CN102231422A - Fluorescent-powder-free single-chip GaN (gallium nitride)-based LED (light-emitting diode) and manufacturing method thereof - Google Patents
Fluorescent-powder-free single-chip GaN (gallium nitride)-based LED (light-emitting diode) and manufacturing method thereof Download PDFInfo
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Abstract
The invention relates to a fluorescent-powder-free single-chip GaN (gallium nitride)-based LED (light-emitting diode). The LED comprises a substrate material, a buffer layer, an n-type GaN material, an active area, a p-type AlGaN barrier layer and a p-type GaN contact layer, wherein the buffer layer, the n-type GaN material, the active area, the p-type AlGaN barrier layer and the p-type GaN contact layer grow in an epitaxial way on the substrate material in sequence; and the active area comprises a blue-light quantum well, a green-light quantum well or a quantum point layer and a red-light quantum point layer. The invention also relates to a manufacturing method of the fluorescent powder-free single-chip GaN-based LED of the single chip. The LED has the advantages of high efficiency, good color rendering property, stable color temperature and low cost, and has wide application prospects in general illumination field and other special illumination fields.
Description
Technical field
The present invention relates to field of semiconductor materials, be specifically related to a kind of no fluorescent material single-chip GaN based light-emitting diode and preparation method thereof.
Background technology
The III hi-nitride semiconductor material that with GaN is representative has good photoelectric characteristic and stable physicochemical characteristic.Be widely used in the white semiconductor illumination with GaN material light-emitting diode at present.The GaN based light-emitting diode is used for white-light illuminating and has the efficient height, and the advantage that the life-span is long realizes that at present GaN base LED white-light illuminating mainly contains three kinds of modes:
1. adopt the GaN base blue LED to excite yellow fluorescent powder to send white light;
2. adopt the GaN base red, indigo plant, white light is sent in green three-color light-emitting diode mixing;
3. adopt GaN base ultraviolet light-emitting diode to excite mixed fluorescent powder to produce and send white light.
These three kinds of modes are not that single-chip is realized white-light illuminating.Present most widely used method is the 1st kind.Its shortcoming comprises: 1) color rendering of LED is bad, and color rendering index has only 60～70, is difficult to satisfy the demand of room lighting; 2) adopt fluorescent material to realize that conversion down can cause the loss of efficient; 3) instability of fluorescent material also is one of key factor that influences LED reliability and life-span.
Summary of the invention
For overcoming defectives such as existing GaN based light-emitting diode color rendering is poor, luminous efficiency is low, the purpose of this invention is to provide a kind of no fluorescent material single-chip GaN based light-emitting diode
Above-mentioned light-emitting diode comprises backing material, and on backing material epitaxially grown successively resilient coating, n type GaN body material, active area, p type AlGaN barrier layer and p type GaN contact layer; Wherein, described active area is made up of blue light quantum well, green glow quantum well or quantum dot layer and red light quantum point layer.
Described active area is divided into three districts according to the light source colour difference, and three districts are grown in successively on the n type GaN body material and are formed with the source region, and wherein, the succession of three light source region is unrestricted.
The number of above-mentioned active area monochromatic light quantum well is 1～10, and the monochromatic light quantum dot number of plies is 1～10 layer.
Described quantum dot layer be the InGaN quantum dot with and go up the composite bed that the GaN cap rock of extension is formed, described quantum dot laterally, longitudinal size is 1～40nm, preferred 10～30nm, the thickness of described GaN cap rock are 10～100nm.
Quantum well is the InGaN/GaN quantum well, and InGaN trap thickness is 1～20nm, and the thickness that GaN builds is 1～100nm, preferred 5～50nm.
The In component of described blue light quantum well is 10～30% by quality, and emission wavelength is 410～480nm; The In component of described green glow quantum well or quantum dot layer is 20～50% by quality, and emission wavelength is 480～570nm; The In component of described red light quantum point layer is 30～60% by quality, and emission wavelength is 620～760nm.
Described backing material is sapphire, Si or SiC substrate; Described backing material is of a size of 2～12 inches, and crystal face is (001), (111) or (110) crystal face.
Described resilient coating is AlN, GaN or AlGaN resilient coating, and thickness is 10～100nm.
Described n type GaN body material thickness is 10nm～100 μ m, preferred 200nm～10 μ m, and electron concentration is 10
17～10
19Cm
-3
Described p type AlGaN barrier layer is 5～50% according to the component of quality Al, and is preferred 10～30%, and thickness is 10～100nm, and hole concentration is 10
15～10
19Cm
-3
Described p type GaN contact layer thickness is 10nm～2 μ m, preferred 100nm～1 μ m, and hole concentration is 10
17～10
19Cm
-3
The present invention also correspondingly provides the preparation method of the described no fluorescent material single-chip GaN based light-emitting diode of technique scheme, may further comprise the steps:
(1) epitaxial growth buffer and n type GaN body material successively on backing material;
(2) on n type GaN body material, do not limit sequentially epitaxial growth blue light quantum well, green glow quantum well or quantum dot layer and red light quantum point layer to be formed with the source region;
(3) epitaxial growth p type AlGaN barrier layer and p type GaN contact layer successively on active area.
The described order of not limitting of step (2) is unrestricted for the order of active area when epitaxial growth of blue, green, red three kinds of colors, and can the luminous and color developing of diode not exerted an influence.Described order can be n type GaN body material → indigo plant → green → red → barrier layer, or blue → red → green, or green → red → combined in any order such as indigo plant.
Described epitaxial growth method has molecular beam epitaxy (MBE), hydride vapour phase epitaxy method (HVPE) or metal-organic chemical vapor deposition equipment method (MOCVD).
Described metal organic source is trimethyl gallium (TMGa), triethyl-gallium (TEGa), trimethyl indium (TMIn), trimethyl aluminium (TMAl), and nitrogenous source is ammonia (NH
3), the carrier gas of metal organic source is hydrogen (H
2) or nitrogen (N
2).
Carry out high temperature with hydrogen before described backing material uses and clean, temperature is 1000～1500 ℃, and reative cell pressure is 100～500mbar.
The growth temperature of described n type GaN body material is 500～1500 ℃, preferred 1000～1500 ℃; The growth temperature of described active area, p type AlGaN barrier layer and p type GaN contact layer is 200～1500 ℃, preferred 500～1000 ℃; The growth temperature of GaN cap rock is 200-800 ℃ on the described quantum dot.
Described reative cell pressure is 1～1000mbar, preferred 100-500mbar.
The preparation method of GaN based light-emitting diode of the present invention is not limited to preparation method of the present invention, can adopt the common technology of preparing of this area light-emitting diode, or all can make diode of the present invention in conjunction with existing quantum dot technology of preparing.
The growing method of described resilient coating, GaN body material, quantum well, InGaN quantum dot and GaN cap rock etc. can adopt the combination of the common technique or the common technique of this area, those skilled in the art can all can realize technique scheme according to different temperature, the pressure and other parameters suitably adjusted of method.
Technical scheme of the present invention adopts three kinds of monochromatic sources of red, green, blue to be combined in and realizes white light emission in the one chip.Wherein blue light is sent by InGaN blue light quantum well, and green glow is sent by InGaN green glow quantum well or quantum dot, and ruddiness is sent by the InGaN quantum dot.With respect to the blue light InGaN quantum well of low In component, the lattice mismatch of high In ingredient InGaN quantum well is bigger, and stress is also bigger.The dislocation that causes by Stress Release and all can make the efficient of light-emitting diode reduce by the piezoelectric polarization effect that stress causes, and quantum dot can be alleviated the influence that lattice mismatch brings for quantum well, reduce stress, improve luminous efficiency, utilize the high In ingredient quantum dot to send wavelength visible and more have superiority, therefore than quantum well, red light-emitting adopts quantum dot, and green wavelength is less than red light wavelength, and the In constituent content is relatively low, and quantum dot is suitable with the quantum well radiation effect.
Technical scheme of the present invention is based on the single-chip GaN base white light emitting diode photoelectric conversion efficiency height of red, green, blue three primary colors, feed the luminous power of testing current chip, compare with conventional white light LED under the equal test condition, photoelectric conversion efficiency can improve 20%-40%; Simultaneously luminescent spectrum is analyzed, the color rendering of chip of the present invention is good, and the colour developing coefficient can be up to 80-85.In addition, diode chip for backlight unit of the present invention need not fluorescent material, colour temperature is stable, prepare easy, can be applicable to various structures such as formal dress, the light-emitting diode chip for backlight unit of upside-down mounting and vertical stratification has reduced cost of manufacture, improved useful life, had broad application prospects at general illumination and some special lighting field.
Description of drawings
Fig. 1 adopts blue light quantum well, green glow quantum well and the red light quantum point structural representation as the GaN base white light emitting diode of active area;
Fig. 2 adopts blue light quantum well, green light quantum point and the red light quantum point structural representation as the GaN base white light emitting diode of active area;
Among the figure: 1, backing material; 2, GaN resilient coating; 3, n type GaN body material; 4, active area; 5, AlGaN barrier layer; 6, p type GaN contact layer; 41, blue light quantum well; 42, green glow quantum well; 42 ', green light quantum point; 43, red light quantum point; 41A, InGaN trap; 41B, GaN build; 42A, InGaN trap; 42B, GaN build.
Embodiment
Following examples are used to illustrate the present invention, but are not used for limiting the scope of the invention.
Adopt MOCVD extension active area on Sapphire Substrate to adopt the white light emitting diode of blue light quantum well, green glow quantum well and red light quantum point, as Fig. 1, its concrete epitaxial growth steps is:
1, will put into the MOCVD reative cell for the Sapphire Substrate that extension is prepared, and earlier Sapphire Substrate be adopted the hydrogen high-temperature degassing, temperature is 1060 ℃, and pressure is 200mbar.
2, according to two traditional one-step growth methods (" GaN Growth Using GaN BufferLayer " JAPANESE JOURNAL OF APPLIED PHYSICS PART2-LETTERS rolls up 30:1705-1707), at the GaN resilient coating of sapphire surface epitaxial growth 30nm.
3, at 1050 ℃, under the condition of 400mbar on the GaN resilient coating growing n-type GaN, dopant is SiH
4, growth thickness is about 4 μ m, and electron concentration is 5 * 10
18Cm
-3
4,5 blue light quantum well of epitaxial growth on n type GaN body material, quantum well structure is: trap is the InGaN (In component 20%) of 3nm, builds the GaN for 10nm.Growth temperature is 800 ℃, and pressure is 400mbar.
5,5 green glow quantum well of extension after the blue light quantum well, quantum well structure is: trap is the InGaN (In component 34%) of 3nm, builds the GaN for 10nm.Growth temperature is 800 ℃, and pressure is 400mbar.
6, extension red light quantum point after the green glow quantum well, wherein the In component of quantum dot is 47%, and lateral dimension is 20nm, and longitudinal size is 10nm, is the cap rock of the GaN of 10nm on it, and the structure of quantum dot cap layer repeats 5 layers.Growth temperature is 500 ℃, and pressure is 400mbar.
7, the p-Al of extension 30nm on the active area
0.2Ga
0.8The N barrier layer.Dopant is DCpMg, and hole concentration is about 1 * 10
17Cm
-3Growth temperature is 900 ℃, and pressure is 100mbar.
8, the p-GaN contact layer of last extension 200nm.Dopant is DCpMg, and hole concentration is about 5 * 10
17Cm
-3Growth temperature is 900 ℃, and pressure is 200mbar.
9, reaction chamber temperature is reduced to room temperature, growth ending.
Gained diode chip for backlight unit photoelectric conversion efficiency can improve 35%, and color rendering index is 85.
Adopt MOCVD extension active area on Sapphire Substrate to adopt the blue light quantum well, the white light emitting diode of green light quantum point and red light quantum point, as Fig. 2, its concrete epitaxial growth steps is:
1, will put into the MOCVD reative cell for the Sapphire Substrate that extension is prepared.Adopt hydrogen to carry out high-temperature degassing to Sapphire Substrate earlier, temperature is 1050 ℃, and pressure is 500mbar.
2, according to embodiment 1 described two one-step growth methods, at the GaN resilient coating of sapphire surface epitaxial growth 20nm.
3, at 1050 ℃, under the condition of 400mbar on the GaN resilient coating growing n-type GaN, dopant is SiH
4, growth thickness is about 4 μ m, and electron concentration is 5 * 10
18Cm
-3
4,5 involuntary doping blue light quantum well of epitaxial growth on n type GaN body material, quantum well structure is: trap is the InGaN (In component 20%) of 3nm, builds the GaN for 10nm.Growth temperature is 800 ℃, and pressure is 400mbar.
5, the involuntary doping green quantum dot of extension after the blue light quantum well, wherein the In component of quantum dot is 34%, and lateral dimension is 20nm, and longitudinal size is 10nm, is the cap rock of the GaN of 10nm on it.The structure of quantum dot cap layer repeats 5 layers.Growth temperature is 500 ℃, and pressure is 400mbar.
6, the involuntary doping red light quantum point of extension behind green light quantum point, wherein the In component of quantum dot is 47%, and lateral dimension is 20nm, and longitudinal size is 10nm, is the cap rock of the GaN of 10nm on it.The structure of quantum dot cap layer repeats 5 layers.Growth temperature is 500 ℃, and pressure is 400mbar.
7, the p-Al of extension 30nm on the active area
0.2Ga
0.8The N barrier layer.Dopant is DCpMg, and hole concentration is about 1 * 10
17Cm
-3Growth temperature is 900 ℃, and pressure is 100mbar.
8, the p-GaN contact layer of last extension 200nm.Dopant is DCpMg, and hole concentration is about 5 * 10
17Cm
-3Growth temperature is 900 ℃, and pressure is 200mbar.
9, reaction chamber temperature is reduced to room temperature, growth ending.
Gained diode chip for backlight unit photoelectric conversion efficiency can improve 40%, and color rendering index is 85.
Adopt MOCVD extension active area on the SiC substrate to adopt the white light emitting diode of blue light quantum well, green glow quantum well and red light quantum point, as Fig. 1, its concrete epitaxial growth steps is:
1, will put in the MOCVD reative cell for the SiC substrate that extension is prepared, and earlier the SiC substrate be adopted the hydrogen high-temperature degassing, temperature is 1150 ℃, and pressure is 200mbar.
2, according to two traditional one-step growth methods, at the AlN resilient coating of SiC substrate surface epitaxial growth 50nm.
3, at 1050 ℃, under the condition of 400mbar on the AlN resilient coating growing n-type GaN, dopant is SiH
4, growth thickness is about 150nm, and electron concentration is 5 * 10
17Cm
-3
4,7 blue light quantum well of epitaxial growth on n type GaN body material, quantum well structure is: trap is the InGaN (In component 27%) of 5nm, builds the GaN for 20nm.Growth temperature is 600 ℃, and pressure is 200mbar.
5,7 green glow quantum well of extension after the blue light quantum well, quantum well structure is: trap is the InGaN (In component 40%) of 5nm, builds the GaN for 20nm.Growth temperature is 700 ℃, and pressure is 400mbar.
6, extension red light quantum point after the green glow quantum well, wherein the In component of quantum dot is 55%, and lateral dimension is 30nm, and longitudinal size is 20nm, is the cap rock of the GaN of 20nm on it, and the structure of quantum dot cap layer repeats 7 layers.Growth temperature is 500 ℃, and pressure is 400mbar.
7, the p-Al of extension 50nm on the active area
0.2Ga
0.8The N barrier layer.Dopant is DCpMg, and hole concentration is about 1 * 10
18Cm
-3Growth temperature is 900 ℃, and pressure is 100mbar.
8, the p-GaN contact layer of last extension 1 μ m.Dopant is DCpMg, and hole concentration is about 2 * 10
19Cm
-3Growth temperature is 800 ℃, and pressure is 200mbar.
9, reaction chamber temperature is reduced to room temperature, growth ending.
Gained diode chip for backlight unit photoelectric conversion efficiency can improve 32%, and color rendering index is 82.
Embodiment 4
Adopt MOCVD extension active area on the Si substrate to adopt the blue light quantum well, the white light emitting diode of green light quantum point and red light quantum point, as Fig. 2, its concrete epitaxial growth steps is:
1, will put into the MOCVD reative cell for the Si substrate that extension is prepared, and adopt hydrogen to carry out high-temperature degassing to the Si substrate earlier, temperature is 1000 ℃, and pressure is 500mbar.
2, according to embodiment 1 described two one-step growth methods, at the GaN resilient coating of Si substrate surface epitaxial growth 100nm.
3, at 1000 ℃, under the condition of 400mbar on the GaN resilient coating growing n-type GaN, dopant is SiH
4, growth thickness is about 8 μ m, and electron concentration is 1 * 10
19Cm
-3
4,3 involuntary doping blue light quantum well of epitaxial growth on n type GaN body material, quantum well structure is: trap is the InGaN (In component 15%) of 15nm, builds the GaN for 20nm.Growth temperature is 1000 ℃, and pressure is 500mbar.
5, the involuntary doping green quantum dot of extension after the blue light quantum well, wherein the In component of quantum dot is 40%, and lateral dimension is 10nm, and longitudinal size is 30nm, is the cap rock of the GaN of 40nm on it, and the structure of quantum dot cap layer repeats 3 layers.Growth temperature is 500 ℃, and pressure is 400mbar.
6, the involuntary doping red light quantum point of extension behind green light quantum point, wherein the In component of quantum dot is 60%, and lateral dimension is 30nm, and longitudinal size is 20nm, is the cap rock of the GaN of 30nm on it.The structure of quantum dot cap layer repeats 3 layers.Growth temperature is 500 ℃, and pressure is 400mbar.
7, the p-Al of extension 80nm on the active area
0.2Ga
0.8The N barrier layer.Dopant is DCpMg, and hole concentration is about 5 * 10
15Cm
-3Growth temperature is 900 ℃, and pressure is 300mbar.
8, the p-GaN contact layer of last extension 500nm.Dopant is DCpMg, and hole concentration is about 2 * 10
19Cm
-3Growth temperature is 700 ℃, and pressure is 300mbar.
9, reaction chamber temperature is reduced to room temperature, growth ending.
Gained diode chip for backlight unit photoelectric conversion efficiency can improve 41%, and color rendering index is 83.
Embodiment 5
Adopt HVPE and MOCVD extension active area on Sapphire Substrate to adopt the blue light quantum well, the white light emitting diode of green light quantum point and red light quantum point, as Fig. 2, its concrete epitaxial growth steps is:
1, will put into the hvpe reactor chamber for the Sapphire Substrate that extension is prepared.Earlier Sapphire Substrate is adopted the hydrogen high-temperature degassing, temperature is 1060 ℃.
2, according to embodiment 1 described two one-step growth methods, at the GaN resilient coating of sapphire surface epitaxial growth 20nm.
3, at the 4 μ m thick-layer GaN body materials of on the GaN resilient coating, growing under 1050 ℃ the condition.
4, the surface there is the Sapphire Substrate taking-up of GaN put into the MOCVD reative cell.
5, at 1050 ℃, under the condition of 400mbar on GaN growing n-type GaN, dopant is SiH
4, growth thickness is about 4 μ m, and electron concentration is 5 * 10
18Cm
-3
6,5 involuntary doping blue light quantum well of epitaxial growth on n type GaN body material, quantum well structure is: trap is the InGaN (In component 20%) of 3nm, builds the GaN for 10nm.Growth temperature is 800 ℃, and pressure is 400mbar.
7, the involuntary doping green quantum dot of extension after the blue light quantum well, wherein the In component of quantum dot is 34%, and lateral dimension is 20nm, and longitudinal size is 10nm, is the cap rock of the GaN of 10nm on it, and the structure of quantum dot cap layer repeats 5 layers.Growth temperature is 500 ℃, and pressure is 400mbar.
8, the involuntary doping red light quantum point of extension behind green light quantum point, wherein the In component of quantum dot is 47%, and lateral dimension is 20nm, and longitudinal size is 10nm, is the cap rock of the GaN of 10nm on it, and the structure of quantum dot cap layer repeats 5 layers.Growth temperature is 500 ℃, and pressure is 400mbar.
9, the p-Al of extension 30nm on the active area
0.2Ga
0.8The N barrier layer.Dopant is DCpMg, and hole concentration is about 1 * 10
17Cm
-3Growth temperature is 900 ℃, and pressure is 100mbar.
10, the p-GaN contact layer of last extension 150nm.Dopant is DCpMg, and hole concentration is about 5 * 10
17Cm
-3Growth temperature is 900 ℃, and pressure is 200mbar.
11, reaction chamber temperature is reduced to room temperature, growth ending.
Gained diode chip for backlight unit photoelectric conversion efficiency can improve 27%, and color rendering index is 80.
Though above used general explanation, embodiment and experiment, the present invention is described in detail, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (14)
1. a no fluorescent material single-chip GaN based light-emitting diode is characterized in that, comprises backing material, and on backing material epitaxially grown successively resilient coating, n type GaN body material, active area, p type AlGaN barrier layer and p type GaN contact layer; Wherein, described active area is made up of blue light quantum well, green glow quantum well or quantum dot layer and red light quantum point layer.
2. light-emitting diode according to claim 1 is characterized in that, the number of described active area monochromatic light quantum well is 1～10, and the monochromatic light quantum dot number of plies is 1～10 layer.
3. light-emitting diode according to claim 2, it is characterized in that, described quantum dot layer be the InGaN quantum dot with and go up the composite bed that the GaN cap rock of extension is formed, horizontal, the longitudinal size of described quantum dot are 1～40nm, preferred 10～30nm, the thickness of described GaN cap rock are 10～100nm.
4. light-emitting diode according to claim 2 is characterized in that, described quantum well is the InGaN/GaN quantum well, and InGaN trap thickness is 1～20nm, and the thickness that GaN builds is 1～100nm, preferred 5～50nm.
5. according to the described light-emitting diode of one of claim 1-4, it is characterized in that the In component of described blue light quantum well is 10～30% by quality, emission wavelength is 410～480nm; The In component of described green glow quantum well or quantum dot layer is 20～50% by quality, and emission wavelength is 480～570nm; The In component of described red light quantum point layer is 30～60% by quality, and emission wavelength is 620～760nm.
6. light-emitting diode according to claim 1 is characterized in that, described backing material is sapphire, Si or SiC substrate.
7. light-emitting diode according to claim 1 is characterized in that, described resilient coating is AlN, GaN or AlGaN resilient coating, and thickness is 10～100nm.
8. light-emitting diode according to claim 1 is characterized in that, described n type GaN body material thickness is 10nm～100 μ m, preferred 200nm～10 μ m, and electron concentration is 10
17～10
19Cm
-3
9. light-emitting diode according to claim 1 is characterized in that, described p type AlGaN barrier layer is 5～50% according to the component of quality Al, and is preferred 10～30%, and thickness is 10～100nm, and hole concentration is 10
15～10
19Cm
-3
10. light-emitting diode according to claim 1 is characterized in that, described p type GaN contact layer thickness is 10nm～2 μ m, preferred 100nm～1 μ m, and hole concentration is 10
17～10
19Cm
-3
11. the preparation method of the described no fluorescent material single-chip GaN based light-emitting diode of claim 1-10 is characterized in that, may further comprise the steps:
(1) epitaxial growth buffer and n type GaN body material successively on backing material;
(2) on n type GaN body material, do not limit sequentially epitaxial growth blue light quantum well, green glow quantum well or quantum dot layer and red light quantum point layer to be formed with the source region;
(3) epitaxial growth p type AlGaN barrier layer and p type GaN contact layer successively on active area.
12. preparation method according to claim 11, it is characterized in that, described epitaxial growth method is metal-organic chemical vapor deposition equipment method, molecular beam epitaxy or hydride vapour phase epitaxy method, metal organic source is trimethyl gallium, trimethyl indium or trimethyl aluminium, nitrogenous source is an ammonia, and the carrier gas of described metal organic source is hydrogen or nitrogen.
13., it is characterized in that carry out high temperature with hydrogen before described backing material uses and clean, temperature is 1000～1500 ℃ according to claim 11 or 12 described preparation methods, reative cell pressure is 100～500mbar.
14., it is characterized in that the growth temperature of described n type GaN body material is 500～1500 ℃, preferred 1000～1500 ℃ according to claim 11 or 12 described preparation methods; The growth temperature of described active area, p type AlGaN barrier layer and p type GaN contact layer is 200～1500 ℃, preferred 500～1000 ℃; The growth temperature of GaN cap rock is 200-800 ℃ on the described quantum dot;
Described reative cell pressure is 1～1000mbar, preferred 100～500mbar.
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| CN116111455A (en) * | 2023-03-08 | 2023-05-12 | 江苏第三代半导体研究院有限公司 | GaN-based laser and preparation method thereof |
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