CN110061103A - GaN base light emitting epitaxial wafer and preparation method thereof - Google Patents
GaN base light emitting epitaxial wafer and preparation method thereof Download PDFInfo
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- CN110061103A CN110061103A CN201910150354.7A CN201910150354A CN110061103A CN 110061103 A CN110061103 A CN 110061103A CN 201910150354 A CN201910150354 A CN 201910150354A CN 110061103 A CN110061103 A CN 110061103A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
- H01L33/0062—Processes for devices with an active region comprising only III-V compounds
- H01L33/0066—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
- H01L33/0062—Processes for devices with an active region comprising only III-V compounds
- H01L33/0075—Processes for devices with an active region comprising only III-V compounds comprising nitride compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/44—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the coatings, e.g. passivation layer or anti-reflective coating
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Abstract
The invention discloses a kind of GaN base light emitting epitaxial wafers and preparation method thereof, belong to GaN base light emitting field.GaTe layer, metal nanoparticle layer, three-dimensional shaped stratum nucleare, layer of undoped gan, n-type doping GaN layer, multiple quantum well layer, electronic barrier layer and the p-type doped gan layer that the LED epitaxial slice includes: substrate, is sequentially deposited over the substrate, the metal nanoparticle layer includes several metal nanoparticles on the GaTe layer and each metal nanoparticle is contacted with described GaTe layers, the diameter of the metal nanoparticle is 1~20nm, and there are gaps between the adjacent metal nanoparticle.
Description
Technical field
The present invention relates to GaN base light emitting field, in particular to a kind of GaN base light emitting epitaxial wafer and its system
Preparation Method.
Background technique
GaN (gallium nitride) has good thermal conductivity, while having the characteristics such as high temperature resistant, acid and alkali-resistance, high rigidity, extensively
Applied to various wave band LED (Light Emitting Diode, light emitting diode).The core component of GaN base LED is chip,
Chip includes epitaxial wafer and the electrode on epitaxial wafer.
GaN base LED epitaxial wafer generally includes: substrate and epitaxial layer.Epitaxial layer includes the buffering of stacked above one another on substrate
Layer, undoped GaN layer, N-type GaN layer, MQW (Multiple Quantum Well, multiple quantum wells) layer and p-type GaN layer.GaN
Base LED electrode includes the N electrode being grown in N-type GaN layer and the P electrode that is grown in p-type GaN layer.According to the installation of electrode
LED chip is divided into horizontal chip and rectilinear chip by the difference of position.In horizontal chip, N electrode and P electrode are located at
The same side；In rectilinear chip, N electrode and P electrode are located at opposite two sides.The N electrode for preparing rectilinear chip it
Before, it needs first to remove substrate from epitaxial layer.How preferably peeling liner bottom becomes the hot spot studied at present.
Summary of the invention
The embodiment of the invention provides a kind of GaN base light emitting epitaxial wafer and preparation method thereof, can preferably by
Substrate is removed from epitaxial layer.The technical solution is as follows:
In a first aspect, providing a kind of GaN base light emitting epitaxial wafer, the LED epitaxial slice includes:
Substrate, the GaTe being sequentially deposited over the substrate layer, metal nanoparticle layer, three-dimensional shaped stratum nucleare, undoped GaN
Layer, n-type doping GaN layer, multiple quantum well layer, electronic barrier layer and p-type doped gan layer, the metal nanoparticle layer include
Several metal nanoparticles on the GaTe layer and each metal nanoparticle is contacted with described GaTe layers,
The diameter of the metal nanoparticle is 1~20nm, and there are gaps between the adjacent metal nanoparticle.
Optionally, the LED epitaxial slice further includes metallic diaphragm, and the metallic diaphragm is located at described GaTe layers
Between the metal nanoparticle layer, the metallic diaphragm includes several metal islands on the GaTe layer and each
The metal island is contacted with described GaTe layers, surrounds the cross section of the metal island and the smallest diameter of a circle of area is 500
~1500nm, there are gaps between the adjacent metal island, and the metal nanoparticle is between the adjacent metal island
On GaTe layer, the metal nanoparticle layer further includes several metal nanoparticles on the metal island.
Optionally, described GaTe layers with a thickness of 1~10nm.
Optionally, the distance between adjacent described metal nanoparticle is 1~20nm.
Optionally, the three-dimensional shaped stratum nucleare is GaN layer or AlN layers, the three-dimensional shaped stratum nucleare with a thickness of 100~
1000nm。
Second aspect provides a kind of preparation method of GaN base light emitting epitaxial wafer, which comprises
Substrate is provided；
GaTe layers are deposited over the substrate；
The deposited metal nanoparticle layers on the GaTe layer, the metal nanoparticle layer include described in several be located at
Metal nanoparticle and each metal nanoparticle on GaTe layer are contacted with described GaTe layers, the metal nano
The diameter of particle is 1~20nm, and there are gaps between the adjacent metal nanoparticle；
Three-dimensional shaped stratum nucleare, layer of undoped gan, n-type doping GaN layer, more is sequentially deposited in the metal nanoparticle layer
Quantum well layer, electronic barrier layer and p-type doped gan layer.
It is optionally, described to deposit GaTe layers over the substrate, comprising:
Described GaTe layers is grown by chemical gaseous phase deposition method, GaTe layers of the growth temperature is 600~1000 DEG C.
Optionally, the deposited metal nanoparticle layers on the GaTe layer, comprising:
Metallic film is grown by magnetically controlled sputter method, the growth temperature of the metallic film is 100~300 DEG C, described
The growth pressure of metallic film is 1~5Pa, and the sputtering power of the metallic film is 10~50W；
The metallic film is made annealing treatment, to form the metal nanoparticle layer.
It is optionally, described that the metallic film is made annealing treatment, comprising:
The metallic film is made annealing treatment by metallo-organic compound chemical gaseous phase deposition method, annealing temperature
It is 400~600 DEG C, annealing atmosphere Ar.
Optionally, the deposited metal nanoparticle layers on the GaTe layer, comprising:
Prepare multiple metal nanoparticles；
The multiple metal nanoparticles being prepared are coated on the GaTe layer.
Technical solution provided in an embodiment of the present invention has the benefit that by being arranged between substrate and epitaxial layer
GaTe layers, since by Covalent bonding together, its stratiform is made of Te-Ga-Ga-Te along c-axis atom in GaTe, interlayer with compared with
Weak Van der Waals for combines, therefore GaTe layers only exist intermolecular Van der Waals force between GaN epitaxial layer, thus is easy stripping
From GaTe layers and epitaxial layer, to realize the removing of substrate and epitaxial layer, and epitaxial layer is facilitated to be transferred to other linings after removing
On bottom, such as glass and flexible substrate, realize photoelectric device flexible, self-supporting GaN material and other substrates are replaced
Become the transparent electrode of GaN base LED for ITO (tin indium oxide)；It is received by the way that metal is arranged between GaTe layers and three-dimensional shaped stratum nucleare
Grain of rice sublayer, metal nanoparticle layer include several metal nanoparticles on GaTe layer and each metal nanoparticle
Being contacted with GaTe layers, the diameter of metal nanoparticle is 1~20nm, and there are gaps between adjacent metal nanoparticle, in this way,
Metal nanoparticle can avoid directly being difficult to be nucleated in growth GaN material on GaTe as the nucleating point of GaN material, from
And promote the generation of nucleating point on GaTe, and conducive to the formation of forming core layer on GaTe, the final crystal matter for improving GaN material on GaTe
Amount, improves the service efficiency and service life of LED component.
Detailed description of the invention
To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment
Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for
For those of ordinary skill in the art, without creative efforts, it can also be obtained according to these attached drawings other
Attached drawing.
Fig. 1 is a kind of structural schematic diagram of GaN base light emitting epitaxial wafer provided in an embodiment of the present invention；
Fig. 2 is a kind of structural schematic diagram of GaN base light emitting epitaxial wafer provided in an embodiment of the present invention；
Fig. 3 is a kind of flow chart of the preparation method of GaN base light emitting epitaxial wafer provided in an embodiment of the present invention；
Fig. 4 is a kind of flow chart of the preparation method of GaN base light emitting epitaxial wafer provided in an embodiment of the present invention.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached drawing to embodiment party of the present invention
Formula is described in further detail.
Fig. 1 shows a kind of GaN base light emitting epitaxial wafer provided in an embodiment of the present invention.Referring to Fig. 1, this luminous two
Pole pipe epitaxial wafer include: substrate 1 and the GaTe being sequentially deposited on substrate 1 (telluride gallium) layer 2, metal nanoparticle layer 3,
Three-dimensional shaped stratum nucleare 4, layer of undoped gan 5, n-type doping GaN layer 6, multiple quantum well layer 7, electronic barrier layer 8 and p-type adulterate GaN
Layer 9.Wherein, metal nanoparticle layer 3 includes several metal nanoparticles on GaTe layer 2 and each metallic nanoparticle
Son is contacted with GaTe layer 2.The diameter of metal nanoparticle is 1~20nm, and there are gaps between adjacent metal nanoparticle.
Wherein, three-dimensional shaped stratum nucleare 4, layer of undoped gan 5, n-type doping GaN layer 6, multiple quantum well layer 7, electronic barrier layer 8,
And p-type doped gan layer 9 constitutes GaN epitaxial layer.GaTe is a kind of novel p-type sulfide, the structure of GaTe layer 2 are as follows: GaTe
Atom is by Covalent bonding together in layer 2, and interlayer is then combined with weaker Van der Waals for, its stratiform is by Te-Ga-Ga-
Te is formed along c-axis.This special layer structure of GaTe layer 2 makes it only exist intermolecular Van der Waals force between GaN,
Thus GaTe layer 2 is arranged between substrate 1 and GaN epitaxial layer, is easily peeled off GaN epitaxial layer and substrate 1.In GaN epitaxial layer
After removing, GaN epitaxial layer is facilitated to be transferred on other substrates, such as glass and flexible substrate, realize photoelectric device flexible, from
The GaN material of support and other substrates substitution ITO is made to become the transparent electrode of GaN base LED, meaning is very great.But
GaTe two-dimensional surface film surface can be very low, and GaN epitaxial layer is grown directly on GaTe and is difficult to be nucleated, Enhancing Nucleation Density is very
It is low, three-dimensional cluster is easily formed, prepared GaN material crystal quality is poor, and practical value is lower.Based on this, at GaTe layers
Metal nanoparticle layer 3 is set between GaN epitaxial layer, and metal nanoparticle layer 3 includes several metals on GaTe layer 2
Nanoparticle and each metal nanoparticle is contacted with GaTe layer 2, the diameter of metal nanoparticle are 1~20nm, adjacent gold
There are gaps between category nanoparticle, in this way, feature lower using surfaces of metal nanoparticles gesture and high chemical activity, with gold
Category nanoparticle is nucleating point, regrowth three-dimensional shaped stratum nucleare 4.The introducing of metal nanoparticle is conducive to three-dimensional shaped stratum nucleare on GaTe
4 formation, and the crystal quality of gallium nitride is further promoted, effectively solve the problems, such as that growth GaN Enhancing Nucleation Density is low on GaTe, mentions
The service efficiency and service life of high LED component have very strong practicability.
Wherein, substrate 1 can be GaN substrate, Sapphire Substrate (Al2O3), SiC substrate, Si substrate, AlN substrate, SiO2
Any one of substrate, diamond substrate.Illustratively, substrate 1 can be (0001) crystal orientation Sapphire Substrate.
Illustratively, the thickness of GaTe layer 2 can be 1~10nm.
Optionally, referring to fig. 2, the LED epitaxial slice further includes metallic diaphragm 10.The metallic diaphragm 10
Between the GaTe layer 2 and the metal nanoparticle layer 3.The metallic diaphragm 10 includes several positioned at the GaTe layer 2
On metal island and each metal island contacted with the GaTe layer 2.Surround the cross section of the metal island and area
The smallest diameter of a circle is 500~1500nm.There are gaps between the adjacent metal island.The metal nanoparticle is located at phase
On GaTe layer 2 between the adjacent metal island.The metal nanoparticle layer further includes several gold on the metal island
Belong to nanoparticle.
Substrate is usually the foreign substrate of GaN material, and existing lattice mismatch and thermal mismatching will between substrate and GaN material
A large amount of dislocation defects are brought, these dislocation defects will extend up in GaN material along GaTe layers, influence length on GaTe layer
The crystal quality of GaN material.Based on this, metallic diaphragm is set at GaTe layers between GaN epitaxial layer, metallic diaphragm includes several
Metal island and each metal island on GaTe layer are contacted with GaTe layers, surround the cross section of metal island and area is minimum
Diameter of a circle be 500~1500nm, there are gaps between adjacent metal island, are covered in this way, metal island can separate metal island
The GaTe layer of cover area is contacted with GaN epitaxial layer, and GaN epitaxial layer is first to grow between metal island, when between all metal islands
Gap fill and lead up after be linked to be again smooth a piece of, i.e., the GaN epitaxy in metal island overlay area is from the sky between metal island
The GaN epitaxy of gap growth is laterally extended growth, can promote GaN cross growth, dislocation defects cannot be laterally extended, therefore
Dislocation defects can be blocked when GaN cross growth, the crystal quality of cross growth is higher；Also, compared to from GaTe layers entire
Upper growth GaN epitaxial layer reduces the contact area of GaTe layers with GaN epitaxial layer since metal island covers part GaTe layers,
Therefore, lattice mismatch and thermal mismatching bring dislocation defects between substrate and GaN material can be reduced or be inhibited, dislocation is avoided to lack
It falls into and is extended in GaN epitaxial layer along GaTe layers, further increase the crystal quality of GaN material on GaTe layer, and then improve LED
The service efficiency and service life of device have very strong practicability.
Wherein, in metallic diaphragm 10, several metal islands can be evenly distributed on GaTe layer 2, can also be with uneven distribution
On GaTe layer 2.Metal island can be polygonal body, coniform or round table-like, and the embodiment of the present invention does not limit metal island
Shape.Preferably, metal island can be semi-spherical shape.When the cross section of metal island is round, the circle of cross section and face are surrounded
The smallest circle of product is cross section itself.When the cross section of metal island is convex polygon, the circle of cross section and area are surrounded most
Small circle is the circumscribed circle of cross section.Illustratively, when the cross section and the smallest diameter of a circle of area that surround metal island are
When 500~1500nm, the distance between adjacent metal island is 10~100nm, and the height of metal island is 500~1500nm.It is preferred that
Ground, the cross section of metal island are circle, surround the cross section of metal island and the smallest diameter of a circle of area is 950~1050nm,
The distance between adjacent metal island is 40~60nm, and the height of metal island is 950~1050nm.At this moment, position can best be inhibited
Wrong defect, the crystal quality highest of obtained GaN material.
Wherein, metallic diaphragm 10 can be any one of Ag film layer, Au film layer, In film layer and Al film layer.Preferably,
Metallic diaphragm 10 can be Ag film layer or Au film layer.
It should be noted that LED epitaxial slice provided in an embodiment of the present invention is suitable for luminous the two of vertical structure
The light emitting diode of pole pipe and inverted structure.
Wherein, in metal nanoparticle layer 3, several metal nanoparticles can be evenly distributed on GaTe layer 2, can also be with
It is non-uniformly distributed on GaTe layer 2.Metal nanoparticle is spherical shape.Illustratively, when metal nano in metal nanoparticle layer 3
When the diameter of particle is 1~20nm, the distance between adjacent metal nanoparticle is 1~20nm.Preferably, metal nanoparticle
Diameter be 8~12nm, the distance between adjacent metal nanoparticle be 8~12nm.At this moment, the GaN material being prepared is brilliant
Weight is best.
Wherein, metal nanoparticle layer 3 can be Ag nanoparticle layers, Au nanoparticle layers, In nanoparticle layers and Al
Any one of nanoparticle layers.Preferably, metal nanoparticle layer 3 can be Ag nanoparticle layers or Au nanoparticle
Layer.It, can also be with it should be noted that the metal material of metallic diaphragm 10 can be identical as the metal material of metal nanoparticle 3
Difference, the embodiment of the present invention is with no restriction.Preferably, the metal material of the metal material of metallic diaphragm 10 and metal nanoparticle 3
Matter is identical.
Wherein, three-dimensional shaped stratum nucleare 4 is used for, using each metal nanoparticle in metal nanoparticle layer 3 as nucleus, and with compared with
Several brilliant islands of high crystalline quality growth.Illustratively, three-dimensional shaped stratum nucleare 4 is GaN layer or AlN layers, the thickness of three-dimensional shaped stratum nucleare 4
Degree can be 100~1000nm.
Wherein, layer of undoped gan 5 is used for, and the lateral growth from each brilliant island makes adjacent brilliant island connect, until extension
Entire surface tends to be smooth.Illustratively, the thickness of layer of undoped gan 5 can be 1 to 5 micron.
Illustratively, n-type doping GaN layer 6 with a thickness of 1 to 5 micron.
Illustratively, n-type doping is Si doping in n-type doping GaN layer 6, and Si doping concentration can be 1 × 1018cm-3~1
×1019cm-3。
Illustratively, multiple quantum well layer 7 includes multiple InGaN well layer and multiple GaN barrier layer, multiple quantum well layer InGaN
The multilayered structure that well layer and GaN barrier layer alternating growth are formed.In multiple quantum well layer 7, InGaN well layer with a thickness of 2~3nm, GaN
Barrier layer with a thickness of 9~20nm, the overall thickness of multiple quantum well layer 7 can be 130~160nm.Based on this, InGaN well layer and GaN
The quantity of barrier layer may each be 5~11.Wherein, the quantity of InGaN well layer and GaN barrier layer can be identical, for example takes 10；
The quantity of InGaN well layer and GaN barrier layer can also be different, for example, the quantity that the quantity of InGaN well layer is 8, GaN barrier layer is 9,
Generally speaking, the quantity of InGaN well layer can bigger than the quantity of GaN barrier layer 1 or small by 1.
In addition, the embodiment of the present invention does not limit the layer contacted in multiple quantum well layer 7 with n-type doping GaN layer 6.Multiple quantum wells
The InGaN well layer that can be in multiple InGaN well layer contacted in layer 7 with n-type doping GaN layer 6 (is assumed to be first
InGaN well layer), the GaN barrier layer (being assumed to be the first GaN barrier layer) being also possible in multiple GaN barrier layer.
Similarly, what is contacted in multiple quantum well layer 7 with electronic barrier layer 8 can be one in multiple InGaN well layer
InGaN well layer (is assumed to be the 2nd InGaN well layer), and a GaN barrier layer being also possible in multiple GaN barrier layer (is assumed to be second
GaN barrier layer).Preferably, it in the multiple InGaN well layer and multiple GaN barrier layer that multiple quantum well layer 7 includes, is connect with electronic barrier layer 8
Touching is one of InGaN well layer (i.e. the 2nd InGaN well layer).In this way, electronic barrier layer 8 can be used as multiple quantum well layer 7
A barrier layer.
Illustratively, electronic barrier layer 8 is AlyGa1-yN layers, y is 0.1~0.5.
Illustratively, electronic barrier layer 8 with a thickness of 20~100nm.
Illustratively, doped with P-type dopant, such as Mg in electronic barrier layer 8, Mg doping concentration can be 1 ×
1018cm-3~1 × 1019cm-3。
Illustratively, p-type doped gan layer 9 with a thickness of 100~800nm.P-type is doped to Mg and mixes in p-type doped gan layer 9
Miscellaneous, Mg doping concentration is 1 × 1020cm-3~1 × 1021cm-3, the Mg doping concentration that is far longer than in electronic barrier layer 8.
Illustratively, referring to fig. 2, which further includes the p-type contact layer 11 being deposited in p-type doped gan layer 9.P-type
The thickness of contact layer 11 can be 5~300nm.
Fig. 3 shows a kind of preparation method of GaN base light emitting epitaxial wafer provided in an embodiment of the present invention.It can adopt
LED epitaxial slice shown in fig. 1 is prepared in the method shown in Fig. 3.Referring to Fig. 3, this method process includes following step
Suddenly.
Step 101 provides substrate.
Wherein, substrate can be GaN substrate, Sapphire Substrate (Al2O3), SiC substrate, Si substrate, AlN substrate, SiO2Lining
Any one of bottom, diamond substrate.
Step 102 deposits GaTe layers on substrate.
Step 103, the deposited metal nanoparticle layers on GaTe layer.
Wherein, metal nanoparticle layer includes several metal nanoparticles on GaTe layer and each metal nano
Particle is contacted with GaTe layers, and the diameter of metal nanoparticle is 1~20nm, and there are gaps between adjacent metal nanoparticle.
Illustratively, metal nanoparticle layer can for Ag nanoparticle layers, Au nanoparticle layers, In nanoparticle layers and
Any one of Al nanoparticle layers.
Step 104 is sequentially deposited three-dimensional shaped stratum nucleare, layer of undoped gan, n-type doping GaN in metal nanoparticle layer
Layer, multiple quantum well layer, electronic barrier layer and p-type doped gan layer.
The embodiment of the present invention between substrate and epitaxial layer by being arranged GaTe layers, since atom passes through covalent bond in GaTe
In conjunction with, and interlayer is then combined with weaker Van der Waals for, its stratiform is made of Te-Ga-Ga-Te along c-axis, therefore
GaTe layers only exist intermolecular Van der Waals force between epitaxial layer, thus are easily peeled off GaTe layers and epitaxial layer, to realize lining
The removing at bottom and epitaxial layer, and epitaxial layer is facilitated to be transferred on other substrates, such as glass and flexible substrate after removing, it realizes
Photoelectric device flexible, self-supporting GaN material and make other substrates substitution ITO (tin indium oxide) become GaN base LED
Transparent electrode；By the way that metal nanoparticle layer is arranged between GaTe layers and three-dimensional shaped stratum nucleare, metal nanoparticle layer includes
Several metal nanoparticles on the GaTe layer and each metal nanoparticle is contacted with GaTe layers, metal nanoparticle
Diameter be 1~20nm, there are gaps between adjacent metal nanoparticle, in this way, metal nanoparticle can be used as GaN material
Nucleating point, avoid the growth GaN material directly on GaTe from being difficult to be nucleated, to promote the generation of nucleating point on GaTe, be conducive to
The formation of the upper forming core layer of GaTe, the final crystal quality for improving GaN material on GaTe improve the service efficiency of LED component and make
Use the service life.
Fig. 4 shows a kind of preparation method of GaN base light emitting epitaxial wafer provided in an embodiment of the present invention.It can adopt
The method shown in Fig. 4 be prepared Fig. 1 or Fig. 2 shows LED epitaxial slice.Referring to fig. 4, this method process includes
Following steps.
Step 201 provides substrate.
Wherein, substrate can be GaN substrate, Sapphire Substrate, SiC substrate, Si substrate, AlN substrate, SiO2Substrate, gold
Any one of hard rock substrate.Illustratively, substrate can be (0001) crystal orientation Sapphire Substrate.
Step 202 is given birth on substrate by CVD (Chemical Vapor Deposition, chemical vapor deposition) method
It is GaTe layers long.
Illustratively, at GaTe layers of the reaction indoor growing of CVD equipment.Specifically, using GaTe powder as growth
Source, and carrier gas is used as using high-purity Ar (argon gas).Wherein, GaTe layers of growth temperature be 600~1000 DEG C, vacuum degree be 1~
10Pa.Growth time be 30~90min (minute), at this moment, obtain GaTe layers with a thickness of 1~10nm.
Step 203, the depositing metal membrane layer on GaTe layer.
Wherein, metallic diaphragm includes several metal islands on GaTe layer and each metal island is contacted with GaTe layers,
The cross section of metal island and the smallest diameter of a circle of area are surrounded as 500~1500nm, there are gaps between adjacent metal island.
Step 203 may include steps of 2031 and step 2032.
Step 2031 deposits one layer of metallic film by magnetically controlled sputter method on GaTe layer.
Specifically, the growth temperature of metallic film is 100~300 DEG C, and growth pressure is 1~5Pa in magnetron sputtering, splash
Penetrating power is 10~50W.
Illustratively, metallic film can be any one of Ag film, Au film, In film and Al film.
Step 2032 makes annealing treatment metallic film, to form metallic diaphragm.
Illustratively, step 2032 may include: and make annealing treatment in high-temperature annealing furnace to metallic film, wherein
Annealing temperature is 400~600 DEG C, and annealing atmosphere Ar ultimately forms the metallic diaphragm in island structure.When in metallic diaphragm 3
Surround metal island cross section and the smallest diameter of a circle of area be 500~1500nm when, the distance between adjacent metal island is
10~100nm, the height of metal island are 500~1500nm.
It should be noted that step 203 is that optional step can execute step 204 when realizing after step 202,
The deposited metal nanoparticle layers i.e. on GaTe layer.
Step 204, the deposited metal nanoparticle layers on metallic diaphragm.
Wherein, metal nanoparticle layer includes several metal nanoparticles on GaTe layer and each metal nano
Particle is contacted with GaTe layers, and the diameter of metal nanoparticle is 1~20nm, and there are gaps between adjacent metal nanoparticle.
Further, on GaTe layer of the metal nanoparticle between the adjacent metal island, the metal nanoparticle layer
It further include several metal nanoparticles on the metal island.
The embodiment of the present invention provides the depositional mode of two kinds of metal nanoparticle layers.The first depositional mode may include as
Lower step 1 and step 2.
Step 1: growing metallic film on metallic diaphragm by magnetically controlled sputter method.
Illustratively, in magnetron sputtering, the growth temperature of metallic film is 100~300 DEG C, and growth pressure is 1~5Pa,
Sputtering power is 10~50W.
Illustratively, metallic film can be with Ag film or Au film.Specifically, the substrate for growing GaTe layers is placed into
In the reaction chamber of PVD (Physical Vapor Deposition, physical vapour deposition (PVD)) equipment, in the reaction chamber of PVD equipment
Grow Ag film or Au film.
Step 2: being made annealing treatment to metallic film, to form metal nanoparticle layer.
Illustratively, step 2 may include: by MOCVD (Metal-organic Chemical Vapor
Deposition, metallo-organic compound chemical gaseous phase deposition) method makes annealing treatment metallic film, wherein annealing temperature
Degree is 400~600 DEG C, annealing atmosphere Ar.Specifically, the substrate for growing Ag film or Au film MOCVD is placed into set
In standby reaction chamber, and Ag film or Au film are made annealing treatment in the reaction chamber of MOCVD device.
Second of depositional mode may include steps of A and step B.
Step A, multiple metal nanoparticles are prepared.
Illustratively, Ag nanoparticle can be prepared using aqueous phase synthesis method, can be prepared using citrate reduction method
Au nanoparticle.
Specifically, aqueous phase synthesis method include: firstly, polyvinylpyrrolidone (PVP) is added in first part of ethyl alcohol, and
1~5h of magnetic agitation (hour), while the temperature of first part of ethyl alcohol being controlled at 50~100 DEG C；Secondly, silver nitrate is added to
In second part of ethyl alcohol, and the temperature for controlling second part of ethyl alcohol is 50 DEG C, applies ultrasonic vibration to second part of ethyl alcohol, until second part
Silver nitrate in ethyl alcohol is completely dissolved；Then, silver nitrate solution is added drop-wise in PVP solution, that is, mixes two parts of ethyl alcohol, and control
The temperature of mixed solution is 50~100 DEG C, magnetic agitation 1~5h of mixed solution, generates Ag nanoparticle.
Specifically, citrate reduction method includes: firstly, aqueous solution of chloraurate is heated to boiling；Secondly, in magnetic stirring
Trisodium citrate aqueous solution, and continuous heating certain time are added during aqueous solution of chloraurate；Then, in aqueous solution of chloraurate
Original volume is restored to distilled water after cooling, finally obtains Au nanoparticle.
Step B, the multiple metal nanoparticles being prepared are coated on metallic diaphragm.
Specifically, metal nanoparticle can be coated on metallic diaphragm using spin-coating method.
Step 205 is sequentially deposited three-dimensional shaped stratum nucleare, layer of undoped gan, n-type doping GaN in metal nanoparticle layer
Layer, multiple quantum well layer, electronic barrier layer, p-type doped gan layer and p-type contact layer.
It should be noted that three-dimensional shaped stratum nucleare, layer of undoped gan, n-type doping GaN layer, multiple quantum well layer, electronic blocking
Layer and p-type doped gan layer constitute epitaxial layer, and epitaxial layer can be grown using MOCVD method.The temperature controlled in growth course
Degree and pressure actually refer to the indoor temperature and pressure of the reaction of MOCVD device.Specifically, using high-purity H2(hydrogen) and/
Or high-purity N2(nitrogen) or high-purity H2And high-purity N2Mixed gas as carrier gas, high-purity N H3As the source N, trimethyl gallium (TMGa)
And triethyl-gallium (TEGa) is used as gallium source, trimethyl indium (TMIn) is used as indium source, silane (SiH4) it is used as N type dopant, front three
Base aluminium (TMAl) is used as silicon source, two luxuriant magnesium (CP2Mg) it is used as P-type dopant.
Illustratively, step 205 may include steps of 2051- step 2057.
Step 2051, the deposition three-dimensional forming core layer in metal nanoparticle layer.
Illustratively, three-dimensional shaped stratum nucleare can be GaN layer.Reaction chamber temperature is 1000~1100 DEG C, chamber pressure control
System is used as carrier gas in 100~500torr, N2 and H2,1~20min of growth, at this moment, three-dimensional shaped stratum nucleare with a thickness of 100~
1000nm。
Step 2052 deposits layer of undoped gan on three-dimensional shaped stratum nucleare.
Illustratively, the growth temperature of layer of undoped gan be 1000~1100 DEG C, growth thickness between 1 to 5 micron,
Growth pressure is in 100Torr between 500Torr.
Step 2053, the deposited n-type doped gan layer in layer of undoped gan.
Illustratively, the thickness of N-type GaN layer is between 1~5 micron, and growth temperature is at 1000~1200 DEG C, growth pressure
In 100~500Torr or so, Si doping concentration is 1 × 1018~1 × 1019cm-3Between.
Step 2054 deposits multiple quantum well layer in n-type doping GaN layer.
Wherein, multiple quantum well layer includes multiple InGaN well layer and multiple GaN barrier layer, multiple quantum well layer be InGaN well layer and
The multilayered structure that GaN barrier layer alternating growth is formed.
Illustratively, when growing multiple quantum well layer, chamber pressure is controlled in 100~500torr.Grow InGaN well layer
When, reaction chamber temperature is 720~829 DEG C.When growing GaN barrier layer, reaction chamber temperature is 850~959 DEG C.
In multiple quantum well layer, InGaN well layer with a thickness of 2~3nm, GaN barrier layer with a thickness of 9~20nm, multiple quantum wells
The overall thickness of layer can be 130~160nm.Based on this, the quantity of InGaN well layer and GaN barrier layer may each be 5~11.
Step 2055 deposits electronic barrier layer on multiple quantum well layer.
Wherein, electronic barrier layer is that p-type adulterates AlGaN layer.P-type is doped to Mg doping in electronic barrier layer, and Mg doping is dense
Degree can be 1 × 1018cm-3~1 × 1019cm-3。
Illustratively, electronic barrier layer AlyGa1-yN layers, y is 0.1~0.5.
Illustratively, the growth temperature of electronic barrier layer is between 200 DEG C and 1000 DEG C, growth pressure 50-
500Torr.The thickness of electronic barrier layer is in 20nm between 100nm.
Step 2056 deposits p-type doped gan layer on electronic barrier layer.
Illustratively, the growth temperature of p-type doped gan layer is 600~1000 DEG C, and growth pressure is 100~300torr, P
The thickness of type doped gan layer can be 100~800nm.
Illustratively, p-type is doped to Mg doping in p-type doped gan layer, and Mg doping concentration is 1 × 1020~1 × 1021cm-3, the Mg doping concentration that is far longer than in electronic barrier layer.
Step 2057 deposits p-type contact layer in p-type doped gan layer.
Illustratively, the growth temperature of p-type contact layer is 850 DEG C~1050 DEG C, and growth pressure is 100~300torr, P
The thickness of type contact layer can be 5~300nm.
Illustratively, after epitaxial growth, the reaction room temperature of MOCVD device is reduced, is moved back in nitrogen atmosphere
Fire processing, annealing temperature section are 650~850 DEG C, make annealing treatment 5 to 15 minutes, are down to room temperature, complete epitaxial growth.
The embodiment of the present invention between substrate and epitaxial layer by being arranged GaTe layers, since atom passes through covalent bond in GaTe
In conjunction with, and interlayer is then combined with weaker Van der Waals for, its stratiform is made of Te-Ga-Ga-Te along c-axis, therefore
GaTe layers only exist intermolecular Van der Waals force between epitaxial layer, thus are easily peeled off GaTe layers and epitaxial layer, to realize lining
The removing at bottom and epitaxial layer, and epitaxial layer is facilitated to be transferred on other substrates, such as glass and flexible substrate after removing, it realizes
Photoelectric device flexible, self-supporting GaN material and make other substrates substitution ITO (tin indium oxide) become GaN base LED
Transparent electrode；By the way that metal nanoparticle layer is arranged between GaTe layers and three-dimensional shaped stratum nucleare, metal nanoparticle layer includes
Several metal nanoparticles on the GaTe layer and each metal nanoparticle is contacted with GaTe layers, metal nanoparticle
Diameter be 1~20nm, there are gaps between adjacent metal nanoparticle, in this way, metal nanoparticle can be used as GaN material
Nucleating point, avoid the growth GaN material directly on GaTe from being difficult to be nucleated, to promote the generation of nucleating point on GaTe, be conducive to
The formation of the upper forming core layer of GaTe, the final crystal quality for improving GaN material on GaTe improve the service efficiency of LED component and make
Use the service life.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of GaN base light emitting epitaxial wafer, which is characterized in that the LED epitaxial slice includes:
Substrate, the GaTe being sequentially deposited over the substrate layer, metal nanoparticle layer, three-dimensional shaped stratum nucleare, layer of undoped gan, N
Type doped gan layer, multiple quantum well layer, electronic barrier layer and p-type doped gan layer, the metal nanoparticle layer include several
Metal nanoparticle and each metal nanoparticle on the GaTe layer are contacted with described GaTe layers, described
The diameter of metal nanoparticle is 1~20nm, and there are gaps between the adjacent metal nanoparticle.
2. epitaxial wafer according to claim 1, which is characterized in that the LED epitaxial slice further includes metal film
Layer, the metallic diaphragm are located at described GaTe layers between the metal nanoparticle layer, and the metallic diaphragm includes several positions
In the metal island on the GaTe layer and each metal island is contacted with described GaTe layers, surrounds the cross of the metal island
Section and the smallest diameter of a circle of area are 500~1500nm, and there are gap between the adjacent metal island, the metal is received
For rice corpuscles on the GaTe layer between the adjacent metal island, the metal nanoparticle layer further includes several positioned at the gold
Belong to the metal nanoparticle on island.
3. epitaxial wafer according to claim 1 or 2, which is characterized in that described GaTe layers with a thickness of 1~10nm.
4. epitaxial wafer according to claim 3, which is characterized in that the distance between adjacent described metal nanoparticle is 1
~20nm.
5. epitaxial wafer according to claim 4, which is characterized in that the three-dimensional shaped stratum nucleare is GaN layer or AlN layers, institute
State three-dimensional shaped stratum nucleare with a thickness of 100~1000nm.
6. a kind of preparation method of GaN base light emitting epitaxial wafer, which is characterized in that the described method includes:
Substrate is provided；
GaTe layers are deposited over the substrate；
The deposited metal nanoparticle layers on the GaTe layer, the metal nanoparticle layer include several positioned at described GaTe layers
On metal nanoparticle and each metal nanoparticle contacted with described GaTe layers, the metal nanoparticle
Diameter is 1~20nm, and there are gaps between the adjacent metal nanoparticle；
Three-dimensional shaped stratum nucleare, layer of undoped gan, n-type doping GaN layer, Multiple-quantum are sequentially deposited in the metal nanoparticle layer
Well layer, electronic barrier layer and p-type doped gan layer.
7. according to the method described in claim 6, it is characterized in that, described deposit GaTe layers over the substrate, comprising:
Described GaTe layers is grown by chemical gaseous phase deposition method, GaTe layers of the growth temperature is 600~1000 DEG C.
8. according to the method described in claim 6, it is characterized in that, the deposited metal nanoparticle on the GaTe layer
Layer, comprising:
Metallic film is grown by magnetically controlled sputter method, the growth temperature of the metallic film is 100~300 DEG C, the metal
The growth pressure of film is 1~5Pa, and the sputtering power of the metallic film is 10~50W；
The metallic film is made annealing treatment, to form the metal nanoparticle layer.
9. according to the method described in claim 8, it is characterized in that, described make annealing treatment the metallic film, comprising:
The metallic film is made annealing treatment by metallo-organic compound chemical gaseous phase deposition method, annealing temperature is
400~600 DEG C, annealing atmosphere Ar.
10. according to the method described in claim 6, it is characterized in that, the deposited metal nanoparticle on the GaTe layer
Layer, comprising:
Prepare multiple metal nanoparticles；
The multiple metal nanoparticles being prepared are coated on the GaTe layer.
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| CN112687774A (en) * | 2020-12-11 | 2021-04-20 | 华灿光电（浙江）有限公司 | Light emitting diode epitaxial wafer and preparation method thereof |
| WO2023092717A1 (en) * | 2021-11-26 | 2023-06-01 | 江苏第三代半导体研究院有限公司 | Semiconductor epitaxial wafer and manufacturing method therefor |
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| CN1892314A (en) * | 2005-06-30 | 2007-01-10 | Lg.菲利浦Lcd株式会社 | Array substrate for liquid crystal display and method for fabricating the same |
| CA2621665A1 (en) * | 2007-11-21 | 2008-05-22 | National Research Council Of Canada | Transparent and/or photovoltaic solar cell and module |
| CN107210336A (en) * | 2015-01-16 | 2017-09-26 | 丸文株式会社 | Deep ultraviolet LED and its manufacture method |
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| CN1892314A (en) * | 2005-06-30 | 2007-01-10 | Lg.菲利浦Lcd株式会社 | Array substrate for liquid crystal display and method for fabricating the same |
| CA2621665A1 (en) * | 2007-11-21 | 2008-05-22 | National Research Council Of Canada | Transparent and/or photovoltaic solar cell and module |
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| WO2023092717A1 (en) * | 2021-11-26 | 2023-06-01 | 江苏第三代半导体研究院有限公司 | Semiconductor epitaxial wafer and manufacturing method therefor |
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