CN102110751A - Self-supporting GaN-based luminescent device and manufacturing method thereof - Google Patents
Self-supporting GaN-based luminescent device and manufacturing method thereof Download PDFInfo
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- CN102110751A CN102110751A CN 201010545467 CN201010545467A CN102110751A CN 102110751 A CN102110751 A CN 102110751A CN 201010545467 CN201010545467 CN 201010545467 CN 201010545467 A CN201010545467 A CN 201010545467A CN 102110751 A CN102110751 A CN 102110751A
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Abstract
The invention discloses a self-supporting GaN-based luminescent device which is successively provided with a GaN protective layer, a GaN buffer layer, an n-type GaN layer, a GaN-based luminescent layer and a p-type GaN layer from down to up. The manufacturing method comprises the following steps: growing a ZnO layer and the GaN protective layer on a SiC substrate in sequence by adopting a molecular beam epitaxy technology; growing the GaN buffer layer, the n-type GaN layer, the GaN-based luminscent layer and the p-type GaN layer on the GaN protective layer in sequence by adopting a metal organic chemical vapor deposition technology; and corroding and removing the ZnO layer with an acid solution, and separating the SiC substrate from a GaN-based device film. The method is simple; the quality of the GaN-based device film is effectively improved by growing the ZnO layer on the SiC substrate firstly; and the substrate is easily separated from the device film, so that the SiC substrate can be recycled, thus the device cost is greatly reduced.
Description
Technical field
The present invention relates to a kind of self-supporting GaN base luminescent device and preparation method thereof, belong to technical field of semiconductor luminescence.
Background technology
The broad stopband III-V hi-nitride semiconductor material that with GaN is representative is having wide application prospect to receive much concern aspect short-wave long light-emitting device, short wavelength laser, photo-detector and high temperature, high frequency and the high-power electronic device, develop very rapid.Typical GaN base luminescent device is to be made of substrate, GaN resilient coating, n type GaN layer, GaN base luminescent layer, p type GaN layer.Wherein GaN resilient coating, n type GaN layer, GaN base luminescent layer, p type GaN layer are referred to as GaN base device thin-film material again.Because lack GaN body single crystalline substrate, present commercial GaN base luminescent device all is to be grown in Al
2O
3On the substrate or on the SiC substrate.And Al
2O
3The lattice mismatch of substrate and GaN is very big, causes the Grown GaN crystal mass bad.While Al
2O
3Substrate has poor heat conductivility and electric conductivity, influences high power GaN base luminescent device service behaviour greatly.Remove Al
2O
3Outside the substrate, being used for the GaN growth substrates at present is exactly SiC, and the occupation rate on market occupies second.Because the electric conductivity and the heat conductivility of SiC substrate excellence do not need picture Al
2O
3Power-type GaN base luminescent device adopts face-down bonding technique to solve heat dissipation problem on the substrate, but employing top-bottom electrode structures, can solve the heat dissipation problem of power-type GaN base luminescent device better, so account for critical role in developing technical field of semiconductor illumination.But not enough is, the SiC substrate costs an arm and a leg, and machining property is poor, and this all makes the production cost of device rise greatly.Be in the process of substrate production GaN base luminescent device with SiC, because the lattice mismatch between SiC itself and the GaN is relatively large, it is too big that chemical property differs, cause not soaking between the two, can't direct growth, present solution is exactly first growth one deck resilient coating between SiC and GaN, growing GaN on resilient coating again, wherein the most generally growing AIN as resilient coating.
ZnO and GaN have a lot of similarities, all are wurtzite structures, and both lattice mismatches and thermal mismatching are very little, and therefore growing GaN on ZnO can obtain the high quality GaN epitaxial material.ZnO can erode fully with acid solution simultaneously, with device thin-film material and substrate separation, obtains the GaN base device film of self-supporting, thereby realizes the repeated use of SiC substrate, reduces device cost greatly.But have a problem, when surpassing 1000 ℃, the ZnO material can decompose, and at present general general MOCVD method growing GaN film, growth temperature all surpasses 1000 ℃; In addition, all be at NH
3, H
2Grow under the atmosphere, the ZnO material easily is corroded.Therefore, on ZnO, be impossible obtain good GaN base luminescent device directly with general MOCVD method growing GaN.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide that a kind of quality is good, the simple self-supporting GaN base luminescent device of technology and preparation method thereof.
Self-supporting GaN base luminescent device of the present invention has GaN protective layer, GaN resilient coating, n type GaN layer, GaN base luminescent layer and p type GaN layer from bottom to top successively.
The preparation method of self-supporting GaN base luminescent device: adopt earlier molecular beam epitaxy technique on the SiC substrate, grow successively ZnO layer and GaN protective layer; Adopt metal-organic chemical vapor deposition equipment technology growing GaN resilient coating, n type GaN layer, GaN base luminescent layer and p type GaN layer successively on the GaN protective layer then; Remove the ZnO layer with acid liquid corrosion again, with SiC substrate and GaN base device divided thin film from.Specifically may further comprise the steps:
1) will put into molecular beam epitaxial device through the SiC of clean substrate, 400～700 ℃ of temperature, regulating growth room's pressure is 1 * 10
-5Torr～6 * 10
-5Torr is earlier with pure O
2Be the O source, the Metal Zn source is a reaction source, and growth thickness is 0.5～5 micron a ZnO layer, then with pure N
2Be the N source, metal Ga source is a reaction source, and growth thickness is 0.5～5 micron a GaN protective layer on the ZnO layer.
2) growth there is the SiC sheet of ZnO layer and GaN protective layer put into metal organic chemical vapor deposition device, with pure NH
3Be the N source, pure H
2Or N
2Being carrier gas, is the Ga source with trimethyl gallium or triethyl-gallium under 1000～1200 ℃ of temperature successively, growing GaN resilient coating and n type GaN layer; Be the Ga source, be the In source with the trimethyl indium with trimethyl gallium or triethyl-gallium, growing GaN/GaInN multilayer is as GaN base luminescent layer, be the Ga source, be the Al source with the trimethyl aluminium perhaps that growing GaN/GaAlN multilayer is as GaN base luminescent layer with trimethyl gallium or triethyl-gallium; Be the Ga source, be Mg source growing p-type GaN layer with trimethyl gallium or triethyl-gallium with two luxuriant magnesium.
3) adopt acid liquid corrosion to remove the ZnO layer,, obtain the GaN base device of self-supporting the SiC substrate desquamation.
Used acid solution is nitric acid, phosphoric acid or the hydrofluoric acid of PH 〉=4.The SiC substrate of peeling off can be recycled.
Beneficial effect of the present invention is:
The inventive method is simple, is easy to realize.Owing to there is one deck GaN protective layer to cover the ZnO layer, therefore can adopt general metal-organic chemical vapor deposition equipment method growing GaN resilient coating, n type GaN layer, GaN base luminescent layer, p type GaN layer successively in the preparation process.With acid solution the ZnO layer is eroded fully at last, make SiC substrate and device divided thin film from, obtain the GaN base device film of self-supporting.The insertion of ZnO layer had both improved GaN base device film growth quality, and the SiC substrate can reclaim repeated use simultaneously, reduces device cost greatly.
Description of drawings
Fig. 1 is a self-supporting GaN base luminescent device structural representation of the present invention.
Fig. 2 is each layer schematic diagram in the preparation process of the present invention.
Among the figure: 1 is that SiC substrate, 2 is that ZnO layer, 3 is that GaN protective layer, 4 is that GaN resilient coating, 5 is that n type GaN layer, 6 is that the basic luminescent layer of GaN, 7 is a p type GaN layer.
Embodiment
Be described in detail the present invention below in conjunction with accompanying drawing.
With reference to Fig. 1, self-supporting GaN base luminescent device of the present invention has GaN protective layer 3, GaN resilient coating 4, n type GaN layer 5, GaN base luminescent layer 6 and p type GaN layer 7 from bottom to top successively.
With reference to Fig. 2, narrate the preparation method of self-supporting GaN base luminescent device of the present invention.
1) SiC substrate 1 is carried out putting into molecular beam epitaxial device after the clean, underlayer temperature is heated to 700 ℃, and regulating growth room's pressure is 1 * 10
-5Torr is earlier with pure O
2(purity 99.9999%) is the O source, and the Metal Zn source is a reaction source, and growth thickness is 5 microns a ZnO layer 2, then with pure N
2(purity 99.9999%) is the N source, and metal Ga source is a reaction source, and growth thickness is 2 microns a GaN protective layer 3 on ZnO layer 2.
2) growth there is the SiC sheet of ZnO layer 2 and GaN protective layer 3 put into metal organic chemical vapor deposition device, adopts general GaN film metal organic chemical vapor deposition growing method.With pure NH
3(purity 99.9999%) is the N source, pure H
2(purity 99.9999%) is carrier gas, under 1100 ℃ of temperature, is that Ga source growth thickness is the n type GaN layer 5 that 1 micron GaN resilient coating 4 and thickness are 300 nanometers with the trimethyl gallium; Be the Ga source with the trimethyl gallium, be that In source growth thickness is that the GaN/GaInN multilayer of 200 nanometers is as GaN base luminescent layer 6 with the trimethyl indium; Be the Ga source with the trimethyl gallium, be that Mg source growth thickness is the p type GaN layer 7 of 300 nanometers with two luxuriant magnesium.
3) adopt the salpeter solution corrosion to remove ZnO layer 2, the GaN base device film of SiC substrate 1 and above-mentioned preparation is peeled off, obtain the GaN base device of self-supporting.Reclaiming SiC substrate 1 simultaneously can utilize again.
1) SiC substrate 1 is carried out putting into molecular beam epitaxial device after the clean, underlayer temperature is heated to 400 ℃, and regulating growth room's pressure is 3 * 10
-5Torr is earlier with pure O
2(purity 99.9999%) is the O source, and the Metal Zn source is a reaction source, and growth thickness is 3 microns a ZnO layer 2, then with pure N
2(purity 99.9999%) is the N source, and metal Ga source is a reaction source, and growth thickness is 1 micron a GaN protective layer 3 on ZnO layer 2.
2) growth there is the SiC sheet of ZnO layer 2 and GaN protective layer 3 put into metal organic chemical vapor deposition device, adopts general GaN film metal organic chemical vapor deposition growing method.With pure NH
3(purity 99.9999%) is the N source, pure H
2(purity 99.9999%) is carrier gas, under 1000 ℃ of temperature, is that Ga source growth thickness is the n type GaN layer 5 that 1 micron GaN resilient coating 4 and thickness are 200 nanometers with the triethyl-gallium; Be the Ga source with the triethyl-gallium, be that In source growth thickness is that the GaN/GaInN multilayer of 80 nanometers is as GaN base luminescent layer 6 with the trimethyl indium; Be the Ga source with the triethyl-gallium, be that Mg source growth thickness is the p type GaN layer 7 of 200 nanometers with two luxuriant magnesium.
3) adopt the phosphoric acid solution corrosion to remove ZnO layer 2, the GaN base device film of SiC substrate 1 and above-mentioned preparation is peeled off, obtain the GaN base device of self-supporting.Reclaiming SiC substrate 1 simultaneously can utilize again.
Embodiment 3
1) SiC substrate 1 is carried out putting into molecular beam epitaxial device after the clean, underlayer temperature is heated to 550 ℃, and regulating growth room's pressure is 5 * 10
-5Torr is with pure O
2(purity 99.9999%) is the O source, and the Metal Zn source is a reaction source, and growth thickness is 1 micron a ZnO layer 2; Underlayer temperature rises to 600 ℃ then, and regulating growth room's pressure is 6 * 10
-5Torr is with pure N
2(purity 99.9999%) is the N source, and metal Ga source is a reaction source, and growth thickness is 4 microns a GaN protective layer 3 on ZnO layer 2.
2) growth there is the SiC sheet of ZnO layer 2 and GaN protective layer 3 put into metal organic chemical vapor deposition device, adopts general GaN film metal organic chemical vapor deposition growing method.With pure NH
3(purity 99.9999%) is the N source, pure N
2(purity 99.9999%) is carrier gas, under 1200 ℃ of temperature, is that Ga source growth thickness is the n type GaN layer 5 that 2 microns GaN resilient coating 4 and thickness are 300 nanometers with the trimethyl gallium; Be the Ga source with the trimethyl gallium, be that Al source growth thickness is that the GaN/GaAlN multilayer of 100 nanometers is as GaN base luminescent layer 6 with the trimethyl aluminium; Be the Ga source with the trimethyl gallium, be that Mg source growth thickness is the p type GaN layer 7 of 300 nanometers with two luxuriant magnesium.
3) adopt the hydrofluoric acid solution corrosion to remove ZnO layer 2, the GaN base device film of SiC substrate 1 and above-mentioned preparation is peeled off, obtain the GaN base device of self-supporting.Reclaiming SiC substrate 1 simultaneously can utilize again.
Claims (2)
1. a self-supporting GaN base luminescent device is characterized in that: GaN protective layer (3), GaN resilient coating (4), n type GaN layer (5), GaN base luminescent layer (6) and p type GaN layer (7) are arranged from bottom to top successively.
2. prepare the method for the described self-supporting GaN base luminescent device of claim 1, may further comprise the steps:
1) will put into molecular beam epitaxial device through the SiC of clean substrate (1), 400～700 ℃ of temperature, regulating growth room's pressure is 1 * 10
-5Torr～6 * 10
-5Torr is earlier with pure O
2Be the O source, the Metal Zn source is a reaction source, and growth thickness is 0.5～5 micron a ZnO layer (2), then with pure N
2Be the N source, metal Ga source is a reaction source, is 0.5～5 micron GaN protective layer (3) at the last growth thickness of ZnO layer (2).
2) growth there is the SiC sheet of ZnO layer (2) and GaN protective layer (3) put into metal organic chemical vapor deposition device, with pure NH
3Be the N source, pure H
2Or N
2Being carrier gas, is the Ga source with trimethyl gallium or triethyl-gallium under 1000～1200 ℃ of temperature successively, growing GaN resilient coating (4) and n type GaN layer (5); Be the Ga source, be the In source with the trimethyl indium with trimethyl gallium or triethyl-gallium, growing GaN/GaInN multilayer is as GaN base luminescent layer (6), be the Ga source, be the Al source with the trimethyl aluminium perhaps that growing GaN/GaAlN multilayer is as GaN base luminescent layer (6) with trimethyl gallium or triethyl-gallium; Be the Ga source, be Mg source growing p-type GaN layer (7) with trimethyl gallium or triethyl-gallium with two luxuriant magnesium.
3) adopt acid liquid corrosion to remove ZnO layer (2), SiC substrate (1) is peeled off, obtain the GaN base device of self-supporting.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103531678A (en) * | 2013-11-01 | 2014-01-22 | 杭州士兰明芯科技有限公司 | Method for removing GaN-based epitaxial layer on substrate |
| CN109308992A (en) * | 2018-09-21 | 2019-02-05 | 苏州汉骅半导体有限公司 | The method for recycling silicon carbide substrates |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1716653A (en) * | 2005-06-09 | 2006-01-04 | 大连理工大学 | GaN light emitting device on ZnO-GaN composite substrate and its preparing method |
| US20080038857A1 (en) * | 2006-08-11 | 2008-02-14 | Samsung Electro-Mechanics Co., Ltd | Method of manufacturing nitride-based semiconductor light-emitting device |
-
2010
- 2010-11-12 CN CN 201010545467 patent/CN102110751A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1716653A (en) * | 2005-06-09 | 2006-01-04 | 大连理工大学 | GaN light emitting device on ZnO-GaN composite substrate and its preparing method |
| US20080038857A1 (en) * | 2006-08-11 | 2008-02-14 | Samsung Electro-Mechanics Co., Ltd | Method of manufacturing nitride-based semiconductor light-emitting device |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103531678A (en) * | 2013-11-01 | 2014-01-22 | 杭州士兰明芯科技有限公司 | Method for removing GaN-based epitaxial layer on substrate |
| CN109308992A (en) * | 2018-09-21 | 2019-02-05 | 苏州汉骅半导体有限公司 | The method for recycling silicon carbide substrates |
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Application publication date: 20110629 |