CN109037291B - Full-color Micro-LED device and preparation method thereof - Google Patents
Full-color Micro-LED device and preparation method thereof Download PDFInfo
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- CN109037291B CN109037291B CN201810863787.2A CN201810863787A CN109037291B CN 109037291 B CN109037291 B CN 109037291B CN 201810863787 A CN201810863787 A CN 201810863787A CN 109037291 B CN109037291 B CN 109037291B
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/30—Devices specially adapted for multicolour light emission
- H10K59/35—Devices specially adapted for multicolour light emission comprising red-green-blue [RGB] subpixels
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/04—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction
- H01L33/06—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction within the light emitting region, e.g. quantum confinement structure or tunnel barrier
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- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/26—Materials of the light emitting region
- H01L33/30—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table
- H01L33/32—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen
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Abstract
The invention discloses a full-color Micro-LED array display and white light device based on a III-nitride/organic semiconductor hybrid structure, which is mixed with an inorganic and organic light emitting diode device to obtain a high-efficiency, ultrahigh-resolution and active Micro-LED display and illumination light source. In having a p-n structurexGa1‑ xRed light, green light or yellow light organic materials are respectively evaporated on an N-type gallium nitride layer of the N/gallium nitride quantum well blue light LED epitaxial wafer, and the N/gallium nitride quantum well blue light LED epitaxial wafer sequentially comprises an electron transport layer, a light emitting layer, an exciton blocking layer, a hole transport layer and a hole injection layer; when one group of materials is evaporated, other pixels are shielded by using a shielding mask. The technology combines organic semiconductor materials and inorganic semiconductor materials, and can realize a novel inorganic/organic semiconductor mixed structure Micro-LED device array with high efficiency, wide color gamut, low power consumption and quick response time.
Description
Technical Field
The invention relates to a full-color Micro-LED array display and white light device based on a III-nitride/organic semiconductor hybrid structure, belonging to the technical field of semiconductor solid illumination and display.
Background
Light emitting diodes are called fourth generation illumination sources because of their advantages of high efficiency, long lifetime, self-luminescence, environmental protection, etc., and have been widely used in various fields of display, illumination, etc. However, with the rapid development of information technology and mobile internet, virtual display (VR), Augmented Reality (AR) and wearable devices are emerging, information presentation modes are more and more diversified, the conventional display technology cannot meet the existing requirements, and the novel low-power consumption, high-brightness, wide color gamut and ultrahigh-resolution micro-display technology becomes more and more important. The III-nitride is an important semiconductor luminescent material, the band gap of the III-nitride is wide and continuously adjustable, the luminescent color covers the whole visible light region, near ultraviolet region and infrared band, and the potential application of the III-nitride in the fields of illumination and display is always an international research hotspot. With the increasing maturity of microstructure III-nitride LED technology, Micro-LEDs as pixel LED Micro-display and illumination technology become possible.
Generally, LEDs are monochromatic light sources, and in order to realize multi-medium color emission or white light emission, Micro-LEDs with three primary colors of red, green and blue or Micro-LED arrays with complementary colors of yellow and blue need to be combined, and currently, the main methods include an RGB three-color LED method, a UV/blue LED + light-emitting medium method, and an optical lens synthesis method. However, the above-mentioned preparation methods have the problems of full color display deviation, low light conversion efficiency, uneven coating of the luminescent medium, high preparation cost, harsh processing conditions, and being not suitable for large-area production, and thus are not suitable for the realization and application of high-quality commercial LED products. In recent years, organic semiconductor materials are widely used in the fields of illumination and display due to their advantages of low cost, simple processing technology, rich luminescent colors, easy integration, and the like. Researchers have also actively tried to combine inorganic semiconductors with organic semiconductors to produce LEDs, and such mixed structure LEDs combine the good electrical properties of inorganic semiconductors with the excellent optical properties of organic semiconductors. Based on the structure, a novel full-color micro LED device based on a III-nitride/organic semiconductor hybrid structure is provided. From the presently disclosed Micro-LED technology, there is no full color Micro-LED combining organic light emitting diode technology with inorganic light emitting diode technology.
Disclosure of Invention
The invention aims to provide a full-color Micro-LED array display and white light device based on a III-nitride/organic semiconductor hybrid structure.
The purpose of the invention is realized by the following technical scheme:
a full-color Micro-LED array display device based on a III-nitride and organic semiconductor hybrid structure comprises the following components from bottom to top:
a sapphire substrate;
a gallium nitride buffer layer grown on the sapphire substrate;
an N-type gallium nitride layer grown on the buffer layer;
an In layer grown on the N-type GaN layerxGa1-xAn N/gallium nitride quantum well active layer;
a P-type gallium nitride layer grown on the quantum well active layer;
the LED array device is etched to form an array type square table structure penetrating through the P-type gallium nitride layer and the quantum well active layer and reaching the N-type gallium nitride layer, and the square table structures are isolated from each other;
the N-type electrode is evaporated on the N-type gallium nitride layer;
every 3 of the square table surface arrays form a pixel unit, the pixel units are arranged in parallel, each pixel unit comprises a blue light LED, a red light LED and a green light LED, the square table surfaces of the red light LED and the green light LED are etched to an n-type gallium nitride layer, the red light LED is formed by evaporating red light organic light emitting diodes on the n-type gallium nitride layer, and the green light LED is formed by evaporating green light organic light emitting diodes on the n-type gallium nitride layer.
Preferably, the red light LED or the green light LED is formed by sequentially evaporating an electron transport layer, a light emitting layer, an exciton blocking layer, a hole transport layer, a hole injection layer and a metal anode on an N-type gallium nitride layer;
the electron transport layer is an organic compound or an N-type doped layer, the organic compound comprises 1,3, 5-tri [ (3-pyridyl) -3-phenyl ] benzene, 2, 5-di (1-naphthyl) -1,3, 4-diazole, 2-biphenyl-5- (4-tert-butylphenyl) -1,3, 4-diazole, 3, 4-diphenyl-5-biphenyl is 1,2, 4-triazole, 8-hydroxyquinoline aluminum, 1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene, 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline, 4, 7-diphenyl-1, 10-phenanthroline or 4, 7-diphenyl-1, 10-phenanthroline cesium carbonate with the thickness of 30-70 nm;
the luminescent layer main body comprises 4,4 '-bis (9-carbazole) biphenyl, 4' -tris (carbazole-9-yl) triphenylamine, 1, 3-dicarbazole benzene or N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, and the thickness is 10-30 nm;
doping red light doping materials, green light doping materials or yellow light doping materials in the light emitting layer to emit red light, green light or yellow light;
the red light doping material comprises 4-dicyanomethylene-2-tert-butyl-6- (1,1,7, 7-tetramethyl julolidine-4-vinyl) -4H-pyran, tri (1- (4-N-hexylphenyl) -isoquinoline-C2, N) iridium (III) and bis (1-phenylisoquinoline-C2, N) iridium (III) acetylacetonate, the light-emitting wavelength is 630nm-660nm, and the doping concentration is 1% -20%;
the green light doping material comprises iridium tri (2-phenylpyridine), iridium bis (2-phenylpyridine-C2, N) acetylacetonate, coumarin and 8-hydroxyquinoline aluminum, the light-emitting wavelength is 520nm-560nm, and the doping concentration is 1% -20%;
the yellow light doped material comprises bis [2- (6-phenyl-4-pyrimidinyl ] (acetylacetone) iridium (III), bis (2 (9-9-diethyl-9-fluoro-2-yl) -1-phenyl-1H-benzimidazole-N, C3) iridium (acetylacetone), rubrene and tetra (tert-butyl) rubrene, the light-emitting wavelength is 570-600nm, and the doping concentration is 1-10%;
the exciton blocking layer comprises 4,4 '-bis (9-carbazole) biphenyl, 4' -tris (carbazole-9-yl) triphenylamine and 1, 3-dicarbazole benzene, and the doping concentration is 1% -20%;
the hole transport layer comprises N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine, 4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ], N ' -diphenyl-N, N ' -bis (3-methylphenyl) -1,1' -biphenyl-4, 4' -diamine, N ' -diphenyl-N, N ' -bis (4-methylphenyl) biphenyl-4, 4' -diamine, 4' -tris [ phenyl (m-tolyl) amino ] triphenylamine and has a thickness of 40-70 nm;
the hole injection layer comprises a transition metal oxide and an organic material, wherein the metal oxide is molybdenum oxide, vanadium pentoxide and tungsten trioxide, the organic material is tetrafluorotetracyanoquinodimethane, 7,8, 8-tetracyanoterephthalquinodimethane, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene, 4' -tris (2-naphthylphenylamino) triphenylamine, and the thickness of the organic material is 2-40 nm;
the anode metal is gold, silver, copper or aluminum, the work function is 4.3eV to 5.2eV, and the thickness is 100-150 nm.
Preferably, an electron injection layer is further directly provided on the N-type gallium nitride layer and the electron transport layer, the electron injection layer is an alkali metal compound or an N-type doped layer, and the alkali metal compound includes lithium fluoride, lithium carbonate, cesium fluoride or lithium: the thickness of the electron injection layer of the 8-hydroxyquinoline aluminum is 0.5-1.5nm, and the alkali metal compound or the N-type doped layer and the N-type gallium nitride layer on the substrate jointly complete the electron injection function.
Preferably, the organic light-emitting diode further comprises a transparent electrode, wherein the transparent electrode is arranged between the electron injection layer and the N-type gallium nitride layer, the transparent electrode is preferably Indium Tin Oxide (ITO), aluminum (Al), silver (Ag) and the like, and the thickness of the transparent electrode is 5-20 nm.
Preferably, the size of the square mesa array is 20-100 μm, the spacing between the arrays is 5-20 μm, and the period is 800-.
Preferably, the light-emitting wavelength of the blue light LED is 450-470 nm.
Preferably, the pixel units have a 2 × 2 structure, and each pixel unit includes a red LED, a green LED, a blue LED, and a spare LED; or the pixel units are in a 3-by-1 structure and each pixel unit comprises a red light LED, a green light LED and a blue light LED, and the pixel units are arranged in parallel.
The preparation method of the full-color Micro-LED array display device comprises the following steps:
1) in with p-n structure by PECVD technologyxGa1-xEvaporating a dielectric layer on the N/gallium nitride quantum well blue light LED epitaxial wafer;
2) spin-coating photoresist on the surface of the dielectric layer, pre-baking the photoresist, forming an ordered square mesa array pattern on the photoresist by using a photoetching plate by using an ultraviolet photoetching technology, and then developing and post-baking;
3) by RIE technique, with O introduction2Removing the residual layer of the photoresist, evaporating a metal mask layer by utilizing a PVD (physical vapor deposition) process, stripping, and removing the photoresist layer and the metal mask layer on the photoresist layer to obtain a large-area ordered metal square table array pattern;
4) adopting RIE technology, taking metal as a mask to longitudinally etch the dielectric layer, and transferring the metal square mesa array structure to the dielectric layer;
5) adopting an ICP (inductively coupled plasma) technology, and anisotropically etching the P-type gallium nitride layer and the quantum well layer by using metal as a mask, so as to etch the groove to the N-type gallium nitride layer, and etching the square table tops of the red light LED and the green light LED to the N-type gallium nitride layer, wherein the square table tops are still separated by etching the groove;
6) removing the metal mask layer and the dielectric layer on the square mesa array structure by adopting wet etching to form a gallium nitride square mesa array structure which is isolated from each other, and repairing etching damage of gallium nitride and the side wall of the quantum well;
7) preparing an N-type electrode, evaporating a dielectric thin film layer by utilizing a PECVD (plasma enhanced chemical vapor deposition) technology, coating photoresist on the surface of the dielectric layer in a spinning mode, forming an N-type electrode pattern on the photoresist by utilizing an ultraviolet lithography technology and using a photoetching plate for alignment, and then etching the dielectric layer by utilizing the photoresist as a mask by adopting an RIE (reactive ion etching) technology to transfer the N-type electrode pattern to the N-type gallium nitride layer; a layer of metal is evaporated by adopting a PVD (physical vapor deposition) process to be used as an N-type electrode; stripping off the photoresist and the metal film on the photoresist layer, cleaning and drying the sample; finally, ohmic contact between the metal and the N-type gallium nitride is realized by thermal annealing;
8) preparing a P-type electrode, evaporating a dielectric thin film layer by utilizing a PECVD (plasma enhanced chemical vapor deposition) technology, coating photoresist on the surface of the dielectric layer in a spinning mode, forming a P-type electrode pattern on the photoresist by utilizing an ultraviolet lithography technology and using a photoetching plate for alignment, and then etching the dielectric layer thin film by utilizing the photoresist as a mask by adopting an RIE (reactive ion etching) technology to transfer the P-type electrode pattern to the P-type gallium nitride layer; a layer of metal is evaporated by adopting a PVD (physical vapor deposition) process to be used as a p-type electrode; removing the photoresist and the metal film on the photoresist layer by wet etching, cleaning and drying the sample; finally, ohmic contact between metal and p-type gallium nitride is realized by thermal annealing;
9) putting the prepared sample into a multi-source organic metal vacuum deposition system to sequentially evaporate an electron injection layer, an electron transport layer, a luminescent layer, an exciton blocking layer, a hole transport layer, a hole injection layer and a metal anode, wherein organic materials and metal are placed in different evaporation sources, the temperature of each evaporation source can be independently controlled, and when one organic material is evaporated, other pixels are shielded by using a shielding mask.
The invention also discloses a full-color Micro-LED array white light device based on the III-nitride and organic semiconductor hybrid structure, which comprises the following components from bottom to top:
a single sapphire substrate;
a gallium nitride buffer layer grown on the sapphire substrate;
an N-type gallium nitride layer grown on the buffer layer;
an In layer grown on the N-type GaN layerxGa1-xAn N/gallium nitride quantum well active layer;
a P-type gallium nitride layer grown on the quantum well active layer;
the LED array device is etched to form an array type square table structure penetrating through the P-type gallium nitride layer and the quantum well active layer and reaching the N-type gallium nitride layer, and the square table structures are isolated from each other;
the N-type electrode is evaporated on the N-type gallium nitride layer;
and red and green light doped organic light emitting diodes or yellow light doped organic light emitting diodes are vapor-plated on the square table surface array.
Preferably, the red and green light-doped organic light-emitting diode or the yellow light-doped organic light-emitting diode sequentially comprises an electron transport layer, a light-emitting layer, an exciton blocking layer, a hole transport layer, a hole injection layer and a metal anode;
the electron injection layer comprises an alkali metal compound or an N-type doping layer, wherein the alkali metal compound is lithium fluoride, lithium carbonate, cesium fluoride or lithium: 8-hydroxyquinoline aluminum, the thickness of the electron injection layer is 0.5-1.5 nm; the alkali metal compound or the N-type doped layer and the N-type gallium nitride layer on the substrate jointly complete the electron injection function.
The electron transport layer is an organic compound or an N-type doped layer, the organic compound comprises 1,3, 5-tri [ (3-pyridyl) -3-phenyl ] benzene, 2, 5-di (1-naphthyl) -1,3, 4-diazole, 2-biphenyl-5- (4-tert-butylphenyl) -1,3, 4-diazole, 3, 4-diphenyl-5-biphenyl is 1,2, 4-triazole, 8-hydroxyquinoline aluminum, 1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene, 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline, 4, 7-diphenyl-1, 10-phenanthroline or 4, 7-diphenyl-1, 10-phenanthroline cesium carbonate with the thickness of 30-70 nm;
the luminescent layer main body comprises 4,4 '-bis (9-carbazole) biphenyl, 4' -tris (carbazole-9-yl) triphenylamine, 1, 3-dicarbazole benzene or N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, and the thickness is 10-30 nm;
the light-emitting layer is doped with a red light-emitting material, a green light-emitting material or a yellow light-emitting material to emit red light, green light or yellow light;
the red light doping material comprises 4-dicyanomethylene-2-tert-butyl-6- (1,1,7, 7-tetramethyl julolidine-4-vinyl) -4H-pyran, tri (1- (4-N-hexylphenyl) -isoquinoline-C2, N) iridium (III) and bis (1-phenylisoquinoline-C2, N) iridium (III) acetylacetonate, the light-emitting wavelength is 630nm-660nm, and the doping concentration is 1% -20%;
the green light doping material comprises iridium tri (2-phenylpyridine), iridium bis (2-phenylpyridine-C2, N) acetylacetonate, coumarin and 8-hydroxyquinoline aluminum, the light-emitting wavelength is 520nm-560nm, and the doping concentration is 1% -20%;
the yellow light doped material comprises bis [2- (6-phenyl-4-pyrimidinyl ] (acetylacetone) iridium (III), bis (2 (9-9-diethyl-9-fluoro-2-yl) -1-phenyl-1H-benzimidazole-N, C3) iridium (acetylacetone), rubrene and tetra (tert-butyl) rubrene, the light-emitting wavelength is 570-600nm, and the doping concentration is 1-10%;
the exciton blocking layer comprises 4,4 '-bis (9-carbazole) biphenyl, 4' -tris (carbazole-9-yl) triphenylamine and 1, 3-dicarbazole benzene, and the doping concentration is 1% -20%;
the hole transport layer comprises N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine, 4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ], N ' -diphenyl-N, N ' -bis (3-methylphenyl) -1,1' -biphenyl-4, 4' -diamine, N ' -diphenyl-N, N ' -bis (4-methylphenyl) biphenyl-4, 4' -diamine, 4' -tris [ phenyl (m-tolyl) amino ] triphenylamine and has a thickness of 40-70 nm;
the hole injection layer is made of transition metal oxide or organic material, the metal oxide comprises molybdenum oxide, vanadium pentoxide and tungsten trioxide, the organic material is tetrafluorotetracyanoquinodimethane, 7,8, 8-tetracyanoterephthalquinodimethane, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene, 4' -tris (2-naphthylphenylamino) triphenylamine, and the thickness of the organic material is 2-40 nm;
the anode metal is gold, silver, copper or aluminum, the work function is 4.3eV to 5.2eV, and the thickness is 100-150 nm.
The full-color Micro-LED array device based on the III-nitride/organic semiconductor hybrid structure can be used for display or illumination, pixel units in the red-green-blue Micro-LED device share an N-type electrode and an electron injection layer of N-type gallium nitride, each pixel unit in the red-green-blue Micro-LED is mutually independent and can be addressed, the red-green-blue Micro-LED device is driven to be lighted independently, electro-optical control is convenient and fast, the device structure is optimized by selecting a proper organic semiconductor light-emitting material, the optimal combination of the brightness ratio and the light effect of the three-element LED device unit can be conveniently carried out, and the white light LED with wide spectrum, high light effect and high color rendering index is obtained. The red-green-blue three-element micron hole LED device unit is in a micron level, the distance between every two pixels is very small, the red, green and blue three elements are efficiently mixed to emit light in a short transmission distance, the problems that the light emitting efficiency is reduced and the color rendering index is low due to a large divergence angle caused by the light emitting distance of the conventional LED are effectively solved, the red-green-blue three-element micron hole LED device unit has the characteristic of self-luminescence without a backlight source, the long service life of an inorganic blue light material is combined, the high stability and the light emitting color of an organic semiconductor material are high, the whole visible light area is covered, the cost is low, the preparation is easy, and the like.
The invention adopts the ultraviolet lithography technology for preparation, has low cost, can realize large-area preparation, overcomes the defect of rough surface of the nitride quantum well LED epitaxial wafer, and has adjustable shape and size of each Micro-LED pixel unit; the device combines good electrical property of an inorganic semiconductor and excellent optical property of an organic semiconductor, has adjustable color and simple preparation process, can realize the ultrathin full-color Micro-LED with high efficiency, wide color gamut and low power consumption by selecting a proper organic luminescent material and optimizing the structure of the device, and the area of the Micro-LED can reach or exceed 4 inches. In addition, the device structure and the process can be popularized to an inorganic/organic semiconductor hybrid structure light-emitting device, are completely compatible with the current standard blue light LED device chip manufacturing process, and are very easy to integrate into the existing Micro-LED lighting and display product production line.
Drawings
Fig. 1-16 are schematic process flow diagrams and schematic surface structures of group III nitride/organic semiconductor hybrid structure-based red-green-blue Micro-LED devices according to example 1.
Fig. 17-28 are schematic process flow diagrams of a group III nitride/organic semiconductor hybrid structure based Micro-LED device of example 2.
Fig. 29-34 are schematic process flow diagrams of the white light Micro-LED device based on the III-nitride/organic semiconductor hybrid structure of example 3.
Fig. 35 is a schematic surface structure diagram of a white light Micro-LED device based on a group III nitride/organic semiconductor hybrid structure of example 3.
Fig. 36 is a schematic structural view of a group III nitride/organic semiconductor hybrid structure-based Micro-LED device of example 4.
FIG. 37 is a schematic structural view of a group III nitride/organic semiconductor hybrid structure-based Micro-LED device of example 5.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1 red-green-blue Micro-LED device based on a group III nitride/organic semiconductor hybrid structure
The embodiment adopts the blue light LED and the red light and green light organic LED to form the red-green-blue micron LED array device based on the III-nitride/organic semiconductor hybrid structure. Selecting In having p-n structurexGa1-xAn N/gallium nitride quantum well blue light LED epitaxial wafer, as shown in FIG. 1, comprises a sapphire substrate 1; a gallium nitride buffer layer 2 grown on the sapphire substrate; an N-type gallium nitride layer 3 grown on the buffer layer; in grown on N-type gallium nitride layerxGa1-xAn N/gallium nitride quantum well active layer 4; a P-type gallium nitride layer 5 grown on the quantum well active layer; the light-emitting wavelength is 450-470 nm; the red organic light emitting diode is formed by doping a main material with a red fluorescent or phosphorescent micromolecular material, and the light emitting wavelength of the red organic light emitting diode is 630-660 nm; the green organic light emitting diode is formed by doping a green fluorescent or phosphorescent micromolecular material with a main material, and the light emitting wavelength of the green organic light emitting diode is 520-560 nm. The specific embodiment is as follows:
(1) as shown In FIG. 2, In having a p-n structure is deposited by Plasma Enhanced Chemical Vapor Deposition (PECVD) techniquexGa1-xDepositing a layer of SiO on the N/gallium nitride quantum well blue light LED epitaxial wafer2Or SiNxThe dielectric layer film serves as a mask layer 6. PECVD (plasma enhanced chemical vapor deposition) growth of SiO2The dielectric layer adopts the following processes: introducing Silane (SiH) into the reaction chamber4) And nitrous oxide (N)2O) by chemical reaction of SiHx+O→SiO2(+H2) Deposition of SiO on P-type GaN layer heated to 350 deg.C2And the thickness of the thin film layer is 150-250 nm. PECVD growthSiNxThe film process comprises the following steps: introducing Silane (SiH) into a reaction cavity of PECVD4) And nitrogen (N)2) Mixed gas source by chemical reaction of SiHx+N→SiNx(+H2) Deposition of SiN on P-type gallium nitride heated to 350 degrees celsiusxThe thickness of the thin film layer is 150-300 nm.
(2) As shown in FIG. 3, SiO2Or SiNxAfter the mask 6 is prepared, spin-coating a photoresist 7 on the dielectric layer, and selecting the thicknesses of the photoresist 7 with different concentrations according to the structural depth of the photoresist, wherein the typical thickness is 150-300 nm; then copying the pattern of the photoetching plate onto the photoresist by utilizing an ultraviolet photoetching technology, and leaving a large-area ordered square table surface array pattern;
(3) as shown in FIG. 4, a Reactive Ion Etching (RIE) technique is used to introduce O2The residual layer of the photoresist 7 is removed. Then, a layer of metal 8 such as nickel (Ni), chromium (Cr) or aluminum (Al) is evaporated by utilizing a Physical Vapor Deposition (PVD) process, wherein the typical thickness is 30-100 nm; then soaking the sample in acetone solution for ultrasonic stripping, and removing the photoresist layer 7 and the metal film 8 on the photoresist layer to obtain a large-area ordered square metal mesa array pattern;
(4) as shown in FIG. 5, CF is introduced using a Reactive Ion Etching (RIE) technique4And O2The metal 8 is used as a mask to longitudinally etch the dielectric layer, and the metal square mesa structure is transferred to the dielectric layer 6; etching conditions are as follows: CF (compact flash)4And O2The flow rate is 30-100 sccm and 4-20 sccm respectively, the power is 30-100W, the pressure is 1.0-10 Pa, and the etching time is 1-20 min.
(5) As shown in FIG. 6, inductively coupled plasma etching (ICP) is used to introduce Cl2And BCl3Anisotropically etching the P-type gallium nitride layer 5 to the N-type gallium nitride layer 3 by using the mixed gas, and isolating a separated large-area low-defect square table top blue light Micro-LED array on an epitaxial wafer; the etching conditions are as follows: cl2And BCl3The flow rate is 24 +/-10 sccm and 8 +/-5 sccm respectively, the ICP power is 300 +/-200W (the frequency is 13.56MHz), and the etching time is 10-20 min.
(6) As shown in fig. 7, the sample is immersed in a solution of inorganic acid and alkali (such as hydrochloric acid, nitric acid, potassium hydroxide, sodium hydroxide, and the like) in a water bath at 40-90 ℃ for heating for 5-20min by wet etching, so as to remove the metal mask layer 8 and the etching damage on the surface; and removing the residual dielectric layer 6 on the surface by using hydrofluoric acid or BOE solution.
(7) As shown in FIG. 8, a layer of SiO 150-250nm thick is evaporated by PECVD technique2Or a SiNx dielectric layer film 6; in SiO2Or SiNxPhotoresist 7 is spin-coated on the dielectric layer, and the thickness of the photoresist 7 with different concentrations is selected according to the structure depth of the photoresist, wherein the typical thickness is 150-300 nm; then, forming an N-type electrode pattern on the photoresist by using an ultraviolet lithography technology and using a photolithography mask;
(8) as shown in FIG. 9, using Reactive Ion Etching (RIE) technique, CF is introduced4And O2Etching SiO with the photoresist 7 as a mask2 A dielectric layer 6, transferring the N-type electrode pattern to the N-type gallium nitride 3; etching conditions are as follows: CF (compact flash)4And O2The flow rate is 30-100 sccm and 4-20 sccm respectively, the power is 30-100W, the pressure is 1.0-10 Pa, and the etching time is 1-20 min.
(9) As shown in FIG. 10, 200-300nm titanium (Ti)/aluminum (Al)/nickel (Ni)/gold (Au) is evaporated by PVD process as N-type electrode. The sample is soaked in acetone to ultrasonically strip the photoresist 7 and the metal film 9 on the photoresist layer. Finally in N2In the environment, the ohmic contact of titanium (Ti)/aluminum (Al)/nickel (Ni)/gold (Au) and N-type gallium nitride is realized by thermal annealing.
(10) As shown in fig. 11, a layer of photoresist 7 is spin-coated on the surface of the sample, a P-type electrode region is formed on the surface of the sample by using an ultraviolet lithography technique, and then CF is introduced by using an RIE technique4And O2Etching SiO with the photoresist 7 as a mask2And a dielectric layer 6 for transferring the P-type electrode pattern to the P-type gallium nitride layer 5. Etching conditions are as follows: CF (compact flash)4And O2The flow rate is 30-100 sccm and 4-20 sccm respectively, the power is 30-100W, the pressure is 1.0-10 Pa, and the etching time is 1-20 min.
(11) As shown in FIG. 12, a metal of nickel (Ni)/gold (Au)150-300nm is evaporated as the p-type electrode 10 by a Physical Vapor Deposition (PVD) process.
(12) As shown in fig. 13, the sample is immersed in acetone to ultrasonically strip off the photoresist 7 and the metal thin film 10 on the photoresist layer, and the sample is washed and dried. Finally in N2In the environment, ohmic contact between nickel (Ni)/gold (Au) metal and P-type gallium nitride is realized by thermal annealing, and finally the blue light Micro-LED pixel array structure with the square mesa structure is obtained.
(13) As shown in FIG. 14, the prepared sample is placed in a multi-source organometallic vacuum deposition system, and the organic material and the metal are placed in different evaporation sources, the temperature of each evaporation source can be controlled independently, when the vacuum degree of the vacuum coating system reaches 5 × 10-4When the voltage is less than pascal, an electron transport layer 11, a red light doping and emitting layer 12, an exciton blocking layer 13, a hole transport layer 14, a hole injection layer 15 and a metal anode 16 are sequentially evaporated on the N-type gallium nitride substrate.
(14) As shown in fig. 15, after the evaporation of the red organic material is completed, the mask is replaced. An electron transport layer 11, a green light-doped light-emitting layer 17, a hole transport layer 14, a hole injection layer 15 and a metal anode 16 are sequentially evaporated on an N-type gallium nitride substrate. The resulting III-nitride/organic semiconductor hybrid structure-based red-green-blue micron LED array device for display has a surface structure as shown in fig. 16, where fig. 16 shows only 2 × 2 pixel units, each pixel unit having a 2 × 2 structure, including a red LED20, a green LED21, a blue LED22, and a spare LED 23. Spare LEDs can also be eliminated, and each pixel unit has a 3 × 1 structure, including a red LED20, a green LED21, and a blue LED22, which are arranged in parallel.
In the present embodiment, the N-type electrode 9 injects current to the inorganic LED and the organic LED simultaneously through the N-type gallium nitride layer 3, and shares the N-type electrode 9 and the N-type gallium nitride layer 3. In this case a bottom emission device, the sapphire substrate 1 is single-side polished. Moreover, can be according to the light type demand, the design is top light-emitting or two-sided luminous, and when the top goes out the light, can be at 1 back evaporation coating reflection stratum of sapphire substrate.
Example 2
The difference between this example and example 1 is that the N-type electrode of the inorganic LED and the organic light emitting diode structure, and the structure of the inorganic LED still adopts the structures of fig. 1 to 7, so the following description focuses on the N-type electrode of the inorganic LED and the organic light emitting diode structure:
(1) as shown in FIG. 17, a layer of SiO was deposited on the sample of FIG. 7 using Plasma Enhanced Chemical Vapor Deposition (PECVD) techniques2Or SiNxThe dielectric layer film serves as a mask layer 6. PECVD (plasma enhanced chemical vapor deposition) growth of SiO2The dielectric layer adopts the following processes: introducing Silane (SiH) into the reaction chamber4) And nitrous oxide (N)2O) by chemical reaction of SiHx+O→SiO2(+H2) Deposition of SiO on P-type GaN layer heated to 350 deg.C2And the thickness of the thin film layer is 150-250 nm. PECVD growth of SiNxThe film process comprises the following steps: introducing Silane (SiH) into a reaction cavity of PECVD4) And nitrogen (N)2) Mixed gas source by chemical reaction of SiHx+N→SiNx(+H2) Deposition of SiN on P-type gallium nitride heated to 350 degrees celsiusxThe thickness of the thin film layer is 150-300 nm.
(2) As shown in fig. 18, a photoresist 7 is spin-coated on the dielectric layer 6, and the thickness of the photoresist 7 with different concentrations is selected according to the structure depth of the photoresist, with a typical thickness of 150-300 nm; then, a transparent electrode area is made on the surface of the sample by utilizing an ultraviolet photoetching technology.
(3) As shown in FIG. 19, using Reactive Ion Etching (RIE) technique, CF is introduced4And O2Etching SiO with the photoresist 7 as a mask2 A dielectric layer 6, which transfers the transparent electrode pattern to the N-type gallium nitride layer 3; etching conditions are as follows: CF (compact flash)4And O2The flow rate is 30-100 sccm and 4-20 sccm respectively, the power is 30-100W, the pressure is 1.0-10 Pa, and the etching time is 1-20 min.
(4) As shown in fig. 20, a layer of transparent electrode 18, such as Indium Tin Oxide (ITO), aluminum (Al), silver (Ag), etc., is evaporated by electron beam evaporation or thermal evaporation, and the thickness is 5 to 20 nm; and removing the photoresist and the metal film on the photoresist layer by wet etching, and cleaning and drying the sample. And finally, annealing the sample at high temperature in a rapid annealing furnace (RTA) for 2-10 min at the annealing temperature of 450-600 ℃.
(5) As shown in FIG. 21, a layer of SiO 150-250nm thick is deposited on the surface of the sample by PECVD technique2Or SiNxA dielectric layer 6; and (3) spin-coating photoresist 7 on the dielectric layer 6, and then forming an N-type electrode area on the surface of the sample by using an ultraviolet lithography technology.
(6) As shown in FIG. 22, using Reactive Ion Etching (RIE) technique, CF is introduced4And O2Etching SiO with the photoresist 7 as a mask2 A dielectric layer 6, which transfers the N-type electrode pattern to the N-type gallium nitride layer 3; etching conditions are as follows: CF (compact flash)4And O2The flow rate is 30-100 sccm and 4-20 sccm respectively, the power is 30-100W, the pressure is 1.0-10 Pa, and the etching time is 1-20 min.
(7) As shown in FIG. 23, 200-300nm titanium (Ti)/aluminum (Al)/nickel (Ni)/gold (Au) was evaporated by PVD process as N-type electrode. The sample is soaked in acetone to ultrasonically strip the photoresist 7 and the metal film 9 on the photoresist layer. Finally in N2In the environment, ohmic contact between titanium (Ti)/aluminum (Al)/nickel (Ni)/gold (Au) and the transparent electrode is realized by thermal annealing.
(8) As shown in fig. 24, a layer of photoresist 7 is spin-coated on the surface of the sample, a P-type electrode region is formed on the surface of the sample by using the ultraviolet lithography technique, and then CF is introduced by using the RIE technique4And O2Etching SiO with the photoresist 7 as a mask2And a dielectric layer 6 for transferring the P-type electrode pattern to the P-type gallium nitride layer 5. Etching conditions are as follows: CF (compact flash)4And O2The flow rate is 30-100 sccm and 4-20 sccm respectively, the power is 30-100W, the pressure is 1.0-10 Pa, and the etching time is 1-20 min.
(9) As shown in FIG. 25, a metal of nickel (Ni)/gold (Au)150-300nm is evaporated as the p-type electrode 10 by a Physical Vapor Deposition (PVD) process.
(10) As shown in fig. 26, the photoresist and the metal thin film 10 on the photoresist layer are removed by wet etching, and the sample is washed and dried. Finally in N2In the ambient, ohmic contact between the nickel (Ni)/gold (Au) metal 10 and the P-type gallium nitride layer 5 is achieved by thermal annealing.
(10) As shown in FIG. 27, the prepared sample is placed in a multi-source organometallic vacuum deposition system, organic materials and metals are placed in different evaporation sources, the temperature of each evaporation source can be controlled independently, and when the vacuum degree of the vacuum coating system reaches 5 × 10 by using the shadow mask technology-4When pascal or less, an electron injection layer 19, an electron transport layer 11, a red-light doped light emitting layer 12, an exciton blocking layer 13, a hole transport layer 14, a hole injection layer 15, and a metal anode 16 are sequentially evaporated on the transparent electrode.
(11) As shown in fig. 28, after the evaporation of the red organic material is completed, the mask is replaced. An electron injection layer 19, an electron transport layer 11, a green light-doped light-emitting layer 17, a hole transport layer 14, a hole injection layer 15, and a metal anode 16 are sequentially deposited on the transparent electrode. Finally, the red-green-blue micron LED array device based on the III-nitride/organic semiconductor hybrid structure which can be used for display is obtained.
In this embodiment, which is a bottom emission device in this case, the sapphire substrate 1 is single-side polished. The design can be the top luminescence or two-sided luminescence according to the light type demand equally, and when the top goes out the light, can be at 1 back evaporation coating reflection stratum of sapphire substrate.
Example 3 white light Micro-LED device based on a group III nitride/organic semiconductor hybrid structure
The embodiment adopts the blue light LED and the yellow light organic LED to form the white light LED array device based on the III-nitride/organic semiconductor hybrid structure. Selecting In having p-n structurexGa1-xThe light-emitting wavelength of the N/gallium nitride quantum well blue light LED epitaxial wafer is 450-470 nm; the yellow organic light emitting diode is formed by doping a main material with a yellow fluorescent or phosphorescent micromolecular material, and the light emitting wavelength of the yellow organic light emitting diode is 570-600 nm.
This example differs from example 1 in that the N-type electrode and the organic light emitting diode structure of the inorganic LED, the blue inorganic Micro-LED array structure and the N-type electrode are prepared by using the structures of fig. 1 to 10, and therefore the following description focuses on the structure of the yellow organic light emitting diode:
(1) as shown in fig. 29, a blue inorganic Micro-LED array structure and an N-type electrode were prepared according to example 1.
(2) As shown in FIG. 30, a layer of SiO was deposited on the sample of FIG. 29 using a Plasma Enhanced Chemical Vapor Deposition (PECVD) technique2Or SiNxThe dielectric layer film serves as a mask layer 6.
(3) As shown in fig. 31, a photoresist 7 is spin-coated on the dielectric layer 6, and then a transparent electrode region is formed on the surface of the sample by using an ultraviolet lithography technique.
(4) As shown in fig. 32, a transparent electrode 18, such as Indium Tin Oxide (ITO), aluminum (Al), silver (Ag), etc., is deposited by electron beam evaporation or thermal evaporation, and has a thickness of 5-20 nm.
(5) As shown in fig. 33, the photoresist and the metal film on the photoresist layer are removed by wet etching, and the sample is washed and dried. And finally, annealing the sample at high temperature in a rapid annealing furnace (RTA) for 2-10 min at the annealing temperature of 450-600 ℃.
(6) As shown in FIG. 34, the prepared sample is placed in a multi-source organometallic vacuum deposition system, and the organic material and the metal are placed in different evaporation sources, the temperature of each evaporation source can be controlled independently, when the vacuum degree of the vacuum coating system reaches 5 × 10-4When the surface structure is less than pascal, the hole injection layer 15, the hole transport layer 14, the exciton blocking layer 13, the yellow light doped light emitting layer 20, the electron transport layer 11, the electron injection layer 19 and the metal cathode 21 are sequentially evaporated on the transparent electrode, and finally the white light Micro-LED device for illumination is obtained, wherein the surface structure of the white light Micro-LED device is shown in fig. 35, and each square mesa is a white light LED 24.
In the present embodiment, the transparent electrode 18 injects current to the inorganic LED and the organic LED at the same time, and shares the P-type electrode. In this case a bottom emission device, the sapphire substrate 1 is single-side polished. The P-type electrode adopts a transparent electrode, so that the light extraction rate can be increased. The design can be the top luminescence or two-sided luminescence according to the light type demand equally, and when the top goes out the light, can be at 1 back evaporation coating reflection stratum of sapphire substrate.
Example 4
In this case, blue light inorganic Micro-LED and red and green organic single-layer light emitting devices are adoptedThe prepared sample is put into a multi-source organic metal vacuum deposition system, organic materials and metals are placed in different evaporation sources, the temperature of each evaporation source can be independently controlled, and when the vacuum degree of the vacuum plating system reaches 5 × 10-4And when the voltage is less than pascal, a hole injection layer 15, a hole transport layer 14, an exciton blocking layer 13, a red and green light-doped light-emitting layer 22, an electron transport layer 11, an electron injection layer 19 and a metal cathode 21 are sequentially evaporated on the transparent electrode.
Example 5
The prepared sample is put into an organic metal vacuum deposition system, organic materials and metals are placed in different evaporation sources, the temperature of each evaporation source can be independently controlled, and when the vacuum degree of a vacuum plating film system reaches 5 × 10, the vacuum degree of the vacuum plating film system can be independently controlled-4When the electron emission efficiency is less than pascal, the hole injection layer 15, the hole transport layer 14, the exciton blocking layer 13, the red-light-doped light-emitting layer 23, the green-light-doped light-emitting layer 24, the electron transport layer 11, the electron injection layer 19 and the metal cathode 21 are sequentially evaporated on the transparent electrode.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A full-color Micro-LED array display device based on a III-nitride/organic semiconductor hybrid structure comprises the following components from bottom to top:
a sapphire substrate;
a gallium nitride buffer layer grown on the sapphire substrate;
an N-type gallium nitride layer grown on the buffer layer;
an In layer grown on the N-type GaN layerxGa1-xAn N/gallium nitride quantum well active layer;
a P-type gallium nitride layer grown on the quantum well active layer;
the full-color Micro-LED array display device is etched to form an array type square table structure penetrating through the P-type gallium nitride layer and the quantum well active layer and reaching the N-type gallium nitride layer, and the square tables are mutually isolated;
the P-type electrode is evaporated on the P-type gallium nitride layer, and the N-type electrode is evaporated on the N-type gallium nitride layer;
the method is characterized in that: the square table board array comprises a plurality of pixel units, the pixel units are arranged repeatedly, each pixel unit at least comprises a blue light LED, a red light LED and a green light LED, the square table boards of the red light LED and the green light LED are etched to the N-type gallium nitride layer, the red light LED is formed by evaporating organic red light emitting diodes on the N-type gallium nitride layer, and the green light LED is formed by evaporating organic green light emitting diodes on the N-type gallium nitride layer.
2. A full color Micro-LED array display device according to claim 1, wherein: the red light LED or the green light LED is formed by sequentially evaporating an electron transport layer, a light emitting layer, an exciton blocking layer, a hole transport layer, a hole injection layer and a metal anode on an N-type gallium nitride layer;
the electron transport layer is an organic compound or an N-type doped layer, the organic compound comprises 1,3, 5-tri [ (3-pyridyl) -3-phenyl ] benzene, 2, 5-di (1-naphthyl) -1,3, 4-diazole, 2-biphenyl-5- (4-tert-butylphenyl) -1,3, 4-diazole, 8-hydroxyquinoline aluminum, 1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene, 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline, 4, 7-diphenyl-1, 10-phenanthroline or 4, 7-diphenyl-1, 10-phenanthroline: cesium carbonate with a thickness of 30-70 nm;
the main body of the luminescent layer is 4,4 '-di (9-carbazole) biphenyl, 4' -tri (carbazole-9-yl) triphenylamine, 1, 3-dicarbazole benzene or N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, and the thickness is 10-30 nm;
doping red light doping materials or green light doping materials in the light emitting layer to emit red light or green light;
the red light doping material comprises 4-dicyanomethylene-2-tert-butyl-6- (1,1,7, 7-tetramethyl julolidine-4-vinyl) -4H-pyran, tri (1- (4-N-hexylphenyl) -isoquinoline-C2, N) iridium (III) and bis (1-phenylisoquinoline-C2, N) iridium (III) acetylacetonate, the light-emitting wavelength is 630nm-660nm, and the doping concentration is 1% -20%;
the green light doping material comprises iridium tri (2-phenylpyridine), iridium bis (2-phenylpyridine-C2, N) acetylacetonate, coumarin and 8-hydroxyquinoline aluminum, the light-emitting wavelength is 520nm-560nm, and the doping concentration is 1% -20%;
the exciton blocking layer comprises 4,4 '-bis (9-carbazole) biphenyl, 4' -tris (carbazole-9-yl) triphenylamine and 1, 3-dicarbazole benzene, and the doping concentration is 1% -20%;
the hole transport layer comprises N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine, 4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ], N ' -diphenyl-N, N ' -bis (3-methylphenyl) -1,1' -biphenyl-4, 4' -diamine, N ' -diphenyl-N, N ' -bis (4-methylphenyl) biphenyl-4, 4' -diamine, 4' -tris [ phenyl (m-tolyl) amino ] triphenylamine and has a thickness of 40-70 nm;
the hole injection layer is made of transition metal oxide or organic material, the transition metal oxide comprises molybdenum oxide, vanadium pentoxide and tungsten trioxide, the organic material comprises tetrafluorotetracyanoquinodimethane, 7,8, 8-tetracyanoterephthalquinodimethane, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene, 4' -tris (2-naphthylphenylamino) triphenylamine, and the thickness of the organic material is 2-40 nm;
the anode metal is gold, silver, copper or aluminum, the work function is 4.3eV to 5.2eV, and the thickness is 100-150 nm.
3. A full color Micro-LED array display device according to claim 2, wherein: an electron injection layer is further arranged between the N-type gallium nitride layer and the electron transmission layer, the electron injection layer is an alkali metal compound or an N-type doping layer, and the alkali metal compound comprises lithium fluoride, lithium carbonate, cesium fluoride or lithium: 8-hydroxyquinoline aluminum, and the thickness of the electron injection layer is 0.5-1.5 nm.
4. A full color Micro-LED array display device according to claim 3, wherein: the transparent electrode is arranged between the electron injection layer and the N-type gallium nitride layer.
5. A full color Micro-LED array display device according to claim 2, wherein: the size of the square mesa array is 20-100 μm, the distance between the arrays is 5-20 μm, and the period is 800-.
6. A full color Micro-LED array display device according to claim 2, wherein: the light-emitting wavelength of the blue light LED is 450-470 nm.
7. A full color Micro-LED array display device according to claim 1 or 2, wherein: the pixel units are of a 2-by-2 structure, and each pixel unit comprises a red LED, a green LED, a blue LED and a standby LED; or the pixel units are in a 3-by-1 structure and each pixel unit comprises a red light LED, a green light LED and a blue light LED, and the pixel units are arranged in parallel.
8. A method of manufacturing a full color Micro-LED array display device according to any of claims 1 to 7, comprising the steps of:
1) in with p-n structure by PECVD technologyxGa1-xEvaporating a dielectric layer on the N/gallium nitride quantum well blue light LED epitaxial wafer;
2) spin-coating photoresist on the surface of the dielectric layer, pre-baking the photoresist, forming an ordered square mesa array pattern on the photoresist by using a photoetching plate by using an ultraviolet photoetching technology, and then developing and post-baking;
3) by RIE technique, with O introduction2Removing the residual layer of the photoresist, evaporating a metal mask layer by utilizing a PVD (physical vapor deposition) process, stripping, and removing the photoresist layer and the metal mask layer on the photoresist layer to obtain a large-area ordered metal square table array pattern;
4) adopting RIE technology, taking metal as a mask to longitudinally etch the dielectric layer, and transferring the metal square mesa array structure to the dielectric layer;
5) adopting an ICP (inductively coupled plasma) technology, and anisotropically etching the P-type gallium nitride layer and the quantum well layer by using metal as a mask, so as to etch the groove to the N-type gallium nitride layer, and etching the square table tops of the red light LED and the green light LED to the N-type gallium nitride layer, wherein the square table tops are still separated by etching the groove;
6) removing the metal mask layer and the dielectric layer on the square mesa array structure by adopting wet etching to form a gallium nitride square mesa array structure which is isolated from each other, and repairing etching damage of gallium nitride and the side wall of the quantum well;
7) preparing an N-type electrode, evaporating a dielectric thin film layer by utilizing a PECVD (plasma enhanced chemical vapor deposition) technology, coating photoresist on the surface of the dielectric layer in a spinning mode, forming an N-type electrode pattern on the photoresist by utilizing an ultraviolet lithography technology and using a photoetching plate for alignment, and then etching the dielectric layer by utilizing the photoresist as a mask by adopting an RIE (reactive ion etching) technology to transfer the N-type electrode pattern to the N-type gallium nitride layer; a layer of metal is evaporated by adopting a PVD (physical vapor deposition) process to be used as an N-type electrode; stripping off the photoresist and the metal film on the photoresist layer, cleaning and drying the sample; finally, ohmic contact between the metal and the N-type gallium nitride is realized by thermal annealing;
8) preparing a P-type electrode, evaporating a dielectric thin film layer by utilizing a PECVD (plasma enhanced chemical vapor deposition) technology, coating photoresist on the surface of the dielectric layer in a spinning mode, forming a P-type electrode pattern on the photoresist by utilizing an ultraviolet lithography technology and using a photoetching plate for alignment, and then etching the dielectric layer thin film by utilizing the photoresist as a mask by adopting an RIE (reactive ion etching) technology to transfer the P-type electrode pattern to the P-type gallium nitride layer; a layer of metal is evaporated by adopting a PVD (physical vapor deposition) process to be used as a p-type electrode; removing the photoresist and the metal film on the photoresist layer by wet etching, cleaning and drying the sample; finally, ohmic contact between metal and p-type gallium nitride is realized by thermal annealing;
9) the prepared sample is put into a multi-source organic metal vacuum deposition system to be evaporated with organic luminescent materials, the organic materials and metals are put in different evaporation sources, the temperature of each evaporation source can be independently controlled, and when one organic material is evaporated, other pixels are shielded by using a shielding mask.
9. A full-color Micro-LED array white light device based on a III-nitride and organic semiconductor hybrid structure comprises the following components from bottom to top:
a sapphire substrate;
a gallium nitride buffer layer grown on the sapphire substrate;
an N-type gallium nitride layer grown on the buffer layer;
an In layer grown on the N-type GaN layerxGa1-xAn N/gallium nitride quantum well active layer;
a P-type gallium nitride layer grown on the quantum well active layer;
the full-color Micro-LED array white light device is etched to form an array square table structure penetrating through the P-type gallium nitride layer and the quantum well active layer and reaching the N-type gallium nitride layer, and the square tables are mutually isolated;
the P-type electrode is evaporated on the P-type gallium nitride layer, and the N-type electrode is evaporated on the N-type gallium nitride layer;
the method is characterized in that: and red and green light doped organic light emitting diodes or yellow light doped organic light emitting diodes are vapor-plated on the square table surface array.
10. The full color Micro-LED array white light device of claim 9, wherein: sequentially evaporating an electron injection layer, an electron transport layer, a light emitting layer, an exciton blocking layer, a hole transport layer, a hole injection layer and a metal anode on the square mesa array;
the electron injection layer is an alkali metal compound or an N-type doped layer, and the alkali metal compound comprises lithium fluoride, lithium carbonate, cesium fluoride or lithium: 8-hydroxyquinoline aluminum, the thickness of the electron injection layer is 0.5-1.5 nm;
the electron transport layer is an organic compound or an N-type doped layer, the organic compound comprises 1,3, 5-tri [ (3-pyridyl) -3-phenyl ] benzene, 2, 5-di (1-naphthyl) -1,3, 4-diazole, 2-biphenyl-5- (4-tert-butylphenyl) -1,3, 4-diazole, 8-hydroxyquinoline aluminum, 1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene, 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline, 4, 7-diphenyl-1, 10-phenanthroline or 4, 7-diphenyl-1, 10-phenanthroline: cesium carbonate with a thickness of 30-70 nm;
the luminescent layer main body comprises 4,4 '-bis (9-carbazole) biphenyl, 4' -tris (carbazole-9-yl) triphenylamine, 1, 3-dicarbazole benzene or N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, and the thickness is 10-30 nm;
doping red light doping materials, green light doping materials or yellow light doping materials in the light emitting layer to emit red light, green light or yellow light;
the red light doping material comprises 4-dicyanomethylene-2-tert-butyl-6- (1,1,7, 7-tetramethyl julolidine-4-vinyl) -4H-pyran, tri (1- (4-N-hexylphenyl) -isoquinoline-C2, N) iridium (III) and bis (1-phenylisoquinoline-C2, N) iridium (III) acetylacetonate, the light-emitting wavelength is 630nm-660nm, and the doping concentration is 1% -20%;
the green light doping material comprises iridium tri (2-phenylpyridine), iridium bis (2-phenylpyridine-C2, N) acetylacetonate, coumarin and 8-hydroxyquinoline aluminum, the light-emitting wavelength is 520nm-560nm, and the doping concentration is 1% -20%;
the yellow light doped material comprises bis [2- (6-phenyl-4-pyrimidinyl ] (acetylacetone) iridium (III), bis (2 (9-9-diethyl-9-fluoro-2-yl) -1-phenyl-1H-benzimidazole-N, C3) iridium (acetylacetone), rubrene and tetra (tert-butyl) rubrene, the light-emitting wavelength is 570-600nm, and the doping concentration is 1-10%;
the exciton blocking layer comprises 4,4 '-bis (9-carbazole) biphenyl, 4' -tris (carbazole-9-yl) triphenylamine and 1, 3-dicarbazole benzene, and the doping concentration is 1% -20%;
the hole transport layer comprises N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine, 4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ], N ' -diphenyl-N, N ' -bis (3-methylphenyl) -1,1' -biphenyl-4, 4' -diamine, N ' -diphenyl-N, N ' -bis (4-methylphenyl) biphenyl-4, 4' -diamine, 4' -tris [ phenyl (m-tolyl) amino ] triphenylamine and has a thickness of 40-70 nm;
the hole injection layer is made of transition metal oxide or organic material, the metal oxide comprises molybdenum oxide, vanadium pentoxide and tungsten trioxide, the organic material is tetrafluorotetracyanoquinodimethane, 7,8, 8-tetracyanoterephthalquinodimethane, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene, 4' -tris (2-naphthylphenylamino) triphenylamine, and the thickness of the organic material is 2-40 nm;
the anode metal is gold, silver, copper or aluminum, the work function is 4.3eV to 5.2eV, and the thickness is 100-150 nm.
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| WO2018073515A1 (en) * | 2016-10-21 | 2018-04-26 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Display device and method for producing such a device |
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| CN103579461A (en) * | 2013-11-08 | 2014-02-12 | 中国科学院半导体研究所 | Method for manufacturing wafer full-color LED display array |
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