CN101009347A - Non polarity A side nitride film growing on the silicon(102) substrate and its making method and use - Google Patents
Non polarity A side nitride film growing on the silicon(102) substrate and its making method and use Download PDFInfo
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Abstract
The invention relates to a nonpolar A side nitride film that comprises a silicon (102) underlay, metal layer which grows upon the silicon underlay sequentially, InGaAlN initial growth layer and the first InGaAlN buffer layer, it characterized in that: said silicon underlay is Si underlay which adopts the (102) side or offset angle. The nonpolar a side nitride film which grows on the silicon underlay can be used in LBD, laser, solar battery. The component extension configuration is adopted according to different component, for example the LBD and laser, and using the mature silicon craft further to produce relative diprosopia electrode component or peeling off component. The advantages of the invention are: the invention can increase the growth quality of nonpolar GaN base material, and decrease the cost; the craft of current component can be simplified greatly, the cost can be decreased, and increase the elimination efficiency and lightening efficiency greatly.
Description
Technical field
The present invention relates to the non polarity A side nitride film of growing on a kind of silicon (102) substrate, and preparation method thereof and the purposes in photoelectron and microelectronic component.
Background technology
With GaN is the wide-band gap material of representative, is the third generation semiconductor after Si and GaAs.Because the breakthrough of epitaxy technology has development fast during the nineties.Why it is subjected to is paid much attention to widely, based on the reason of three aspects: at first be to make the brightness blue light luminous tube, thereby make the mankind can obtain high duplication, long-life panchromatic white light source that comprises; The secondth, can make short wavelength laser, for Long Wavelength Laser, beam spot size is little, can realize the high density data optical storage; The 3rd is its high temperature resistant, high thermal conductance, high voltage endurance, can develop high temperature (300～500 ℃), high linearity, high power electronic device and ultraviolet detector.
Present GaN sill is that (In) and the combination of N, thereby there are electronegativity in Ga, Al, and make its monocrystalline have polar surface, be i.e. III family element (Ga, Al, In) face or N face by III family element.The extension of present GaN all is grown on (0001) face basically, so polarity problems still is important.Growth on different polar surface because the arrangement of the key of III and V group element is different, thereby makes defect concentration, the configuration difference of Grown GaN.The foreign atom of absorption has great difference when the more important thing is growth, thereby the electricity and the optical characteristics of material exerted an influence.And GaN base heterojunction both sides exist difference on spontaneous polarization and piezoelectric polarization, thereby make this heterojunction boundary place produce certain density electric charge.These electric charges produce the higher internal electric field of intensity in epitaxial loayer, make band curvature, inclination, and level of energy changes, and are that emission wavelength produces red shift; The electric field that is produced by interface charge also can make positive negative carrier spatially separate simultaneously, and the crossover of electronics and hole wave function diminishes, and the luminous efficiency of material is reduced greatly.In addition, having the charge carrier electrically opposite with interface charge attracted to and forms two-dimensional electron gas or hole gas at the interface.Because at the interface polar scattering and alloy scattering intensity are very big, two-dimentional mobility of charge carrier rate can be very low; And the separated charge carrier of opening of another part is deposited in the surface of sample, has influenced surface physical characteristic.As doing ohmic contact, often be difficult to obtain the Ohmic electrode of P type at Ga face sample surfaces.
If growing and preparing goes out well behaved non-polar GaN, then can overcome above-mentioned existing problem, improve the luminous efficiency of light-emitting diode greatly.
The direction of growing nonpolar GaN is at sapphire R (101 now
) growth (11 on the face
0) research of A face GaN, the result of light fluorescence shows the height of the luminous efficiency of A face InGaN/GaN quantum well than C face, the result of LED device shows that the GaN base blue LED of luminous strength ratio C face of A face is strong 1 times.But the lattice mismatch of the A face of sapphire R face and GaN is 1% in [0001] GaN direction, [1
00] GaN direction lattice mismatch is 16%, differ greatly, therefore the A face GaN that grows on sapphire R face exists defectives such as a large amount of faults, dislocation, rough surface, only on graph substrate, just can obtain low, the flat surface of defect concentration by the growth of HVPE method.
Another direction of growing nonpolar GaN is to LiAlO
3(100) growth M face (1 on the face
00) GaN studies, and the lattice mismatch of itself and GaN has only 1%, is well low mismatch substrate, but LiAlO
3Poor heat stability, epitaxial growth GaN intrinsic carrier concentration height is difficult to preparation P type GaN.
Summary of the invention
The objective of the invention is to have polarity problems for the GaN sill (InGaAlN) that overcomes on existing being grown in (0001) face, and at existing substrate (R surface sapphire and LiAlO
3(100) problem of the high defective of growing nonpolar GaN base film existence face).The lattice constant of silicon (102) face is 5.42 dusts on one side, and another side is 4.84 dusts, and GaN (11
0) lattice constant of a direction of A face is 5.5183 dusts, the lattice constant of other direction is 5.178 dusts, be respectively 1.8% and 7% with the corresponding lattice mismatch of silicon (102) face, promptly the lattice mismatch of the silicon substrate of this particular crystal orientation and GaN is less, be the epitaxially grown good substrate of GaN, thus provide a kind of on the silicon substrate of silicon (102) face and drift angle, grow nonpolar (11
0) A side nitride film, and preparation method thereof, light-emitting diode of growing thereon and preparing and laser, and further utilize ripe silicon technology, the double-face electrode device that preparation is corresponding or adopt the device of stripping technology: or the method is used for other photoelectron and microelectronic component.
The objective of the invention is to realize by the following technical solutions:
The invention provides grow on a kind of silicon (102) substrate nonpolar (11
0) A side nitride film, its structural representation comprise a silicon substrate 1, thereon metal level 2, InGaAlN initial growth layer 3 and an InGaAlN resilient coating 4 of growth successively as shown in Figure 1, it is characterized in that:
Described silicon substrate is for adopting the Si substrate of (102) face or drift angle;
The substrate of described Si (102) face and drift angle is: Si (102) substrate and to all directions drift angle be no more than 12 the degree, and Si (102) substrate and to all directions drift angle be no more than 12 the degree various graph substrate:
Described graph substrate is etching (wet method and the dry method) figure of a peacekeeping X-Y scheme, or passes through the graph substrate of the peacekeeping X-Y scheme mask formation of metal, nitride, oxide:
Described metal level is that metal deposits such as In, Ga, Al, Zn form, and thickness is 0～100 dust;
Described InGaAlN initial growth layer is the transition zone of extension on foreign substrate, the material of this transition zone is the combination of GaN, AlGaN, InAlN, InAlGaN or these several alloys, promptly can be single layer structure, superlattice, content gradually variational layer, thickness be 10～2000 dusts;
A described InGaAlN resilient coating is the transition zone of extension on InGaAlN initial growth layer, the material of this transition zone is the combination of GaN, AlGaN, InAlN, InAlGaN or these several alloys, promptly can be single layer structure, superlattice, content gradually variational layer, thickness be 100～40000 dusts.
The invention provides grow on a kind of above-mentioned silicon (102) substrate nonpolar (11
0) preparation method of A side nitride film comprises following step:
1) in the MOCVD reative cell, design temperature is 600～1100 ℃ of scopes, the surface of silicon that the cleans up desorption of annealing is handled, to remove the oxide layer of substrate surface;
2) utilize metal organic source as metal source material, deposit one metal level on the Si substrate of this (102) face or drift angle, 400～1100 ℃ of reaction chamber temperature scopes;
3) at 400～1100 ℃, epitaxial growth InGaAlN initial growth layer on above-mentioned metal level; This layer material is the combination of GaN, AlGaN, InAlN, InAlGaN or these several alloys, promptly can be single layer structure, superlattice, content gradually variational layer, and thickness is 10～2000 dusts;
4) at 800～1100 ℃, epitaxial growth the one InGaAlN resilient coating on above-mentioned InGaAlN initial growth layer, this layer material is the combination of GaN, AlGaN, InAlN, InAlGaN or these several alloys, promptly can be single layer structure, superlattice, content gradually variational layer, thickness is 100～40000 dusts, obtain growing on silicon of the present invention (102) substrate nonpolar (11
0) A side nitride film.
Grow on silicon provided by the invention (102) substrate nonpolar (11
0) the A side nitride film can be applied to fields such as light-emitting diode, laser, solar cell.Thereon according to different device application growth corresponding devices epitaxial structures, the light-emitting diode and the laser of for example growing and preparing, and the further silicon technology that utilizes maturation, the device of double-face electrode device that preparation is corresponding or employing stripping technology; Or the method is used for other photoelectron and microelectronic component.
The invention provides a kind of light-emitting diode of high-luminous-efficiency, as shown in Figure 2, comprise grow on above-mentioned silicon (102) substrate nonpolar (11
0) A side nitride film reaches growth the 2nd InGaAlN resilient coating 5, n type InAlGaN layer 6, luminescent layer 7, p type limiting layer 8 and p type GaN layer 9 thereon successively, it is characterized in that:
Described the 2nd InGaAlN resilient coating is the combination of GaN, AlGaN, InAlN, InAlGaN or these several alloys, promptly can be single layer structure, superlattice, content gradually variational layer, and thickness is 50nm～3 μ m;
Described n type InAlGaN layer is the combination of GaN, InAlN, AlGaN, InAlGaN or these several alloys for the contact layer of preparation n type ohmic contact, and thickness is 50nm～3 μ m;
Described luminescent layer is the active layer of light-emitting diode, and this layer is by barrier layer GaN or In
yGa
1-yN and quantum well layer In
xGa
1-xThe Multiple Quantum Well that N forms, wherein 0.05＜x＜0.3,0＜y＜0.15, and y＜x, the periodicity of quantum well is 1～20, and wherein barrier layer thickness is 5～20nm, and quantum well layer thickness is 1～10nm;
Described p type limiting layer is for improving the carrier confining layer of luminous efficiency, and this layer is the combination of GaN, InAlN, AlGaN, InAlGaN or these several alloys, and thickness is 0～1 μ m; Perhaps be the superlattice that above several alloy constitutes, the periodicity of superlattice is 1～20, and wherein barrier layer thickness is 1～20nm, and the trap layer thickness is 1～20nm:
Described p type GaN layer is the contact layer of preparation p type ohmic contact, and this layer is the combination of GaN, InAlN, AlGaN, InAlGaN or these several alloys, and thickness is 20nm～1 μ m.
The light-emitting diode of above-mentioned high-luminous-efficiency be with grow on silicon of the present invention (102) substrate nonpolar (11
0) the further processing of A side nitride film makes:
5) in the MOCVD reative cell, utilize conventional MOCVD growth technology, at 400～1100 ℃, on silicon of the present invention (102) substrate, grow nonpolar (11
0) epitaxial growth the 2nd InGaAlN resilient coating on the A side nitride film;
6) at 800～1100 ℃, epitaxial growth n type InAlGaN layer on the InGaAlN resilient coating;
7) at 400～900 ℃, epitaxial growth luminescent layer on n type InAlGaN layer;
8) at 600～1000 ℃, epitaxial growth p type limiting layer on luminescent layer;
9) at 600～1000 ℃, epitaxial growth p type GaN layer on p type limiting layer obtains the light-emitting diode of high-luminous-efficiency of the present invention.
The invention provides a kind of laser of high-luminous-efficiency, as shown in Figure 3, comprise grow on above-mentioned silicon (102) substrate nonpolar (11
0) A side nitride film reaches growth the 2nd InGaAlN resilient coating 5, n type InAlGaN layer 6, n type limiting layer 10, luminescent layer 7, p type limiting layer 8 and p type GaN layer 9 thereon successively, it is characterized in that:
Described the 2nd InGaAlN resilient coating is the combination of GaN, AlGaN, InAlN, InAlGaN or these several alloys, promptly can be single layer structure, superlattice, content gradually variational layer, and thickness is 50nm～3 μ m;
Described n type InAlGaN layer is the combination of GaN, InAlN, AlGaN, InAlGaN or these several alloys for the contact layer of preparation n type ohmic contact, and thickness is 50nm～3 μ m;
Described n type limiting layer is for improving the carrier confining layer of luminous efficiency, and this layer is the combination of GaN, InAlN, AlGaN, InAlGaN or these several alloys, and thickness is 100 dusts～1 μ m; Perhaps be the superlattice that above several alloy constitutes, the periodicity of superlattice is 1～20, and wherein barrier layer thickness is 1～20nm, and the trap layer thickness is 1～20nm;
Described luminescent layer is the active layer of light-emitting diode, and this layer is by barrier layer GaN or In
yGa
1-yN and quantum well layer In
xGa
1-xThe Multiple Quantum Well that N forms, wherein 0.05＜x＜0.3,0＜y＜0.15, and y＜x, the periodicity of quantum well is 1～20, and wherein barrier layer thickness is 5～20nm, and quantum well layer thickness is 1～10nm;
Described p type limiting layer is for improving the carrier confining layer of luminous efficiency, and this layer is the combination of GaN, InAlN, AlGaN, InAlGaN or these several alloys, and thickness is 100 dusts～1 μ m; Perhaps be the superlattice that above several alloy constitutes, the periodicity of superlattice is 1～20, and wherein barrier layer thickness is 1～20nm, and the trap layer thickness is 1～20nm;
Described p type GaN layer is the contact layer of preparation p type ohmic contact, and this layer is the combination of GaN, InAlN, AlGaN, InAlGaN or these several alloys, and thickness is 20nm～1 μ m.
The laser of above-mentioned high-luminous-efficiency be with grow on silicon of the present invention (102) substrate nonpolar (11
0) the further processing of A side nitride film makes:
5) in the MOCVD reative cell, utilize conventional MOCVD growth technology, at 400～1100 ℃, on silicon of the present invention (102) substrate, grow nonpolar (11
0) epitaxial growth the 2nd InGaAlN resilient coating on the A side nitride film;
6) at 800～1100 ℃, epitaxial growth n type InAlGaN layer on the InGaAlN resilient coating;
7) at 600～1000 ℃, epitaxial growth n type limiting layer on n type InAlGaN layer;
8) at 400～900 ℃, epitaxial growth luminescent layer on n type limiting layer;
9) at 600～1000 ℃, epitaxial growth p type limiting layer on luminescent layer;
10) at 600～1000 ℃, epitaxial growth p type GaN layer on p type limiting layer obtains the laser of high-luminous-efficiency of the present invention.
Further, utilize ripe silicon technology, above-mentioned light-emitting diode and laser further are prepared into corresponding double-face electrode device.At first at the p of above-mentioned light-emitting diode or laser type GaN surface preparation p electrode, described p electrode is combined by multiple layer metal, electrode material commonly used is Ti, Al, Pt, Au, Ni, Cr, Pd, Zn, In, Sn, or the combination in any of these metals, thickness range 0nm～10 μ m; Then with the silicon substrate of above-mentioned light-emitting diode or laser, be thinned to 50 μ m～raw material thickness according to modes such as the wet etching of routine, dry etching, mechanical lappings, and the surface of silicon behind this attenuate prepares the n electrode, described n electrode is combined by multiple layer metal, electrode material commonly used is Ti, Al, Pt, Au, Ni, Cr, Pd, Zn, In, Sn, or the combination in any of these metals, thickness range 0nm～10 μ m; Obtain corresponding double-face electrode device.
Or utilize ripe silicon technology, above-mentioned light-emitting diode and laser further are prepared into the device of corresponding employing stripping technology.At first at the p of above-mentioned light-emitting diode or laser type GaN surface preparation p electrode, described p electrode is combined by multiple layer metal, electrode material commonly used is Ti, Al, Pt, Au, Ni, Cr, Pd, Zn, In, Sn, or the combination in any of these metals, thickness range 0nm～10 μ m; Then with silicon substrate, metal level and the InGaAlN initial growth layer of above-mentioned light-emitting diode or laser, after peeling off removal according to modes such as the mechanical lapping of routine, wet etching, dry etchings, expose the InGaAlN doped layer, and at the InGaAlN of this exposure doped layer surface preparation n electrode, described n electrode is combined by multiple layer metal, electrode material commonly used is Ti, Al, Pt, Au, Ni, Cr, Pd, Zn, In, Sn, or the combination in any of these metals, thickness range 0nm～10 μ m; Obtain the device of corresponding employing stripping technology.
Compared with prior art, the invention has the advantages that:
1, the present invention adopts on silicon (102) substrate nonpolar (11
0) A face GaN growing technology is applied to fields such as light-emitting diode, laser, solar cell, can weaken the positive negative carrier separation spatially that polarity effect causes, increase the crossover of electronics and hole wave function, the luminous efficiency of material is increased substantially;
2, silicon substrate Heat stability is good adopts its substrate as growing nonpolar GaN, and both lattice mismatches are little, and Grown GaN material back of the body end doping content is low, can avoid that r surface sapphire substrate lattice mismatch noted earlier is big, LiAlO
3(100) problem brought of face substrate poor heat stability has effectively improved the growth quality of non-polar GaN sill, reduces cost;
3, silicon substrate is widely used, technical maturity, and cost is low, adopts silicon substrate to prepare devices such as non-polar GaN based light-emitting diode, laser, solar cell, adopts double-face electrode technology, can significantly simplify existing device technology, reduces cost.
4, adopt non-polar GaN based light-emitting diode, the laser class device of silicon substrate preparation, be applicable to substrate desquamation technology, can increase substantially radiating efficiency, luminous efficiency.
Description of drawings
Fig. 1 be grow on silicon of the present invention (102) substrate nonpolar (11
0) structural representation of A side nitride film;
Fig. 2 is the structural representation of high efficient LED of the present invention;
Fig. 3 is the structural representation of high efficiency laser of the present invention;
Wherein, 1 silicon substrate, 2 metal levels, 3 InGaAlN initial growth layers, 4 the one InGaAlN resilient coatings, 5 the 2nd InGaAlN resilient coatings, 6n type InAlGaN layer, 7 luminescent layers, 8p type limiting layer 8,9p type GaN layer, 10n type limiting layer.
Embodiment
The non polarity A side nitride film of growing on embodiment 1, the preparation silicon substrate
Adopt the substrate of silicon (102) to (010) direction deflection angle 5 degree, 300 microns of silicon wafer thicknesses, silicon chip mixes low-resistivity for the N type.After this silicon chip employing organic solvent and hydrofluoric acid treatment, send the MOCVD reative cell to.Reative cell is warming up to 1100 ℃, and reative cell atmosphere is hydrogen, desorption is carried out in the surface of silicon annealing that cleans up handle, to remove the oxide layer of substrate surface.Reaction chamber temperature is reduced to 450 ℃, is carrier gas with hydrogen, feeds trimethyl aluminium, by the pyrolytic reaction of trimethyl aluminium, is the Al metal level of 10 dusts at surface of silicon deposit growth thickness.Reative cell is warming up to 500 ℃, epitaxial growth InGaAlN initial growth layer on above-mentioned metal level, and this layer material is AlN, thickness is 60 dusts.Reative cell is warming up to 800 ℃, epitaxial growth the one InGaAlN resilient coating on above-mentioned InGaAlN initial growth layer, and this layer material is Al
0.1Ga
0.9N, thickness is 2000 dusts, obtain growing on silicon of the present invention (102) substrate nonpolar (11
0) the A side nitride film 1.
The non polarity A side nitride film of growing on embodiment 2, the preparation silicon substrate
Adopt the graph substrate of silicon (102) to (010) direction deflection angle 12 degree, the silicon chip surface figure is an one-dimensional grating shape figure, 6 microns of raster widths, 2 microns of height, 6 microns of spacings adopt the dry etching method preparation, 300 microns of silicon wafer thicknesses, silicon chip mixes low-resistivity for the N type.After this silicon chip employing organic solvent and hydrofluoric acid treatment, send the MOCVD reative cell to.Reative cell is warming up to 600 ℃, and reative cell atmosphere is hydrogen, desorption is carried out in the surface of silicon annealing that cleans up handle, to remove the oxide layer of substrate surface.Reaction chamber temperature is reduced to 400 ℃, is carrier gas with hydrogen, feeds trimethyl aluminium, by the pyrolytic reaction of trimethyl aluminium, is the Al metal level of 100 dusts at surface of silicon deposit growth thickness.Reative cell is warming up to 600 ℃, epitaxial growth InGaAlN initial growth layer on above-mentioned metal level, and this layer material elder generation growing AIN, thickness is 100 dusts, regrowth Al
0.2Ga
0.8N, thickness are 1900 dusts, and gross thickness is 2000 dusts.Reative cell is warming up to 800 ℃, epitaxial growth the one InGaAlN resilient coating on above-mentioned InGaAlN initial growth layer, this layer material is In
0.05Al
0.1Ga
0.85N, thickness is 2000 dusts, obtain growing on silicon of the present invention (102) substrate nonpolar (11
0) the A side nitride film 2.
The non polarity A side nitride film of growing on embodiment 3, the preparation silicon substrate
Adopt silicon (102) substrate, 300 microns of silicon wafer thicknesses, silicon chip mixes low-resistivity for the N type.After this silicon chip employing organic solvent and hydrofluoric acid treatment, send the MOCVD reative cell to.Reative cell is warming up to 600 ℃, and reative cell atmosphere is hydrogen, desorption is carried out in the surface of silicon annealing that cleans up handle, to remove the oxide layer of substrate surface.Reaction chamber temperature is reduced to 400 ℃, and direct growth InGaAlN initial growth layer is carrier gas with hydrogen, feeds trimethyl aluminium, feeds ammonia, by both reactions, is the AlN layer of 100 dusts at surface of silicon deposit growth thickness; Reative cell is warming up to 600 ℃, and continuing the deposit growth thickness is the AlN layer of 300 dusts; Reative cell is warming up to 800 ℃, feeds trimethyl gallium again, growth Al
0.1Ga
0.9N, thickness are 1000 dusts.Reative cell is warming up to 900 ℃, epitaxial growth the one InGaAlN resilient coating on above-mentioned InGaAlN initial growth layer, this layer material is In
0.05Al
0.1Ga
0.85N, thickness is 2000 dusts, obtain growing on silicon of the present invention (102) substrate nonpolar (11
0) the A side nitride film 3.
The non polarity A side nitride film of growing on embodiment 4, the preparation silicon substrate
Adopt the substrate of silicon (102) face, 300 microns of silicon wafer thicknesses, silicon chip mixes low-resistivity for the N type.After this silicon chip employing organic solvent and hydrofluoric acid treatment, send the MOCVD reative cell to.Reative cell is warming up to 600 ℃, desorption is carried out in the surface of silicon annealing that cleans up handle, to remove the oxide layer of substrate surface.Reaction chamber temperature is reduced to 400 ℃, is the In metal level of 100 dusts at surface of silicon deposit growth thickness.At 400 ℃, epitaxial growth InGaAlN initial growth layer on above-mentioned metal level, this layer material is InAlN, thickness is 2000 dusts.At 1100 ℃, epitaxial growth the one InGaAlN resilient coating on the long layer of the initial dirt of above-mentioned InGaAlN, this layer material is InAlN, thickness is 40000 dusts, obtain growing on silicon of the present invention (102) substrate nonpolar (11
0) the A side nitride film 4.
The non polarity A side nitride film of growing on embodiment 5, the preparation silicon substrate
Adopt the one dimension graph substrate of silicon (102) to (010) direction deflection angle 12 degree, the silicon chip surface figure is an one-dimensional grating shape figure, 8 microns of raster widths, 1.5 microns of height, 5 microns of spacings adopt the dry etching method preparation, 300 microns of silicon wafer thicknesses, silicon chip mixes low-resistivity for the N type.After this silicon chip employing organic solvent and hydrofluoric acid treatment, send the MOCVD reative cell to.Reative cell is warming up to 800 ℃, desorption is carried out in the surface of silicon annealing that cleans up handle, to remove the oxide layer of substrate surface.Reaction chamber temperature is 1100 ℃, is the Al metal level of 40 dusts at surface of silicon deposit growth thickness.At 1100 ℃, epitaxial growth InGaAlN initial growth layer on above-mentioned metal level, this layer material is AlN, thickness is 10 dusts.At 900 ℃, epitaxial growth the one InGaAlN resilient coating on above-mentioned InGaAlN initial growth layer, this layer material of at first growing is AlN, thickness is 60 dusts: regrowth Al
0.1Ga
0.9N, thickness are 1000 dusts: reative cell is warming up to 900 ℃ again, In grows on above-mentioned epitaxial loayer
0.05Al
0.1Ga
0.85N, thickness is 2000 dusts, obtain growing on silicon of the present invention (102) substrate nonpolar (11
0) the A side nitride film 5.
The light-emitting diode of embodiment 6, preparation high-luminous-efficiency
In the MOCVD reative cell, utilize conventional MOCVD growth technology, at 1100 ℃, epitaxial growth the 2nd InGaAlN resilient coating on the non polarity A side nitride film of growing on the silicon substrate that embodiment 1 obtains, this layer material is GaN, and thickness is 30000 dusts, silicon doping concentration 5E18cm
-3At 800 ℃, epitaxial growth n type InAlGaN layer on the InGaAlN resilient coating, this layer material is GaN, thickness is 50nm.At 400 ℃, epitaxial growth luminescent layer on n type InAlGaN layer, this layer material is by barrier layer GaN and quantum well layer In
0.1Ga
0.9The Multiple Quantum Well in 5 cycles that N forms, wherein the thickness of barrier layer GaN is 10nm, quantum well layer In
0.1Ga
0.9The thickness of N is 3nm.At 900 ℃, epitaxial growth p type limiting layer on luminescent layer, this layer is GaN, Al
0.1Ga
0.9The superlattice that N constitutes, the periodicity of superlattice is 5, wherein Al
0.1Ga
0.9The N barrier layer thickness is 10nm, and GaN trap layer thickness is 10nm.At 600 ℃, the p type GaN layer of epitaxial growth 200nm on p type limiting layer, the magnesium doping content is 5E20cm
-3, obtaining emission wavelength is the royal purple light GaN light-emitting diode of 430nm.
The light-emitting diode of embodiment 7, preparation high-luminous-efficiency
In the MOCVD reative cell, utilize conventional MOCVD growth technology, at 400 ℃, epitaxial growth the 2nd InGaAlN resilient coating on the nonpolar nitride film of growing on the silicon substrate that embodiment 1 obtains, this layer material is In
0.05Ga
0.95N, thickness are 500 dusts, silicon doping concentration 5E18cm
-3Be warming up to 800 ℃, epitaxial growth n type InAlGaN layer on the 2nd InGaAlN resilient coating, this layer material is GaN, thickness is 3 μ m.Be cooled to 900 ℃, epitaxial growth luminescent layer on n type InAlGaN layer, this layer material is by barrier layer GaN and quantum well layer In
0.15Ga
0.85The Multiple Quantum Well in 20 cycles that N forms, wherein the thickness of barrier layer GaN is 20nm, quantum well layer In
0.15Ga
0.85The thickness of N is 2nm.At 1000 ℃, epitaxial growth p type limiting layer on luminescent layer, this layer is GaN, thickness is 100nm.At 1000 ℃, the p type GaN layer of epitaxial growth 100nm on p type limiting layer, the magnesium doping content is 5E20cm
-3, obtaining emission wavelength is the purple light GaN light-emitting diode of 400nm.
The light-emitting diode of embodiment 8, preparation high-luminous-efficiency
In the MOCVD reative cell, utilize conventional MOCVD growth technology, at 1000 ℃, epitaxial growth the 2nd InGaAlN resilient coating on the nonpolar nitride film of growing on the silicon substrate that embodiment 1 obtains, this layer material is Al
0.05Ga
0.95N, thickness are 500 dusts, silicon doping concentration 5E18cm
-3Continuation is at 1000 ℃, epitaxial growth n type InAlGaN layer on the 2nd InGaAlN resilient coating, and this layer material is GaN, thickness is 2 μ m.Be cooled to 800 ℃, epitaxial growth luminescent layer on n type InAlGaN layer, this layer material is by barrier layer In
0.01Ga
0.99N and quantum well layer In
0.15Ga
0.85The Multiple Quantum Well in 10 cycles that N forms, wherein barrier layer In
0.01Ga
0.99The thickness of N is 15nm, quantum well layer In
0.15Ga
0.85The thickness of N is 2nm.Be cooled to 600 ℃, epitaxial growth p type limiting layer on luminescent layer, this layer is GaN, thickness is 20nm.Be warming up to 800 ℃, the p type GaN layer of epitaxial growth 100nm on p type limiting layer, the magnesium doping content is 5E20cm
-3, obtaining emission wavelength is the blue light GaN light-emitting diode of 450nm.
The laser of embodiment 9, preparation high-luminous-efficiency
In the MOCVD reative cell, utilize conventional MOCVD growth technology, at 1100 ℃, epitaxial growth the 2nd InGaAlN resilient coating on the nonpolar nitride film of growing on the silicon substrate that embodiment 1 obtains, this layer material is GaN, and thickness is 30000 dusts, silicon doping concentration 5E18cm
-3At 800 ℃, epitaxial growth n type InAlGaN layer on the InGaAlN resilient coating, this layer material is GaN, thickness is 50nm.At 800 ℃, epitaxial growth n type limiting layer on luminescent layer, this layer is GaN, Al
0.1Ga
0.9The superlattice that N constitutes, the periodicity of superlattice is 5, wherein Al
0.1Ga
0.9The N barrier layer thickness is 10nm, and GaN trap layer thickness is 10nm.At 400 ℃, epitaxial growth luminescent layer on n type InAlGaN layer, this layer material is by barrier layer GaN and quantum well layer In
0.1Ga
0.9The Multiple Quantum Well in 5 cycles that N forms, wherein the thickness of barrier layer GaN is 10nm, quantum well layer In
0.1Ga
0.9The thickness of N is 3nm.At 900 ℃, epitaxial growth p type limiting layer on luminescent layer, this layer is GaN, Al
0.1Ga
0.9The superlattice that N constitutes, the periodicity of superlattice is 5, wherein Al
0.1Ga
0.9The N barrier layer thickness is 10nm, and GaN trap layer thickness is 10nm.At 600 ℃, the p type GaN layer of epitaxial growth 200nm on p type limiting layer, the magnesium doping content is 5E20cm
-3, obtaining emission wavelength is the royal purple light GaN laser of 430nm.
The laser of embodiment 10, preparation high-luminous-efficiency
In the MOCVD reative cell, utilize conventional MOCVD growth technology, at 400 ℃, epitaxial growth the 2nd InGaAlN resilient coating on the nonpolar nitride film of growing on the silicon substrate that embodiment 1 obtains, this layer material is In
0.05Ga
0.95N, thickness are 500 dusts, silicon doping concentration 5E18cm
-3Be warming up to 800 ℃, epitaxial growth n type InAlGaN layer on the 2nd InGaAlN resilient coating, this layer material is GaN, thickness is 3 μ m.The growing n-type limiting layer, 1000 ℃ of reaction chamber temperatures, this layer is Al
0.1Ga
0.9N, thickness are 50nm.Be cooled to 900 ℃, epitaxial growth luminescent layer on n type InAlGaN layer, this layer material is by barrier layer GaN and quantum well layer In
0.15Ga
0.85The Multiple Quantum Well in 20 cycles that N forms, wherein the thickness of barrier layer GaN is 20nm, quantum well layer In
0.15Ga
0.85The thickness of N is 2nm.At 1000 ℃, epitaxial growth p type limiting layer on luminescent layer, this layer is GaN, thickness is 100nm.At 1000 ℃, the p type GaN layer of epitaxial growth 100nm on p type limiting layer, the magnesium doping content is 5E20cm
-3, obtaining emission wavelength is the purple light GaN laser of 400nm.
The laser of embodiment 11, preparation high-luminous-efficiency
In the MOCVD reative cell, utilize conventional MOCVD growth technology, at 1000 ℃, epitaxial growth the 2nd InGaAlN resilient coating on the nonpolar nitride film of growing on the silicon substrate that embodiment 1 obtains, this layer material is Al
0.05Ga
0.95N, thickness are 500 dusts, silicon doping concentration 5E18cm
-3Continuation is at 1000 ℃, epitaxial growth n type InAlGaN layer on the 2nd InGaAlN resilient coating, and this layer material is GaN, thickness is 2 μ m.Growing n-type limiting layer, 1000 ℃ of reaction chamber temperatures, this layer are the superlattice that GaN, Al0.1Ga0.9N constitute, and the periodicity of superlattice is 5, wherein Al
0.1Ga
0.9The N barrier layer thickness is 10nm, and GaN trap layer thickness is 10nm.Be cooled to 800 ℃, epitaxial growth luminescent layer on n type InAlGaN layer, this layer material is by barrier layer In
0.01Ga
0.99N and quantum well layer In
0.15Ga
0.85The Multiple Quantum Well in 10 cycles that N forms, wherein barrier layer In
0.01Ga
0.99The thickness of N is 15nm, quantum well layer In
0.15Ga
0.85The thickness of N is 2nm.Be warming up to 1000 ℃, epitaxial growth p type limiting layer on luminescent layer, this layer is Al
0.1Ga
0.9N, thickness are 20nm.Be cooled to 800 ℃, the p type GaN layer of epitaxial growth 100nm on p type limiting layer, the magnesium doping content is 5E20cm
-3, obtaining emission wavelength is the blue light GaN laser of 450nm.
Claims (10)
1, the non polarity A side nitride film of growing on a kind of silicon (102) substrate, comprise a silicon substrate, thereon metal level, InGaAlN initial growth layer and an InGaAlN resilient coating of growth successively, it is characterized in that: described silicon substrate is for adopting the Si substrate of (102) face or drift angle.
2, the non polarity A side nitride film of growing on silicon as claimed in claim 1 (102) substrate, it is characterized in that: the substrate of described Si (102) face and drift angle comprises: Si (102) substrate and to all directions drift angle be no more than 12 the degree, and Si (102) substrate and to all directions drift angle be no more than 12 the degree various graph substrate.
3, the non polarity A side nitride film of growing on silicon as claimed in claim 2 (102) substrate, it is characterized in that: described graph substrate is the etching figure of a peacekeeping X-Y scheme, or passes through the graph substrate of the peacekeeping X-Y scheme mask formation of metal, nitride, oxide.
4, the non polarity A side nitride film of growing on silicon as claimed in claim 1 (102) substrate is characterized in that:
Described metal level is that In, Ga, Al, the deposit of Zn metal form, and thickness is 0～100 dust;
Described InGaAlN initial growth layer is the transition zone of extension on foreign substrate, the material of this transition zone is the combination of GaN, AlGaN, InAlN, InAlGaN or these several alloys, be single layer structure, superlattice or content gradually variational layer, thickness is 10～2000 dusts;
A described InGaAlN resilient coating is the transition zone of extension on InGaAlN initial growth layer, the material of this transition zone is the combination of GaN, AlGaN, InAlN, InAlGaN or these several alloys, be single layer structure, superlattice or content gradually variational layer, thickness is 100～40000 dusts.
5, the preparation method of the non polarity A side nitride film of growing on the described silicon of one of a kind of claim 1 to 4 (102) substrate comprises following step:
1) in the MOCVD reative cell, design temperature is 600～1100 ℃ of scopes, the surface of silicon that the cleans up desorption of annealing is handled, to remove the oxide layer of substrate surface;
2) utilize metal organic source as metal source material, deposit one metal level on the Si substrate of this (100) face, (110) face or drift angle, 400～1100 ℃ of reaction chamber temperature scopes;
3) at 400～1100 ℃, epitaxial growth InGaAlN initial growth layer on above-mentioned metal level; This layer material is the combination of GaN, AlGaN, InAlN, InAlGaN or these several alloys, promptly can be single layer structure, superlattice, content gradually variational layer, and thickness is 10～2000 dusts;
4) at 800～1100 ℃, epitaxial growth the one InGaAlN resilient coating on above-mentioned InGaAlN initial growth layer, this layer material is the combination of GaN, AlGaN, InAlN, InAlGaN or these several alloys, promptly can be single layer structure, superlattice, content gradually variational layer, thickness is 100～40000 dusts, obtains the non polarity A side nitride film of growing on silicon of the present invention (102) substrate.
6, the non polarity A side nitride film of growing on the described silicon of one of a kind of claim 1 to 4 (102) substrate is in the application of light-emitting diode, laser, area of solar cell.
7, a kind of light-emitting diode of high-luminous-efficiency, comprise the non polarity A side nitride film of growing on the described silicon of one of claim 1 to 4 (102) substrate, reach growth the 2nd InGaAlN resilient coating, n type InAlGaN layer, luminescent layer, p type limiting layer and p type GaN layer thereon successively, it is characterized in that:
Described the 2nd InGaAlN resilient coating is the combination of GaN, AlGaN, InAlN, InAlGaN or these several alloys, and thickness is 50nm～3 μ m;
Described n type InAlGaN layer is the combination of GaN, InAlN, AlGaN, InAlGaN or these several alloys for the contact layer of preparation n type ohmic contact, and thickness is 50nm～3 μ m;
Described luminescent layer is the active layer of light-emitting diode, and this layer is by barrier layer GaN or In
yGa
1-yN and quantum well layer In
xGa
1-xThe Multiple Quantum Well that N forms, wherein 0.05＜x＜0.3,0＜y＜0.15, and y＜x, the periodicity of quantum well is 1～20, and wherein barrier layer thickness is 5～20nm, and quantum well layer thickness is 1～10nm;
Described p type limiting layer is for improving the carrier confining layer of luminous efficiency, and this layer is the combination of GaN, InAlN, AlGaN, InAlGaN or these several alloys, and thickness is 0～1 μ m; Perhaps be the superlattice that above several alloy constitutes, the periodicity of superlattice is 1～20, and wherein barrier layer thickness is 1～20nm, and the trap layer thickness is 1～20nm;
Described p type GaN layer is the contact layer of preparation p type ohmic contact, and this layer is the combination of GaN, InAlN, AlGaN, InAlGaN or these several alloys, and thickness is 20nm～1 μ m.
8, the preparation method of the light-emitting diode of the described high-luminous-efficiency of a kind of claim 7 comprises following step:
5) in the MOCVD reative cell, utilize conventional MOCVD growth technology, at 400～1100 ℃, epitaxial growth the 2nd InGaAlN resilient coating on the non polarity A side nitride film of growing on the described silicon of one of claim 1 to 4 (102) substrate;
6) at 800～1100 ℃, epitaxial growth n type InAlGaN layer on the InGaAlN resilient coating;
7) at 400～900 ℃, epitaxial growth luminescent layer on n type InAlGaN layer;
8) at 600～1000 ℃, epitaxial growth p type limiting layer on luminescent layer;
9) at 600～1000 ℃, epitaxial growth p type GaN layer on p type limiting layer obtains the light-emitting diode of high-luminous-efficiency of the present invention.
9, a kind of laser of high-luminous-efficiency, comprise the non polarity A side nitride film of growing on the described silicon of one of claim 1 to 4 (102) substrate, reach growth the 2nd InGaAlN resilient coating, n type InAlGaN layer, n type limiting layer, luminescent layer, p type limiting layer and p type GaN layer thereon successively, it is characterized in that:
Described the 2nd InGaAlN resilient coating is the combination of GaN, AlGaN, InAlN, InAlGaN or these several alloys, and thickness is 50nm～3 μ m;
Described n type InAlGaN layer is the combination of GaN, InAlN, AlGaN, InAlGaN or these several alloys for the contact layer of preparation n type ohmic contact, and thickness is 50nm～3 μ m;
Described n type limiting layer is for improving the carrier confining layer of luminous efficiency, and this layer is the combination of GaN, InAlN, AlGaN, InAlGaN or these several alloys, and thickness is 100 dusts～1 μ m; Perhaps be the superlattice that above several alloy constitutes, the periodicity of superlattice is 1～20, and wherein barrier layer thickness is 1～20nm, and the trap layer thickness is 1～20nm;
Described luminescent layer is the active layer of light-emitting diode, and this layer is by barrier layer GaN or In
yGa
1-yN and quantum well layer In
xGa
1-xThe Multiple Quantum Well that N forms, wherein 0.05＜x＜0.3,0＜y＜0.15, and y＜x, the periodicity of quantum well is 1～20, and wherein barrier layer thickness is 5～20nm, and quantum well layer thickness is 1～10nm;
Described p type limiting layer is for improving the carrier confining layer of luminous efficiency, and this layer is the combination of GaN, InAlN, AlGaN, InAlGaN or these several alloys, and thickness is 100 dusts～1 μ m; Perhaps be the superlattice that above several alloy constitutes, the periodicity of superlattice is 1～20, and wherein barrier layer thickness is 1～20nm, and the trap layer thickness is 1～20nm;
Described p type GaN layer is the contact layer of preparation p type ohmic contact, and this layer is the combination of GaN, InAlN, AlGaN, InAlGaN or these several alloys, and thickness is 20nm～1 μ m.
10, the preparation method of the laser of the described high-luminous-efficiency of a kind of claim 9 comprises following step:
5) in the MOCVD reative cell, utilize conventional MOCVD growth technology, at 400～1100 ℃, epitaxial growth the 2nd InGaAlN resilient coating on the non polarity A side nitride film of growing on the described silicon of one of claim 1 to 4 (102) substrate;
6) at 800～1100 ℃, epitaxial growth n type InAlGaN layer on the InGaAlN resilient coating;
7) at 600～1000 ℃, epitaxial growth n type limiting layer on n type InAlGaN layer;
8) at 400～900 ℃, epitaxial growth luminescent layer on n type limiting layer;
9) at 600～1000 ℃, epitaxial growth p type limiting layer on luminescent layer;
10) at 600～1000 ℃, epitaxial growth p type GaN layer on p type limiting layer obtains the laser of high-luminous-efficiency of the present invention.
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|---|---|---|---|
| CNA2006100112958A CN101009347A (en) | 2006-01-27 | 2006-01-27 | Non polarity A side nitride film growing on the silicon(102) substrate and its making method and use |
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