WO2024036680A1 - Method for preparing single crystal nitride micro-led array based on non-single crystal substrate - Google Patents

Method for preparing single crystal nitride micro-led array based on non-single crystal substrate Download PDF

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WO2024036680A1
WO2024036680A1 PCT/CN2022/118960 CN2022118960W WO2024036680A1 WO 2024036680 A1 WO2024036680 A1 WO 2024036680A1 CN 2022118960 W CN2022118960 W CN 2022118960W WO 2024036680 A1 WO2024036680 A1 WO 2024036680A1
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single crystal
layer
nitride
dimensional material
array
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Chinese (zh)
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王新强
刘放
陈兆营
郭昱成
王涛
盛博文
沈波
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北京大学
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/005—Processes
    • H01L33/0093—Wafer bonding; Removal of the growth substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/15—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components with at least one potential-jump barrier or surface barrier specially adapted for light emission
    • H01L27/153—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components with at least one potential-jump barrier or surface barrier specially adapted for light emission in a repetitive configuration, e.g. LED bars
    • H01L27/156—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components with at least one potential-jump barrier or surface barrier specially adapted for light emission in a repetitive configuration, e.g. LED bars two-dimensional arrays
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/005—Processes
    • H01L33/0062—Processes for devices with an active region comprising only III-V compounds
    • H01L33/0066—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound
    • H01L33/007—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound comprising nitride compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/005—Processes
    • H01L33/0095—Post-treatment of devices, e.g. annealing, recrystallisation or short-circuit elimination

Definitions

  • the present invention relates to the preparation technology of semiconductor light-emitting devices, and in particular to a preparation method of a single crystal nitride Micro-LED array based on a non-single crystal substrate.
  • nitride semiconductors are usually heteroepitaxially grown on single crystal substrates with matching lattice symmetry.
  • high-transmittance single-crystal sapphire substrates are usually selected to prepare nitride light-emitting devices
  • single-crystal silicon or single-crystal silicon carbide substrates are usually selected to prepare electronic devices.
  • the above-mentioned single crystal substrates cannot fully meet the requirements of light emitting efficiency, transparency, heat dissipation and other aspects of light-emitting devices.
  • Single crystal nitride films can be realized by using single crystal two-dimensional material-assisted epitaxy on non-single crystal substrates such as quartz.
  • the epitaxial film will The interface interaction of 2D materials will be stronger than the interface interaction between 2D materials and non-single crystal substrates, causing the epitaxial film to be broken due to partial interface separation during growth or cooling;
  • the thickness of the epitaxial film is less than 1 micron, The dislocation density of epitaxial films is usually higher than 3 ⁇ 10 10 cm -2 , and the half-width of the rocking curve of the corresponding X-ray diffraction (0002) crystal plane is greater than 1 degree, resulting in low electro-optical conversion efficiency of light-emitting devices prepared on it, and electronic devices
  • the current leakage is serious and cannot meet the application requirements in fields such as flexible LED, ultraviolet LED, and radio frequency power devices, especially the research and development requirements in the field of micro-light-
  • the present invention proposes a method for preparing a single crystal nitride Micro-LED array based on a non-single crystal substrate.
  • the preparation method of the single crystal nitride Micro-LED array based on a non-single crystal substrate of the present invention includes the following steps:
  • a) Provide a non-single crystal substrate, which is made of rigid non-metallic materials; perform double-sided polishing of the non-single crystal substrate;
  • the two-dimensional atomic crystal induction layer has a single crystal structure with doped atoms and is exposed to the two-dimensional atomic crystal.
  • the doped atoms on the surface of the induction layer provide surface unsaturated dangling bonds, which serve as nucleation sites for single crystal nitride and provide the required modified surface for single crystal nitride growth;
  • a first through hole array composed of a plurality of periodically two-dimensionally arranged through holes is formed on the first two-dimensional material mask layer, with equal periods of rows and columns. , the depth of each through hole is consistent with the thickness of the first two-dimensional material mask layer, and the diameter of the through hole is less than 2/3 of the first through hole array period;
  • c) Deposit a second layer of single crystal nitride on the first two-dimensional material mask layer.
  • the surface of the first two-dimensional material mask layer other than the first through hole array does not have surface unsaturated dangling bonds and cannot grow single crystals.
  • Nitride the area of the corresponding template layer below the first via array, has surface unsaturated dangling bonds and can grow single crystal nitride to achieve the first dislocation filtering, that is, in the template layer not corresponding to the first via array Dislocations cannot enter the upper second layer of single crystal nitride;
  • a second through hole array composed of a plurality of periodically two-dimensionally arranged through holes on the second two-dimensional material mask layer.
  • the depth of each through hole The thickness of the second two-dimensional material mask layer is consistent, and the period and shape of the second via hole array are consistent with the first via hole array, but the position of the second via hole array is horizontally offset from the first via hole array, and the horizontal offset is Move so that the outer edge of the through holes of the second through hole array is tangent to the outer edge of the through holes of the first through hole array;
  • c) Deposit a third layer of single crystal nitride on the second two-dimensional material mask layer.
  • the surface on the second two-dimensional material mask layer other than the second through hole array area does not have surface unsaturated dangling bonds and cannot grow single crystal nitride.
  • Crystal nitride, the area of the corresponding dislocation filter layer below the second via hole array can grow single crystal nitride to achieve the second dislocation filtering, that is, dislocations in the dislocation filter layer corresponding to the non-second via hole array It cannot enter the third layer of single crystal nitride in the upper layer;
  • a third through hole array composed of a plurality of periodically two-dimensionally arranged through holes is formed on the third two-dimensional material mask layer, with equal periods of rows and columns.
  • the depth of each through hole is consistent with the thickness of the third two-dimensional material mask layer
  • the diameter of the through hole is 1/2 to 3/4 of the third through hole array period
  • the third through hole array period is the same as the first through hole array period. The hole array period is consistent;
  • c) Deposit a single crystal nitride functional structure on the third two-dimensional material mask layer.
  • the surface on the third two-dimensional material mask layer other than the third via hole array area does not have surface unsaturated dangling bonds and cannot grow single crystals.
  • Nitride functional structure, the corresponding area of the single crystal nitride film under the third through hole array can grow the nitride functional structure in a single crystal, and the single crystal nitride functional structure is one of the ultraviolet or visible light emitting diode structures; by controlling the deposition
  • the growth temperature and the stoichiometric ratio of the nitrogen source and Group III source flow rates during the process are such that the lateral size of the single crystal nitride functional structure is equal to the lateral size of the circular via area, and only longitudinal growth is performed, the single crystal nitride functional structure
  • the height is greater than the thickness of the third two-dimensional material mask layer, forming a single crystal nitride Micro-LED array with the same periodic
  • c) Laser is incident from the back of the non-single crystal substrate, and the laser heats the two-dimensional atomic crystal induction layer between the non-single crystal substrate and the template layer through lattice resonance absorption, and melts the two-dimensional atomic crystal induction layer to achieve non-single crystal substrate.
  • the single crystal substrate is separated from the structure above the two-dimensional atomic crystal induction layer to obtain a flexible single crystal nitride Micro-LED array and a reusable non-single crystal substrate.
  • the bandgap width of the non-single crystal substrate is greater than 5eV
  • the lattice mismatch with the nitride semiconductor is greater than 20%
  • the thermal expansion coefficient mismatch is greater than 50%
  • the visible light transparency is greater than 0.99
  • the melting point is high
  • one of quartz, mica, corundum and diamond is used.
  • the two-dimensional atomic crystal induction layer adopts graphene with a single crystal structure having doped atoms.
  • the doped atoms are nitrogen atoms or oxygen atoms, and the proportion of nitrogen atoms or oxygen atoms is greater than 1%.
  • the thickness is 1 to 10nm, and the doped atoms provide surface unsaturated dangling bonds as nucleation sites for nitrides, without the need for additional modification of the two-dimensional atomic crystal induction layer.
  • the first layer of single crystal nitride is grown using metal-organic chemical vapor deposition technology, molecular beam epitaxy, hydride vapor phase epitaxy, magnetron sputtering or pulsed laser deposition technology, and the growth temperature is 900°C ⁇ 1250°C, the stoichiometric ratio of the flow rates of nitrogen source and III source, that is, V/III, is 300 to 1000.
  • the III source is a metal or metal organic source
  • the nitrogen source is ammonia or nitrogen
  • the compound is AlN or a composite structure of AlGaN and AlN, the band gap is greater than 5eV, the thickness of the template layer is 500nm ⁇ 1000nm, and the dislocation density of the template layer is lower than 5 ⁇ 10 10 cm -2 and higher than 1 ⁇ 10 9 cm -2 .
  • the first two-dimensional material mask layer is made of polycrystalline or amorphous graphene, boron nitride or transition metal chalcogenide, with a thickness of 10 nm to 30 nm.
  • step 2) the specific process of mask protection and selective etching is as follows: spin-coat photoresist on the upper surface of the first two-dimensional material mask layer, and pass through the mask with a set periodic shape.
  • the photoresist is processed by template exposure, and the photoresist denatured by exposure is removed through chemical etching, and the undenatured photoresist with a set periodic shape provides mask protection; selective etching uses plasma etching.
  • the first two-dimensional material mask layer with mask protection is directly etched by techniques such as etching or reactive ion etching. The areas without mask protection are etched, and the areas with mask protection are not etched and are removed by chemical cleaning.
  • the remaining photoresist layer will have a set periodic shape transferred from the photoresist layer to the first two-dimensional material mask layer.
  • the shape of the through hole is a cylinder; the period of the first through hole array is 0.1 ⁇ m to 50 ⁇ m.
  • the second layer of single crystal nitride is grown using metal-organic chemical vapor deposition technology, molecular beam epitaxy, hydride vapor phase epitaxy, magnetron sputtering or pulsed laser deposition technology, and the growth temperature is 900°C ⁇ At 1250°C, the stoichiometric ratio of the flow rate of the nitrogen source and the III source, that is, V group/III group, is 300 to 1000.
  • the second layer of single crystal nitride is AlN or a composite structure of AlGaN and AlN, and the bandgap width is greater than 5eV.
  • step 2) the growth temperature is increased to 1000°C to 1350°C, and the group V/group III ratio is increased to 1500 to 5000.
  • the thickness of the dislocation filtering layer is 500nm ⁇ 2000nm, and the dislocation density is lower than 1 ⁇ 10 9 cm -2 .
  • the second two-dimensional material mask layer is composed of polycrystalline or amorphous graphene, boron nitride, transition metal chalcogenide, etc., and has a thickness of 10 nm to 30 nm.
  • the third layer of single crystal nitride is grown using metal-organic chemical vapor deposition technology, molecular beam epitaxy, hydride vapor phase epitaxy, magnetron sputtering or pulsed laser deposition technology, and the growth temperature is 900°C ⁇ At 1250°C, the stoichiometric ratio of the flow rate of the nitrogen source and the III source, that is, V group/III group, is 300 to 1000.
  • the third layer of single crystal nitride is AlN or a composite structure of AlGaN and AlN, and the bandgap width is greater than 5eV.
  • the growth temperature is increased to 1000°C to 1350°C, and the group V/group III ratio is increased to 1500 to 5000.
  • the thickness of the single crystal nitride film is 500nm to 2000nm, and the dislocation density is less than 1 ⁇ 10 8 cm -2 .
  • the third two-dimensional material mask layer is composed of polycrystalline or amorphous graphene, boron nitride, transition metal chalcogenide, etc., and has a thickness of 10 nm to 30 nm.
  • the growth temperature is 900°C to 1250°C, and the stoichiometric ratio of the flow rate of the nitrogen source and the group III source, that is, group V/group III, is 300 to 1000;
  • the single crystal nitride functional structure is the array element It is composed of n-type layer, quantum structure and p-type layer, with a height of 0.5 ⁇ m ⁇ 3 ⁇ m.
  • step 5) a), polymethylmethacrylate (PPMA) or polydimethylsiloxane (PDMS) is spin-coated.
  • PPMA polymethylmethacrylate
  • PDMS polydimethylsiloxane
  • the flexible protective layer is composed of PMMA, transparent conductive film or other flexible organic materials.
  • infrared laser, ultraviolet laser or visible laser is incident from the back side of the non-single crystal substrate; the wavelength of the infrared laser is greater than 800 nm.
  • the present invention obtains a dislocation filter layer with a dislocation density lower than 1 ⁇ 10 9 cm -2 by preparing a two-dimensional material mask layer, and further obtains a single crystal nitride with a dislocation density lower than 1 ⁇ 10 8 cm -2 Thin films can achieve ultra-high quality single crystal nitride functional structures on non-single crystal substrates with large lattice mismatch and large thermal expansion coefficient mismatch.
  • Radio frequency devices, power devices, light-emitting devices and detection devices, etc. have process universality; using laser to destroy the interface between the epitaxial structure and the non-single crystal substrate can achieve lossless separation of the epitaxial structure and multiple times of the non-single crystal substrate Reusable, energy-saving and environmentally friendly, simple process and suitable for mass production.
  • Figure 1 is a cross-sectional view of the template layer obtained by the preparation method of a single crystal nitride Micro-LED array based on a non-single crystal substrate according to the present invention
  • Figure 2 is a cross-sectional view of a dislocation filter layer obtained according to the preparation method of a single crystal nitride Micro-LED array based on a non-single crystal substrate of the present invention
  • Figure 3 is a cross-sectional view of a single crystal nitride film obtained according to the preparation method of a single crystal nitride Micro-LED array based on a non-single crystal substrate of the present invention
  • Figure 4 is a cross-sectional view of a single crystal nitride Micro-LED array prepared according to the method for preparing a single crystal nitride Micro-LED array based on a non-single crystal substrate of the present invention
  • Figure 5 is a cross-sectional view of a flexible single crystal nitride Micro-LED array obtained by the method for preparing a single crystal nitride Micro-LED array based on a non-single crystal substrate of the present invention.
  • a) Provide a non-single crystal substrate 1.
  • the band gap of the non-single crystal substrate is greater than 5eV
  • the lattice mismatch with the nitride semiconductor is greater than 20%
  • the thermal expansion coefficient mismatch is greater than 50%
  • the visible light transparency is greater than 0.99
  • the melting point is greater than Quartz at 1200°C; double-sided polishing of non-single crystal substrates;
  • the two-dimensional atomic crystal induction layer is a single crystal structure with nitrogen doped atoms, and nitrogen atoms account for It is 1.2% and has a thickness of 5nm.
  • 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 for nitride and provide the required modified surface for single crystal nitride growth. ;
  • the first two-dimensional material mask layer is polycrystalline graphene with a thickness of 15 nm;
  • the shape of the through hole is a cylinder; forming a first through hole array composed of a plurality of periodically two-dimensionally arranged through holes on the first two-dimensional material mask layer, rows Equal to the period of the column, the depth of each through hole is consistent with the thickness of the first two-dimensional material mask layer, the diameter of the 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 ⁇ m;
  • c) Use metal-organic chemical vapor deposition technology to deposit single crystal AlN on the first two-dimensional material mask layer to form a second layer of single crystal nitride.
  • the growth temperature is 1050°C
  • the stoichiometric ratio of the flow rate of the nitrogen source and the III source is That is, Group V/III is 500
  • the bandgap width of the second layer of single crystal nitride is greater than 5eV
  • the surface of the first two-dimensional material mask layer other than the first through hole array does not have surface unsaturated dangling bonds and cannot grow.
  • Single crystal nitride the area of the corresponding template layer below the first via array, has surface unsaturated dangling bonds that can grow single crystal nitride to achieve the first dislocation filtering, that is, the template layer corresponding to the non-first via array
  • the dislocations in cannot enter the upper second layer of single crystal nitride;
  • the growth temperature increases to 1150°C and the Group V/III ratio increases to 2000, causing the thickness of the second layer of single crystal nitride to exceed the thickness of the first two-dimensional material mask layer and continue to grow vertically while expanding laterally.
  • the nearly stress-free state of the lateral expansion process causes the dislocation propagation direction to change from the area of the template layer corresponding to the first via array to the second layer of single crystal nitride. , causing partial annihilation of dislocations to obtain a dislocation filter layer 5 with a dislocation density lower than 1 ⁇ 10 9 cm -2 .
  • the thickness of the dislocation filter layer 5 is 1500nm, as shown in Figure 2;
  • the second two-dimensional material mask layer 6 is made of polycrystalline graphene and has a thickness of 20nm;
  • a second through hole array composed of a plurality of periodically two-dimensionally arranged through holes on the second two-dimensional material mask layer.
  • the depth of each through hole The thickness of the second two-dimensional material mask layer is consistent, and the period and shape of the second through-hole array are consistent with the first through-hole array of the first two-dimensional material mask, but the position of the second through-hole array is consistent with the first through-hole array.
  • the array is offset horizontally along the row direction by the diameter of the through hole;
  • c) Use metal-organic chemical vapor deposition technology to deposit single crystal AlN on the second two-dimensional material mask layer to form the third layer of single crystal nitride.
  • the growth temperature is 1050°C
  • the stoichiometric ratio of the flow rate of the nitrogen source and the III source is That is, Group V/III is 500
  • the bandgap width of the third layer of single crystal nitride is greater than 5eV
  • the surface of the second two-dimensional material mask layer outside the second through hole array area does not have surface unsaturated dangling bonds and cannot Single crystal nitride is grown, and the area of the corresponding dislocation filter layer below the second via hole array can grow single crystal nitride to achieve the second dislocation filtering, that is, the area in the dislocation filter layer corresponding to the second via hole array is not Dislocations cannot enter the upper third layer of single crystal nitride;
  • the growth temperature increases to 1150°C and the Group V/III ratio increases to 2000, causing the thickness of the third layer of single crystal nitride to exceed the thickness of the second two-dimensional material mask layer and continue to grow vertically while expanding laterally.
  • the nearly stress-free state of the lateral expansion process causes the area of the dislocation filter layer corresponding to the second via hole array to expand to the dislocation propagation direction of the third layer of single crystal nitride. Changes occur, causing some dislocations to be annihilated, and a single crystal nitride film 7 with a dislocation density lower than 1 ⁇ 10 8 cm -2 is obtained.
  • the thickness of the single crystal nitride film 7 is 1500nm, as shown in Figure 3;
  • the third two-dimensional material mask layer 8 uses polycrystalline graphene with a thickness of 20nm;
  • a third through hole array composed of a plurality of periodically two-dimensionally arranged through holes is formed on the third two-dimensional material mask layer, with equal periods of rows and columns. , the depth of each through hole is consistent with the thickness of the third two-dimensional material mask layer, the diameter of the through hole is 3/5 of the third through hole array period, and the third through hole array period is consistent with the first through hole array period;
  • the growth temperature is 1050°C
  • the stoichiometric ratio of the flow rate of the nitrogen source and the group III source, that is, group V/group III is 500
  • the nitride is deposited on the third two-dimensional material mask layer Functional structure.
  • the surface of the third two-dimensional material mask layer outside the third via hole array area does not have surface unsaturated dangling bonds and cannot grow nitride functional structures.
  • the corresponding single crystal nitride film below the third via hole array has The area can grow a nitride functional structure, which is one of the ultraviolet or visible light emitting diode structures; by controlling the growth temperature during the deposition process and the stoichiometric ratio of the flow rate of the nitrogen source and the III source, the nitride functional structure can be grown.
  • the lateral size of the structure is equal to the lateral size of the circular through hole area, and only longitudinal growth is performed to form a single crystal nitride Micro-LED array 9 with the same periodic distribution as the third through hole array, and the nitride function in each through hole is
  • the structure is an array element of a single crystal nitride Micro-LED array with a height of 1 ⁇ m, as shown in Figure 4;
  • Infrared laser is incident from the back of the non-single crystal substrate, with a wavelength greater than 800nm.
  • the infrared laser heats the two-dimensional atomic crystal induction layer between the non-single crystal substrate and the template layer through lattice resonance absorption, and melts the two-dimensional atoms.
  • the crystal induction layer realizes the structural separation above the non-single crystal substrate and the two-dimensional atomic crystal induction layer, and obtains a flexible single crystal nitride Micro-LED array and a reusable non-single crystal substrate, as shown in Figure 5.

Abstract

A method for preparing a single crystal nitride Micro-LED array based on a non-single crystal substrate. A two-dimensional material mask layer is prepared to obtain a dislocation filter layer having a dislocation density less than 1×109cm-2, and to further obtain a single crystal nitride thin film having a dislocation density less than 1×108cm-2, so that an ultra-high quality single crystal nitride functional structure can be implemented on a non-single crystal substrate having large lattice mismatch and large coefficient of thermal expansion mismatch. In addition to being used for preparing a Micro-LED device, the method can further be used for preparing a radio frequency device, a power device, a light emitting device, a detection device, and the like, and has process universality. The interface bonding between an epitaxial structure and the non-single crystal substrate is destroyed by using a laser, so that nondestructive separation of the epitaxial structure and repeated utilization of the non-single crystal substrate can be realized, and the method is energy-saving, environment-friendly, and simple, and is suitable for batch production.

Description

一种基于非单晶衬底的单晶氮化物Micro-LED阵列的制备方法A preparation method for single crystal nitride Micro-LED array based on non-single crystal substrate 技术领域Technical field
本发明涉及半导体发光器件的制备技术，具体涉及一种基于非单晶衬底的单晶氮化物Micro-LED阵列的制备方法。The present invention relates to the preparation technology of semiconductor light-emitting devices, and in particular to a preparation method of a single crystal nitride Micro-LED array based on a non-single crystal substrate.
背景技术Background technique
由于同质衬底匮乏，氮化物半导体通常异质外延于晶格对称性匹配的单晶衬底上。例如，制备氮化物发光器件通常选择高透光度的单晶蓝宝石衬底，制备电子器件通常选择单晶硅或单晶碳化硅衬底。但是，上述单晶衬底尚不能充分满足发光器件的出光效率、透明度、散热能力等方面的要求，亟需探索非单晶衬底上的单晶氮化物制备技术，提高器件热管理能力与综合性能、降低成本并扩展器件应用领域。Due to the lack of homogeneous substrates, nitride semiconductors are usually heteroepitaxially grown on single crystal substrates with matching lattice symmetry. For example, high-transmittance single-crystal sapphire substrates are usually selected to prepare nitride light-emitting devices, and single-crystal silicon or single-crystal silicon carbide substrates are usually selected to prepare electronic devices. However, the above-mentioned single crystal substrates cannot fully meet the requirements of light emitting efficiency, transparency, heat dissipation and other aspects of light-emitting devices. There is an urgent need to explore single crystal nitride preparation technology on non-single crystal substrates to improve device thermal management capabilities and comprehensive performance, reduce costs and expand device application areas.
在石英等非单晶衬底上采用单晶二维材料辅助外延的方法可以实现单晶氮化物薄膜，但是存在以下几方面的问题：(1)外延薄膜厚度超过1微米时，外延薄膜与二维材料的界面相互作用将强于二维材料与非单晶衬底的界面相互作用，导致外延薄膜在生长或降温时因部分界面分离而破碎；(2)当外延薄膜厚度小于1微米时，外延薄膜的位错密度通常高于3×10 10cm -2，对应的X射线衍射(0002)晶面的摇摆曲线半宽大于1度，导致其上制备的发光器件电光转换效率低、电子器件漏电严重，不能满足柔性LED、紫外LED、射频功率器件等领域的应用要求，特别是不能满足材料质量要求极高的微型发光二极管(Micro-LED)领域的研发要求。 Single crystal nitride films can be realized by using single crystal two-dimensional material-assisted epitaxy on non-single crystal substrates such as quartz. However, there are several problems: (1) When the thickness of the epitaxial film exceeds 1 micron, the epitaxial film will The interface interaction of 2D materials will be stronger than the interface interaction between 2D materials and non-single crystal substrates, causing the epitaxial film to be broken due to partial interface separation during growth or cooling; (2) When the thickness of the epitaxial film is less than 1 micron, The dislocation density of epitaxial films is usually higher than 3×10 10 cm -2 , and the half-width of the rocking curve of the corresponding X-ray diffraction (0002) crystal plane is greater than 1 degree, resulting in low electro-optical conversion efficiency of light-emitting devices prepared on it, and electronic devices The current leakage is serious and cannot meet the application requirements in fields such as flexible LED, ultraviolet LED, and radio frequency power devices, especially the research and development requirements in the field of micro-light-emitting diodes (Micro-LED) where material quality requirements are extremely high.
发明内容Contents of the invention
为了克服以上现有技术的不足，本发明提出了一种基于非单晶衬底的单晶氮化物Micro-LED阵列的制备方法。In order to overcome the above shortcomings of the prior art, the present invention proposes a method for preparing a single crystal nitride Micro-LED array based on a non-single crystal substrate.
本发明的基于非单晶衬底的单晶氮化物Micro-LED阵列的制备方法，包括以下步骤：The preparation method of the single crystal nitride Micro-LED array based on a non-single crystal substrate of the present invention includes the following steps:
1)制备模板层：1) Prepare template layer:
a)提供非单晶衬底，非单晶衬底采用刚性非金属材料；对非单晶衬底进行双面抛光；a) Provide a non-single crystal substrate, which is made of rigid non-metallic materials; perform double-sided polishing of the non-single crystal substrate;
b)通过湿法或干法转移的方式在非单晶衬底的上表面形成二维原子晶体诱导层，二维原子晶体诱导层为具有掺杂原子的单晶结构，暴露在二维原子晶体诱导层表面的掺杂原子提供表面不饱和悬挂键，作为单晶氮化物的成核位点，为单晶氮化物生长提供所需的改性表面；b) Form a two-dimensional atomic crystal induction layer on the upper surface of the non-single crystal substrate by wet or dry transfer. The two-dimensional atomic crystal induction layer has a single crystal structure with doped atoms and is exposed to the two-dimensional atomic crystal. The doped atoms on the surface of the induction layer provide surface unsaturated dangling bonds, which serve as nucleation sites for single crystal nitride and provide the required modified surface for single crystal nitride growth;
c)在二维原子晶体诱导层上沉积第一层单晶氮化物，形成模板层；c) Deposit the first layer of single crystal nitride on the two-dimensional atomic crystal induction layer to form a template layer;
2)制备位错过滤层：2) Prepare the dislocation filter layer:
a)将第一二维材料掩膜层转移至模板层的上表面；a) Transfer the first two-dimensional material mask layer to the upper surface of the template layer;
b)通过掩膜保护与选择性刻蚀的方法，在第一二维材料掩膜层上形成由多个周期性二维排列的通孔构成的第一通孔阵列，行与列的周期相等，每一个通孔的深度与第一二维材料掩膜层厚度一致，通孔的直径小于第一通孔阵列周期的2/3；b) Through mask protection and selective etching, a first through hole array composed of a plurality of periodically two-dimensionally arranged through holes is formed on the first two-dimensional material mask layer, with equal periods of rows and columns. , the depth of each through hole is consistent with the thickness of the first two-dimensional material mask layer, and the diameter of the through hole is less than 2/3 of the first through hole array period;
c)在第一二维材料掩膜层上沉积第二层单晶氮化物，第一二维材料掩膜层上第一通孔阵列以外的表面不具有表面不饱和悬挂键而不能生长单晶氮化物，第一通孔阵列下方对应的模板层的区域，具有表面不饱和悬挂键能够生长单晶氮化物，实现第一次位错过滤，即非第一通孔阵列对应的模板层中的位错不能进入到上层的第二层单晶氮化物中；c) Deposit a second layer of single crystal nitride on the first two-dimensional material mask layer. The surface of the first two-dimensional material mask layer other than the first through hole array does not have surface unsaturated dangling bonds and cannot grow single crystals. Nitride, the area of the corresponding template layer below the first via array, has surface unsaturated dangling bonds and can grow single crystal nitride to achieve the first dislocation filtering, that is, in the template layer not corresponding to the first via array Dislocations cannot enter the upper second layer of single crystal nitride;
d)增加生长温度和氮源与III族源的流量的化学计量比，促使第二层单晶氮化物的厚度超过第一二维材料掩膜层的厚度后，继续纵向生长的同时横向扩展，直至完全包裹第一二维材料掩膜层，横向扩展过程处于近无应力状态，导致位错自第一通孔阵列对应的模板层的区域扩展至第二层单晶氮化物时，位错的繁衍方向发生改变，使得部分位错湮灭，得到位错密度低于模板层的位错过滤层；d) Increase the growth temperature and the stoichiometric ratio of the flow rate of the nitrogen source and the III source, so that after the thickness of the second layer of single crystal nitride exceeds the thickness of the first two-dimensional material mask layer, it continues to grow vertically and expand laterally, Until the first two-dimensional material mask layer is completely wrapped, the lateral expansion process is in a nearly stress-free state, causing dislocations to expand from the area of the template layer corresponding to the first via array to the second layer of single crystal nitride. The propagation direction changes, causing some dislocations to be annihilated, resulting in a dislocation filter layer with a lower dislocation density than the template layer;
3)制备单晶氮化物薄膜：3) Preparation of single crystal nitride film:
a)将第二二维材料掩膜层转移至位错过滤层的上表面；a) Transfer the second two-dimensional material mask layer to the upper surface of the dislocation filter layer;
b)通过掩膜保护与选择性刻蚀的方法，在第二二维材料掩膜层上形成由多个周期性二维排列的通孔构成的第二通孔阵列，每一个通孔的深度与第二二维材料掩膜层厚度一致，第二通孔阵列的周期和形状与第一通孔阵列一致，但第二通孔阵列的位置与第一通孔阵列具有水平偏移，水平偏移使得第二通孔阵列的通孔外边缘与第一通孔阵列的通孔外边缘相切；b) Through mask protection and selective etching, form a second through hole array composed of a plurality of periodically two-dimensionally arranged through holes on the second two-dimensional material mask layer. The depth of each through hole The thickness of the second two-dimensional material mask layer is consistent, and the period and shape of the second via hole array are consistent with the first via hole array, but the position of the second via hole array is horizontally offset from the first via hole array, and the horizontal offset is Move so that the outer edge of the through holes of the second through hole array is tangent to the outer edge of the through holes of the first through hole array;
c)在第二二维材料掩膜层上沉积第三层单晶氮化物，第二二维材料掩膜层上第二通孔阵列区域以外的表面不具有表面不饱和悬挂键而不能生长单晶氮化物，第二通孔阵列下方对应的位错过滤层的区域能够生长单晶氮化物，实现第二次位错过滤，即非第二通孔阵列对应的位错过滤层中的位错不能进入到上层的第三层单晶氮化物中；c) Deposit a third layer of single crystal nitride on the second two-dimensional material mask layer. The surface on the second two-dimensional material mask layer other than the second through hole array area does not have surface unsaturated dangling bonds and cannot grow single crystal nitride. Crystal nitride, the area of the corresponding dislocation filter layer below the second via hole array can grow single crystal nitride to achieve the second dislocation filtering, that is, dislocations in the dislocation filter layer corresponding to the non-second via hole array It cannot enter the third layer of single crystal nitride in the upper layer;
d)增加生长温度和氮源与III族源的流量的化学计量比，促使第三层单晶氮化物的厚度超过第二二维材料掩膜层的厚度后，继续纵向生长的同时横向扩展，直至完全包裹第二二维材料掩膜层，横向扩展过程处于近无应力状态，导致位错自第二通孔阵列对应的位错过滤层的区域扩展至第三层单晶氮化物时，位错的繁衍方向发生改变，使得部分位错湮灭，得到位错密度低于位错过滤层的单晶氮化物薄膜；d) Increase the growth temperature and the stoichiometric ratio of the flow rates of the nitrogen source and the Group III source, so that after the thickness of the third layer of single crystal nitride exceeds the thickness of the second two-dimensional material mask layer, it continues to grow vertically while expanding laterally, Until the second two-dimensional material mask layer is completely wrapped, the lateral expansion process is in a nearly stress-free state, causing dislocations to expand from the area of the dislocation filter layer corresponding to the second via hole array to the third layer of single crystal nitride. The propagation direction of dislocations changes, causing some dislocations to be annihilated, resulting in a single crystal nitride film with a dislocation density lower than that of the dislocation filter layer;
4)制备单晶氮化物Micro-LED阵列：4) Preparation of single crystal nitride Micro-LED array:
a)将第三二维材料掩膜层转移至单晶氮化物薄膜的上表面；a) Transfer the third two-dimensional material mask layer to the upper surface of the single crystal nitride film;
b)通过掩膜保护与选择性刻蚀的方法，在第三二维材料掩膜层上形成由多个周期性二维排列的通孔构成的第三通孔阵列，行与列的周期相等，每一个通孔的深度与第三二维材料掩膜层的厚度一致，通孔的直径为第三通孔阵列周期的1/2至3/4，第三通孔阵列周期与第一通孔阵列周期一致；b) Through mask protection and selective etching, a third through hole array composed of a plurality of periodically two-dimensionally arranged through holes is formed on the third two-dimensional material mask layer, with equal periods of rows and columns. , the depth of each through hole is consistent with the thickness of the third two-dimensional material mask layer, the diameter of the through hole is 1/2 to 3/4 of the third through hole array period, and the third through hole array period is the same as the first through hole array period. The hole array period is consistent;
c)在第三二维材料掩膜层上沉积单晶氮化物功能结构，第三二维材料掩膜层上第三通孔阵列区域以外的表面不具有表面不饱和悬挂键而不能生长单晶氮化物功能结构，第三通孔阵列下方对应的单晶氮化物薄膜的区域能够单晶生长氮化物功能结构，单晶氮化物功能结构为紫外或者可见光发光二极管结构中的一种；通过控制沉积过程中的生长温度和氮源与III族源流量的化学计量比，使得单晶氮化物功能结构的横向尺寸等于圆形通孔区的横向尺寸，仅进行纵向生长，单晶氮化物功能结构的高度大于第三二维材料掩膜层的厚度，形成与第三通孔阵列相同周期性分布的单晶氮化物Micro-LED阵列，每个通孔内的单晶氮化物功能结构作为单晶氮化物Micro-LED阵列的一个阵列元；c) Deposit a single crystal nitride functional structure on the third two-dimensional material mask layer. The surface on the third two-dimensional material mask layer other than the third via hole array area does not have surface unsaturated dangling bonds and cannot grow single crystals. Nitride functional structure, the corresponding area of the single crystal nitride film under the third through hole array can grow the nitride functional structure in a single crystal, and the single crystal nitride functional structure is one of the ultraviolet or visible light emitting diode structures; by controlling the deposition The growth temperature and the stoichiometric ratio of the nitrogen source and Group III source flow rates during the process are such that the lateral size of the single crystal nitride functional structure is equal to the lateral size of the circular via area, and only longitudinal growth is performed, the single crystal nitride functional structure The height is greater than the thickness of the third two-dimensional material mask layer, forming a single crystal nitride Micro-LED array with the same periodic distribution as the third through hole array, and the single crystal nitride functional structure in each through hole serves as a single crystal nitrogen An array element of a chemical Micro-LED array;
5)得到柔性单晶氮化物Micro-LED阵列：5) Obtain flexible single crystal nitride Micro-LED array:
a)采用旋涂的方式填充阵列元之间的缝隙，填充高度与阵列元的高度相同，得到平片结构；a) Use spin coating to fill the gaps between the array elements, and the filling height is the same as the height of the array elements to obtain a flat sheet structure;
b)在平片结构的表面贴附柔性保护层；b) Attach a flexible protective layer to the surface of the flat sheet structure;
c)从非单晶衬底的背面入射激光，激光通过晶格共振吸收的方式加热非单晶衬底与模板层之间的二维原子晶体诱导层，熔化二维原子晶体诱导层，实现非单晶衬底与二维原子晶体诱导层以上的结构分离，得到柔性单晶氮化物Micro-LED阵列和可重复使用的非单晶衬底。c) Laser is incident from the back of the non-single crystal substrate, and the laser heats the two-dimensional atomic crystal induction layer between the non-single crystal substrate and the template layer through lattice resonance absorption, and melts the two-dimensional atomic crystal induction layer to achieve non-single crystal substrate. The single crystal substrate is separated from the structure above the two-dimensional atomic crystal induction layer to obtain a flexible single crystal nitride Micro-LED array and a reusable non-single crystal substrate.
其中，在步骤1)的a)中，非单晶衬底的禁带宽度大于5eV、与氮化物半导体晶格失配大于20％、热膨胀系数失配大于50％、可见光透明度大于0.99且熔点高于1200℃，采用石英、云母、刚玉和金刚石中的一种。Among them, in a) of step 1), the bandgap width of the non-single crystal substrate is greater than 5eV, the lattice mismatch with the nitride semiconductor is greater than 20%, the thermal expansion coefficient mismatch is greater than 50%, the visible light transparency is greater than 0.99, and the melting point is high At 1200℃, one of quartz, mica, corundum and diamond is used.
在步骤1)的b)中，二维原子晶体诱导层采用具有掺杂原子的单晶结构的石墨烯，掺杂原子为氮原子或者氧原子，氮原子或氧原子的占比大于1％，厚度为1～10nm，掺杂原子提供表面不饱和悬挂键作为氮化物的成核位点，不需要对二维原子晶体诱导层进行额外的改性处理。In b) of step 1), the two-dimensional atomic crystal induction layer adopts graphene with a single crystal structure having doped atoms. The doped atoms are nitrogen atoms or oxygen atoms, and the proportion of nitrogen atoms or oxygen atoms is greater than 1%. The thickness is 1 to 10nm, and the doped atoms provide surface unsaturated dangling bonds as nucleation sites for nitrides, without the need for additional modification of the two-dimensional atomic crystal induction layer.
在步骤1)的c)中，采用金属有机物化学气相沉积技术、分子束外延、氢化物气相外延、磁控溅射或脉冲激光沉积技术生长第一层单晶氮化物，生长温度为900℃～1250℃，氮源与III族源的流量的化学计量比即V族/III族为300～1000，III族源为金属或金属有机源，氮源为氨气或氮气，第一层单晶氮化物为AlN或者AlGaN和AlN复合结构，禁带宽度大于5eV， 模板层的厚度为500nm～1000nm，模板层的位错密度低于5×10 10cm -2且高于1×10 9cm -2。 In c) of step 1), the first layer of single crystal nitride is grown using metal-organic chemical vapor deposition technology, molecular beam epitaxy, hydride vapor phase epitaxy, magnetron sputtering or pulsed laser deposition technology, and the growth temperature is 900°C~ 1250℃, the stoichiometric ratio of the flow rates of nitrogen source and III source, that is, V/III, is 300 to 1000. The III source is a metal or metal organic source, the nitrogen source is ammonia or nitrogen, and the first layer of single crystal nitrogen The compound is AlN or a composite structure of AlGaN and AlN, the band gap is greater than 5eV, the thickness of the template layer is 500nm~1000nm, and the dislocation density of the template layer is lower than 5×10 10 cm -2 and higher than 1×10 9 cm -2 .
在步骤2)的a)中，第一二维材料掩膜层采用多晶或者非晶结构的石墨烯、氮化硼或者过渡金属硫族化合物，厚度为10nm～30nm。In a) of step 2), the first two-dimensional material mask layer is made of polycrystalline or amorphous graphene, boron nitride or transition metal chalcogenide, with a thickness of 10 nm to 30 nm.
在步骤2)的b)中，掩膜保护与选择性刻蚀的具体工艺如下：在第一二维材料掩膜层的上表面旋涂光刻胶，通过具有设定的周期性形状的掩模版曝光处理光刻胶，通过化学腐蚀的方法除去因曝光变性的光刻胶，由未变性的具有设定的周期性形状的光刻胶提供掩膜保护；选择性刻蚀即采用等离子体刻蚀或者反应离子刻蚀等技术直接刻蚀具有掩膜保护的第一二维材料掩膜层，无掩膜保护区域被刻蚀，有掩膜保护区域未被刻蚀，采用化学清洗的方式除去残留的光刻胶层，将具有设定的周期性形状从光刻胶层转移到第一二维材料掩膜层。通孔的形状为圆柱体；第一通孔阵列的周期为0.1μm～50μm。In b) of step 2), the specific process of mask protection and selective etching is as follows: spin-coat photoresist on the upper surface of the first two-dimensional material mask layer, and pass through the mask with a set periodic shape. The photoresist is processed by template exposure, and the photoresist denatured by exposure is removed through chemical etching, and the undenatured photoresist with a set periodic shape provides mask protection; selective etching uses plasma etching. The first two-dimensional material mask layer with mask protection is directly etched by techniques such as etching or reactive ion etching. The areas without mask protection are etched, and the areas with mask protection are not etched and are removed by chemical cleaning. The remaining photoresist layer will have a set periodic shape transferred from the photoresist layer to the first two-dimensional material mask layer. The shape of the through hole is a cylinder; the period of the first through hole array is 0.1 μm to 50 μm.
在步骤2)的c)中，采用金属有机物化学气相沉积技术、分子束外延、氢化物气相外延、磁控溅射或脉冲激光沉积技术生长第二层单晶氮化物，生长温度为900℃～1250℃，氮源与III族源的流量的化学计量比即V族/III族为300～1000，第二层单晶氮化物为AlN或者AlGaN和AlN复合结构，禁带宽度大于5eV。In c) of step 2), the second layer of single crystal nitride is grown using metal-organic chemical vapor deposition technology, molecular beam epitaxy, hydride vapor phase epitaxy, magnetron sputtering or pulsed laser deposition technology, and the growth temperature is 900°C~ At 1250°C, the stoichiometric ratio of the flow rate of the nitrogen source and the III source, that is, V group/III group, is 300 to 1000. The second layer of single crystal nitride is AlN or a composite structure of AlGaN and AlN, and the bandgap width is greater than 5eV.
在步骤2)的d)中，生长温度增至1000℃～1350℃，V族/III族比增至1500～5000。位错过滤层的厚度为500nm～2000nm，位错密度低于1×10 9cm -2。 In d) of step 2), the growth temperature is increased to 1000°C to 1350°C, and the group V/group III ratio is increased to 1500 to 5000. The thickness of the dislocation filtering layer is 500nm~2000nm, and the dislocation density is lower than 1×10 9 cm -2 .
在步骤3)的a)中，第二二维材料掩膜层采用多晶或者非晶结构的石墨烯、氮化硼或者过渡金属硫族化合物等中的一种组成，厚度为10nm～30nm。In a) of step 3), the second two-dimensional material mask layer is composed of polycrystalline or amorphous graphene, boron nitride, transition metal chalcogenide, etc., and has a thickness of 10 nm to 30 nm.
在步骤3)的c)中，采用金属有机物化学气相沉积技术、分子束外延、氢化物气相外延、磁控溅射或脉冲激光沉积技术生长第三层单晶氮化物，生长温度为900℃～1250℃，氮源与III族源的流量的化学计量比即V族/III族为300～1000，第三层单晶氮化物为AlN或者AlGaN和AlN复合结构，禁带宽度大于5eV。In c) of step 3), the third layer of single crystal nitride is grown using metal-organic chemical vapor deposition technology, molecular beam epitaxy, hydride vapor phase epitaxy, magnetron sputtering or pulsed laser deposition technology, and the growth temperature is 900°C~ At 1250°C, the stoichiometric ratio of the flow rate of the nitrogen source and the III source, that is, V group/III group, is 300 to 1000. The third layer of single crystal nitride is AlN or a composite structure of AlGaN and AlN, and the bandgap width is greater than 5eV.
在步骤3)的d)中，生长温度增至1000℃～1350℃，V族/III族比增至1500～5000。单晶氮化物薄膜的厚度为500nm～2000nm，位错密度低于1×10 8cm -2。 In d) of step 3), the growth temperature is increased to 1000°C to 1350°C, and the group V/group III ratio is increased to 1500 to 5000. The thickness of the single crystal nitride film is 500nm to 2000nm, and the dislocation density is less than 1×10 8 cm -2 .
在步骤4)的a)中，第三二维材料掩膜层采用多晶或者非晶结构的石墨烯、氮化硼或者过渡金属硫族化合物等中的一种组成，厚度为10nm～30nm。In a) of step 4), the third two-dimensional material mask layer is composed of polycrystalline or amorphous graphene, boron nitride, transition metal chalcogenide, etc., and has a thickness of 10 nm to 30 nm.
在步骤4)的c)中，生长温度为900℃～1250℃，氮源与III族源的流量的化学计量比即V族/III族为300～1000；单晶氮化物功能结构即阵列元由n型层、量子结构和p型层组成，高度为0.5μm～3μm。In c) of step 4), the growth temperature is 900°C to 1250°C, and the stoichiometric ratio of the flow rate of the nitrogen source and the group III source, that is, group V/group III, is 300 to 1000; the single crystal nitride functional structure is the array element It is composed of n-type layer, quantum structure and p-type layer, with a height of 0.5μm~3μm.
在步骤5)的a)中，旋涂聚甲基丙烯酸甲酯(PPMA)或聚二甲基硅氧烷(PDMS)。In step 5) a), polymethylmethacrylate (PPMA) or polydimethylsiloxane (PDMS) is spin-coated.
在步骤5)的b)中，柔性保护层由PMMA、透明导电薄膜或其他柔性有机物材料组成。In b) of step 5), the flexible protective layer is composed of PMMA, transparent conductive film or other flexible organic materials.
在步骤5)的c)中，从非单晶衬底的背面入射红外激光、紫外激光或可见激光；红外激光的波长大于800nm。In c) of step 5), infrared laser, ultraviolet laser or visible laser is incident from the back side of the non-single crystal substrate; the wavelength of the infrared laser is greater than 800 nm.
本发明的优点：Advantages of the invention:
本发明通过制备二维材料掩膜层，得到位错密度低于1×10 9cm -2的位错过滤层，并进一步得到位错密度低于1×10 8cm -2的单晶氮化物薄膜，能够在大晶格失配、大热膨胀系数失配的非单晶衬底上实现超高质量的单晶氮化物功能结构，除能够用于制备Micro-LED器件，还能够扩展用于制备射频器件、功率器件、发光器件和探测器件等，具有工艺普适性；采用激光破坏外延结构与非单晶衬底的界面结合，能够实现外延结构的无损分离和非单晶衬底的多次重复利用，节能环保、工艺简单并适于批量生产。 The present invention obtains a dislocation filter layer with a dislocation density lower than 1×10 9 cm -2 by preparing a two-dimensional material mask layer, and further obtains a single crystal nitride with a dislocation density lower than 1×10 8 cm -2 Thin films can achieve ultra-high quality single crystal nitride functional structures on non-single crystal substrates with large lattice mismatch and large thermal expansion coefficient mismatch. In addition to being used to prepare Micro-LED devices, it can also be expanded to prepare Radio frequency devices, power devices, light-emitting devices and detection devices, etc., have process universality; using laser to destroy the interface between the epitaxial structure and the non-single crystal substrate can achieve lossless separation of the epitaxial structure and multiple times of the non-single crystal substrate Reusable, energy-saving and environmentally friendly, simple process and suitable for mass production.
附图说明Description of the drawings
图1为根据本发明的基于非单晶衬底的单晶氮化物Micro-LED阵列的制备方法得到模板层的剖面图；Figure 1 is a cross-sectional view of the template layer obtained by the preparation method of a single crystal nitride Micro-LED array based on a non-single crystal substrate according to the present invention;
图2为根据本发明的基于非单晶衬底的单晶氮化物Micro-LED阵列的制备方法得到位错过滤层的剖面图；Figure 2 is a cross-sectional view of a dislocation filter layer obtained according to the preparation method of a single crystal nitride Micro-LED array based on a non-single crystal substrate of the present invention;
图3为根据本发明的基于非单晶衬底的单晶氮化物Micro-LED阵列的制备方法得到单晶氮化物薄膜的剖面图；Figure 3 is a cross-sectional view of a single crystal nitride film obtained according to the preparation method of a single crystal nitride Micro-LED array based on a non-single crystal substrate of the present invention;
图4为根据本发明的基于非单晶衬底的单晶氮化物Micro-LED阵列的制备方法制备单晶氮化物Micro-LED阵列的剖面图；Figure 4 is a cross-sectional view of a single crystal nitride Micro-LED array prepared according to the method for preparing a single crystal nitride Micro-LED array based on a non-single crystal substrate of the present invention;
图5为根据本发明的基于非单晶衬底的单晶氮化物Micro-LED阵列的制备方法得到柔性单晶氮化物Micro-LED阵列的剖面图。Figure 5 is a cross-sectional view of a flexible single crystal nitride Micro-LED array obtained by the method for preparing a single crystal nitride Micro-LED array based on a non-single crystal substrate of the present invention.
具体实施方式Detailed ways
下面结合附图，通过具体实施例，进一步阐述本发明。The present invention will be further described below through specific embodiments in conjunction with the accompanying drawings.
本实施例的基于非单晶衬底的单晶氮化物Micro-LED阵列的制备方法，包括以下步骤：The method for preparing a single crystal nitride Micro-LED array based on a non-single crystal substrate in this embodiment includes the following steps:
1)制备模板层：1) Prepare template layer:
a)提供非单晶衬底1，非单晶衬底的禁带宽度大于5eV，与氮化物半导体晶格失配大于 20％，热膨胀系数失配大于50％，可见光透明度大于0.99、熔点高于1200℃的石英；对非单晶衬底进行双面抛光；a) Provide a non-single crystal substrate 1. The band gap of the non-single crystal substrate is greater than 5eV, the lattice mismatch with the nitride semiconductor is greater than 20%, the thermal expansion coefficient mismatch is greater than 50%, the visible light transparency is greater than 0.99, and the melting point is greater than Quartz at 1200℃; double-sided polishing of non-single crystal substrates;
b)通过湿法或干法转移的方式在非单晶衬底的上表面形成二维原子晶体诱导层2，二维原子晶体诱导层为具有氮掺杂原子的单晶结构，氮原子占比为1.2％，厚度为5nm，暴露在二维原子晶体诱导层表面的掺杂原子提供表面不饱和悬挂键，作为氮化物的成核位点，为单晶氮化物生长提供所需的改性表面；b) Form a two-dimensional atomic crystal induction layer 2 on the upper surface of the non-single crystal substrate by wet or dry transfer. The two-dimensional atomic crystal induction layer is a single crystal structure with nitrogen doped atoms, and nitrogen atoms account for It is 1.2% and has a thickness of 5nm. 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 for nitride and provide the required modified surface for single crystal nitride growth. ;
c)采用金属有机物化学气相沉积技术在二维原子晶体诱导层上沉积单晶AlN形成第一层单晶氮化物，形成模板层3，厚度为800nm，模板层的位错密度低于5×10 10cm -2且高于1×10 9cm -2，如图1所示； c) Use metal-organic chemical vapor deposition technology to deposit single crystal AlN on the two-dimensional atomic crystal induction layer to form the first layer of single crystal nitride to form template layer 3 with a thickness of 800nm. The dislocation density of the template layer is less than 5×10 10 cm -2 and higher than 1×10 9 cm -2 , as shown in Figure 1;
2)制备位错过滤层：2) Prepare the dislocation filter layer:
a)将第一二维材料掩膜层4转移至模板层的上表面，第一二维材料掩膜层为多晶的石墨烯，厚度为15nm；a) Transfer the first two-dimensional material mask layer 4 to the upper surface of the template layer. The first two-dimensional material mask layer is polycrystalline graphene with a thickness of 15 nm;
b)在第一二维材料掩膜层的上表面旋涂光刻胶，通过具有设定的周期性形状的掩模版曝光处理光刻胶，通过化学腐蚀的方法除去因曝光变性的光刻胶，由未变性的具有设定的周期性形状的光刻胶提供掩膜保护；选择性刻蚀即采用等离子体刻蚀或者反应离子刻蚀等技术直接刻蚀具有掩膜保护的第一二维材料掩膜层，无掩膜保护区域被刻蚀，有掩膜保护区域未被刻蚀，采用化学清洗的方式除去残留的光刻胶层，将具有设定的周期性形状从光刻胶层转移到第一二维材料掩膜层，通孔的形状为圆柱体；在第一二维材料掩膜层上形成由多个周期性二维排列的通孔构成的第一通孔阵列，行与列的周期相等，每一个通孔的深度与第一二维材料掩膜层厚度一致，通孔的直径为第一通孔阵列周期的1/2，第一通孔阵列的周期为5μm；b) Spin-coat photoresist on the upper surface of the first two-dimensional material mask layer, expose the photoresist through a mask with a set periodic shape, and remove the photoresist denatured by exposure through chemical etching. , mask protection is provided by an undenatured photoresist with a set periodic shape; selective etching uses technologies such as plasma etching or reactive ion etching to directly etch the first two-dimensional layer with mask protection. Material mask layer, the area without mask protection is etched, and the area with mask protection is not etched. Chemical cleaning is used to remove the remaining photoresist layer, and the set periodic shape is removed from the photoresist layer. Transferring to the first two-dimensional material mask layer, the shape of the through hole is a cylinder; forming a first through hole array composed of a plurality of periodically two-dimensionally arranged through holes on the first two-dimensional material mask layer, rows Equal to the period of the column, the depth of each through hole is consistent with the thickness of the first two-dimensional material mask layer, the diameter of the 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 μm;
c)采用金属有机物化学气相沉积技术在第一二维材料掩膜层上沉积单晶AlN形成第二层单晶氮化物，生长温度为1050℃，氮源与III族源的流量的化学计量比即V族/III族为500，第二层单晶氮化物的禁带宽度大于5eV，第一二维材料掩膜层上第一通孔阵列以外的表面不具有表面不饱和悬挂键而不能生长单晶氮化物，第一通孔阵列下方对应的模板层的区域，具有表面不饱和悬挂键能够生长单晶氮化物，实现第一次位错过滤，即非第一通孔阵列对应的模板层中的位错不能进入到上层的第二层单晶氮化物中；c) Use metal-organic chemical vapor deposition technology to deposit single crystal AlN on the first two-dimensional material mask layer to form a second layer of single crystal nitride. The growth temperature is 1050°C, and the stoichiometric ratio of the flow rate of the nitrogen source and the III source is That is, Group V/III is 500, the bandgap width of the second layer of single crystal nitride is greater than 5eV, and the surface of the first two-dimensional material mask layer other than the first through hole array does not have surface unsaturated dangling bonds and cannot grow. Single crystal nitride, the area of the corresponding template layer below the first via array, has surface unsaturated dangling bonds that can grow single crystal nitride to achieve the first dislocation filtering, that is, the template layer corresponding to the non-first via array The dislocations in cannot enter the upper second layer of single crystal nitride;
d)生长温度增至1150℃，V族/III族比增至2000，促使第二层单晶氮化物的厚度超过第一二维材料掩膜层的厚度后，继续纵向生长的同时横向扩展，直至完全包裹第一二维材料掩膜层，横向扩展过程的近无应力状态，导致自第一通孔阵列对应的模板层的区域扩展至第二层单晶氮化物的位错繁衍方向发生改变，使得部分位错湮灭，得到位错密度低于1×10 9cm -2的位错过滤层5，位错过滤层5的厚度为1500nm，如图2所示； d) The growth temperature increases to 1150°C and the Group V/III ratio increases to 2000, causing the thickness of the second layer of single crystal nitride to exceed the thickness of the first two-dimensional material mask layer and continue to grow vertically while expanding laterally. Until the first two-dimensional material mask layer is completely wrapped, the nearly stress-free state of the lateral expansion process causes the dislocation propagation direction to change from the area of the template layer corresponding to the first via array to the second layer of single crystal nitride. , causing partial annihilation of dislocations to obtain a dislocation filter layer 5 with a dislocation density lower than 1×10 9 cm -2 . The thickness of the dislocation filter layer 5 is 1500nm, as shown in Figure 2;
3)制备单晶氮化物薄膜：3) Preparation of single crystal nitride film:
a)将第二二维材料掩膜层6转移至位错过滤层的上表面，第二二维材料掩膜层采用多晶石墨烯，厚度为20nm；a) Transfer the second two-dimensional material mask layer 6 to the upper surface of the dislocation filter layer. The second two-dimensional material mask layer is made of polycrystalline graphene and has a thickness of 20nm;
b)通过掩膜保护与选择性刻蚀的方法，在第二二维材料掩膜层上形成由多个周期性二维排列的通孔构成的第二通孔阵列，每一个通孔的深度与第二二维材料掩膜层厚度一致，第二通孔阵列的周期和形状与第一二维材料掩膜的第一通孔阵列一致，但第二通孔阵列的位置与第一通孔阵列沿着行的方向水平偏移，水平偏移量为通孔的直径；b) Through mask protection and selective etching, form a second through hole array composed of a plurality of periodically two-dimensionally arranged through holes on the second two-dimensional material mask layer. The depth of each through hole The thickness of the second two-dimensional material mask layer is consistent, and the period and shape of the second through-hole array are consistent with the first through-hole array of the first two-dimensional material mask, but the position of the second through-hole array is consistent with the first through-hole array. The array is offset horizontally along the row direction by the diameter of the through hole;
c)采用金属有机物化学气相沉积技术在第二二维材料掩膜层上沉积单晶AlN形成第三层单晶氮化物，生长温度为1050℃，氮源与III族源的流量的化学计量比即V族/III族为500，第三层单晶氮化物的禁带宽度大于5eV，第二通孔阵列区域以外的第二二维材料掩膜层的表面不具有表面不饱和悬挂键而不能生长单晶氮化物，第二通孔阵列下方对应的位错过滤层的区域能够生长单晶氮化物，实现第二次位错过滤，即非第二通孔阵列对应的位错过滤层中的位错不能进入到上层的第三层单晶氮化物中；c) Use metal-organic chemical vapor deposition technology to deposit single crystal AlN on the second two-dimensional material mask layer to form the third layer of single crystal nitride. The growth temperature is 1050°C, and the stoichiometric ratio of the flow rate of the nitrogen source and the III source is That is, Group V/III is 500, the bandgap width of the third layer of single crystal nitride is greater than 5eV, and the surface of the second two-dimensional material mask layer outside the second through hole array area does not have surface unsaturated dangling bonds and cannot Single crystal nitride is grown, and the area of the corresponding dislocation filter layer below the second via hole array can grow single crystal nitride to achieve the second dislocation filtering, that is, the area in the dislocation filter layer corresponding to the second via hole array is not Dislocations cannot enter the upper third layer of single crystal nitride;
d)生长温度增至1150℃，V族/III族比增至2000，促使第三层单晶氮化物的厚度超过第二二维材料掩膜层的厚度后，继续纵向生长的同时横向扩展，直至完全包裹第二二维材料掩膜层，横向扩展过程的近无应力状态，导致自第二通孔阵列对应的位错过滤层的区域扩展至第三层单晶氮化物的位错繁衍方向发生改变，使得部分位错湮灭，得到位错密度低于1×10 8cm -2的单晶氮化物薄膜7，单晶氮化物薄膜7的厚度为1500nm，如图3所示； d) The growth temperature increases to 1150°C and the Group V/III ratio increases to 2000, causing the thickness of the third layer of single crystal nitride to exceed the thickness of the second two-dimensional material mask layer and continue to grow vertically while expanding laterally. Until the second two-dimensional material mask layer is completely wrapped, the nearly stress-free state of the lateral expansion process causes the area of the dislocation filter layer corresponding to the second via hole array to expand to the dislocation propagation direction of the third layer of single crystal nitride. Changes occur, causing some dislocations to be annihilated, and a single crystal nitride film 7 with a dislocation density lower than 1×10 8 cm -2 is obtained. The thickness of the single crystal nitride film 7 is 1500nm, as shown in Figure 3;
4)制备单晶氮化物Micro-LED阵列：4) Preparation of single crystal nitride Micro-LED array:
a)将第三二维材料掩膜层8转移至单晶氮化物薄膜的上表面，第三二维材料掩膜层采用多晶石墨烯，厚度为20nm；a) Transfer the third two-dimensional material mask layer 8 to the upper surface of the single crystal nitride film. The third two-dimensional material mask layer uses polycrystalline graphene with a thickness of 20nm;
b)通过掩膜保护与选择性刻蚀的方法，在第三二维材料掩膜层上形成由多个周期性二维排列的通孔构成的第三通孔阵列，行与列的周期相等，每一个通孔的深度与第三二维材料掩膜层厚度一致，通孔的直径为第三通孔阵列周期的3/5，第三通孔阵列周期与第一通孔阵列周期一致；b) Through mask protection and selective etching, a third through hole array composed of a plurality of periodically two-dimensionally arranged through holes is formed on the third two-dimensional material mask layer, with equal periods of rows and columns. , the depth of each through hole is consistent with the thickness of the third two-dimensional material mask layer, the diameter of the through hole is 3/5 of the third through hole array period, and the third through hole array period is consistent with the first through hole array period;
c)采用金属有机物化学气相沉积技术，生长温度为1050℃，氮源与III族源的流量的化学计量比即V族/III族为500，在第三二维材料掩膜层上沉积氮化物功能结构，第三通孔阵列区域以外的第三二维材料掩膜层的表面不具有表面不饱和悬挂键而不能生长氮化物功能结构，第三通孔阵列下方对应的单晶氮化物薄膜的区域能够生长氮化物功能结构，氮化物功能结构为紫外或者可见光发光二极管结构中的一种；通过控制沉积过程中的生长温度、氮源与III族源的流量的化学计量比，使得氮化物功能结构的横向尺寸等于圆形通孔区的横向尺寸，仅 进行纵向生长，形成与第三通孔阵列相同周期性分布的单晶氮化物Micro-LED阵列9，每个通孔内的氮化物功能结构作为单晶氮化物Micro-LED阵列的一个阵列元，高度为1μm，如图4所示；c) Using metal-organic chemical vapor deposition technology, the growth temperature is 1050°C, the stoichiometric ratio of the flow rate of the nitrogen source and the group III source, that is, group V/group III, is 500, and the nitride is deposited on the third two-dimensional material mask layer Functional structure. The surface of the third two-dimensional material mask layer outside the third via hole array area does not have surface unsaturated dangling bonds and cannot grow nitride functional structures. The corresponding single crystal nitride film below the third via hole array has The area can grow a nitride functional structure, which is one of the ultraviolet or visible light emitting diode structures; by controlling the growth temperature during the deposition process and the stoichiometric ratio of the flow rate of the nitrogen source and the III source, the nitride functional structure can be grown. The lateral size of the structure is equal to the lateral size of the circular through hole area, and only longitudinal growth is performed to form a single crystal nitride Micro-LED array 9 with the same periodic distribution as the third through hole array, and the nitride function in each through hole is The structure is an array element of a single crystal nitride Micro-LED array with a height of 1 μm, as shown in Figure 4;
5)得到柔性单晶氮化物Micro-LED阵列：5) Obtain flexible single crystal nitride Micro-LED array:
a)采用旋涂聚甲基丙烯酸甲酯10的方式填充阵列元之间的缝隙，填充高度与阵列元的高度相同，得到平片结构；a) Fill the gaps between the array elements by spin-coating polymethyl methacrylate 10, and the filling height is the same as the height of the array elements to obtain a flat sheet structure;
b)在平片结构的表面贴附透明导电薄膜作为柔性保护层11；b) Attach a transparent conductive film to the surface of the flat sheet structure as a flexible protective layer 11;
c)从非单晶衬底的背面入射红外激光，波长大于800nm，红外激光通过晶格共振吸收的方式加热非单晶衬底与模板层之间的二维原子晶体诱导层，熔化二维原子晶体诱导层，实现非单晶衬底与二维原子晶体诱导层以上的结构分离，得到柔性单晶氮化物Micro-LED阵列和可重复使用的非单晶衬底，如图5所示。c) Infrared laser is incident from the back of the non-single crystal substrate, with a wavelength greater than 800nm. The infrared laser heats the two-dimensional atomic crystal induction layer between the non-single crystal substrate and the template layer through lattice resonance absorption, and melts the two-dimensional atoms. The crystal induction layer realizes the structural separation above the non-single crystal substrate and the two-dimensional atomic crystal induction layer, and obtains a flexible single crystal nitride Micro-LED array and a reusable non-single crystal substrate, as shown in Figure 5.
最后需要注意的是，公布实施例的目的在于帮助进一步理解本发明，但是本领域的技术人员可以理解：在不脱离本发明及所附的权利要求的精神和范围内，各种替换和修改都是可能的。因此，本发明不应局限于实施例所公开的内容，本发明要求保护的范围以权利要求书界定的范围为准。Finally, it should be noted that the purpose of publishing the embodiments is to help further understand the present invention, but those skilled in the art can understand that various substitutions and modifications can be made without departing from the spirit and scope of the present invention and the appended claims. It is possible. Therefore, the present invention should not be limited to the contents disclosed in the embodiments, and the scope of protection claimed by the present invention shall be subject to the scope defined by the claims.

Claims (10)

  1. 一种基于非单晶衬底的单晶氮化物Micro-LED阵列的制备方法，其特征在于，所述制备方法包括以下步骤：A method for preparing a single crystal nitride Micro-LED array based on a non-single crystal substrate, characterized in that the preparation method includes the following steps:
    1)制备模板层：1) Prepare template layer:
    a)提供非单晶衬底，非单晶衬底采用刚性非金属材料；对非单晶衬底进行双面抛光；a) Provide a non-single crystal substrate, which is made of rigid non-metallic materials; perform double-sided polishing of the non-single crystal substrate;
    b)通过湿法或干法转移的方式在非单晶衬底的上表面形成二维原子晶体诱导层，二维原子晶体诱导层为具有掺杂原子的单晶结构，暴露在二维原子晶体诱导层表面的掺杂原子提供表面不饱和悬挂键，作为单晶氮化物的成核位点，为单晶氮化物生长提供所需的改性表面；b) Form a two-dimensional atomic crystal induction layer on the upper surface of the non-single crystal substrate by wet or dry transfer. The two-dimensional atomic crystal induction layer has a single crystal structure with doped atoms and is exposed to the two-dimensional atomic crystal. The doped atoms on the surface of the induction layer provide surface unsaturated dangling bonds, which serve as nucleation sites for single crystal nitride and provide the required modified surface for single crystal nitride growth;
    c)在二维原子晶体诱导层上沉积第一层单晶氮化物，形成模板层；c) Deposit the first layer of single crystal nitride on the two-dimensional atomic crystal induction layer to form a template layer;
    2)制备位错过滤层：2) Prepare the dislocation filter layer:
    a)将第一二维材料掩膜层转移至模板层的上表面；a) Transfer the first two-dimensional material mask layer to the upper surface of the template layer;
    b)通过掩膜保护与选择性刻蚀的方法，在第一二维材料掩膜层上形成由多个周期性二维排列的通孔构成的第一通孔阵列，行与列的周期相等，每一个通孔的深度与第一二维材料掩膜层厚度一致，通孔的直径小于第一通孔阵列周期的2/3；b) Through mask protection and selective etching, a first through hole array composed of a plurality of periodically two-dimensionally arranged through holes is formed on the first two-dimensional material mask layer, with equal periods of rows and columns. , the depth of each through hole is consistent with the thickness of the first two-dimensional material mask layer, and the diameter of the through hole is less than 2/3 of the first through hole array period;
    c)在第一二维材料掩膜层上沉积第二层单晶氮化物，第一二维材料掩膜层上第一通孔阵列以外的表面不具有表面不饱和悬挂键而不能生长单晶氮化物，第一通孔阵列下方对应的模板层的区域，具有表面不饱和悬挂键能够生长单晶氮化物，实现第一次位错过滤，即非第一通孔阵列对应的模板层中的位错不能进入到上层的第二层单晶氮化物中；c) Deposit a second layer of single crystal nitride on the first two-dimensional material mask layer. The surface of the first two-dimensional material mask layer other than the first through hole array does not have surface unsaturated dangling bonds and cannot grow single crystals. Nitride, the area of the corresponding template layer below the first via array, has surface unsaturated dangling bonds and can grow single crystal nitride to achieve the first dislocation filtering, that is, in the template layer not corresponding to the first via array Dislocations cannot enter the upper second layer of single crystal nitride;
    d)增加生长温度和氮源与III族源的流量的化学计量比，促使第二层单晶氮化物的厚度超过第一二维材料掩膜层的厚度后，继续纵向生长的同时横向扩展，直至完全包裹第一二维材料掩膜层，横向扩展过程处于近无应力状态，导致位错自第一通孔阵列对应的模板层的区域扩展至第二层单晶氮化物时，位错的繁衍方向发生改变，使得部分位错湮灭，得到位错密度低于模板层的位错过滤层；d) Increase the growth temperature and the stoichiometric ratio of the flow rate of the nitrogen source and the III source, so that after the thickness of the second layer of single crystal nitride exceeds the thickness of the first two-dimensional material mask layer, it continues to grow vertically and expand laterally, Until the first two-dimensional material mask layer is completely wrapped, the lateral expansion process is in a nearly stress-free state, causing dislocations to expand from the area of the template layer corresponding to the first via array to the second layer of single crystal nitride. The propagation direction changes, causing some dislocations to be annihilated, resulting in a dislocation filter layer with a lower dislocation density than the template layer;
    3)制备单晶氮化物薄膜：3) Preparation of single crystal nitride film:
    a)将第二二维材料掩膜层转移至位错过滤层的上表面；a) Transfer the second two-dimensional material mask layer to the upper surface of the dislocation filter layer;
    b)通过掩膜保护与选择性刻蚀的方法，在第二二维材料掩膜层上形成由多个周期性二维排列的通孔构成的第二通孔阵列，每一个通孔的深度与第二二维材料掩膜层厚度一致，第二通孔阵列的周期和形状与第一通孔阵列一致，但第二通孔阵列的位置与第一通孔阵列具有水平偏移，水平偏移使得第二通孔阵列的通孔外边缘与第一通孔阵列的通孔外边缘相切；b) Through mask protection and selective etching, form a second through hole array composed of a plurality of periodically two-dimensionally arranged through holes on the second two-dimensional material mask layer. The depth of each through hole The thickness of the second two-dimensional material mask layer is consistent, and the period and shape of the second via hole array are consistent with the first via hole array, but the position of the second via hole array is horizontally offset from the first via hole array, and the horizontal offset is Move so that the outer edge of the through holes of the second through hole array is tangent to the outer edge of the through holes of the first through hole array;
    c)在第二二维材料掩膜层上沉积第三层单晶氮化物，第二二维材料掩膜层上第二通孔阵列区域以外的表面不具有表面不饱和悬挂键而不能生长单晶氮化物，第二通孔阵列下方对应的位错过滤层的区域能够生长单晶氮化物，实现第二次位错过滤，即非第二通孔阵列对应的位错过滤层中的位错不能进入到上层的第三层单晶氮化物中；c) Deposit a third layer of single crystal nitride on the second two-dimensional material mask layer. The surface on the second two-dimensional material mask layer other than the second through hole array area does not have surface unsaturated dangling bonds and cannot grow single crystal nitride. Crystal nitride, the area of the corresponding dislocation filter layer below the second via hole array can grow single crystal nitride to achieve the second dislocation filtering, that is, dislocations in the dislocation filter layer corresponding to the non-second via hole array It cannot enter the third layer of single crystal nitride in the upper layer;
    d)增加生长温度和氮源与III族源的流量的化学计量比，促使第三层单晶氮化物的厚度超过第二二维材料掩膜层的厚度后，继续纵向生长的同时横向扩展，直至完全包裹第二二维材料掩膜层，横向扩展过程处于近无应力状态，导致位错自第二通孔阵列对应的位错过滤层的区域扩展至第三层单晶氮化物时，位错的繁衍方向发生改变，使得部分位错湮灭，得到位错密度低于位错过滤层的单晶氮化物薄膜；d) Increase the growth temperature and the stoichiometric ratio of the flow rates of the nitrogen source and the Group III source, so that after the thickness of the third layer of single crystal nitride exceeds the thickness of the second two-dimensional material mask layer, it continues to grow vertically while expanding laterally, Until the second two-dimensional material mask layer is completely wrapped, the lateral expansion process is in a nearly stress-free state, causing dislocations to expand from the area of the dislocation filter layer corresponding to the second via hole array to the third layer of single crystal nitride. The propagation direction of dislocations changes, causing some dislocations to be annihilated, resulting in a single crystal nitride film with a dislocation density lower than that of the dislocation filter layer;
    4)制备单晶氮化物Micro-LED阵列：4) Preparation of single crystal nitride Micro-LED array:
    a)将第三二维材料掩膜层转移至单晶氮化物薄膜的上表面；a) Transfer the third two-dimensional material mask layer to the upper surface of the single crystal nitride film;
    b)通过掩膜保护与选择性刻蚀的方法，在第三二维材料掩膜层上形成由多个周期性二维排列的通孔构成的第三通孔阵列，行与列的周期相等，每一个通孔的深度与第三二维材料掩膜层厚度一致，通孔的直径为第三通孔阵列周期的1/2至3/4，第三通孔阵列周期与第一通孔阵列周期一致；b) Through mask protection and selective etching, a third through hole array composed of a plurality of periodically two-dimensionally arranged through holes is formed on the third two-dimensional material mask layer, with equal periods of rows and columns. , the depth of each through hole is consistent with the thickness of the third two-dimensional material mask layer, the diameter of the through hole is 1/2 to 3/4 of the third through hole array period, and the third through hole array period is the same as the first through hole The array period is consistent;
    c)在第三二维材料掩膜层上沉积单晶氮化物功能结构，第三二维材料掩膜层上第三通孔阵列区域以外的表面不具有表面不饱和悬挂键而不能生长单晶氮化物功能结构，第三通孔阵列下方对应的单晶氮化物薄膜的区域能够单晶生长氮化物功能结构，单晶氮化物功能结构为紫外或者可见光发光二极管结构中的一种；通过控制沉积过程中的生长温度和氮源与III族源流量的化学计量比，使得单晶氮化物功能结构的横向尺寸等于圆形通孔区的横向尺寸，仅进行纵向生长，单晶氮化物功能结构的高度大于第三二维材料掩膜层的厚度，形成与第三通孔阵列相同周期性分布的单晶氮化物Micro-LED阵列，每个通孔内的单晶氮化物功能结构作为单晶氮化物Micro-LED阵列的一个阵列元；c) Deposit a single crystal nitride functional structure on the third two-dimensional material mask layer. The surface on the third two-dimensional material mask layer other than the third via hole array area does not have surface unsaturated dangling bonds and cannot grow single crystals. Nitride functional structure, the corresponding area of the single crystal nitride film under the third through hole array can grow the nitride functional structure in a single crystal, and the single crystal nitride functional structure is one of the ultraviolet or visible light emitting diode structures; by controlling the deposition The growth temperature and the stoichiometric ratio of the nitrogen source and Group III source flow rates during the process are such that the lateral size of the single crystal nitride functional structure is equal to the lateral size of the circular via area, and only longitudinal growth is performed, the single crystal nitride functional structure The height is greater than the thickness of the third two-dimensional material mask layer, forming a single crystal nitride Micro-LED array with the same periodic distribution as the third through hole array, and the single crystal nitride functional structure in each through hole serves as a single crystal nitrogen An array element of a chemical Micro-LED array;
    5)得到柔性单晶氮化物Micro-LED阵列：5) Obtain flexible single crystal nitride Micro-LED array:
    a)采用旋涂的方式填充阵列元之间的缝隙，填充高度与阵列元的高度相同，得到平片结构；a) Use spin coating to fill the gaps between the array elements, and the filling height is the same as the height of the array elements to obtain a flat sheet structure;
    b)在平片结构的表面贴附柔性保护层；b) Attach a flexible protective layer to the surface of the flat sheet structure;
    c)从非单晶衬底的背面入射激光，激光通过晶格共振吸收的方式加热非单晶衬底与模板层之间的二维原子晶体诱导层，熔化二维原子晶体诱导层，实现非单晶衬底与二维原子晶体诱导层以上的结构分离，得到柔性单晶氮化物Micro-LED阵列和可重复使用 的非单晶衬底。c) Laser is incident from the back of the non-single crystal substrate, and the laser heats the two-dimensional atomic crystal induction layer between the non-single crystal substrate and the template layer through lattice resonance absorption, and melts the two-dimensional atomic crystal induction layer to achieve non-single crystal substrate. The single crystal substrate is separated from the structure above the two-dimensional atomic crystal induction layer to obtain a flexible single crystal nitride Micro-LED array and a reusable non-single crystal substrate.
  2. 如权利要求1所述的制备方法，其特征在于，在步骤1)的a)中，非单晶衬底的禁带宽度大于5eV、与氮化物半导体晶格失配大于20％、热膨胀系数失配大于50％、可见光透明度大于0.99且熔点高于1200℃。The preparation method according to claim 1, characterized in that, in a) of step 1), the bandgap width of the non-single crystal substrate is greater than 5 eV, the lattice mismatch with the nitride semiconductor is greater than 20%, and the thermal expansion coefficient is mismatched. The formula is greater than 50%, the visible light transparency is greater than 0.99, and the melting point is greater than 1200°C.
  3. 如权利要求1所述的制备方法，其特征在于，在步骤1)的b)中，二维原子晶体诱导层采用具有掺杂原子的单晶结构的石墨烯，掺杂原子为氮原子或者氧原子，氮原子或氧原子的占比大于1％，厚度为1～10nm。The preparation method according to claim 1, characterized in that, in step 1) b), the two-dimensional atomic crystal induction layer adopts graphene with a single crystal structure having doped atoms, and the doped atoms are nitrogen atoms or oxygen atoms. Atoms, nitrogen atoms or oxygen atoms account for more than 1%, and the thickness is 1 to 10 nm.
  4. 如权利要求1所述的制备方法，其特征在于，在步骤1)的c)中，采用金属有机物化学气相沉积技术、分子束外延、氢化物气相外延、磁控溅射或脉冲激光沉积技术生长第一层单晶氮化物，生长温度为900℃～1250℃，氮源与III族源的流量的化学计量比即V族/III族为300～1000，III族源为金属或金属有机源，氮源为氨气或氮气，第一层单晶氮化物为AlN或者AlGaN和AlN复合结构，禁带宽度大于5eV，模板层的厚度为500nm～1000nm，模板层的位错密度低于5×10 10cm -2且高于1×10 9cm -2。 The preparation method according to claim 1, characterized in that, in c) of step 1), metal-organic chemical vapor deposition technology, molecular beam epitaxy, hydride vapor phase epitaxy, magnetron sputtering or pulse laser deposition technology is used for growth The growth temperature of the first layer of single crystal nitride is 900°C to 1250°C. The stoichiometric ratio of the flow rate of the nitrogen source and the group III source, that is, 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 AlN or a composite structure of AlGaN and AlN, the bandgap width is greater than 5eV, the thickness of the template layer is 500nm~1000nm, and the dislocation density of the template layer is less than 5×10 10 cm -2 and higher than 1×10 9 cm -2 .
  5. 如权利要求1所述的制备方法，其特征在于，在步骤2)的a)中，第一二维材料掩膜层采用多晶或者非晶结构的石墨烯、氮化硼或者过渡金属硫族化合物，厚度为10nm～30nm。The preparation method according to claim 1, characterized in that, in a) of step 2), the first two-dimensional material mask layer adopts polycrystalline or amorphous structure graphene, boron nitride or transition metal chalcogenide. Compound, thickness is 10nm~30nm.
  6. 如权利要求1所述的制备方法，其特征在于，在步骤2)的c)中，在步骤2)的c)中，采用金属有机物化学气相沉积技术、分子束外延、氢化物气相外延、磁控溅射或脉冲激光沉积技术生长第二层单晶氮化物，生长温度为900℃～1250℃，氮源与III族源的流量的化学计量比即V族/III族为300～1000，第二层单晶氮化物为AlN或者AlGaN和AlN复合结构，禁带宽度大于5eV。The preparation method according to claim 1, characterized in that, in c) of step 2), metal-organic chemical vapor deposition technology, molecular beam epitaxy, hydride vapor phase epitaxy, magnetic The second layer of single crystal nitride is grown by controlled sputtering or pulsed laser deposition technology. The growth temperature is 900°C to 1250°C. The stoichiometric ratio of the flow rate of the nitrogen source and the group III source, that is, group V/group III, is 300 to 1000. The two-layer single crystal nitride is AlN or a composite structure of AlGaN and AlN, with a bandgap width greater than 5eV.
  7. 如权利要求1所述的制备方法，其特征在于，在步骤2)的d)中，生长温度增至1000℃～1350℃，V族/III族比增至1500～5000；位错过滤层的厚度为500nm～2000nm，位错密度低于1×10 9cm -2。 The preparation method according to claim 1, characterized in that, in d) of step 2), the growth temperature is increased to 1000°C to 1350°C, and the group V/group III ratio is increased to 1500 to 5000; The thickness is 500nm~2000nm, and the dislocation density is less than 1×10 9 cm -2 .
  8. 如权利要求1所述的制备方法，其特征在于，在步骤4)的c)中，生长温度为900℃～1250℃，氮源与III族源的流量的化学计量比即V族/III族为300～1000；阵列元由n型层、量子结构和p型层组成，高度为0.5μm～3μm。The preparation method according to claim 1, characterized in that, in c) of step 4), the growth temperature is 900°C to 1250°C, and the stoichiometric ratio of the flow rates of the nitrogen source and the group III source is group V/group III. It is 300~1000; the array element is composed of n-type layer, quantum structure and p-type layer, with a height of 0.5μm~3μm.
  9. 如权利要求1所述的制备方法，其特征在于，在步骤5)的a)中，旋涂聚甲基丙烯酸甲酯或聚二甲基硅氧烷。The preparation method according to claim 1, characterized in that, in a) of step 5), polymethylmethacrylate or polydimethylsiloxane is spin-coated.
  10. 如权利要求1所述的制备方法，其特征在于，在步骤5)的c)中，从非单晶衬底的背面入射红外激光、紫外激光或可见激光。The preparation method according to claim 1, characterized in that, in c) of step 5), infrared laser, ultraviolet laser or visible laser is incident from the back side of the non-single crystal substrate.
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