KR20140086591A - GaN LED using Nano Wire structure including Quantum Dots and preparation method thereof - Google Patents
GaN LED using Nano Wire structure including Quantum Dots and preparation method thereof Download PDFInfo
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- KR20140086591A KR20140086591A KR1020120157275A KR20120157275A KR20140086591A KR 20140086591 A KR20140086591 A KR 20140086591A KR 1020120157275 A KR1020120157275 A KR 1020120157275A KR 20120157275 A KR20120157275 A KR 20120157275A KR 20140086591 A KR20140086591 A KR 20140086591A
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- gallium nitride
- nitride semiconductor
- type gallium
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02587—Structure
- H01L21/0259—Microstructure
- H01L21/02603—Nanowires
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- 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
- H01L33/12—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 stress relaxation structure, e.g. buffer layer
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- H01L33/20—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 particular shape, e.g. curved or truncated substrate
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- H01L33/36—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 electrodes
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Abstract
Description
The present invention relates to a gallium nitride light emitting diode having a nanowire structure doped with quantum dots and a method of manufacturing the same.
BACKGROUND ART [0002] Light emitting diodes (LEDs) using semiconductors are used in various fields such as displays, optical communication, automobiles, and general lighting as a high efficiency and environmentally friendly light source. Particularly, the demand for white light emitting diodes is increasing. As a method of realizing white light, a phosphor can be used. After ultraviolet light is emitted from an ultraviolet (UV) LED, red, green and blue phosphors are excited by ultraviolet light to emit red light and green light, Can be obtained. In addition, white light can be obtained by emitting yellow light by exciting a yellow phosphor having a complementary color with the blue LED as a light source.
As a method of realizing a white color with only an LED without a phosphor, a combination of LEDs that emit red, green, and blue visible light, respectively, is used. For example, in the case of an LED using an InGaN layer as a light emitting material, the fact that a luminescent color changes in accordance with a change in the mole fraction of In in the InGaN layer is utilized. However, in the case of an LED using an InGaN layer as a light emitting material, the luminescence color shifts to a longer wavelength as the In content increases, and as the In content increases, the lattice constant increases and a large lattice constant mismatch between the thin InGaN layer and the substrate mismatch is generated and the emission efficiency is lowered as it moves to a longer wavelength.
In addition, when a plurality of light emitting diodes having red, green, and blue colors are arranged and mixed to be used as a white light source, a plurality of active light emitting diode devices are assembled and assembled to increase the manufacturing cost, There is a disadvantage in that the performance of the white light source is uneven due to the unevenness of the device characteristics and the difference in the deterioration pattern.
On the other hand, the OPTICS EXPRESS on July 4, 2011 has a quantum well structure of multiple layers rather than a simple quantum well structure, so that the light emission rate is improved. By having a quantum well structure of three layers, the FWHM maximum is reduced so that light of the correct red, green and blue can be obtained. Accordingly, there is a demand for the development of light emitting diodes having improved efficiency by using the characteristics of such a multilayered quantum well structure.
A first problem to be solved by the present invention is to provide a gallium nitride light emitting diode having a nanowire structure doped with a quantum dot.
A second problem to be solved by the present invention is to provide a method of manufacturing a gallium nitride light emitting diode having a nanowire structure to which the quantum dots are added.
According to an exemplary aspect of the present invention,
Board;
A buffer layer formed on one surface of the substrate;
An N-type gallium nitride semiconductor layer formed on the buffer layer;
A nanowire grown on the surface of the N-type gallium nitride semiconductor layer;
A nanowire shell layer coated over the N-type gallium nitride semiconductor layer on which the nanowires are grown;
A P-type gallium nitride semiconductor layer formed on the N-type gallium nitride semiconductor layer coated with the nanowire shell layer; And
And a transparent electrode formed on the P-type gallium nitride semiconductor layer, the gallium nitride light-
The nanowire has a diameter of 20-60 nm, a height of 100-200 nm,
Quantum dots are additionally provided on the N-type gallium nitride semiconductor layer and the surface of the nanowire,
And a nano-structured gallium nitride light-emitting diode doped with quantum dots, wherein the nanowires coated with the nanowire shell layer are filled with the P-type gallium nitride semiconductor to form a thin film.
According to another aspect of the present invention,
(1) forming a buffer layer over the substrate;
(2) forming an N-type gallium nitride semiconductor layer on the buffer layer;
(3) forming a catalyst layer on the N-type gallium nitride semiconductor layer, liquefying the catalyst layer at a eutectic point, growing a nanowire, and removing the catalyst layer;
(4) applying quantum dots on the N-type gallium nitride semiconductor layer on which the nanowires and the nanowires are grown;
(5) coating the N-type gallium nitride semiconductor layer coated with the quantum dot with a nanowire shell layer;
(6) forming a P-type gallium nitride semiconductor layer on the nanowire shell layer coating; And
(7) forming a transparent electrode on the P-type gallium nitride semiconductor thin film; and (8) forming a gallium nitride light emitting diode having a nanowire structure added with a quantum dot.
The gallium nitride light emitting diode having a nanowire structure to which a quantum dot is added according to the present invention includes nanowires grown on a N-type semiconductor layer doped with silicon (Si) and quantum dots of a core shell structure added. The surface area of the boundary layer where light is generated is greatly increased due to the formation of surface irregularities. The quantum dots of the core shell structure coated on the N-type semiconductor layer and the nanowire exhibit a fluorescence resonance energy transfer phenomenon And strengthened the light, and the efficiency of the light was improved by forming a multilayer quantum well structure.
1 is a perspective view and a cross-sectional view of a gallium nitride reducing layer formed on a sapphire substrate according to an embodiment of the present invention.
FIG. 2 is a perspective view and a cross-sectional view of a step in which an N-type semiconductor layer doped with gallium nitride (GaN) is formed on a gallium nitride reducing layer formed on a sapphire substrate according to an embodiment of the present invention.
3 is a perspective view and a cross-sectional view of a step of forming a nickel catalyst layer on an N-type semiconductor layer according to an embodiment of the present invention.
4 is a stereoscopic view and a cross-sectional view of a step in which a nickel catalyst is dispersed by surface tension at a eutectic point according to an embodiment of the present invention.
FIG. 5 is a three-dimensional view and a cross-sectional view of a step of forming a nanowire using a nickel catalyst by a VLS process (vapor liquid solid method) according to an embodiment of the present invention.
FIG. 6 is a perspective view and a cross-sectional view illustrating a step of removing residual nickel on a nano-wire according to an embodiment of the present invention.
FIG. 7 is a perspective view and a cross-sectional view of a CdSe / ZnS core / shell quantum dot uniformly spread on a nickel-removed nanowire according to an embodiment of the present invention.
8 is a stereoscopic view and a cross-sectional view of a nanowire shell layer formed by coating indium gallium nitride (InGaN) on a gallium nitride layer and a gallium nitride layer on which quantum dots are spread according to an embodiment of the present invention.
9 is a perspective view and a cross-sectional view of a step of applying and planarizing a P-type semiconductor layer in which gallium nitride is doped with magnesium (Mg) over a nanowire shell layer coated with indium gallium nitride (InGaN) according to an embodiment of the present invention .
10 is a perspective view and a cross-sectional view of a step in which an electrode layer is formed of indium tin oxide (ITO) on a P-type semiconductor layer and a circuit is formed according to an embodiment of the present invention.
11 is a schematic view showing an electron transfer path in a gallium nitride light emitting diode device having a nanowire structure added with quantum dots according to an embodiment of the present invention.
12 illustrates a bandgap energy structure according to a movement path of a light emitting diode device manufactured according to an embodiment of the present invention.
FIG. 13 is a perspective view and a cross-sectional view of a gallium nitride light emitting diode device and a light emitting diode chip of a nanowire structure to which quantum dots are added according to an embodiment of the present invention.
FIG. 14 is a flowchart illustrating a method of manufacturing a gallium nitride light emitting diode device having a nanowire structure added with quantum dots according to an embodiment of the present invention.
Gallium nitride (GaN) is a wide band gap semiconductor with a direct band gap of 3.39 eV. Since the early 1970s, it has been studied for the application of various photoelectric devices and protective films including blue light emitting devices. It is the material that has been. Gallium nitride has a lattice constant of a = 3.189 Å and c = 5.185 Å at room temperature. It has a wurtzite structure in a stable state and a Zinc-blende structure in a semi-perfect state because of its high electronegativity of nitrogen.
Since the gallium nitride (GaN) is indium nitride (InN, Eg = 1.92 eV) and aluminum nitride (AlN, Eg = 6.2 eV) Ⅲ-Ⅴ type nitride semiconductor and have a continuous solubility, such as In x Ga 1 - x N Or Ga x Al 1-x N can be formed. Since the bandgap varies in accordance with the composition of these ternary nitrides as a linear function of the composition, various light emitting devices including red to ultraviolet transmission regions can be fabricated by controlling the composition of these III-V nitrides .
The indium gallium nitride quantum well light emitting diode has a deeper bandgap energy structure as it goes from a simple arrangement to a multilayered quantum well structure.
When the bandgap energy structure is further deepened through the staggered array structure, the emission rate of the generated light is improved by 1.5 to 2.5 times, and the full width at half maximum (FWHM) of the function maximum value is reduced, Red, green and blue light can be obtained, and the output power per area is improved at room temperature, so that the utility value is high as a light emitting diode. Further, when the nanowire structure is introduced into the light emitting diode to increase the contact of the light emitting layer, the light emitted through the vertically arranged nanowire waveguide phenomenon can be concentrated in one direction, thereby increasing the efficiency of the light emitting diode.
Further, according to the present invention, by coating the quantum dots of the core-shell structure on the nano-wire and the n-type gallium nitride semiconductor layer on which the nanowires are grown, when fluorescent materials of two different wavelength regions are adjacent to each other, Energy can be transferred to other fluorescent materials to cause the fluorescence resonance energy transfer phenomenon, which represents another fluorescence, to absorb loss energy generated by non-radiative recombination of electrons and holes, And the efficiency of the light emitting diode can be improved by transferring the absorbed energy to light energy having a wavelength to emit light.
Hereinafter, the present invention will be described in detail.
A gallium nitride light emitting diode having a nanowire structure to which a quantum dot is added according to the present invention includes a
The
According to an embodiment of the present invention, the substrate may include a
In addition, the N-type
The
According to another embodiment of the present invention, there is provided a method of manufacturing a gallium nitride light emitting diode having a nanowire structure doped with quantum dots.
A gallium nitride light emitting diode having a nanowire structure doped with quantum dots according to the present invention includes the steps of (1) forming a
According to an embodiment of the present invention, the
The
In addition, the N-type gallium
According to another embodiment of the present invention, a
The
The removal of the catalyst layer comprises the steps of: (i) reacting the catalyst layer with carbon monoxide at 40-100 DEG C and then volatilizing the reactant; (Ii) dissolving the remaining unvolatile residue in benzene to remove it; And (iii) drying at 80-100 DEG C for 10-15 minutes to remove the benzene.
According to another embodiment of the present invention, the
The application of the
According to another embodiment of the present invention, the
The step of coating the
According to another embodiment of the present invention, the P-type gallium
The magnesium-doped P-type
The P-type gallium nitride semiconductor layer may be planarized by polishing the upper surface thereof by chemo-mechanical polishing.
The
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as set forth in the following claims. Such variations and modifications are intended to be within the scope of the appended claims.
Example One. Buffer layer deposition
Ammonium gas was flowed at 15 L / min and hydrogen at 1 L / min for 1 hour on a sapphire substrate at 600 ° C. and 120 torr using a metal organic chemical vapor deposition (MOCVD) process to form a 3 μm thick To form a gallium nitride buffer layer.
Example 2. N type Gallium nitride The semiconductor layer deposition
(SiH 4 ) gas at 20 nmol / min and ammonia gas at a rate of 1 L / min at 1000 ° C and 150 torr on the gallium nitride buffer layer by metal organic chemical vapor deposition (MOCVD) Hydrogen was flowed at 200 cm < 3 > per minute for 3 minutes to produce an N-type gallium nitride semiconductor layer with a thickness of 23 nm, and then a silicon oxide mask was applied to a part of the edge of the resulting N-type gallium nitride semiconductor (Si: GaN) layer.
Example 3. Nickel catalyst layer produce
A nickel catalyst layer was coated on the N-type gallium nitride semiconductor layer by an electron beam thermal evaporation method. The electron beam was emitted at an energy of 15 to 17 KeV and a substrate temperature of 700 ° C and an ambient pressure of about 1.5 × 10 -3 Pa for 10 minutes to form a nickel catalyst layer having a thickness of about 8 nm. To form droplets uniformly distributed by surface tension.
Example 4. Narrow growth
(Trimethyl gallium gas) to 100 μmol / minute and ammonia (NH 3 ) gas to 7500 cm 3 / minute at 800 ° C. and 250 torr on the N-type gallium nitride semiconductor layer having the nickel catalyst layer formed thereon by MOCVD (Si: GaN) nanowire having a height of 163 nm and a diameter of 47 nm at the interface between the nickel catalyst and the N-type gallium nitride semiconductor by flowing silane (SiH 4 ) gas at 5 cm 3 / min for 20 minutes. .
Example 5. Nickel catalyst layer remove
The nickel catalyst layer was reacted with carbon monoxide at 60 ° C to form tetracarbonyl nickel (Ni (CO) 4 ) which was colorless and volatile. The tetracarbonyl nickel remaining after the volatilization was dissolved in benzene was removed, The residue was dried to volatilize the remaining benzene.
Example 6. Cadmium selenide Quantum dot Produce
To the three-necked flask, 20 ml of toluene was added, and 0.3 mmol of cadmium oxide and 1 mmol of stearic acid were added. The mixture was heated at 150 ° C under an argon atmosphere to completely dissolve the cadmium oxide and then cooled to room temperature. 4.5 mmol of trioctylphosphine oxide and 7.2 mmol of hexadecylamine were added to the cooled flask, and the mixture was heated at 320 DEG C under argon atmosphere until the mixture became clear.
A selenium solution was prepared by mixing 2 mmol of selenium powder, 2.3 mmol of tributylphosphine and 13.6 mmol of dioctylamine in the flask, adding to the previously reacted cadmium oxide solution, and reacting at 300 ° C for 25 minutes. An excess amount of methanol was added to the reaction mixture and centrifuged to prepare a colloid solution in which cadmium selenide quantum dots were dispersed.
Example 7. Zinc sulfide Of the shell solution Produce
0.088 mmol of zinc stearate, 0.088 mmol of sulfur powder, 5 ml of trioctylphosphine and 3 ml of toluene were mixed and reacted at 100 ° C for 500 seconds to prepare a zinc sulfide shell solution.
Example 8. Core / shell structure CdSe / ZnS Qdot Produce
12 mmol of trioctylphosphine oxide and 10 mmol of hexadecylamine were added to the reaction vessel and the inside of the reaction vessel was adjusted to an argon gas atmosphere using a Schlenk line apparatus. The solvent of the colloidal solution in which the cadmium selenide quantum dots were dispersed was removed by a rotary evaporator, and 10 ml of heptane was added thereto to dissolve the solution. Then, the solution was poured into a reaction vessel and heated to 200 ° C. The zinc sulfide shell solution was slowly injected at a rate of 0.1 ml / min using a syringe, stirred at 200 ° C for 1 hour, and rapidly cooled to 90 ° C to prepare CdSe / ZnS quantum dots of core / shell structure.
Example 9. Qdot coating
After the entire substrate was dried at 80 ° C for 4 hours using an oven, a solution containing the CdSe / ZnS quantum dots of the core / shell structure prepared in Example 8 was uniformly dropped onto the nanowire and the substrate, And then dried. At this time, the nanomaterials were well dispersed in the solution by Coulomb force.
Example 10. Narrow Shell layer coating
On the substrate coated with quantum dots, trimethylgallium gas was used at 15 μmol / min, trimethylindium gas was used at 10 μmol / min, and ammonia gas was changed to 10 L / min at 600 ° C. and 150 torr, using organometallic chemical vapor deposition (MOCVD) Was flown at 200 cm < 3 > per minute for 2 minutes to coat an active region of indium gallium nitride having a thickness of 3 nm.
Example 11. P type Gallium nitride Semiconductor layer deposition
On the substrate coated with the indium gallium nitride nanowhoon shell layer, trimethyl gallium gas was added to 15 μmol / min and magnesium hydride (MgH 2 ) gas to 20 nmol / min at 1000 ° C. and 150 torr using chemical vapor deposition (MOCVD) Was flowed at a rate of 1 L / min and hydrogen at 200 cm < 3 > for 6 minutes to produce a P-type gallium nitride semiconductor layer having a thickness of 103 nm, and then a top portion was ground to produce a P-type gallium nitride semiconductor layer having a thickness of 100 nm.
Example 12. Formation of transparent electrode
On the P-type gallium nitride semiconductor layer is deposited substrate gives flowing a mixed gas of argon and oxygen per minute at a rate of 60 cm 3, and the substrate distance of 15 cm, the power current 1 A, a 0.1 kW 2.5 x 10 -3 torr pressure and room temperature for 10 minutes to generate a plasma. The ITO (tin oxide) layer having an electrical resistance of 10 -4 Ω · cm 2 and a thickness of 84 nm with a transparency of 80% or more with respect to light in the visible light band by RF sputtering ) Electrode.
100
120 N-type gallium
140 P-type gallium
160 Mask
210
220
Claims (12)
A buffer layer formed on one surface of the substrate and made of gallium nitride;
An N-type gallium nitride semiconductor layer formed on the buffer layer;
A nanowire grown on the surface of the N-type gallium nitride semiconductor layer;
A nanowire shell layer made of indium gallium nitride, the nanowire being coated on the grown N-type gallium nitride semiconductor layer;
A P-type gallium nitride semiconductor layer formed on the N-type gallium nitride semiconductor layer coated with the nanowire shell layer; And
And a transparent electrode formed on the P-type gallium nitride semiconductor layer, the gallium nitride light-
Quantum dots are additionally provided on the N-type gallium nitride semiconductor layer and the surface of the nanowire,
Wherein the N-type gallium nitride semiconductor is gallium nitride doped with silicon (Si), and the P-type gallium nitride semiconductor is gallium nitride doped with magnesium (Mg). diode.
The thickness of the buffer layer is 1-5 占 퐉,
The nanowire has a diameter of 20-60 nm and a height of 100-200 nm,
The quantum dot has a size of 1-10 nm,
The thickness of the N-type gallium nitride semiconductor layer is 20-25 nm, the thickness of the P-type gallium nitride semiconductor layer is 20-120 nm,
Wherein the nanowire shell layer has a thickness of 2-4 nm. ≪ RTI ID = 0.0 > 8. < / RTI >
(2) forming an N-type gallium nitride semiconductor layer on the buffer layer;
(3) forming a catalyst layer on the N-type gallium nitride semiconductor layer, liquefying the catalyst layer at a eutectic point, growing a nanowire, and removing the catalyst layer;
(4) applying quantum dots on the N-type gallium nitride semiconductor layer on which the nanowires and the nanowires are grown;
(5) coating the N-type gallium nitride semiconductor layer coated with the quantum dot with a nanowire shell layer;
(6) forming a P-type gallium nitride semiconductor layer on the nanowire shell layer coating; And
(7) forming a transparent electrode on the P-type gallium nitride semiconductor thin film; and (7) forming a transparent electrode on the P-type gallium nitride semiconductor thin film.
(I) reacting the catalyst layer with carbon monoxide at 40-100 < 0 > C and then volatilizing the reactants;
(Ii) dissolving the remaining unvolatile residue in benzene to remove it; And
(Iii) drying at 80 to 100 DEG C for 10 to 15 minutes to remove benzene. The method of claim 1, wherein the quantum dot is added to the nanowire structure.
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| CN113964003A (en) * | 2021-10-09 | 2022-01-21 | 电子科技大学长三角研究院(湖州) | GaN photocathode with nanotube structure and preparation method thereof |
| CN115000244A (en) * | 2022-05-31 | 2022-09-02 | 北京工业大学 | Manufacturing method of high-performance self-driven GaN nanowire ultraviolet detector |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113964003A (en) * | 2021-10-09 | 2022-01-21 | 电子科技大学长三角研究院(湖州) | GaN photocathode with nanotube structure and preparation method thereof |
| CN115000244A (en) * | 2022-05-31 | 2022-09-02 | 北京工业大学 | Manufacturing method of high-performance self-driven GaN nanowire ultraviolet detector |
| CN115000244B (en) * | 2022-05-31 | 2023-09-26 | 北京工业大学 | Manufacturing method of high-performance self-driven GaN nanowire ultraviolet detector |
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