completely fills gaps between the adjacent polycrystalline nitride elements in the transverse dimension and is consistent with the height of each polycrystalline nitride element in the longitudinal dimension, and the upper surface of the polycrystalline nitride substrate is flat.
In the step 1) c), removing the bearing substrate below the integrated polycrystalline nitride element by using a room-temperature chemical etching or mechanical stripping method, wherein the room-temperature chemical etching adopts a hydrochloric acid solution, a ferric chloride solution or an ammonium sulfate solution; then, depositing polycrystalline AlN with the thickness of 100 nm to 1000 nm on the upper surface and the lower surface of the polycrystalline nitride block by adopting a pulse laser deposition, physical vapor deposition or magnetron sputtering method in sequence to form an upper nitride cover layer and a lower nitride cover layer respectively; and finally, depositing 10-50 mu m of polycrystalline AlN on the side wall of the polycrystalline nitride element by adopting methods such as physical vapor deposition, magnetron sputtering and the like to form a side wall nitride cover layer.
In the step 2), the first monocrystal h-BN thin layer has a hexagonal layered structure, is a two-dimensional material, has the thickness of 1-10 nm, and is used for covering the surface of the upper nitride cover layer; the first monocrystal BAlN thin film is used for realizing transition from the first monocrystal h-BN thin layer to the first monocrystal AlN thin layer on the upper layer, has a wurtzite structure, and has the thickness of 5-20 nm, and the component B is less than 15%; the first monocrystal AlN film has a wurtzite structure, has a thickness of 10-100 nm, and is used as a template layer for subsequent monocrystal nitride epitaxy.
In the step 2) b), annealing at a high temperature of 1000-1700 ℃ and a pressure of 10-1000 Pa for 10-100 min under the nitrogen atmosphere. The first monocrystal h-BN thin layer, the first monocrystal BAlN thin layer and the first monocrystal AlN thin layer which are fastened and combined among the layers form a first interface BAlN functional layer, the first interface BAlN functional layer is used for shielding a polycrystalline structure of a lower layer, transition from a polycrystalline structure of a bottom layer to a monocrystal structure is realized, and a required growth interface is provided for epitaxy of a first monocrystal AlN induction layer of an upper layer.
In the step 2) c), a first monocrystal AlN induction layer with the thickness of 100-1000 mu m is deposited on the upper surface of the first monocrystal AlN thin layer by adopting metal organic chemical vapor deposition, molecular beam epitaxy or pulse laser deposition or hydride vapor phase epitaxy at the temperature range of 800-1400 ℃, and the dislocation density of the first monocrystal AlN induction layer close to the upper surface is lower than 1 multiplied by 10 6 cm -2 。
In step 3), the ultraviolet laser etching technology uses ultraviolet laser with the wavelength shorter than 200 nm to etch the boron-oxygen nitride compound in the nitride cap layer and the gaps of the adjacent polycrystalline nitride elements under the condition of no mask.
In the step b) of the step 3), annealing treatment is performed on the polycrystalline nitride powder for 30-90 min at a temperature range of 1050-1700 ℃ under a nitrogen atmosphere at normal pressure, so that the polycrystalline nitride powder is melted and fills gaps between adjacent polycrystalline nitride elements, and the side walls of the adjacent polycrystalline nitride elements are solidified and connected after cooling.
In the step 4), the second single crystal h-BN thin layer has a hexagonal layered structure, is a two-dimensional material, has a thickness of 1-10 nm, and is used for covering the lower surface of the reconstructed carrier nitride substrate with a polycrystalline structure; the second monocrystal BAlN thin layer has a wurtzite structure, the thickness of the second monocrystal BAlN thin layer is 5-20 nm, the boron component is less than 15%, and the second monocrystal BAlN thin layer is used for realizing transition from the second monocrystal h-BN thin layer on the upper layer to the second monocrystal AlN thin layer on the bottom layer; the second monocrystal h-BN thin layer has a wurtzite structure, the thickness is 10-100 nm, and the second monocrystal h-BN thin layer is used as a template layer for subsequent monocrystal nitride epitaxy.
In the step 4), in the b), annealing at a high temperature of 1000-1700 ℃ and a pressure of 10-1000 Pa for 10-100 min under the nitrogen atmosphere. And the second single crystal h-BN thin layer, the second single crystal BAlN thin layer and the second single crystal AlN thin layer which are fastened and combined among the layers form a second interface BAlN functional layer, the second interface BAlN functional layer is used for shielding the polycrystalline structure of the upper layer, transition from the polycrystalline structure of the upper layer to the single crystal structure is realized, and a required growth interface is provided for the epitaxy of the second single crystal AlN induction layer of the lower layer.
In the step 4), metal organic chemical vapor deposition, molecular beam epitaxy, pulse laser deposition or hydride vapor phase epitaxy is adopted on the lower surface of the second monocrystal AlN thin layer, a second monocrystal AlN induction layer with the thickness of 5-20 mu m is deposited in the temperature range of 800-1400 ℃, and the dislocation density of the second monocrystal AlN layer close to the surface is lower than 1 multiplied by 10 9 cm -2 。
In the step 5), the step of butt-splicing and welding the single-crystal AlN inducers at the center of the upper surface of the first single-crystal AlN inducer layer specifically includes the following steps: adopting ultraviolet laser with wavelength shorter than 200 nm to weld the single crystal AlN inductor at the center of the upper surface of the first single crystal AlN inductor layer, wherein the single crystal AlN inductor and the first single crystal AlN inductor layer are arrangedAligning the centers, and aligning the in-plane lattices of the single crystal AlN inductor and the first single crystal AlN inductor layer; wherein the monocrystal AlN inductor is cylindrical, and has dislocation density lower than 2 × 10 4 cm -2 The thickness is more than 0.1 mm, and the diameter of the bottom surface of the cylinder is less than 10 mm.
In step 5) b), the basic temperature T of the temperature gradient field is 2000-2400 ℃, the thickness direction is along the Z direction, the lower surface of the single crystal cut-off layer is taken as the zero point of the Z direction, the temperature gradient DT from the single crystal cut-off layer to the single crystal expansion layer along the Z direction is 10-100 ℃/cm, the corresponding temperatures at different positions are T + DT xz, and Z is the position along the Z direction; the single crystal AlN inducer is high-temperature resistant, the lattice arrangement is stable under a thermal field, the lattice arrangement is conducted downwards in a temperature gradient field, the surface layer of the whole nitride structure from the single crystal expansion layer to the single crystal stop layer is not decomposed, the lattice arrangement of the whole nitride structure from the single crystal expansion layer to the single crystal stop layer is expanded from a high temperature position to a low temperature position only through the temperature gradient difference, the whole nitride structure from the single crystal expansion layer to the single crystal stop layer is induced to have the same lattice arrangement as the single crystal AlN inducer in the highest temperature region, namely the temperature gradient field enables the regular lattice arrangement of the single crystal AlN inducer to point to the single crystal stop layer from the single crystal AlN inducer to the single crystal expansion layer under the driving of the temperature gradient, namely, the crystal is directionally recrystallized, and finally a single crystal block of the nitride object is formed.
The invention has the advantages that:
the method can prepare the large-size nitride object single crystal with centimeter-level thickness and more than 100 mm diameter, prepare different nitride object single crystals such as GaN or AlN, and obtain the nitride object single crystal with extremely high crystal quality by inducing recrystallization through the ultra-high-quality monocrystal AlN inducer, and has small process difficulty and suitability for batch production; the invention is suitable for the preparation industry of nitride semiconductor single crystal substrates, and after the nitride object single crystal is cut, the nitride object single crystal can be used as a substrate for manufacturing high-performance light-emitting devices and electronic devices, and has important application in the fields of laser illumination, radio frequency communication and the like.
Drawings
FIG. 1 is a plan view showing how a plurality of polycrystalline nitride elements are arranged closely on a carrier substrate, which is obtained from a polycrystalline nitride element according to one embodiment of the method for producing a single crystal of a large-sized nitride object from a single-crystal two-dimensional material according to the present invention;
FIG. 2 is a cross-sectional view of the formation of a boron-oxygen-nitrogen compound according to one embodiment of the method of the present invention for producing a single crystal of a large-sized nitride object using a single-crystal two-dimensional material;
FIG. 3 is a cross-sectional view of a carrier nitride substrate obtained according to an embodiment of the method for preparing a large-sized single crystal of a nitride object using a single-crystal two-dimensional material according to the present invention;
FIG. 4 is a cross-sectional view of a single crystal extension layer obtained according to an embodiment of the method for producing a large-sized single crystal of a nitride object using a single crystal two-dimensional material according to the present invention;
FIG. 5 is a cross-sectional view of a reconstituted carrier nitride substrate obtained according to one embodiment of the method of preparing a large-sized single crystal of a nitride object using a single-crystal two-dimensional material according to the present invention;
FIG. 6 is a cross-sectional view of a single crystal stopper layer obtained according to an embodiment of the method for preparing a large-sized single crystal of a nitride object using a single crystal two-dimensional material according to the present invention;
FIG. 7 is a cross-sectional view of a single crystal of a nitrided object obtained by one embodiment of the method for producing a large-sized single crystal of a nitrided object using a single-crystal two-dimensional material according to the present invention.
Detailed Description
The invention will be further elucidated by means of specific embodiments in the following with reference to the drawing.
The method for preparing the large-size nitride object single crystal by using the single crystal two-dimensional material comprises the following steps:
1) preparing a carrier nitride substrate:
a) providing a bearing substrate 2 made of copper and a plurality of hexagonal prism-shaped polycrystalline nitride elements 1 with the same size, wherein the bearing substrate is made of AlN, the side length of a hexagon on the bottom surface is 30 mm, and the thickness of the hexagon is 5 mm, the plurality of polycrystalline nitride elements are closely arranged on the bearing substrate like a honeycomb, and the distance between adjacent side walls is 0.15 mm, as shown in figure 1;
b) filling boron-oxygen-nitrogen powder into gaps between the side walls of adjacent polycrystalline nitride elements, wherein the ratio of the boron nitride to the boron oxide mixed powder is 2:3, the filling height is consistent with the height of the polycrystalline nitride elements, heating is carried out at a temperature range of 600 ℃ to form boron-oxygen-nitrogen compounds 3, so that the adjacent polycrystalline nitride elements are tightly connected through the boron-oxygen-nitrogen compounds, and a plurality of tightly arranged polycrystalline nitride elements are spliced into a whole on a bearing substrate, as shown in fig. 2;
c) removing the bearing substrate by a hydrochloric acid solution etching method to obtain a polycrystalline nitride substrate formed by splicing a plurality of polycrystalline nitrides into a whole, respectively depositing an upper nitride cover layer 41 and a lower nitride cover layer 42 with the thickness of 500 nm on the upper surface and the lower surface of the polycrystalline nitride substrate, covering the upper surface and the lower surface of the polycrystalline nitride substrate, and depositing a side wall nitride cover layer 5 with the thickness of 20 mu m on the side wall of the polycrystalline nitride substrate to obtain a carrier nitride substrate, wherein the carrier nitride substrate is shown in figure 3;
2) preparing a single crystal expansion layer:
a) sequentially transferring a first monocrystalline h-BN thin layer 6 with the thickness of 5 nm, a first monocrystalline BAlN thin layer 7 with the thickness of 10 nm and the component B of 10% and a first monocrystalline AlN thin layer 8 with the thickness of 50 nm on an upper nitride cover layer of a carrier nitride substrate;
b) performing high-temperature annealing treatment for 60 min at 1700 ℃, 1000 Pa and a nitrogen atmosphere, so that the first single-crystal h-BN thin layer is connected with the upper surface of the carrier nitride substrate by van der Waals force at the interface, the first single-crystal h-BN thin layer is connected with the first single-crystal BAlN thin layer by adopting a mixed van der Waals force and covalent bond form at the interface, the first single-crystal BAlN thin layer is connected with the first single-crystal AlN thin layer by adopting a covalent bond at the interface, the interlayer fastening combination of the upper surface of the carrier nitride substrate, the first single-crystal h-BN thin layer, the first single-crystal BAlN thin layer and the first single-crystal AlN thin layer is realized, and the first single-crystal h-BN thin layer, the first single-crystal BAlN thin layer and the first single-crystal AlN thin layer after the interlayer fastening combination form a first interface BAlN functional layer;
c) growing a first monocrystal AlN induction layer 9 with the thickness of 500 mu m on the first monocrystal AlN thin layer of the first interface BAlN functional layer at the temperature of 1200 ℃ by adopting a hydride vapor phase epitaxy technology, wherein the first interface BAlN functional layer and the first monocrystal AlN induction layer form a monocrystal expansion layer,the dislocation density of the single-crystal AlN near the upper surface was 9.5X 10 5 cm -2 As shown in fig. 4;
3) preparing a reconstructed carrier nitride substrate:
a) adopting ultraviolet laser etching technology with the wavelength of 177 nm to enter from the lower surface of the carrier nitride substrate, and removing boron-oxygen-nitrogen compounds in gaps between the lower nitride cap layer and the adjacent polycrystalline nitride elements under the condition of no mask;
b) refilling polycrystalline nitride powder AlN with the same components as the polycrystalline nitride elements into gaps of the adjacent polycrystalline nitride elements, annealing for 60 min at 1700 ℃ under the atmosphere of nitrogen at normal pressure to melt and agglomerate the polycrystalline nitride powder, welding the adjacent polycrystalline nitride elements, welding the polycrystalline nitride elements into a whole by the polycrystalline nitride powder to obtain a reconstructed carrier nitride substrate 10, and polishing the lower surface to ensure that the lower surface is flat, compact, continuous and uniform, as shown in FIG. 5;
4) preparing a single crystal cut-off layer:
a) sequentially aligning and transferring a second monocrystalline h-BN thin layer 11 with the thickness of 5 nm, a second monocrystalline BALN thin layer 12 with the thickness of 10 nm and the component B of 10% and a second monocrystalline AlN thin layer 13 with the thickness of 50 nm on the lower surface of the reconstructed carrier nitride substrate;
b) performing high-temperature annealing treatment for 60 min at 1700 ℃, 1000 Pa and nitrogen atmosphere to ensure that the second single-crystal h-BN thin layer is connected with the lower surface of the reconstructed carrier nitride substrate by Van der Waals force at the interface, the second single-crystal h-BN thin layer is connected with the second single-crystal BAlN thin layer by adopting mixed Van der Waals force and covalent bonds at the interface, and the second single-crystal BAlN thin layer is connected with the second single-crystal AlN thin layer by adopting covalent bonds at the interface, so that interlayer fastening combination of the lower surface of the reconstructed carrier nitride substrate, the second single-crystal h-BN thin layer, the second single-crystal BAlN thin layer and the second single-crystal AlN thin layer is realized, and the second single-crystal h-BN thin layer, the second single-crystal BAlN thin layer and the second single-crystal AlN thin layer after interlayer fastening combination form a second interface BAlN functional layer;
c) growing a second monocrystal AlN thin layer of a second interface BAlN functional layer at the temperature of 1200 ℃ by adopting a hydride vapor phase epitaxy technologyA second single-crystal AlN inducing layer 14 of 5 μm thickness having a dislocation density of single-crystal AlN of 5.0X 10 near the lower surface 8 cm -2 The second interface BAlN functional layer and the second single-crystal AlN inducing layer constitute a single-crystal cut-off layer, as shown in fig. 6;
5) obtaining a nitride object single crystal:
a) splicing and welding a single crystal AlN inducer 15 pair at the center of the upper surface of a first single crystal AlN inducer layer by adopting ultraviolet laser with the wavelength of 177 nm, aligning the single crystal AlN inducer with the center of the single crystal AlN inducer layer, and aligning the single crystal AlN inducer with the in-plane lattice arrangement of the single crystal AlN inducer layer, wherein the single crystal AlN inducer is cylindrical in shape, and the dislocation density is 1 multiplied by 10 4 cm -2 The thickness is 0.2 mm, and the diameter of the cylinder is 1 mm;
b) constructing a high-temperature high-pressure temperature gradient field, wherein the basic temperature T of the temperature gradient field is 2200 ℃, the thickness direction of the temperature gradient field is along the Z direction, the lower surface of the single crystal cut-off layer is taken as the zero point of the Z direction, namely the temperature of the lower surface of the single crystal cut-off layer is 2200 ℃, the temperature gradient DT from the single crystal cut-off layer to the single crystal expansion layer along the Z direction is 80 ℃/cm, the corresponding temperatures of different positions are T + DT xz, and Z is the position along the Z direction; the monocrystal AlN inducer resists high temperature, the lattice arrangement is stable under a thermal field, the lattice arrangement is conducted downwards in a temperature gradient field, the surface layer of the whole nitride structure from the monocrystal expansion layer to the monocrystal stopping layer is not decomposed, the lattice arrangement of the whole nitride structure from the monocrystal expansion layer to the monocrystal stopping layer is expanded from a high temperature position to a low temperature position only through the temperature gradient difference, the whole nitride structure from the monocrystal expansion layer to the monocrystal stopping layer is induced to have the same lattice arrangement as the monocrystal AlN inducer in the highest temperature region, namely, the temperature gradient field leads the regular lattice arrangement of the monocrystal AlN inducer to point to the monocrystal stopping layer from the monocrystal AlN inducer to the monocrystal expansion layer under the driving of the temperature gradient, namely, the monocrystal AlN inducer is directionally recrystallized, and the dislocation density is not higher than 2 multiplied by 10 4 cm -2 As shown in fig. 7, is a high-quality single crystal bulk of a nitride object.
Finally, it is noted that the disclosed embodiments are intended to aid in further understanding of the invention, but those skilled in the art will appreciate that: various substitutions and modifications are possible without departing from the spirit and scope of the invention and the appended claims. Therefore, the invention should not be limited by the disclosure of the embodiments, but should be defined by the scope of the appended claims.
Claims (10)
1. A method for preparing a large-sized single crystal of a nitrided object using a single-crystal two-dimensional material, the method comprising the steps of:
1) preparing a carrier nitride substrate:
a) providing a carrier substrate and a plurality of hexagonal prism-shaped polycrystalline nitride elements with the same size, and closely arranging the plurality of polycrystalline nitride elements on the carrier substrate;
b) filling boron-oxygen-nitrogen powder in gaps between the side walls of the adjacent polycrystalline nitride elements, wherein the filling height is consistent with the height of the polycrystalline nitride elements, heating to form boron-oxygen-nitrogen compounds, so that the adjacent polycrystalline nitride elements are tightly connected through the boron-oxygen-nitrogen compounds, and a plurality of tightly arranged polycrystalline nitride elements are spliced on the bearing substrate to form a whole;
c) removing the bearing substrate to obtain a polycrystalline nitride substrate formed by splicing a plurality of polycrystalline nitride elements into a whole, respectively depositing an upper nitride cover layer and a lower nitride cover layer on the upper surface and the lower surface of the polycrystalline nitride substrate, covering the upper surface and the lower surface of the polycrystalline nitride substrate, and depositing a side wall nitride cover layer on the side wall of the polycrystalline nitride substrate to obtain a carrier nitride substrate;
2) preparing a single crystal expansion layer:
a) sequentially transferring a first single crystal h-BN thin layer with a hexagonal layered structure, a first single crystal BAlN thin layer with a wurtzite structure and a first single crystal AlN thin layer with a wurtzite structure on an upper nitride cover layer of a carrier nitride substrate;
b) high-temperature annealing is carried out, so that the first single crystal h-BN thin layer is connected with the upper surface of the carrier nitride substrate by Van der Waals force at the interface, the first single crystal h-BN thin layer is connected with the first single crystal BAlN thin layer by mixed Van der Waals force and covalent bonds at the interface, and the first single crystal BAlN thin layer is connected with the first single crystal AlN thin layer by covalent bonds at the interface, so that interlayer fastening combination of the upper surface of the carrier nitride substrate, the first single crystal h-BN thin layer, the first single crystal BAlN thin layer and the first single crystal AlN thin layer is realized;
c) growing a first monocrystal AlN induction layer on the first monocrystal AlN thin layer, wherein the first monocrystal h-BN thin layer, the first monocrystal BAlN thin layer, the first monocrystal AlN thin layer and the first monocrystal AlN induction layer form a monocrystal expansion layer;
3) preparing a reconstructed carrier nitride substrate:
a) removing boron-oxygen nitride compounds in gaps between the lower nitride cap layer and the adjacent polycrystalline nitride elements by adopting an ultraviolet laser etching technology;
b) filling polycrystalline nitride powder with the same components as the polycrystalline nitride elements again at the gaps of the adjacent polycrystalline nitride elements, fusing the adjacent polycrystalline nitride elements by melting and condensing the polycrystalline nitride powder, fusing the polycrystalline nitride elements into a whole by fusing the polycrystalline nitride powder to obtain a reconstructed carrier nitride substrate, and grinding and polishing the lower surface to enable the lower surface to be flat, compact, continuous and uniform;
4) preparing a single crystal cut-off layer:
a) sequentially aligning and transferring a second single crystal h-BN thin layer with a hexagonal layered structure, a second single crystal BAlN thin layer with a wurtzite structure and a second single crystal AlN thin layer with the wurtzite structure on the lower surface of the reconstructed carrier nitride substrate;
b) high-temperature annealing is carried out, so that the second single crystal h-BN thin layer is connected with the lower surface of the reconstructed carrier nitride substrate by Van der Waals force at the interface, the second single crystal h-BN thin layer is connected with the second single crystal BAlN thin layer by mixed Van der Waals force and covalent bonds at the interface, and the second single crystal BAlN thin layer is connected with the second single crystal AlN thin layer by covalent bonds at the interface, and interlayer fastening combination of the lower surface of the reconstructed carrier nitride substrate, the second single crystal h-BN thin layer, the second single crystal BAlN thin layer and the second single crystal AlN thin layer is realized;
c) growing a second monocrystal AlN induction layer on the second monocrystal AlN thin layer, wherein the second monocrystal h-BN thin layer, the second monocrystal BALN thin layer, the second monocrystal AlN thin layer and the second monocrystal AlN induction layer form a monocrystal cut-off layer;
5) obtaining a nitride object single crystal:
a) splicing and welding a single crystal AlN inducer at the center of the upper surface of the first single crystal AlN inducer;
b) and constructing a high-temperature high-pressure temperature gradient field, and driving recrystallization from the single crystal AlN inducer to the direction of the single crystal cut-off layer, so that the whole nitride structure from the single crystal expansion layer to the single crystal cut-off layer has the same lattice arrangement as the single crystal AlN inducer, and the nitride object single crystal is obtained.
2. The method as claimed in claim 1, wherein in the step 1) a), the material of the carrier substrate is one of titanium, nickel, copper and iron; the polycrystalline nitride element is made of AlN, GaN, AlGaN, BN, BALN, BGaN or ScAlN; the side length of a hexagon on the bottom surface of the hexagonal prism of the polycrystalline nitride element is more than 20 mm, and the thickness of the hexagonal prism is more than 1 mm; each poly-nitride element is aligned with a respective sidewall of an adjacent poly-nitride element, with a spacing between adjacent sidewalls of less than 0.2 mm.
3. The method of claim 1, wherein in step 2) a) the first thin layer of single-crystal h-BN is a two-dimensional material with a thickness of 1 to 10 nm for masking the surface of the upper nitride cap layer; the thickness of the first monocrystal BAlN thin film is 5-20 nm, the boron component is less than 15%, and the first monocrystal BAlN thin film is used for realizing transition from the first monocrystal h-BN thin film to the first monocrystal AlN thin film; the thickness of the first monocrystal AlN thin film is 10-100 nm.
4. The method according to claim 1, wherein in step 2) c), a first single-crystal AlN inducing layer with a thickness of 100-1000 μm is deposited on the upper surface of the first single-crystal AlN thin layer by metal-organic chemical vapor deposition, molecular beam epitaxy, or pulsed laser deposition or hydride vapor phase epitaxy at a temperature range of 800-1400 ℃.
5. The method according to claim 1, wherein in step 3) a) the uv laser etching technique uses uv laser light with a wavelength shorter than 200 nm to etch the boron-oxygen-nitride compound in the lower nitride cap layer and the gaps between adjacent polycrystalline nitride elements without a mask.
6. The method according to claim 1, wherein in step 3) b), annealing is performed at 1050-1700 ℃ under nitrogen atmosphere at normal pressure for 30-90 min to melt the polycrystalline nitride powder and fill gaps between adjacent polycrystalline nitride elements, and the sidewall of the adjacent polycrystalline nitride elements is solidified and connected after cooling.
7. The method according to claim 1, wherein in step 4) a) the second thin layer of monocrystalline h-BN is a two-dimensional material with a thickness of 1 to 10 nm for masking the lower surface of the reconstituted carrier nitride substrate with a polycrystalline structure; the thickness of the second monocrystal BAlN thin layer is 5-20 nm, the boron component is less than 15%, and the second monocrystal BAlN thin layer is used for realizing transition from the second monocrystal h-BN thin layer on the upper layer to the second monocrystal AlN thin layer on the bottom layer; the thickness of the second monocrystal h-BN thin layer is 10-100 nm.
8. The method according to claim 1, wherein in step 4) c), a second single-crystal AlN inducing layer with a thickness of 5-20 μm is deposited on the lower surface of the second single-crystal AlN thin layer by metal-organic chemical vapor deposition, molecular beam epitaxy, or pulsed laser deposition or hydride vapor phase epitaxy at a temperature range of 800-1400 ℃.
9. The method according to claim 1, wherein in step 5) a) the single-crystal AlN inducer is butt-spliced at the center of the upper surface of the first single-crystal AlN inducer layer, comprising the specific steps of: adopting ultraviolet laser with the wavelength shorter than 200 nm to weld the single crystal AlN inductor at the center of the upper surface of the first single crystal AlN inductor layer, aligning the single crystal AlN inductor with the center of the first single crystal AlN inductor layer, and aligning the single crystal AlN inductor with the in-plane lattice arrangement of the first single crystal AlN inductor layer; whereinThe monocrystal AlN inductor is cylindrical and has dislocation density lower than 2 × 10 4 cm -2 The thickness is more than 0.1 mm, and the diameter of the bottom surface of the cylinder is less than 10 mm.
10. The method according to claim 1, wherein in step 5) b), a base temperature T of the temperature gradient field is 2000 to 2400 ℃, a thickness direction is along a Z direction, a temperature gradient DT directed from the single crystal cut-off layer to the single crystal extension layer along the Z direction is 10 to 100 ℃/cm with a lower surface of the single crystal cut-off layer as a zero point of the Z direction, corresponding temperatures at different positions are T + DT × Z, and Z is a position along the Z direction; the single crystal AlN inducer is high-temperature resistant, the lattice arrangement is stable under a thermal field, the lattice arrangement is conducted downwards in a temperature gradient field, the surface layer of the whole nitride structure from the single crystal expansion layer to the single crystal stop layer is not decomposed, the lattice arrangement of the whole nitride structure from the single crystal expansion layer to the single crystal stop layer is expanded from a high temperature position to a low temperature position only through the temperature gradient difference, the whole nitride structure from the single crystal expansion layer to the single crystal stop layer is induced to have the same lattice arrangement as the single crystal AlN inducer in the highest temperature region, namely the temperature gradient field enables the regular lattice arrangement of the single crystal AlN inducer to point to the single crystal stop layer from the single crystal AlN inducer to the single crystal expansion layer under the driving of the temperature gradient, namely, the crystal is directionally recrystallized, and finally a single crystal block of the nitride object is formed.
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| US7012016B2 (en) * | 2003-11-18 | 2006-03-14 | Shangjr Gwo | Method for growing group-III nitride semiconductor heterostructure on silicon substrate |
| FR2938120B1 (en) * | 2008-10-31 | 2011-04-08 | Commissariat Energie Atomique | PROCESS FOR FORMATION OF A MONOCRYSTALLINE LAYER IN THE MICROELECTRONIC DOMAIN |
| US9650723B1 (en) * | 2013-04-11 | 2017-05-16 | Soraa, Inc. | Large area seed crystal for ammonothermal crystal growth and method of making |
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| US20070256630A1 (en) * | 2006-05-04 | 2007-11-08 | Fairfield Crystal Technology, Llc | Method and apparatus for aluminum nitride monocrystal boule growth |
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