CN115050864B - Preparation method of single crystal nitride Micro-LED array based on non-single crystal substrate - Google Patents
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Abstract
The invention discloses a preparation method of a single crystal nitride Micro-LED array based on a non-single crystal substrate. The invention obtains the dislocation density lower than 1 multiplied by 10 by preparing the two-dimensional material mask layer 9 cm ‑2 And further obtaining a dislocation filter layer having a dislocation density of less than 1X 10 8 cm ‑2 The single crystal nitride film can realize a super-high-quality single crystal nitride functional structure on a non-single crystal substrate with large lattice mismatch and large thermal expansion coefficient mismatch, can be used for preparing Micro-LED devices, can also be expanded to prepare radio frequency devices, power devices, light emitting devices, detection devices and the like, and has process universality; the laser is adopted to destroy the interface combination of the epitaxial structure and the non-single crystal substrate, so that the nondestructive separation of the epitaxial structure and the repeated utilization of the non-single crystal substrate can be realized, the energy is saved, the environment is protected, the process is simple, and the method is suitable for batch production.
Description
Technical Field
The invention relates to a preparation technology of a semiconductor light-emitting device, in particular to a preparation method of a single crystal nitride Micro-LED array based on a non-single crystal substrate.
Background
Due to the scarcity of homogeneous substrates, nitride semiconductors are typically heteroepitaxial on lattice symmetry matched single crystal substrates. For example, a single crystal sapphire substrate having high transmittance is generally selected for the production of nitride light emitting devices, and a single crystal silicon or single crystal silicon carbide substrate is generally selected for the production of electronic devices. However, the single crystal substrate cannot sufficiently satisfy the requirements of the light emitting device in terms of light extraction efficiency, transparency, heat dissipation capability, and the like, and it is urgently needed to explore a single crystal nitride preparation technology on a non-single crystal substrate, improve the heat management capability and the comprehensive performance of the device, reduce the cost, and expand the application field of the device.
On stoneThe method of using single crystal two-dimensional material to assist epitaxy on non-single crystal substrate such as quartz can realize single crystal nitride film, but has the following problems: (1) When the thickness of the epitaxial film exceeds 1 micron, the interface interaction between the epitaxial film and the two-dimensional material is stronger than that between the two-dimensional material and the non-single crystal substrate, so that the epitaxial film is broken due to partial interface separation during growth or temperature reduction; (2) When the epitaxial film thickness is less than 1 μm, the dislocation density of the epitaxial film is generally higher than 3X 10 10 cm -2 The half width of the rocking curve of the corresponding X-ray diffraction (0002) crystal face is greater than 1 degree, so that the light-emitting device prepared on the light-emitting device has low electro-optic conversion efficiency and serious electric leakage of an electronic device, and cannot meet the application requirements in the fields of flexible LEDs, ultraviolet LEDs, radio frequency power devices and the like, and particularly cannot meet the research and development requirements in the field of Micro light-emitting diodes (Micro-LEDs) with extremely high material quality requirements.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of a single crystal nitride Micro-LED array based on a non-single crystal substrate.
The invention relates to a preparation method of a single crystal nitride Micro-LED array based on a non-single crystal substrate, which comprises the following steps:
1) Preparing a template layer:
a) Providing a non-single crystal substrate, wherein the non-single crystal substrate is made of rigid non-metal materials; carrying out double-sided polishing on the non-single crystal substrate;
b) Forming a two-dimensional atomic crystal induction layer on the upper surface of the non-single crystal substrate in a wet or dry transfer mode, wherein the two-dimensional atomic crystal induction layer is of a single crystal structure with doped atoms, and the doped atoms exposed on the surface of the two-dimensional atomic crystal induction layer provide surface unsaturated dangling bonds which serve as nucleation sites of single crystal nitrides and provide a required modified surface for the growth of the single crystal nitrides;
c) Depositing a first layer of single crystal nitride on the two-dimensional atomic crystal inducing layer to form a template layer;
2) Preparing a dislocation filter layer:
a) Transferring the first two-dimensional material mask layer to the upper surface of the template layer;
b) Forming a first through hole array consisting of a plurality of through holes which are periodically arranged in a two-dimensional way on the first two-dimensional material mask layer by a mask protection and selective etching method, wherein the periods of rows and columns are equal, the depth of each through hole is consistent with the thickness of the first two-dimensional material mask layer, and the diameter of each through hole is smaller than 2/3 of the period of the first through hole array;
c) Depositing a second layer of single crystal nitride on the first two-dimensional material mask layer, wherein the surface of the first two-dimensional material mask layer, except the first through hole array, is not provided with a surface unsaturated dangling bond and can not grow the single crystal nitride, and the area of the template layer, corresponding to the lower part of the first through hole array, is provided with a surface unsaturated dangling bond and can grow the single crystal nitride, so that first dislocation filtering is realized, namely dislocations in the template layer, which are not corresponding to the first through hole array, can not enter the second layer of single crystal nitride on the upper layer;
d) Increasing the growth temperature and the stoichiometric ratio of the flow of the nitrogen source and the III-group source, and after the thickness of the second layer of single crystal nitride exceeds the thickness of the first two-dimensional material mask layer, continuing to grow longitudinally and simultaneously expand transversely until the first two-dimensional material mask layer is completely wrapped, wherein the transverse expansion process is in a near-stress-free state, so that when the dislocations are expanded from the region of the template layer corresponding to the first through hole array to the second layer of single crystal nitride, the propagation direction of the dislocations is changed, part of the dislocations are annihilated, and a dislocation filter layer with the dislocation density lower than that of the template layer is obtained;
3) Preparing a single crystal nitride film:
a) Transferring the second two-dimensional material mask layer to the upper surface of the dislocation filter layer;
b) Forming a second through hole array consisting of a plurality of through holes which are periodically arranged in a two-dimensional manner on the second two-dimensional material mask layer by a mask protection and selective etching method, wherein the depth of each through hole is consistent with the thickness of the second two-dimensional material mask layer, the period and the shape of the second through hole array are consistent with those of the first through hole array, but the position of the second through hole array and the first through hole array have horizontal offset, and the horizontal offset ensures that the outer edge of each through hole of the second through hole array is tangent to the outer edge of each through hole of the first through hole array;
c) Depositing a third layer of single crystal nitride on the second two-dimensional material mask layer, wherein the surface of the second two-dimensional material mask layer, except the second through hole array region, does not have surface unsaturated dangling bonds and can not grow the single crystal nitride, and the region of the corresponding dislocation filter layer below the second through hole array can grow the single crystal nitride, so that second dislocation filtration is realized, namely, dislocations in the dislocation filter layer which is not corresponding to the second through hole array can not enter the third layer of single crystal nitride on the upper layer;
d) Increasing the growth temperature and the stoichiometric ratio of the flow of the nitrogen source and the group III source, and after the thickness of the third layer of single crystal nitride exceeds the thickness of the second two-dimensional material mask layer, continuing to grow longitudinally and simultaneously expand transversely until the second two-dimensional material mask layer is completely wrapped, wherein the transverse expansion process is in a near-stress-free state, so that when dislocations are expanded from the region of the dislocation filter layer corresponding to the second through hole array to the third layer of single crystal nitride, the propagation direction of the dislocations is changed, and partial dislocations are annihilated to obtain the single crystal nitride film with the dislocation density lower than that of the dislocation filter layer;
4) Preparing a single crystal nitride Micro-LED array:
a) Transferring the third two-dimensional material mask layer to the upper surface of the single crystal nitride film;
b) Forming a third through hole array consisting of a plurality of through holes which are periodically arranged in a two-dimensional manner on the third two-dimensional material mask layer by a mask protection and selective etching method, wherein the periods of rows and columns are equal, the depth of each through hole is consistent with the thickness of the third two-dimensional material mask layer, the diameter of each through hole is 1/2 to 3/4 of the period of the third through hole array, and the period of the third through hole array is consistent with the period of the first through hole array;
c) Depositing a single crystal nitride functional structure on a third two-dimensional material mask layer, wherein the surface of the third two-dimensional material mask layer, except for a third through hole array region, does not have a surface unsaturated dangling bond and cannot grow the single crystal nitride functional structure, the region of the single crystal nitride film, corresponding to the lower part of the third through hole array, can grow the nitride functional structure in a single crystal manner, and the single crystal nitride functional structure is one of ultraviolet or visible light emitting diode structures; by controlling the growth temperature and the stoichiometric ratio of the nitrogen source to the III-group source flow in the deposition process, the transverse dimension of the single crystal nitride functional structure is equal to the transverse dimension of the circular through hole area, only longitudinal growth is carried out, the height of the single crystal nitride functional structure is greater than the thickness of the third two-dimensional material mask layer, a single crystal nitride Micro-LED array which is the same as the third through hole array and is periodically distributed is formed, and the single crystal nitride functional structure in each through hole is used as an array element of the single crystal nitride Micro-LED array;
5) Obtaining a flexible single crystal nitride Micro-LED array:
a) Filling gaps among the array elements in a spin coating mode, wherein the filling height is the same as the height of the array elements, and obtaining a flat sheet structure;
b) Attaching a flexible protective layer on the surface of the flat sheet structure;
c) Laser is incident from the back of the non-single crystal substrate, the laser heats the two-dimensional atomic crystal induction layer between the non-single crystal substrate and the template layer in a lattice resonance absorption mode, the two-dimensional atomic crystal induction layer is melted, the structural separation of the non-single crystal substrate and the two-dimensional atomic crystal induction layer is realized, and the flexible single crystal nitride Micro-LED array and the reusable non-single crystal substrate are obtained.
Wherein, in the step 1) a), the non-single crystal substrate has a forbidden band width of more than 5 eV, a lattice mismatch with the nitride semiconductor of more than 20%, a coefficient of thermal expansion mismatch of more than 50%, a visible light transparency of more than 0.99, and a melting point of more than 1200 ℃, and one of quartz, mica, corundum, and diamond is used.
In the step 1) b), the two-dimensional atomic crystal induction layer adopts graphene with a single crystal structure of doped atoms, the doped atoms are nitrogen atoms or oxygen atoms, the proportion of the nitrogen atoms or the oxygen atoms is more than 1%, the thickness is 1 to 10 nm, the doped atoms provide surface unsaturated dangling bonds to serve as nucleation sites of nitrides, and the two-dimensional atomic crystal induction layer does not need to be subjected to additional modification treatment.
In step 1) c), metal organic compounds are usedGrowing a first layer of single crystal nitride by a chemical vapor deposition technology, a molecular beam epitaxy, a hydride vapor phase epitaxy, a magnetron sputtering technology or a pulse laser deposition technology, wherein the growth temperature is 900-1250 ℃, the stoichiometric ratio of the flow of a nitrogen source to the flow of a group III source, namely, V group/III group is 300-1000, the group III source is a metal or a metal organic source, the nitrogen source is ammonia or nitrogen, the first layer of single crystal nitride is AlN or an AlGaN and AlN composite structure, the forbidden bandwidth is more than 5 eV, the thickness of a template layer is 500-1000 nm, and the dislocation density of the template layer is less than 5 multiplied by 10 10 cm -2 And is higher than 1 x 10 9 cm -2 。
In the step 2), the first two-dimensional mask layer is made of polycrystalline or amorphous graphene, boron nitride or a transition metal chalcogenide with the thickness of 10 nm to 30 nm.
In step 2) b), the specific process of mask protection and selective etching is as follows: spin-coating a photoresist on the upper surface of the first two-dimensional mask layer, exposing the photoresist through a mask plate with a set periodic shape, removing the photoresist denatured due to exposure through a chemical corrosion method, and providing mask protection through the undenatured photoresist with the set periodic shape; the selective etching is to directly etch the first two-dimensional material mask layer with mask protection by adopting the technologies of plasma etching or reactive ion etching and the like, etch the area without mask protection, remove the residual photoresist layer by adopting a chemical cleaning mode, and transfer the set periodic shape from the photoresist layer to the first two-dimensional material mask layer. The through hole is cylindrical; the period of the first through hole array is 0.1-50 μm.
In the step 2) c), a second layer of single crystal nitride is grown by adopting a metallorganic chemical vapor deposition technology, molecular beam epitaxy, hydride vapor phase epitaxy, magnetron sputtering or a pulsed laser deposition technology, the growth temperature is 900-1250 ℃, the stoichiometric ratio of the flow of the nitrogen source to the flow of the III group source, namely V group/III group is 300-1000, the second layer of single crystal nitride is AlN or an AlGaN and AlN composite structure, and the forbidden bandwidth is more than 5 eV.
In step d) of step 2),the growth temperature is increased to 1000-1350 ℃, and the ratio of V family/III family is increased to 1500-5000. The thickness of the dislocation filter layer is 500 nm to 2000 nm, and the dislocation density is lower than 1 × 10 9 cm -2 。
In the step 3), the second two-dimensional mask layer is made of one of polycrystalline or amorphous graphene, boron nitride or transition metal chalcogenide, and the thickness of the second two-dimensional mask layer is 10 nm to 30 nm.
In the step 3) c), a metallorganic chemical vapor deposition technology, a molecular beam epitaxy technology, a hydride vapor phase epitaxy technology, a magnetron sputtering technology or a pulse laser deposition technology is adopted to grow a third layer of single crystal nitride, the growth temperature is 900-1250 ℃, the stoichiometric ratio of the flow of the nitrogen source and the flow of the III group source, namely V group/III group is 300-1000, the third layer of single crystal nitride is AlN or an AlGaN and AlN composite structure, and the forbidden bandwidth is more than 5 eV.
In the step 3) d), the growth temperature is increased to 1000-1350 ℃, and the ratio of V family/III family is increased to 1500-5000. The thickness of the single crystal nitride film is 500 nm-2000 nm, and the dislocation density is less than 1 multiplied by 10 8 cm -2 。
In the step 4), the third two-dimensional mask layer is made of one of polycrystalline or amorphous graphene, boron nitride or transition metal chalcogenide, and the thickness of the third two-dimensional mask layer is 10 nm to 30 nm.
In the step 4) c), the growth temperature is 900-1250 ℃, and the stoichiometric ratio of the flow rates of the nitrogen source and the III source, namely V group/III group, is 300-1000; the single crystal nitride functional structure, namely the array element, consists of an n-type layer, a quantum structure and a p-type layer, and the height of the array element is 0.5-3 mu m.
In step 5) a), polymethylmethacrylate (PPMA) or Polydimethylsiloxane (PDMS) is spin-coated.
In step 5), the flexible protective layer is made of PMMA, transparent conductive film or other flexible organic materials.
In c) of step 5), incident infrared laser light, ultraviolet laser light, or visible laser light from the back surface of the non-single crystal substrate; the wavelength of the infrared laser is more than 800 nm.
The invention has the advantages that:
the invention obtains the dislocation density lower than 1 multiplied by 10 by preparing the two-dimensional material mask layer 9 cm -2 And further obtaining a dislocation density of less than 1 x 10 8 cm -2 The single crystal nitride film can realize a super-high-quality single crystal nitride functional structure on a non-single crystal substrate with large lattice mismatch and large thermal expansion coefficient mismatch, can be used for preparing Micro-LED devices, can also be expanded to prepare radio frequency devices, power devices, light emitting devices, detection devices and the like, and has process universality; the laser is adopted to destroy the interface combination of the epitaxial structure and the non-single crystal substrate, so that the nondestructive separation of the epitaxial structure and the repeated utilization of the non-single crystal substrate can be realized, the energy is saved, the environment is protected, the process is simple, and the method is suitable for batch production.
Drawings
FIG. 1 is a cross-sectional view of a template layer obtained by a method for fabricating a non-single crystal substrate-based single crystal nitride Micro-LED array according to the present invention;
FIG. 2 is a cross-sectional view of a dislocation filtering layer obtained by the method for fabricating a non-single crystal substrate based single crystal nitride Micro-LED array according to the present invention;
FIG. 3 is a cross-sectional view of a single crystal nitride thin film obtained by the method for fabricating a non-single crystal substrate-based single crystal nitride Micro-LED array according to the present invention;
FIG. 4 is a cross-sectional view of a single crystal nitride Micro-LED array fabricated according to a method of fabricating a non-single crystal substrate based single crystal nitride Micro-LED array according to the present invention;
FIG. 5 is a cross-sectional view of a flexible single-crystal nitride Micro-LED array obtained by the method for manufacturing a single-crystal nitride Micro-LED array based on a non-single-crystal substrate 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 preparation method of the single crystal nitride Micro-LED array based on the non-single crystal substrate comprises the following steps:
1) Preparing a template layer:
a) Providing a non-single crystal substrate 1, wherein the forbidden bandwidth of the non-single crystal substrate is more than 5 eV, the lattice mismatch with a nitride semiconductor is more than 20%, the thermal expansion coefficient mismatch is more than 50%, the visible light transparency is more than 0.99, and the melting point of the quartz is higher than 1200 ℃; carrying out double-sided polishing on the non-single crystal substrate;
b) Forming a two-dimensional atomic crystal induction layer 2 on the upper surface of the non-single crystal substrate in a wet or dry transfer mode, wherein the two-dimensional atomic crystal induction layer is of a single crystal structure with nitrogen doped atoms, the nitrogen atom proportion is 1.2%, the thickness is 5nm, the doped atoms exposed on the surface of the two-dimensional atomic crystal induction layer provide surface unsaturated dangling bonds which serve as nucleation sites of nitrides and provide a required modified surface for the growth of the single crystal nitrides;
c) Depositing single crystal AlN on the two-dimensional atomic crystal inducing layer by metal organic chemical vapor deposition to form a first layer of single crystal nitride, forming a template layer 3 with a thickness of 800 nm and a dislocation density lower than 5 x 10 10 cm -2 And is higher than 1X 10 9 cm -2 As shown in fig. 1;
2) Preparing a dislocation filter layer:
a) Transferring the first two-dimensional material mask layer 4 to the upper surface of the template layer, wherein the first two-dimensional material mask layer is polycrystalline graphene and has the thickness of 15nm;
b) Spin-coating a photoresist on the upper surface of the first two-dimensional mask layer, exposing the photoresist through a mask with a set periodic shape, removing the photoresist denatured by exposure through a chemical corrosion method, and providing mask protection by the undenatured photoresist with the set periodic shape; the selective etching is to directly etch the first two-dimensional material mask layer with mask protection by adopting the technologies of plasma etching or reactive ion etching and the like, the area without mask protection is etched, the area with mask protection is not etched, the residual photoresist layer is removed by adopting a chemical cleaning mode, the set periodic shape is transferred from the photoresist layer to the first two-dimensional material mask layer, and the through hole is cylindrical; forming a first through hole array consisting of a plurality of through holes which are periodically arranged in a two-dimensional way on the first two-dimensional material mask layer, wherein the period of rows is equal to that of columns, the depth of each through hole is consistent with the thickness of the first two-dimensional material mask layer, the diameter of each through hole is 1/2 of the period of the first through hole array, and the period of the first through hole array is 5 mu m;
c) Depositing single crystal AlN on a first two-dimensional material mask layer by adopting a metallorganic chemical vapor deposition technology to form a second layer of single crystal nitride, wherein the growth temperature is 1050 ℃, the stoichiometric ratio of the flow of a nitrogen source to the flow of a group III source, namely V group/III group is 500, the forbidden bandwidth of the second layer of single crystal nitride is more than 5 eV, the surface of the first two-dimensional material mask layer, except for a first through hole array, is not provided with a surface unsaturated dangling bond so that the single crystal nitride can not grow, the area of a template layer, corresponding to the lower part of the first through hole array, is provided with the surface unsaturated dangling bond so that the single crystal nitride can grow, and the first dislocation filtration is realized, namely, the dislocation in the template layer, which is not corresponding to the first through hole array, can not enter the second layer of single crystal nitride on the upper layer;
d) The growth temperature is increased to 1150 ℃, the group V/group III ratio is increased to 2000, the thickness of the second layer of single crystal nitride is promoted to exceed the thickness of the first two-dimensional material mask layer, the second layer of single crystal nitride continues to grow longitudinally and simultaneously expands transversely until the first two-dimensional material mask layer is completely wrapped, the dislocation propagation direction of the second layer of single crystal nitride expanding from the area of the template layer corresponding to the first through hole array is changed due to the near stress-free state of the transverse expansion process, partial dislocation is annihilated, and the obtained dislocation density is lower than 1 x 10 9 cm -2 The dislocation filter layer 5 of (a), the dislocation filter layer 5 having a thickness of 1500 nm, as shown in fig. 2;
3) Preparing a single crystal nitride film:
a) Transferring a second two-dimensional material mask layer 6 to the upper surface of the dislocation filter layer, wherein the second two-dimensional material mask layer is made of polycrystalline graphene and has the thickness of 20 nm;
b) Forming a second through hole array consisting of a plurality of through holes which are periodically arranged in a two-dimensional manner on the second two-dimensional material mask layer by a mask protection and selective etching method, wherein the depth of each through hole is consistent with the thickness of the second two-dimensional material mask layer, the period and the shape of the second through hole array are consistent with those of the first through hole array of the first two-dimensional material mask, but the position of the second through hole array and the first through hole array horizontally deviate along the row direction, and the horizontal deviation is the diameter of the through hole;
c) Depositing single crystal AlN on the second two-dimensional material mask layer by adopting a metal organic chemical vapor deposition technology to form a third layer of single crystal nitride, wherein the growth temperature is 1050 ℃, the stoichiometric ratio of the flow of a nitrogen source to a group III source, namely V group/III group is 500, the forbidden bandwidth of the third layer of single crystal nitride is more than 5 eV, the surface of the second two-dimensional material mask layer outside the area of the second through hole array does not have a surface unsaturated dangling bond and can not grow the single crystal nitride, the area of the dislocation filter layer corresponding to the lower part of the second through hole array can grow the single crystal nitride, and the second dislocation filtration is realized, namely, the dislocation in the dislocation filter layer not corresponding to the second through hole array can not enter the upper layer of the third layer of single crystal nitride;
d) The growth temperature is increased to 1150 ℃, the group V/group III ratio is increased to 2000, the thickness of the third layer of single crystal nitride is promoted to exceed that of the second two-dimensional material mask layer, the third layer of single crystal nitride continues to grow longitudinally and expand transversely at the same time until the second two-dimensional material mask layer is completely wrapped, the dislocation propagation direction from the region of the dislocation filter layer corresponding to the second through hole array to the third layer of single crystal nitride is changed due to the near-stress-free state in the transverse expansion process, partial dislocation is annihilated, and the dislocation density is lower than 1 x 10 8 cm -2 The single crystal nitride thin film 7 of (2), the thickness of the single crystal nitride thin film 7 being 1500 nm, as shown in fig. 3;
4) Preparing a single crystal nitride Micro-LED array:
a) Transferring a third two-dimensional material mask layer 8 to the upper surface of the single crystal nitride film, wherein the third two-dimensional material mask layer is made of polycrystalline graphene and is 20 nm thick;
b) Forming a third through hole array consisting of a plurality of through holes periodically arranged in two dimensions on the third two-dimensional material mask layer by a mask protection and selective etching method, wherein the periods of rows and columns are equal, the depth of each through hole is consistent with the thickness of the third two-dimensional material mask layer, the diameter of each through hole is 3/5 of the period of the third through hole array, and the period of the third through hole array is consistent with the period of the first through hole array;
c) By adopting a metal organic chemical vapor deposition technology, the growth temperature is 1050 ℃, the stoichiometric ratio of the flow of a nitrogen source to the flow of a group III source, namely the group V/group III is 500, a nitride functional structure is deposited on a third two-dimensional material mask layer, the surface of the third two-dimensional material mask layer outside a third through hole array region does not have a surface unsaturated dangling bond and cannot grow the nitride functional structure, the region of a corresponding single crystal nitride film below the third through hole array region can grow the nitride functional structure, and the nitride functional structure is one of ultraviolet or visible light emitting diode structures; by controlling the growth temperature and the stoichiometric ratio of the flow of the nitrogen source and the III-group source in the deposition process, the transverse dimension of the nitride functional structure is equal to the transverse dimension of the circular through hole area, only longitudinal growth is carried out, a single crystal nitride Micro-LED array 9 which is the same as the third through hole array and is periodically distributed is formed, the nitride functional structure in each through hole is used as an array element of the single crystal nitride Micro-LED array, the height is 1 mu m, and the nitride functional structure is shown in FIG. 4;
5) Obtaining a flexible single crystal nitride Micro-LED array:
a) Filling gaps among the array elements by spin-coating polymethyl methacrylate (PMMA) 10, wherein the filling height is the same as the height of the array elements, and obtaining a flat sheet structure;
b) Attaching a transparent conductive film as a flexible protective layer 11 on the surface of the flat sheet structure;
c) Infrared laser with the wavelength larger than 800 nm is incident from the back of the non-single crystal substrate, and heats the two-dimensional atomic crystal induction layer between the non-single crystal substrate and the template layer in a lattice resonance absorption mode, so that the two-dimensional atomic crystal induction layer is melted, the structural separation of the non-single crystal substrate and the two-dimensional atomic crystal induction layer is realized, and the flexible single crystal nitride Micro-LED array and the reusable non-single crystal substrate are obtained, as shown in FIG. 5.
It is finally noted that the disclosed embodiments are intended to aid in the further understanding of the invention, but that 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 to the embodiments disclosed, but the scope of the invention is defined by the appended claims.
Claims (10)
1. A preparation method of a single crystal nitride Micro-LED array based on a non-single crystal substrate is characterized by comprising the following steps:
1) Preparing a template layer:
a) Providing a non-single crystal substrate, wherein the non-single crystal substrate is made of rigid non-metal materials; carrying out double-sided polishing on the non-single crystal substrate;
b) Forming a two-dimensional atomic crystal induction layer on the upper surface of the non-single crystal substrate in a wet or dry transfer mode, wherein the two-dimensional atomic crystal induction layer is of a single crystal structure with doping atoms, the doping atoms exposed on the surface of the two-dimensional atomic crystal induction layer provide surface unsaturated dangling bonds which serve as nucleation sites of single crystal nitride and provide a required modified surface for growth of the single crystal nitride;
c) Depositing a first layer of single crystal nitride on the two-dimensional atomic crystal inducing layer to form a template layer;
2) Preparing a dislocation filter layer:
a) Transferring the first two-dimensional material mask layer to the upper surface of the template layer;
b) Forming a first through hole array consisting of a plurality of through holes periodically arranged in two dimensions on the first two-dimensional material mask layer by a mask protection and selective etching method, wherein the periods of rows and columns are equal, the depth of each through hole is consistent with the thickness of the first two-dimensional material mask layer, and the diameter of each through hole is less than 2/3 of the period of the first through hole array;
c) Depositing a second layer of single crystal nitride on the first two-dimensional material mask layer, wherein the surface of the first two-dimensional material mask layer, except the first through hole array, is not provided with a surface unsaturated dangling bond and can not grow the single crystal nitride, and the area of the template layer, corresponding to the lower part of the first through hole array, is provided with a surface unsaturated dangling bond and can grow the single crystal nitride, so that first dislocation filtering is realized, namely dislocations in the template layer, which are not corresponding to the first through hole array, can not enter the second layer of single crystal nitride on the upper layer;
d) Increasing the growth temperature and the stoichiometric ratio of the flow of the nitrogen source and the III-group source, and after the thickness of the second layer of single crystal nitride exceeds the thickness of the first two-dimensional material mask layer, continuing to grow longitudinally and simultaneously expand transversely until the first two-dimensional material mask layer is completely wrapped, wherein the transverse expansion process is in a near-stress-free state, so that when the dislocations are expanded from the region of the template layer corresponding to the first through hole array to the second layer of single crystal nitride, the propagation direction of the dislocations is changed, part of the dislocations are annihilated, and a dislocation filter layer with the dislocation density lower than that of the template layer is obtained;
3) Preparing a single crystal nitride film:
a) Transferring the second two-dimensional material mask layer to the upper surface of the dislocation filter layer;
b) Forming a second through hole array consisting of a plurality of through holes which are periodically arranged in a two-dimensional manner on the second two-dimensional material mask layer by a mask protection and selective etching method, wherein the depth of each through hole is consistent with the thickness of the second two-dimensional material mask layer, the period and the shape of the second through hole array are consistent with those of the first through hole array, but the position of the second through hole array and the first through hole array have horizontal offset, and the horizontal offset ensures that the outer edge of each through hole of the second through hole array is tangent to the outer edge of each through hole of the first through hole array;
c) Depositing a third layer of single crystal nitride on the second two-dimensional material mask layer, wherein the surface of the second two-dimensional material mask layer, except the second through hole array region, does not have a surface unsaturated dangling bond and cannot grow the single crystal nitride, and the single crystal nitride can grow in the corresponding dislocation filter layer region below the second through hole array, so that second dislocation filtration is realized, namely dislocation in the dislocation filter layer not corresponding to the second through hole array cannot enter the upper layer of the third layer of single crystal nitride;
d) Increasing the growth temperature and the stoichiometric ratio of the flow of the nitrogen source and the group III source, and after the thickness of the third layer of single crystal nitride exceeds the thickness of the second two-dimensional material mask layer, continuing to grow longitudinally and simultaneously expand transversely until the second two-dimensional material mask layer is completely wrapped, wherein the transverse expansion process is in a near-stress-free state, so that when dislocations are expanded from the region of the dislocation filter layer corresponding to the second through hole array to the third layer of single crystal nitride, the propagation direction of the dislocations is changed, and partial dislocations are annihilated to obtain the single crystal nitride film with the dislocation density lower than that of the dislocation filter layer;
4) Preparing a single crystal nitride Micro-LED array:
a) Transferring the third two-dimensional material mask layer to the upper surface of the single crystal nitride film;
b) Forming a third through hole array consisting of a plurality of through holes which are periodically arranged in a two-dimensional manner on the third two-dimensional material mask layer by a mask protection and selective etching method, wherein the periods of rows and columns are equal, the depth of each through hole is consistent with the thickness of the third two-dimensional material mask layer, the diameter of each through hole is 1/2 to 3/4 of the period of the third through hole array, and the period of the third through hole array is consistent with the period of the first through hole array;
c) Depositing a single crystal nitride functional structure on a third two-dimensional material mask layer, wherein the surface of the third two-dimensional material mask layer, except for a third through hole array region, is not provided with a surface unsaturated dangling bond so that the single crystal nitride functional structure cannot grow, the region of a single crystal nitride film corresponding to the lower part of the third through hole array can grow the nitride functional structure in a single crystal manner, and the single crystal nitride functional structure is one of ultraviolet or visible light emitting diode structures; by controlling the growth temperature and the stoichiometric ratio of the nitrogen source to the III-group source flow in the deposition process, the transverse dimension of the single crystal nitride functional structure is equal to the transverse dimension of the circular through hole area, only longitudinal growth is carried out, the height of the single crystal nitride functional structure is greater than the thickness of the third two-dimensional material mask layer, a single crystal nitride Micro-LED array which is the same as the third through hole array and is periodically distributed is formed, and the single crystal nitride functional structure in each through hole is used as an array element of the single crystal nitride Micro-LED array;
5) Obtaining a flexible single crystal nitride Micro-LED array:
a) Filling gaps among the array elements in a spin coating mode, wherein the filling height is the same as the height of the array elements, and obtaining a flat sheet structure;
b) Attaching a flexible protective layer on the surface of the flat sheet structure;
c) Laser is incident from the back of the non-single crystal substrate, the laser heats the two-dimensional atomic crystal induction layer between the non-single crystal substrate and the template layer in a lattice resonance absorption mode, the two-dimensional atomic crystal induction layer is melted, the structural separation of the non-single crystal substrate and the two-dimensional atomic crystal induction layer is realized, and the flexible single crystal nitride Micro-LED array and the reusable non-single crystal substrate are obtained.
2. The method of manufacturing according to claim 1, wherein in the step 1) a), the non-single crystal substrate has a forbidden band width of more than 5 eV, a lattice mismatch with the nitride semiconductor of more than 20%, a coefficient of thermal expansion mismatch of more than 50%, a visible light transparency of more than 0.99, and a melting point of more than 1200 ℃.
3. The preparation method according to claim 1, wherein in step 1) b), the two-dimensional atomic crystal inducing layer is made of graphene having a single crystal structure with doping atoms, the doping atoms are nitrogen atoms or oxygen atoms, the proportion of the nitrogen atoms or the oxygen atoms is more than 1%, and the thickness is 1 to 10 nm.
4. The preparation method of claim 1, wherein in step 1) c), a first layer of single crystal nitride is grown by metal organic chemical vapor deposition, molecular beam epitaxy, hydride vapor phase epitaxy, magnetron sputtering or pulsed laser deposition, the growth temperature is 900 ℃ to 1250 ℃, the stoichiometric ratio of the flow rates of the nitrogen source and the group III source, namely, the group V/group III is 300 to 1000, the group III source is a metal or metal organic source, the nitrogen source is ammonia or nitrogen, the first layer of single crystal nitride is an AlN or AlGaN and AlN composite structure, the forbidden bandwidth is more than 5 eV, the thickness of the template layer is 500 nm to 1000 nm, and the dislocation density of the template layer is less than 5 x 10 10 cm -2 And is higher than 1 x 10 9 cm -2 。
5. The method of claim 1, wherein in step 2) a), the first two-dimensional mask layer is made of graphene, boron nitride or a transition metal chalcogenide with a polycrystalline or amorphous structure, and has a thickness of 10 nm to 30 nm.
6. The preparation method according to claim 1, wherein in step 2) c), a second layer of single crystal nitride is grown by using a metal organic chemical vapor deposition technology, molecular beam epitaxy, hydride vapor phase epitaxy, magnetron sputtering or a pulsed laser deposition technology, the growth temperature is 900 ℃ to 1250 ℃, the stoichiometric ratio of the flow rates of the nitrogen source and the group III source, namely, group V/group III is 300 to 1000, the second layer of single crystal nitride is AlN or a composite structure of AlGaN and AlN, and the forbidden bandwidth is more than 5 eV.
7. The method of claim 1, wherein in step 2) d), the growth temperature is increased to 1000 ℃ to 1350 ℃ and the group V/group III ratio is increased to 1500 to 5000; the thickness of the dislocation filter layer is 500 nm to 2000 nm, and the dislocation density is less than 1 multiplied by 10 9 cm -2 。
8. The method of claim 1, wherein in step 4) c) the growth temperature is 900 ℃ to 1250 ℃, the stoichiometric ratio of the flow rates of the nitrogen source and the group III source, i.e. group V/group III, is 300 to 1000; the array element consists of an n-type layer, a quantum structure and a p-type layer, and the height of the array element is 0.5-3 mu m.
9. The method of claim 1, wherein in step 5) a) the polymethylmethacrylate or polydimethylsiloxane is spin-coated.
10. The production method according to claim 1, wherein in c) of step 5), an infrared laser, an ultraviolet laser, or a visible laser is incident from the back surface of the non-single crystal substrate.
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| EP0996173A2 (en) * | 1998-10-23 | 2000-04-26 | Xerox Corporation | Light-emitting devices including polycrystalline GaN layers and method of forming devices |
| CN108878265A (en) * | 2018-07-03 | 2018-11-23 | 北京大学 | A method of growing mono-crystal gallium nitride film on Si (100) substrate |
| CN109585270A (en) * | 2018-11-15 | 2019-04-05 | 中国科学院半导体研究所 | Method and structure based on amorphous substrate growing nitride |
| CN111697115A (en) * | 2019-03-15 | 2020-09-22 | 中国科学院半导体研究所 | Nitride thin film structure based on amorphous substrate and preparation method thereof |
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| EP0996173A2 (en) * | 1998-10-23 | 2000-04-26 | Xerox Corporation | Light-emitting devices including polycrystalline GaN layers and method of forming devices |
| CN108878265A (en) * | 2018-07-03 | 2018-11-23 | 北京大学 | A method of growing mono-crystal gallium nitride film on Si (100) substrate |
| CN109585270A (en) * | 2018-11-15 | 2019-04-05 | 中国科学院半导体研究所 | Method and structure based on amorphous substrate growing nitride |
| CN111697115A (en) * | 2019-03-15 | 2020-09-22 | 中国科学院半导体研究所 | Nitride thin film structure based on amorphous substrate and preparation method thereof |
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