CN101920184B - Photocatalysis biochemical device based on nitride light-emitting diode and preparation method thereof - Google Patents
Photocatalysis biochemical device based on nitride light-emitting diode and preparation method thereof Download PDFInfo
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- CN101920184B CN101920184B CN2010102490825A CN201010249082A CN101920184B CN 101920184 B CN101920184 B CN 101920184B CN 2010102490825 A CN2010102490825 A CN 2010102490825A CN 201010249082 A CN201010249082 A CN 201010249082A CN 101920184 B CN101920184 B CN 101920184B
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Abstract
The invention relates to a photocatalysis biochemical device based on a nitride light-emitting diode and a preparation method thereof. A nitride light-emitting diode material and a photocatalysis material with an InGaN nano structure are combined to form an integrated chip, and the integrated chip is used for sterilization, cancer resistance, and the like in an organism, wherein the nitride light-emitting diode is used for illumination, and the photocatalysis material with the InGaN nano structure is used as a photocatalyst. The invention has the advantages that: the miniaturization of the device is realized, the illumination energy is utilized to the maximum degree, the light emitted by the nitride light-emitting diode is visible light safe to the organism and can generate a high-efficiency photocatalysis reaction, the InGaN nano structure on the surface is located on a substrate of the nitride light-emitting diode, can not spread into the organism and is convenient to recovery, and the nitride material has stable physicochemical properties and can not be decomposed in the organism, thereby being applicable to the inside of the organism and nontoxic to the organism.
Description
Technical field
The invention belongs to the crossing domain of nanometer technology, new material technology and biochemical technology, be specifically related to a kind of photocatalysis biochemical device based on iii-nitride light emitting devices and preparation method thereof.
Background technology
Light-catalyzed reaction is meant, it is right that semi-conducting material receives the illumination meeting to produce light induced electron-hole, the compound again again surface that migrates to semi-conducting material in electronics and hole, can with the organic substance generation redox reaction in the external world.The energy gap of semi-conducting material had both determined absorbent optical wavelength, had also determined the chemism in light induced electron and hole.
Present modal photocatalysis biochemical device is based on TiO
2Photocatalysis biochemical device, utilize its photocatalysis can carry out sterilization and anticancer.But it only has response to ultraviolet light usually, and such energy gap has influenced its range of application, and the suitable light source in the organism that is used for can't be provided in practical application.See from above-mentioned present situation, light-catalyzed reaction is applied to organism faces two problems: one is to have the response wave length of photochemical catalyst now at ultraviolet band, and ultraviolet light is harmful to for organism under some situation; The secondth, the suitable light source in the organism that is used for can't be provided.
Summary of the invention
In order to overcome the deficiency that above-mentioned prior art exists; The object of the present invention is to provide a kind of photocatalysis biochemical device based on iii-nitride light emitting devices and preparation method thereof; Catalysis material through with iii-nitride light emitting devices material and InGaN nanostructure combines, and by iii-nitride light emitting devices illumination is provided, and the catalysis material of InGaN nanostructure is as photochemical catalyst; Form an integrated chip, be used for sterilization and application such as anticancer in the organism; Advantage of the present invention is for to integrate iii-nitride light emitting devices and photocatalytic nanometer structural material; Realized miniaturization of devices; And can farthest utilize the illumination energy, this design can be so that device can act on any part of organism; In component through InGaN active area materials in the adjustment iii-nitride light emitting devices; What can make iii-nitride light emitting devices luminously is the visible light to organism safety; The In component of adjusting surperficial InGaN nanostructure simultaneously can make it that this light-emitting diode is sent visible light effectively to absorb; Because the influence of polarity effect in the InGaN material, light induced electron and the hole recombination probability under the polarized electric field effect descends, and therefore light-catalyzed reaction efficiently can take place; The InGaN nanostructure on surface is positioned in the iii-nitride light emitting devices substrate; Can not diffuse in the organism, be convenient to reclaim, and the physicochemical properties of nitride material be stable; Can not decompose in vivo, so just be applicable to that organism is inner and harmless to organism.
In order to achieve the above object, the technical scheme that the present invention adopted is:
A kind of photocatalysis biochemical device based on iii-nitride light emitting devices upwards distributes successively on the low temperature GaN of Sapphire Substrate 1 resilient coating 2 and mixes n type GaN layer 3, the In of Si
xGa
1-xN/GaN multiple quantum well layer 4, p type AlGaN layer 5, p type GaN layer 6 and In
yGa
1-yN surface nano-structure layer, wherein n type GaN layer 3, In
xGa
1-xN/GaN multiple quantum well layer 4, p type AlGaN layer 5, p type GaN layer 6 have constituted iii-nitride light emitting devices, In
yGa
1-yN surface nano-structure layer has constituted surperficial InGaN nanostructure, this In
xGa
1-xThe scope of the In component of N/GaN multiple quantum well layer 4 is 0.05≤x≤0.50, In
yGa
1-yThe scope of the In component of N surface nano-structure is 0.05≤y≤0.50, and x＜y; The thickness of described low temperature GaN resilient coating 2 is 15～35nm, and wherein the content ratio of Si is 1/1000-1/10000, and the thickness of the n type GaN layer 3 of the described Si of mixing is 2～4 μ m, and the concentration of Si is 1 * 10 in this n-GaN layer 3
18～1 * 10
19Cm
-3, the MQW In that described InxGa1-xN/GaN multiple quantum well layer 4 is 1.5～3.5nm by 1～10 trap layer thickness
xGa
1-xN/GaN forms, and the thickness of described p type AlGaN layer 5 is 10～40nm, and wherein the content of Al is 5～30%, and the thickness of described p type GaN layer 6 is 100～300nm, described In
yGa
1-yN surface nano-structure layer is nano dot structure 8 or nano wire rod structure 7, and the diameter of nano dot is 10～100nm, highly is that 0.3～50nm, density are 1 * 10
9～1 * 10
13Ugcm
-2, the diameter of nanometer terminal is 10～100nm, highly is that 100～10000nm, density are 1 * 10
9～1 * 10
13Ugcm
-2
The preparation method of above-mentioned photocatalysis biochemical device based on iii-nitride light emitting devices: at first in the MOCVD reative cell, Sapphire Substrate 1 is heated to 1050～1070 ℃, at 10～15L/min H
2Following heat treatment 5～15 minutes is cooled to 530 ℃ then naturally, and forming thickness range is the low temperature GaN resilient coating 2 of 15～35nm, then is warming up to 1030～1050 ℃, with the H of 10～15L/min
2Flow is carrier gas, and the Si that mixes synchronously to constitute with 2.0 μ m/ hours growth rate extension the n-GaN layer 3 of the thick doping Si of 2～4 μ m, and the concentration of Si is 1 * 10 in this n-GaN layer 3
18～1 * 10
19Cm
-3Naturally cool to 740 ℃ then, carrier gas switches to the N of 10～15L/min flow
2, simultaneously with feeding TEGa, TMIn and NH
31～10 In of method growth in source
xGa
1-xThe N/GaN SQW, 0.05≤x≤0.50 wherein, in growth course, the molar flow of TEGa is 1 * 10
-5～3 * 10
-5Mol/min, the molar flow of TMIn is 1 * 10
-5～3 * 10
-5Mol/min, NH
3Flow be 10～20L/min; Afterwards, be increased to 850～950 ℃ to temperature, with the H of 5～10L/min flow
2As carrier gas, simultaneously with feeding TMGa, TMAl and NH
3The method growth thickness be the p type AlGaN layer 5 of 10～40nm and the p type GaN layer 6 of 100～300nm, wherein the content range of Al is 5%～30%, in growth course, the molar flow of TEGa is 1 * 10
-5～3 * 10
-5Mol/min, the molar flow of TMAl is 1 * 10
-5～3 * 10
-5Mol/min, NH
3Flow be 10～20L/min; So just constituted iii-nitride light emitting devices; This iii-nitride light emitting devices is taken out from the MOCVD reative cell, after adopting the thermal annealing mode to activate Mg to be led, at the top surface using plasma enhanced chemical vapor deposition deposition SiO of this iii-nitride light emitting devices
2Or SiN
xMask material, the method that adopts electron beam exposure or nano impression is at this SiO
2Or SiN
xProduce preset nano dot or nanometer terminal figure on the mask material; Wherein the diameter of nano dot figure is 10～100nm; The diameter of nanometer terminal figure is 10～100nm; Then its this iii-nitride light emitting devices that has mask pattern being reentered into the MOCVD reative cell, is 550～750 ℃ in temperature, and carrier gas is the N of 10～20L/min flow
2Condition under, simultaneously with feeding TEGa, TMIn and NH
3Method grow preset nano dot structure 8 or nano wire rod structure 7 figures, wherein the height of nano dot is that 0.3～50nm, density are 1 * 10
9～1 * 10
13Ugcm
-2, the height of nanometer terminal is that 100～10000nm, density are 1 * 10
9～1 * 10
13Ugcm
-2, and 0.05≤y≤0.50, x＜y has so just constituted In in addition
yGa
1-yN surface nano-structure layer, in growth course, the molar flow of TEGa is 1 * 10
-5～3 * 10
-5Mol/min, the molar flow of TMIn is 2 * 10
-5～5 * 10
-5Mol/min, NH
3Flow be 10～20L/min.
Catalysis material through with iii-nitride light emitting devices material and InGaN nanostructure combines; By iii-nitride light emitting devices illumination is provided; The catalysis material of InGaN nanostructure forms an integrated chip as photochemical catalyst, is used for sterilization and application such as anticancer in the organism.Advantage of the present invention is for to integrate iii-nitride light emitting devices and photocatalytic nanometer structural material; Realized miniaturization of devices; And can farthest utilize the illumination energy, this design can be so that device can act on any part of organism; In component through InGaN active area materials in the adjustment iii-nitride light emitting devices; What can make iii-nitride light emitting devices luminously is the visible light to organism safety; The In component of adjusting surperficial InGaN nanostructure simultaneously can make it that this light-emitting diode is sent visible light effectively to absorb; Because the influence of polarity effect in the InGaN material, light induced electron and the hole recombination probability under the polarized electric field effect descends, and therefore light-catalyzed reaction efficiently can take place; The InGaN nanostructure on surface is positioned in the iii-nitride light emitting devices substrate; Can not diffuse in the organism, be convenient to reclaim, and the physicochemical properties of nitride material be very stable; Can not decompose in vivo, so just be applicable to that organism is inner and harmless to organism.
Description of drawings
Fig. 1 is the structural representation that contains the nanometer terminal of the present invention.
Fig. 2 is the structural representation that contains nano dot of the present invention.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is done more detailed explanation.
Embodiment 1:
As shown in Figure 1, based on the photocatalysis biochemical device of iii-nitride light emitting devices, on the low temperature GaN of Sapphire Substrate 1 resilient coating 2, upwards distribute successively and mix n type GaN layer 3, the In of Si
xGa
1-xN/GaN multiple quantum well layer 4, p type AlGaN layer 5, p type GaN layer 6 and In
yGa
1-yN surface nano-structure layer, wherein n type GaN layer 3, In
xGa
1-xN/GaN multiple quantum well layer 4, p type AlGaN layer 5, p type GaN layer 6 have constituted iii-nitride light emitting devices, In
yGa
1-yN surface nano-structure layer has constituted surperficial InGaN nanostructure, this In
xGa
1-xThe x value of the In component of N/GaN multiple quantum well layer 4 is 0.15, In
yGa
1-yThe y value of the In component of N surface nano-structure is 0.30; The thickness of described low temperature GaN resilient coating 2 is 15nm, and wherein the content of Si is 1/1000, and the thickness of the n type GaN layer 3 of the described Si of mixing is 2 μ m, and the concentration of Si is 1 * 10 in this n-GaN layer
18Cm
-3, the MQW In that described InxGa1-xN/GaN multiple quantum well layer 4 is 1.5nm by 5 trap layer thicknesses
xGa
1-xN/GaN forms, and the thickness of described p type AlGaN layer 5 is 10nm, and wherein the content of Al is 5%, and the thickness of described p type GaN layer 6 is 100nm, described In
yGa
1-yN surface nano-structure layer is a nano wire rod structure 7, and the diameter of nanometer terminal is 10nm, highly is 1 * 10 for 100nm, density
9Cm
-2
The preparation method based on the photocatalysis biochemical device of iii-nitride light emitting devices of present embodiment:
At first in the MOCVD reative cell, Sapphire Substrate 1 is heated to 1050 ℃, at 10L/min H
2Following heat treatment 5 minutes is cooled to 530 ℃ then naturally, and forming thickness range is the low temperature GaN resilient coating 2 of 15nm, then is warming up to 1030 ℃, with the H of 10L/min
2Flow is carrier gas, and the Si that mixes synchronously to constitute with 2.0 μ m/ hours growth rate extension the n-GaN layer 3 of the thick doping Si of 2 μ m, and the concentration of Si is 1 * 10 in this n-GaN layer 3
18Cm
-3Naturally cool to 740 ℃ then, carrier gas switches to the N of 10L/min flow
2, simultaneously with feeding TEGa, TMIn and NH
35 In of method growth in source
xGa
1-xThe N/GaN SQW, wherein the value of x is 0.15, in growth course, the molar flow of TEGa is 1 * 10
-5Mol/min, the molar flow of TMIn is 1 * 10
-5Mol/min, NH
3Flow be 10L/min; Afterwards, be increased to 850 ℃ to temperature, with the H of 5L/min flow
2As carrier gas, simultaneously with feeding TMGa, TMAl and NH
3The method growth thickness be the p type AlGaN layer 5 of 10nm and the p type GaN layer 6 of 100nm, wherein the content range of Al is 5%, in growth course, the molar flow of TEGa is 1 * 10
-5Mol/min, the molar flow of TMAl is 1 * 10
-5Mol/min, NH
3Flow be 10L/min; So just constituted iii-nitride light emitting devices; This iii-nitride light emitting devices is taken out from the MOCVD reative cell, after adopting the thermal annealing mode to activate Mg to be led, at the top surface using plasma enhanced chemical vapor deposition deposition SiO of this iii-nitride light emitting devices
2Mask material, the method that adopts electron beam exposure or nano impression is at this SiO
2Produce preset nano dot or nanometer terminal figure on the mask material; The diameter of nano wire/nano-pillar figure is 10nm; Then its this iii-nitride light emitting devices that has mask pattern being reentered into the MOCVD reative cell, is 550 ℃ in temperature, and carrier gas is the N of 10L/min flow
2Condition under, simultaneously with feeding TEGa, TMIn and NH
3Method grow preset nano wire rod structure 7, the height of nanometer terminal is 100nm, density is 1 * 10
9Cm
-2, and the y value is 0.3, so just constituted In
yGa
1-yN surface nano-structure layer, in growth course, the molar flow of TEGa is 1 * 10
-5Mol/min, the molar flow of TMIn is 2 * 10
-5Mol/min, NH
3Flow be 10L/min.
Embodiment 2:
As shown in Figure 2, based on the photocatalysis biochemical device of iii-nitride light emitting devices, on the low temperature GaN of Sapphire Substrate 1 resilient coating 2, upwards distribute successively and mix n type GaN layer 3, the In of Si
xGa
1-xN/GaN multiple quantum well layer 4, p type AlGaN layer 5, p type GaN layer 6 and In
yGa
1-yN surface nano-structure layer, wherein n type GaN layer 3, In
xGa
1-xN/GaN multiple quantum well layer 4, p type AlGaN layer 5, p type GaN layer 6 have constituted iii-nitride light emitting devices, In
yGa
1-yN surface nano-structure layer has constituted surperficial InGaN nanostructure, this In
xGa
1-xThe x value of the In component of N/GaN multiple quantum well layer 4 is 0.30, In
yGa
1-yThe y value of the In component of N nanostructure is 0.40; The thickness of described low temperature GaN resilient coating 2 is 35nm, and wherein the content of Si is 1/10000, and the thickness of the n type GaN layer 3 of the described Si of mixing is 4 μ m, and the concentration of Si is 1 * 10 in this n-GaN layer 3
19Cm
-3, the MQW In that described InxGa1-xN/GaN multiple quantum well layer 4 is 3.5nm by 5 trap layer thicknesses
xGa
1-xN/GaN forms, and the thickness of described p type AlGaN layer 5 is 40nm, and wherein the content of Al is 30%, and the thickness of described p type GaN layer 6 is 300nm, described In
yGa
1-yN surface nano-structure layer is a nano dot structure 8, and the diameter of nano dot is 100nm, highly is 1 * 10 for 50nm, density
13Cm
-2
The preparation method based on the photocatalysis biochemical device of iii-nitride light emitting devices of present embodiment:
At first in the MOCVD reative cell, Sapphire Substrate 1 is heated to 1070 ℃, at 15L/min H
2Following heat treatment 15 minutes is cooled to 530 ℃ then naturally, and forming thickness range is the low temperature GaN resilient coating 2 of 35nm, then is warming up to 1050 ℃, with the H of 15L/min
2Flow is carrier gas, and the Si that mixes synchronously to constitute with 2.0 μ m/ hours growth rate extension the n-GaN layer 3 of the thick doping Si of 4 μ m, and the concentration of Si is 1 * 10 in this n-GaN layer
19Cm
-3Naturally cool to 740 ℃ then, carrier gas switches to the N of 15L/min flow
2, simultaneously with feeding TEGa, TMIn and NH
35 In of method growth in source
xGa
1-xThe N/GaN SQW, wherein the value of x is 0.30, in growth course, the molar flow of TEGa is 3 * 10
-5Mol/min, the molar flow of TMIn is 3 * 10
-5Mol/min, NH
3Flow be 20L/min; Afterwards, be increased to 950 ℃ to temperature, with the H of 10L/min flow
2As carrier gas, simultaneously with feeding TMGa, TMAl and NH
3The method growth thickness be the p type AlGaN layer 5 of 40nm and the p type GaN layer 6 of 300nm, wherein the content range of Al is 30%, in growth course, the molar flow of TEGa is 3 * 10
-5Mol/min, the molar flow of TMAl is 3 * 10
-5Mol/min, NH
3Flow be 20L/min; So just constituted iii-nitride light emitting devices; This iii-nitride light emitting devices is taken out from the MOCVD reative cell, after adopting the thermal annealing mode to activate Mg to be led, at the top surface using plasma enhanced chemical vapor deposition deposition SiN of this iii-nitride light emitting devices
xMask material, this x value is 0.30, the method that adopts electron beam exposure or nano impression is at this SiN
xProduce preset nano dot figure on the mask material, wherein the diameter of nano dot figure is 100nm, then its this iii-nitride light emitting devices that has mask pattern is reentered into the MOCVD reative cell, is 750 ℃ in temperature, and carrier gas is the N of 20L/min flow
2Condition under, simultaneously with feeding TEGa, TMIn and NH
3Method grow preset nano dot structure 8 figures, wherein the height of nano dot is that 50nm, density are 1 * 10
13Cm
-2, and the y value is 0.40, so just constituted In
yGa
1-yN surface nano-structure layer, in growth course, the molar flow of TEGa is 3 * 10
-5Mol/min, the molar flow of TMIn is 5 * 10
-5Mol/min, NH
3Flow be 20L/min.
Operation principle of the present invention is: add that on iii-nitride light emitting devices this iii-nitride light emitting devices based on the photocatalysis biochemical device of iii-nitride light emitting devices sent visible light when forward voltage made its conducting work, visible light is by its In
yGa
1-yThe InGaN nanostructure that N surface nano-structure layer 7 constitutes absorbs; At inner light induced electron and the photohole of producing of nanostructure, electronics and hole are to the diffusion into the surface of nanostructure, at surface and extraneous biological substance generation chemical reaction; Produce the gain and loss process of electronics, i.e. light-catalyzed reaction.Catalysis material through with iii-nitride light emitting devices material and InGaN nanostructure combines; By iii-nitride light emitting devices illumination is provided; The catalysis material of InGaN nanostructure forms an integrated chip as photochemical catalyst, is used for sterilization and application such as anticancer in the organism.Advantage of the present invention is for to integrate iii-nitride light emitting devices and photocatalytic nanometer structural material; Realized miniaturization of devices; And can farthest utilize the illumination energy, this design can be so that device can act on any part of organism; In component through InGaN active area materials in the adjustment iii-nitride light emitting devices; What can make iii-nitride light emitting devices luminously is the visible light to organism safety; The In component of adjusting surperficial InGaN nanostructure simultaneously can make it that this light-emitting diode is sent visible light effectively to absorb; Because the influence of polarity effect in the InGaN material, light induced electron and the hole recombination probability under the polarized electric field effect descends, and therefore light-catalyzed reaction efficiently can take place; The InGaN nanostructure on surface is positioned in the iii-nitride light emitting devices substrate; Can not diffuse in the organism, be convenient to reclaim, and the physicochemical properties of nitride material be very stable; Can not decompose in vivo, so just be applicable to that organism is inner and harmless to organism.
Claims (6)
1. the photocatalysis biochemical device based on iii-nitride light emitting devices is characterized in that: on the low temperature GaN resilient coating (2) that contains Si of Sapphire Substrate (1), upwards distribute successively and mix n type GaN layer (3), the In of Si
xGa
1-xN/GaN multiple quantum well layer (4), p type AlGaN layer (5), p type GaN layer (6) and In
yGa
1-yN surface nano-structure layer, wherein n type GaN layer (3), In
xGa
1-xN/GaN multiple quantum well layer (4), p type AlGaN layer (5), p type GaN layer (6) have constituted iii-nitride light emitting devices, ln
yGa
1-yN surface nano-structure layer has constituted surperficial InGaN nanostructure, this In
xGa
1-xThe scope of the In component of N/GaN multiple quantum well layer (4) is 0.05≤x≤0.50, In
yGa
1-yThe scope of the In component of N surface nano-structure is 0.05≤y≤0.50, and x＜y; The thickness of described low temperature GaN resilient coating (2) is 15～35nm, and wherein the content ratio of Si is 1/1000-1/10000, and the thickness of the n type GaN layer (3) of the described Si of mixing is 2～4 μ m, is 1 * 10 in this concentration of mixing Si in the n type GaN layer (3) of Si
18～1 * 10
19Cm
-3, described In
xGa
1-xThe MQW In that N/GaN multiple quantum well layer (4) is 1.5～3.5nm by 1～10 trap layer thickness
xGa
1-xN/GaN forms, and the thickness of described p type AlGaN layer (5) is 10～40nm, and wherein the content of Al is 5～30%, and the thickness of described p type GaN layer (6) is 100～300nm, described In
yGa
1-yN surface nano-structure layer is nano dot structure (8) or nano wire rod structure (7), and the diameter of nano dot is 10～100nm, highly is that 0.3～50nm, density are 1 * 10
9～1 * 10
13Cm
-2, the diameter of nanometer terminal is 10～100nm, highly is that 100～10000nm, density are 1 * 10
9～1 * 10
13Cm
-2
2. the photocatalysis biochemical device based on iii-nitride light emitting devices according to claim 1 is characterized in that: described In
xGa
1-xThe x value of the In component of N/GaN multiple quantum well layer (4) is 0.15, In
yGa
1-yThe y value of the In component of N surface nano-structure is 0.30; The thickness of described low temperature GaN resilient coating (2) is 15nm, and wherein the content of Si is that ratio is 1/1000, and the thickness of the n type GaN layer (3) of the described Si of mixing is 2 μ m, is 1 * 10 in this concentration of mixing Si in the n type GaN layer (3) of Si
18Cm
-3, described InxGa
L-xThe MQW In that N/GaN multiple quantum well layer (4) is 1.5nm by 5 trap layer thicknesses
xGa
1-xN/GaN forms, and the thickness of described p type AlGaN layer (5) is 10nm, and wherein the content of Al is 5%, and the thickness of described p type GaN layer (6) is 100nm, described In
yGa
1-yN surface nano-structure layer is nano wire rod structure (7), and the diameter of nanometer terminal is 10nm, highly is 1 * 10 for 100nm, density
9Cm
-2
3. the photocatalysis biochemical device based on iii-nitride light emitting devices according to claim 1 is characterized in that: described In
xGa
1-xThe x value of the In component of N/GaN multiple quantum well layer (4) is 0.30, In
yGa
1-yThe y value of the In component of N nanostructure is 0.40; The thickness of described low temperature GaN resilient coating (2) is 35nm, and wherein the content of Si is that ratio is 1/10000, and the thickness of the n type GaN layer (3) of the described Si of mixing is 4 μ m, is 1 * 10 in this concentration of mixing Si in the n type GaN layer (3) of Si
19Cm
-3, described In
xGa
1-xThe MQW In that N/GaN multiple quantum well layer (4) is 3.5nm by 5 trap layer thicknesses
xGa
1-xN/GaN forms, and the thickness of described p type AlGaN layer (5) is 40nm, and wherein the content of Al is 30%, and the thickness of described p type GaN layer (6) is 300nm, described In
yGa
1-yN surface nano-structure layer is nano dot structure (8), and the diameter of nano dot is 100nm, highly is 1 * 10 for 50nm, density
13Cm
-2
4. the preparation method of the photocatalysis biochemical device based on iii-nitride light emitting devices according to claim 1 is characterized in that: at first in the MOCVD reative cell, Sapphire Substrate (1) is heated to 1050～1070 ℃, at 10～15L/min H
2Following heat treatment 5～15 minutes is cooled to 530 ℃ then naturally, and forming thickness range is the low temperature GaN resilient coating (2) of 15～35nm, then is warming up to 1030～1050 ℃, with the H of 10～15L/min
2Flow is carrier gas, and the Si that mixes synchronously comes the growth rate extension with 2.0 μ m/ hours to constitute the thick n type GaN layer (3) of mixing Si of 2～4 μ m, is 1 * 10 in this concentration of mixing Si in the n type GaN layer (3) of Si
18～1 * 10
19Cm
-3Naturally cool to 740 ℃ then, carrier gas switches to the N of 10～15L/min flow
2, simultaneously with feeding TEGa, TMIn and NH
31～10 In of method growth in source
xGa
1-xThe N/GaN SQW, 0.05≤x≤0.50 wherein, in growth course, the molar flow of TEGa is 1 * 10
-5～3 * 10
-5Mol/min, the molar flow of TMIn is 1 * 10
-5～3 * 10
-5Mol/min, NH
3Flow be 10～20L/min; Afterwards, be increased to 850～950 ℃ to temperature, with the H of 5～10L/min flow
2As carrier gas, simultaneously with feeding TMGa, TMAl and NH
3The method growth thickness be the p type AlGaN layer (5) of 10～40nm and the p type GaN layer (6) of 100～300nm, wherein the content range of Al is 5%～30%, in growth course, the molar flow of TEGa is 1 * 10
-5～3 * 10
-5Mol/min, the molar flow of TMAl is 1 * 10
-5～3 * 10
-5Mol/min, NH
3Flow be 10～20L/min; So just constituted iii-nitride light emitting devices; This iii-nitride light emitting devices is taken out from the MOCVD reative cell, after adopting the thermal annealing mode to activate Mg to be led, at the top surface using plasma enhanced chemical vapor deposition deposition SiO of this iii-nitride light emitting devices
2Or SiN
xMask material, the method that adopts electron beam exposure or nano impression is at this SiO
2Or SiN
xProduce preset nano dot or nanometer terminal figure on the mask material; Wherein the diameter of nano dot figure is 10～100nm; The diameter of nanometer terminal figure is 10～100nm; Then its this iii-nitride light emitting devices that has mask pattern being reentered into the MOCVD reative cell, is 550～750 ℃ in temperature, and carrier gas is the N of 10～20L/min flow
2Condition under, simultaneously with feeding TEGa, TMIn and NH
3Method grow preset nano dot structure (8) or nano wire rod structure (7) figure, wherein the height of nano dot is that 0.3～50nm, density are 1 * 10
9～1 * 10
13Cm
-2, the height of nanometer terminal is that 100～10000nm, density are 1 * 10
9～1 * 10
13Cm
-2, and 0.05≤y≤0.50, x＜y has so just constituted In in addition
yGa
1-yN surface nano-structure layer, in growth course, the molar flow of TEGa is 1 * 10
-5～3 * 10
-5Mol/min, the molar flow of TMIn is 2 * 10
-5～5 * 10
-5Mol/min, NH
3Flow be 10～20L/min.
5. the preparation method of the photocatalysis biochemical device based on iii-nitride light emitting devices according to claim 2 is characterized in that: at first in the MOCVD reative cell, Sapphire Substrate (1) is heated to 1050 ℃, at 10L/min H
2Following heat treatment 5 minutes is cooled to 530 ℃ then naturally, and forming thickness range is the low temperature GaN resilient coating (2) of 15nm, then is warming up to 1030 ℃, with the H of 10L/min
2Flow is carrier gas, and the Si that mixes synchronously comes the growth rate extension with 2.0 μ m/ hours to constitute the thick n type GaN layer (3) of mixing Si of 2 μ m, is 1 * 10 in this concentration of mixing Si in the n type GaN layer (3) of Si
18Cm
-3Naturally cool to 740 ℃ then, carrier gas switches to the N of 10L/min flow
2, simultaneously with feeding TEGa, TMIn and NH
35 In of method growth in source
xGa
1-xThe N/GaN SQW, wherein the value of x is 0.15, in growth course, the molar flow of TEGa is 1 * 10
-5Mol/min, the molar flow of TMIn is 1 * 10
-5Mol/min, NH
3Flow be 10L/min; Afterwards, be increased to 850 ℃ to temperature, with the H of 5L/min flow
2As carrier gas, simultaneously with feeding TMGa, TMAl and NH
3The method growth thickness be the p type AlGaN layer (5) of 10nm and the p type GaN layer (6) of 100nm, wherein the content range of Al is 5%, in growth course, the molar flow of TEGa is 1 * 10
-5Mol/min, the molar flow of TMAl is 1 * 10
-5Mol/min, NH
3Flow be 10L/min; So just constituted iii-nitride light emitting devices; This iii-nitride light emitting devices is taken out from the MOCVD reative cell, after adopting the thermal annealing mode to activate Mg to be led, at the top surface using plasma enhanced chemical vapor deposition deposition SiO of this iii-nitride light emitting devices
2Mask material, the method that adopts electron beam exposure or nano impression is at this SiO
2Produce preset nanometer terminal figure on the mask material, the diameter of nano wire/nano-pillar figure is 10nm, then its this iii-nitride light emitting devices that has mask pattern is reentered into the MOCVD reative cell, is 550 ℃ in temperature, and carrier gas is the N of 10L/min flow
2Condition under, simultaneously with feeding TEGa, TMIn and NH
3Method grow preset nano wire rod structure (7), the height of nanometer terminal is 100nm, density is 1 * 10
9Cm
-2, and the y value is 0.3, so just constituted In
yGa
1-yN surface nano-structure layer, in growth course, the molar flow of TEGa is 1 * 10
-5Mol/min, the molar flow of TMIn is 2 * 10
-5Mol/min, NH
3Flow be 10L/min.
6. the preparation method of the photocatalysis biochemical device based on iii-nitride light emitting devices according to claim 3 is characterized in that: at first in the MOCVD reative cell, Sapphire Substrate (1) is heated to 1070 ℃, at 15L/min H
2Following heat treatment 15 minutes is cooled to 530 ℃ then naturally, and forming thickness range is the low temperature GaN resilient coating (2) of 35nm, then is warming up to 1050 ℃, with the H of 15L/min
2Flow is carrier gas, and the Si that mixes synchronously comes the growth rate extension with 2.0 μ m/ hours to constitute the thick n type GaN layer (3) of mixing Si of 4 μ m, and the concentration of Si is 1 * 10 in mixing the n type GaN layer (3) of Si
19Cm
-3Naturally cool to 740 ℃ then, carrier gas switches to the N of 15L/min flow
2, simultaneously with feeding TEGa, TMIn and NH
35 In of method growth in source
xGa
1-xThe N/GaN SQW, wherein the value of x is 0.30, in growth course, the molar flow of TEGa is 3 * 10
-5Mol/min, the molar flow of TMIn is 3 * 10
-5Mol/min, NH
3Flow be 20L/min; Afterwards, be increased to 950 ℃ to temperature, with the H of 10L/min flow
2As carrier gas, simultaneously with feeding TMGa, TMAl and NH
3The method growth thickness be the p type AlGaN layer (5) of 40nm and the p type GaN layer (6) of 300nm, wherein the content range of Al is 30%, in growth course, the molar flow of TEGa is 3 * 10
-5Mol/min, the molar flow of TMAl is 3 * 10
-5Mol/min, NH
3Flow be 20L/min; So just constituted iii-nitride light emitting devices; This iii-nitride light emitting devices is taken out from the MOCVD reative cell, after adopting the thermal annealing mode to activate Mg to be led, at the top surface using plasma enhanced chemical vapor deposition deposition SiN of this iii-nitride light emitting devices
xMask material, this x value is 0.30, the method that adopts electron beam exposure or nano impression is at this SiN
xProduce preset nano dot figure on the mask material, wherein the diameter of nano dot figure is 100nm, then its this iii-nitride light emitting devices that has mask pattern is reentered into the MOCVD reative cell, is 750 ℃ in temperature, and carrier gas is the N of 20L/min flow
2Condition under, simultaneously with feeding TEGa, TMIn and NH
3Method grow preset nano dot structure (8) figure, wherein the height of nano dot is that 50nm, density are 1 * 10
13Cm
-2, and the y value is 0.40, so just constituted In
yGa
1-yN surface nano-structure layer, in growth course, the molar flow of TEGa is 3 * 10
-5Mol/min, the molar flow of TMIn is 5 * 10
-5Mol/min, NH
3Flow be 20L/min.
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| CN1707820A (en) * | 2005-04-29 | 2005-12-14 | 清华大学 | Method for producing GaN-based illuminator device and its device structure |
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| JP2006191071A (en) * | 2004-12-28 | 2006-07-20 | Samsung Electro Mech Co Ltd | Semiconductor light emitting device and manufacturing method of the same |
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