CN103456852A - LED epitaxial wafer and production method thereof - Google Patents

LED epitaxial wafer and production method thereof Download PDF

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Publication number
CN103456852A
CN103456852A CN2012101714230A CN201210171423A CN103456852A CN 103456852 A CN103456852 A CN 103456852A CN 2012101714230 A CN2012101714230 A CN 2012101714230A CN 201210171423 A CN201210171423 A CN 201210171423A CN 103456852 A CN103456852 A CN 103456852A
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layer
substrate
gan layer
epitaxial wafer
inn
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CN103456852B (en
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吴明驰
谢春林
刘函
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BYD Semiconductor Co Ltd
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BYD Co Ltd
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Abstract

The invention provides an LED epitaxial wafer comprising a substrate. A buffer layer, a type-n GaN layer, a light-emitting layer and a type-p GaN layer are formed on the substrate sequentially. The buffer layer comprises an InN layer forming on the substrate, a first intrinsic GaN layer, an SiNx layer, and a second intrinsic layer. Holes exposing the substrate are formed in the InN layer. The first intrinsic GaN layer forms on the InN layer. The SiNx layer forms on the first intrinsic GaN layer. Holes exposing the first intrinsic GaN layer are formed in the SiNx layer. The second intrinsic GaN layer forms on the SiNx layer. The LED epitaxial wafer and the production method thereof have the advantages that defects of the epitaxial layer can be decreased and crystal quality is improved.

Description

A kind of LED epitaxial wafer and preparation method
Technical field
The invention belongs to semiconductor applications, relate in particular to a kind of LED epitaxial wafer and preparation method.
Background technology
In recent years, due to the extensive use on the opto-electronic devices such as light-emitting diode, the wide bandgap semiconductor GaN material in third generation semi-conducting material extensively is subject to people's concern, and the GaN base epitaxial wafer of growing high-quality becomes the emphasis of people's research.
At present, what be most widely used is that the employing sapphire is backing material growing GaN base epitaxial wafer, and the GaN material can be grown from 500 ℃ to 1100 ℃ on Sapphire Substrate.Yet due to sapphire and GaN differing greatly of lattice mismatch and chemical property between the two, directly more in Grown on Sapphire Substrates epitaxial loayer defect, have a strong impact on crystal mass.In order to obtain smooth surface, GaN epitaxial loayer that crystal mass is higher, the method of growing GaN epitaxial loayer mainly contains two kinds: one, the two step epitaxial growth technologies of GaN, utilize AlN or GaN resilient coating that MOCVD technology low-temperature epitaxy on Sapphire Substrate is thin, then high growth temperature GaN epitaxial loayer.Two, the side direction of GaN covers growth, and deposition mask layer on substrate in advance, provide follow-up GaN extension required grain of crystallization.
The two step epitaxial growth technologies of GaN, the method epitaxial loayer Dislocations density is still higher, promotes crystal mass limited.The side direction of GaN covers growth, and the method can obtain higher GaN crystal mass, improve luminosity, but there are many deficiencies in this method, and for example: on substrate, the deposition mask layer may increase technical process in addition to substrate generation pollution, cost is higher.
Summary of the invention
The present invention, for solving the second-rate technical problem of LED epitaxial growth crystal, provides a kind of LED epitaxial wafer and preparation method thereof, can reduce the defect of LED epitaxial wafer, significantly improves the crystal mass of LED epitaxial wafer.
The invention provides a kind of LED epitaxial wafer, comprise substrate, the resilient coating, N-shaped GaN layer, luminescent layer and the p-type GaN layer that on substrate, form successively, described resilient coating comprises:
Be formed on the InN layer on substrate, described InN layer is distributed with the cavity that exposes substrate;
Be formed on the first intrinsic GaN layer on described InN layer;
Be formed on the SiN on described the first intrinsic GaN layer xlayer, described SiN xlayer is distributed with the cavity that exposes the first intrinsic GaN layer; And
Be formed on described SiN xthe second intrinsic GaN layer on layer.
The present invention also provides a kind of preparation method of LED epitaxial wafer, comprises the following steps:
Substrate is provided;
The InN layer that there is the cavity that exposes substrate at Grown;
There is growth the first intrinsic GaN layer on empty InN layer;
On the first intrinsic GaN layer, growth has the SiN in the cavity that exposes the first intrinsic GaN layer xlayer;
At SiN xform the second intrinsic GaN layer on layer;
Form N-shaped GaN layer on the second intrinsic GaN layer;
Form luminescent layer on N-shaped GaN layer;
Form p-type GaN layer on luminescent layer.
LED epitaxial wafer provided by the invention and preparation method have following effect:
1, the present invention, by substrate growth InN layer, can effectively reduce the stress produced because of lattice mismatch between substrate and GaN layer, thereby reduce the generation of dislocation; And the InN layer can play the mask layer effect, the threading dislocation of substrate ends at the interface between substrate and InN layer and is blocked.
2, the present invention has empty SiN by insert growth in resilient coating xlayer, realize the laterally overgrown in later stage, reduce injection defect, and effectively the stop portions dislocation extends to N-shaped GaN layer or luminescent layer simultaneously, and another part dislocation is concentrated on to SiN xlayer hole region, thus epitaxial loayer low dislocation zone increased, reduce dislocation density, improved the epitaxial wafer crystal mass.
3, the present invention covers the method for growth than existing GaN side direction, does not need deposition mask layer on substrate in advance, but by the outer layer growth process, depositing SiN xlayer serves as mask layer, has simplified technique, has avoided mask layer to pollute substrate, and has reduced production cost.
The accompanying drawing explanation
Fig. 1 is the structural representation of embodiment of the present invention LED epitaxial wafer;
Fig. 2 is the structural representation of LED epitaxial wafer resilient coating of the present invention;
Fig. 3 is the structural representation of another embodiment of the present invention LED epitaxial wafer;
Fig. 4 is SiN in LED epitaxial wafer resilient coating of the present invention xthe structural representation of layer;
Fig. 5 is the design sketch of LED epitaxial wafer resilient coating of the present invention.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
As shown in Figure 1 and Figure 2, the invention provides a kind of LED epitaxial wafer, comprise substrate 1, the resilient coating 2, N-shaped GaN layer 3, luminescent layer 4 and the p-type GaN layer 5 that form successively on substrate 1.
Described resilient coating 2 comprises:
Be formed on the InN layer 21 on substrate 1, described InN layer 21 is distributed with the cavity that exposes substrate;
Be formed on the first intrinsic GaN layer 22 on described InN layer 21;
Be formed on the SiN on described the first intrinsic GaN layer 22 xlayer 23, described SiN xlayer 23 is distributed with the cavity that exposes the first intrinsic GaN layer 22; And
Be formed on described SiN xthe second intrinsic GaN layer 24 on layer 23.
In an embodiment of the present invention, described substrate 1 is plane or patterned substrate, preferred patterned substrate, and patterned substrate can reduce the epitaxial wafer defect of growth, improves the epitaxial wafer crystal mass; The shape of described patterned substrate comprises strip, column, cone-shaped or spherical crown shape.
The material of substrate 1 can be selected sapphire, SiC or Si, preferably adopts Sapphire Substrate.
Preferably, the intrinsic GaN layer that described the first intrinsic GaN layer 22 is growth under 850～900 ℃, the intrinsic GaN layer that the second intrinsic GaN layer 24 is growth under 1000～1100 ℃.The thickness of the first intrinsic GaN layer 22 is 50～100nm, and the thickness of the second intrinsic GaN layer 24 is 2～3um.
Described InN layer 21 and SiN xbe distributed with cavity on layer 23, the out-of-shape in cavity.Preferably, the thickness of described InN layer 21 is 1～5nm, SiN xthe thickness of layer 23 is 1～5nm.
As shown in Figure 3, in another embodiment of the present invention, the LED epitaxial wafer also comprises the AlGaN barrier layer 6 be formed between luminescent layer 4 and p-type GaN layer 5, overflow from active area on AlGaN barrier layer 6 effectively block electrons, thereby increase the quantity of active area electronics, improve charge carrier combined efficiency in luminescent layer 4, promote the LED chip luminous efficiency.
Preferably, luminescent layer 4 is multiple quantum well layer, comprising: be formed on the doping multiple quantum well layer 41 on N-shaped GaN layer, be formed on the non-doping multiple quantum well layer 42 on the doping multiple quantum well layer.So, can effectively improve the luminous efficiency of LED chip.
The present invention also provides the preparation method of above-mentioned LED epitaxial wafer, said method comprising the steps of:
S101, provide substrate;
S102, there is the InN layer in the cavity that exposes substrate at Grown;
S103, there is on empty InN layer growth the first intrinsic GaN layer;
S104, on the first intrinsic GaN layer, growth has the SiN in the cavity that exposes the first intrinsic GaN layer xlayer;
S105, at SiN xform the second intrinsic GaN layer on layer;
S106, form N-shaped GaN layer on the second intrinsic GaN layer;
S107, on N-shaped GaN layer, form luminescent layer;
S108, form p-type GaN layer on luminescent layer.
Elaborate the preparation method of LED epitaxial wafer of the present invention below in conjunction with accompanying drawing, also can elaborate in the preparation method to LED epitaxial wafer and beneficial effect thereof in the present invention.
The preparation method of LED epitaxial wafer provided by the invention adopts NH 3(ammonia) as the N source, the TMGa(trimethyl gallium), the TEGa(triethyl-gallium) as the Ga source, the TMIn(trimethyl indium) as In source, SiH 4(silane) as the Si doped source, the luxuriant magnesium of Cp2Mg(bis-) as the Mg doped source, and with N 2(nitrogen), H 2(hydrogen) is as carrier gas.
Step S101, provide substrate 1.
In an embodiment of the present invention, described substrate 1 is plane or patterned substrate, preferred patterned substrate, and patterned substrate can reduce the epitaxial wafer defect of growth, improves the epitaxial wafer crystal mass; The shape of described patterned substrate comprises strip, column, cone-shaped or spherical crown shape.
The material of substrate 1 can be selected sapphire, SiC or Si, preferably adopts Sapphire Substrate.
Step S102, on substrate 1, growth has the InN layer 21 in the cavity that exposes substrate.
In concrete enforcement, can adopt MOCVD(metallo-organic compound chemical vapour deposition technique), specifically comprise the following steps:
S201, the InN layer 21 of growing on substrate 1;
S202, InN layer 21 is carried out to high-temperature process, make InN layer 21 that the cavity that exposes substrate occur to decompose and form.
Particularly, in step S201, with NH 3with TMIn be source, under 500～700 ℃ of conditions, grow 100～200s time, on substrate 1, deposition obtains the InN layer 21 that thickness is 1～5nm.
Particularly, in step S202, close TMIn and keep passing into NH 3, the InN layer is carried out to high-temperature process, the temperature to 850 that raises～900 ℃, maintain 60s under 850～900 ℃ of conditions by temperature, makes InN layer 21 that the cavity that exposes substrate 1 occur to decompose and form.
Step S103, have growth the first intrinsic GaN layer on empty InN layer.
Particularly, pass into TMGa, obtain the first intrinsic GaN layer 22 being distributed with on the InN layer 21 in the cavity that exposes substrate 1 deposition, the thickness of described the first intrinsic GaN layer is 50～100nm.
InN layer 21 subregion in heating up and maintaining the process of 850～900 ℃ can be decomposed, and substrate 1 surface is exposed in the zone that occurs to decompose, thereby obtains having empty InN layer 21, the out-of-shape in cavity.Have empty InN layer 21 and can play the effect of mask layer, the threading dislocation of substrate 1 can be blocked while extending to the interface between substrate 1 and InN layer 21, effectively reduces the impact of the threading dislocation of substrate 1 on epitaxial loayer.
In embodiments of the present invention, substrate 1 is selected Sapphire Substrate, another effect of InN layer 21 is, alleviate the compression that Sapphire Substrate and GaN layer cause because of lattice mismatch, the lattice mismatch of sapphire and InN is 25%, and the crystal mismatch-9.9% of InN and GaN, introduce tensile stress by deposition InN layer 21 on Sapphire Substrate, can alleviate the compression that the lattice mismatch of sapphire and GaN interlayer causes, stress is effectively discharged, thereby reduces the generation of dislocation.
Step S104, SiN grows on the first intrinsic GaN layer 22 xlayer 23, described SiN xlayer 23 is distributed with the cavity that exposes the first intrinsic GaN layer 22.
Particularly, close TMGa and keep passing into NH3, rising temperature to 1000～1100 ℃, then pass into SiH 4, the SiN that deposition growing thickness is 1～5nm on the first intrinsic GaN layer 22 xlayer 23.
Step S105, at SiN xform the second intrinsic GaN layer 24 on layer 23.
Particularly, close SiH 4, pass into TMGa, at SiN xthe second intrinsic GaN layer 24 that on layer 23, deposition growing thickness is 2～3um.
As shown in Figure 4, due to the SiN grown on the first intrinsic GaN layer 22 xlayer 23 is thinner, only has 1～5nm, in the process of deposition, suitably controls, and the zone that can make can not deposit SiN xfilm, thereby at SiN xform the cavity 231 that exposes the first intrinsic GaN layer 22 on layer 23, the out-of-shape in cavity 231.
As shown in Figure 5, there is empty SiN xlayer 23 can play the mask layer effect equally, can realize GaN layer lateral growth, simultaneously SiN xlayer 23 can stop that dislocation extends upward.In figure in epitaxial wafer upwardly extending lines be dislocation line, at SiN xon layer 23, carry out in the laterally overgrown process, a part of dislocation is at the first intrinsic GaN layer 22 and SiN xinterface between layer 23 is blocked; Other threading dislocations that extend up from the first intrinsic GaN layer 22 continue to extend up to intrinsic GaN layer by cavity 231, when the cross section on the GaN island at empty 231 region growings forms trapezoidal or triangle, the inclination crystal face on dislocation line Hui GaN island turns to, extend to horizontal direction, so reduced upwardly extending threading dislocation quantity.Along with the deposition growing of the second intrinsic GaN layer 24, the growing up gradually and merge with adjacent GaN island of the GaN island of empty 231 location, what the threading dislocation originally extended to horizontal direction had turns to again in adjacent GaN island merging place 241, and extends upward.But, because this part threading dislocation only extends upward in adjacent GaN island merging place 241, make low dislocation zone in epitaxial loayer increase, therefore improved the epitaxial wafer crystal mass of growth.
Step S106, form N-shaped GaN layer 3 on the second intrinsic GaN layer 24.The GaN layer that described N-shaped GaN layer 3 is doping Si, the Si doping content is 8e18cm -3, growth thickness is 2～3um.
Step S107, form luminescent layer 4 on N-shaped GaN layer 3.
Step S108, form p-type GaN layer 5 on luminescent layer 4.
In concrete enforcement, described p-type GaN layer 5 is magnesium Doped GaN layer.
In another embodiment of the present invention, described luminescent layer 4 is multiple quantum well layer, comprising:
Be formed on the doping multiple quantum well layer 41 on N-shaped GaN layer;
Be formed on the non-doping multiple quantum well layer 42 on doping multiple quantum well layer 41.
In concrete enforcement, in described 41 5～7 cycles of growth of doping multiple quantum well layer, wherein the trap thickness of quantum well is 2～3nm, and the thickness at base is 10～15nm; The material of doping is Si, and the Si doping content is 1e17 ~ 1e18cm -3.
In concrete enforcement, in described non-42 2～3 cycles of growth of doping multiple quantum well layer, the trap thickness of quantum well is consistent with doping Multiple Quantum Well 41 with barrier thickness.So, can improve the luminous efficiency of LED chip.
After growth completes multiple quantum well layer, continue to grow successively AlGaN barrier layer 6 and p-type GaN layer 5, overflow from active area on AlGaN barrier layer 6 effectively block electrons, thereby increase the quantity of active area electronics, improve the charge carrier combined efficiency of multiple quantum well layer, promote the LED chip luminous efficiency.
After completing the growth of p-type GaN layer 5, be placed in the preparation that the annealing of carrying out 20 minutes under the nitrogen environment of 710 ~ 740 ℃ completes the LED epitaxial wafer.
In sum, LED epitaxial wafer provided by the invention and preparation method, by substrate growth InN layer, can effectively reduce the stress produced because of lattice mismatch between substrate and GaN layer, thereby reduce the generation of dislocation; And the InN layer can play the mask layer effect, the threading dislocation of substrate ends at the interface between substrate and InN layer and is blocked.
And the present invention has empty SiN by insert growth in resilient coating xlayer, realize the laterally overgrown in later stage, reduce injection defect, and effectively the stop portions dislocation extends to N-shaped GaN layer or luminescent layer simultaneously, and another part dislocation is concentrated on to SiN xlayer hole region, thus epitaxial loayer low dislocation zone increased, reduce dislocation density, improved the epitaxial wafer crystal mass.
Finally, the present invention covers growth than the side direction of GaN, does not need deposition mask layer on substrate in advance, but by the outer layer growth process, depositing SiN xlayer serves as mask layer, has simplified technique, has avoided mask layer to pollute substrate, and has reduced production cost.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.

Claims (13)

1. a LED epitaxial wafer, comprise substrate, and the resilient coating, N-shaped GaN layer, luminescent layer and the p-type GaN layer that on substrate, form successively, is characterized in that, described resilient coating comprises:
Be formed on the InN layer on substrate, described InN layer is distributed with the cavity that exposes substrate;
Be formed on the first intrinsic GaN layer on described InN layer;
Be formed on the SiN on described the first intrinsic GaN layer xlayer, described SiN xlayer is distributed with the cavity that exposes the first intrinsic GaN layer; And
Be formed on described SiN xthe second intrinsic GaN layer on layer.
2. a kind of LED epitaxial wafer as claimed in claim 1, is characterized in that, the intrinsic GaN layer that described the first intrinsic GaN layer is growth under 850～900 ℃, the intrinsic GaN layer that described the second intrinsic GaN layer is growth under 1000～1100 ℃.
3. a kind of LED epitaxial wafer as claimed in claim 1, is characterized in that, the thickness of described the first intrinsic GaN layer is 50～100nm, and the thickness of the second intrinsic GaN layer is 2～3um.
4. a kind of LED epitaxial wafer as claimed in claim 1, is characterized in that, the thickness of described InN layer is 1～5nm.
5. a kind of LED epitaxial wafer as claimed in claim 1, is characterized in that described SiN xthe thickness of layer is 1～5nm.
6. a kind of LED epitaxial wafer as claimed in claim 1, is characterized in that, also comprises: be formed on the AlGaN barrier layer between luminescent layer and p-type GaN layer.
7. a kind of LED epitaxial wafer as claimed in claim 1, is characterized in that, described substrate is patterned substrate.
8. a kind of LED epitaxial wafer as claimed in claim 1, is characterized in that, described substrate is Si substrate, GaN substrate or Sapphire Substrate.
9. a kind of LED epitaxial wafer as claimed in claim 1, is characterized in that, described luminescent layer comprises:
Be formed on the doping multiple quantum well layer on N-shaped GaN layer;
Be formed on the non-doping multiple quantum well layer on the doping multiple quantum well layer.
10. the preparation method of a LED epitaxial wafer, is characterized in that, comprises the following steps:
Substrate is provided;
The InN layer that there is the cavity that exposes substrate at Grown;
There is growth the first intrinsic GaN layer on empty InN layer;
On the first intrinsic GaN layer, growth has the SiN in the cavity that exposes the first intrinsic GaN layer xlayer;
At SiN xform the second intrinsic GaN layer on layer;
Form N-shaped GaN layer on the second intrinsic GaN layer;
Form luminescent layer on N-shaped GaN layer;
Form p-type GaN layer on luminescent layer.
11. the preparation method of a kind of LED epitaxial wafer as claimed in claim 10, is characterized in that, has the InN layer in the cavity that exposes substrate at Grown, comprising:
At Grown InN layer;
The InN layer is carried out to high-temperature process, make the InN layer that the cavity that exposes substrate occur to decompose and form.
12. the preparation method of a kind of LED epitaxial wafer as claimed in claim 10, is characterized in that, also comprises: form the AlGaN barrier layer between luminescent layer and p-type GaN layer.
13. the preparation method of a kind of LED epitaxial wafer as claimed in claim 10, is characterized in that, on N-shaped GaN layer, forms luminescent layer, comprising:
Form the doping multiple quantum well layer on N-shaped GaN layer;
Form non-doping multiple quantum well layer on the doping multiple quantum well layer.
CN201210171423.0A 2012-05-30 2012-05-30 A kind of LED and preparation method Expired - Fee Related CN103456852B (en)

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CN104465899A (en) * 2014-11-28 2015-03-25 西安神光皓瑞光电科技有限公司 Preparation method for LED perpendicular structure
CN104485399A (en) * 2014-12-01 2015-04-01 西安神光皓瑞光电科技有限公司 Epitaxial growth method for improving epitaxial crystal quality
CN104900774A (en) * 2015-05-07 2015-09-09 西北工业大学明德学院 Transverse epitaxial growth method for double buffer layers for improving brightness of LED (Light Emitting Diode)
CN106480498A (en) * 2016-10-12 2017-03-08 北京邮电大学 A kind of nano graph substrate side epitaxial silicon based quantum dot laser equipment material and preparation method thereof
CN110767785A (en) * 2019-11-12 2020-02-07 佛山市国星半导体技术有限公司 High-quality epitaxial structure and manufacturing method thereof
CN111554785A (en) * 2020-03-27 2020-08-18 华灿光电(苏州）有限公司 Light emitting diode epitaxial wafer and preparation method thereof

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104465899A (en) * 2014-11-28 2015-03-25 西安神光皓瑞光电科技有限公司 Preparation method for LED perpendicular structure
CN104485399A (en) * 2014-12-01 2015-04-01 西安神光皓瑞光电科技有限公司 Epitaxial growth method for improving epitaxial crystal quality
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CN104900774A (en) * 2015-05-07 2015-09-09 西北工业大学明德学院 Transverse epitaxial growth method for double buffer layers for improving brightness of LED (Light Emitting Diode)
CN104900774B (en) * 2015-05-07 2017-05-17 西北工业大学明德学院 Transverse epitaxial growth method for double buffer layers for improving brightness of LED (Light Emitting Diode)
CN106480498A (en) * 2016-10-12 2017-03-08 北京邮电大学 A kind of nano graph substrate side epitaxial silicon based quantum dot laser equipment material and preparation method thereof
CN106480498B (en) * 2016-10-12 2019-05-17 北京邮电大学 A kind of nano graph substrate side epitaxial silicon based quantum dot laser equipment material and preparation method thereof
CN110767785A (en) * 2019-11-12 2020-02-07 佛山市国星半导体技术有限公司 High-quality epitaxial structure and manufacturing method thereof
CN111554785A (en) * 2020-03-27 2020-08-18 华灿光电(苏州）有限公司 Light emitting diode epitaxial wafer and preparation method thereof
CN111554785B (en) * 2020-03-27 2021-10-08 华灿光电(苏州）有限公司 Light emitting diode epitaxial wafer and preparation method thereof

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Address after: 518119 No.1 Yan'an Road, Kuiyong street, Dapeng New District, Shenzhen City, Guangdong Province

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Address before: 518119 No.1 Yan'an Road, Kuiyong street, Dapeng New District, Shenzhen City, Guangdong Province

Patentee before: SHENZHEN BYD MICROELECTRONICS Co.,Ltd.

Address after: 518119 No.1 Yan'an Road, Kuiyong street, Dapeng New District, Shenzhen City, Guangdong Province

Patentee after: BYD Semiconductor Co.,Ltd.

Address before: 518119 No.1 Yan'an Road, Kuiyong street, Dapeng New District, Shenzhen City, Guangdong Province

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Granted publication date: 20160907