CN108630792A - Based on Ga2O3Vertical structure ultraviolet LED of substrate and preparation method thereof - Google Patents
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- 239000000758 substrate Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910002704 AlGaN Inorganic materials 0.000 claims abstract description 69
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims description 11
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers 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 semiconductor bodies
- H01L33/12—Semiconductor devices having potential barriers 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 semiconductor bodies with a stress relaxation structure, e.g. buffer layer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers 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
- H01L33/007—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound comprising nitride compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers 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 semiconductor bodies
- H01L33/04—Semiconductor devices having potential barriers 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 semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction
- H01L33/06—Semiconductor devices having potential barriers 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 semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction within the light emitting region, e.g. quantum confinement structure or tunnel barrier
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers 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 semiconductor bodies
- H01L33/26—Materials of the light emitting region
- H01L33/30—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table
- H01L33/32—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen
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Abstract
One kind being based on Ga2O3The structure of vertical structure ultraviolet LED of substrate and preparation method thereof, the ultraviolet LED includes β Ga successively from bottom to top2O3Substrate, low temperature AI N buffer layers, AlGaN stress release layers, N-shaped AlGaN layer, multi-quantum well active region, p-type AlGaN layer, p-type GaN layer and mirror layer；And p-electrode is made on mirror layer, in β Ga2O3N-electrode is made on substrate floor, to realize high efficiency, high-power vertical structure ultraviolet LED.
Description
Technical field
The invention belongs to semiconductor applications, refer in particular to a kind of realization high efficiency, it is high-power, be based on Ga2O3The vertical junction of substrate
Structure UV LED (Light Emitting Diode, LED) and preparation method thereof.
Background technology
In recent years, with progress prepared by AlGaN material, tri-nitride ultraviolet LED achieves certain progress, with biography
System mercury lamp ultraviolet source compare, tri-nitride ultraviolet LED have low-power consumption, low-voltage, energy saving, efficient, mercury-free is environmentally friendly, small and exquisite
Portable equal significant advantages, optical sensor, sterilizing, polymer solidification, it is biochemical visit away from, non line of sight communication, special lighting,
There is boundless application prospect in the fields such as ultraviolet light authentication.But compared to blue-ray LED, the quantum efficiency of ultraviolet LED
Still have greatly improved space.
The typically ultraviolet LED based on Sapphire Substrate, since AlGaN layer and Sapphire Substrate lattice mismatch are larger, very
High quality AlGaN material is extended outside difficult；And since Sapphire Substrate is non-conductive, p/n electrodes are not only sacrificed in this way in the same side
The area of active area, and electric current must flow transversely through n-AlGaN layers, lead to electric current congestion, and injection efficiency is low, generates a large amount of
Joule heat；In addition, the poor thermal conductivity of Sapphire Substrate, limits the heat dissipation of UV LED chip, the reliability of device is reduced.
Although and SiC substrate has a clear superiority on Lattice Matching and electric conductivity relative to Sapphire Substrate, due to SiC substrate
To the absorption characteristic of ultraviolet light, its application is largely limited.
Vertical structure ultraviolet LED can then efficiently solve the above problem.Vertical structure ultraviolet LED need not etch platform
Face can fully utilize active region area, eliminate congestion effect, improve injection efficiency, device thermal losses be reduced, to realize
Higher luminous efficiency and longer service life.Realize that the technology path of AlGaN based vertical structure ultraviolet LEDs mainly uses at present
After sapphire, SiC substrate hetero-epitaxy AlGaN base ultraviolet LEDs, it is real that substrate is removed by the methods of laser lift-off or mechanical lapping
The transfer of existing nitride film.Main problem is existing for this method：By stripping, repeatedly light-emitting film is realized in bonding
Transfer, complex process, yield rate are relatively low and laser equipment is expensive, are unfavorable for the production of commercial quantities metaplasia, and cause lining
The waste of bottom material.
β-Ga2O3It is the novel substrate material that developed recently gets up, belongs to monoclinic system, it is small with AlN lattice mismatches, and have
There is high energy gap (4.8eV), can pass through the wavelength most short ultraviolet light for 260nm.β-Ga2O3For n-type semiconductor, Ke Yitong
Overdoping Sn and Si realizes 1019cm-3N-shaped concentration, resistivity is 0.005 Ω cm or so, has good electric conductivity, because
β-Ga can be used in this2O3As UV transparent conductive substrates, on the basis of extension obtains high quality AlGaN films, without stripping
From complicated technologies such as, transfers, p/n electrodes directly are deposited in chip both sides to realize small high-power of homogeneous current distribution, resistance
Vertical structure ultraviolet LED.The AlGaN that the present invention designs a kind of variation of composition gradient is used as stress release layer, inhibition epitaxial process
In thermal mismatching and lattice mismatch, realize the AlGaN growths of adequate thickness, be directly realized by vertical structure ultraviolet LED, push ultraviolet
LED industry develops.
Invention content
In view of this, the main purpose of the present invention is to provide one kind being based on Ga2O3The well-behaved straight structure ultraviolet LED knot of substrate
Structure and preparation method thereof, to solve above-mentioned technical problem.
To achieve the goals above, it as one aspect of the present invention, provides a kind of based on Ga2O3The vertical junction of substrate
The preparation method of structure ultraviolet LED, which is characterized in that include the following steps：
Step 1：In β-Ga2O3Grown low temperature AI N buffer layers；
Step 2：AlGaN stress release layers are grown on low temperature AI N buffer layers；
Step 3：The growing n-type AlGaN layer on AlGaN stress release layers；
Step 4：Multi-quantum well luminescence layer is grown in N-shaped AlGaN layer；
Step 5：P-type AlGaN layer is grown in multi-quantum well luminescence layer；
Step 6：P-type GaN layer is grown in p-type AlGaN layer；
Step 7：Mirror layer is prepared in p-type GaN layer；
Step 8：P-electrode and n-electrode are prepared, is obtained described based on Ga2O3The vertical structure ultraviolet LED of substrate.
As another aspect of the present invention, a kind of base that basis preparation method as described above is prepared is additionally provided
In Ga2O3The vertical structure ultraviolet LED of substrate.
Based on the above-mentioned technical proposal it is found that vertical structure ultraviolet LED of the present invention and preparation method thereof is with following beneficial
Effect：Using the mocvd method epitaxial nitride film that can industrially quantify production, direct growth of vertical structure AlGaN bases are purple
Outer LED, provide it is a kind of it is simple for process, effectively reduce cost and can obtain high efficiency, high-power ultraviolet LED new technology road
Line.
Description of the drawings
Fig. 1 is the structural schematic diagram of the vertical structure ultraviolet LED based on Ga2O3 substrates of the present invention；
Fig. 2 is according to an embodiment of the invention based on Ga2O3The stream of the preparation method of the vertical structure ultraviolet LED of substrate
Cheng Tu.
Specific implementation mode
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, and reference
Attached drawing, the present invention is described in further detail.
The invention discloses a kind of using conductive, light transmission β-Ga2O3Substrate realizes the preparation method of vertical structure ultraviolet LED,
Structure includes β-Ga from bottom to top2O3Substrate, low temperature AI N buffer layers, content gradually variational AlGaN stress release layers, N-shaped AlGaN layer,
Multi-quantum well active region, p-type AlGaN layer, p-type GaN layer and mirror layer.P-electrode is made on mirror layer, in β-Ga2O3
Substrate floor makes n-electrode, to realize high efficiency, high-power vertical structure ultraviolet LED.
β-Ga2O3It is a kind of novel nitride substrate material, it is very low with the lattice mismatch of AlGaN；Energy gap is larger
(4.8eV), it is very high to ultraviolet band light transmission rate；And β-Ga2O3For n-type semiconductor, there is certain electric conductivity, pass through
The element dopings such as Sn, Si, carrier concentration is up to 2 × 1018cm-3~9 × 1018cm-3.In summary it analyzes, using β-Ga2O3
Transparent conductive substrate of the monocrystalline as extension AlGaN base ultraviolet LEDs can get high efficiency, powerful ultraviolet LED.
The present invention is based on the above-mentioned discoveries of the present inventor, are accurately controlled in conjunction with metal organic chemical vapor deposition (MOCVD) method
System growth AlGaN base ultraviolet LED structures only can be obtained vertical junction without complicated technologies such as stripping, transfers by an extension
Structure ultraviolet LED, for high efficiency, high-power vertical structure ultraviolet LED preparation provide it is simple for process, effectively reduce cost it is new
Technology path.
Specifically, of the invention based on Ga2O3The preparation method of the vertical structure ultraviolet LED of substrate, includes the following steps：
Step A, in β-Ga2O3Grown low temperature AI N buffer layers；
Step B, the growth components gradual change AlGaN stress release layers on low temperature AI N buffer layers；
Step C, the growing n-type AlGaN layer on AlGaN stress release layers；
Step D grows multi-quantum well luminescence layer in N-shaped AlGaN layer；
Step E grows p-type AlGaN layer in multi-quantum well luminescence layer；
Step F grows p-type GaN layer in p-type AlGaN layer；
Step G, prepares mirror layer in p-type GaN layer；
Step H prepares p-electrode and n-electrode, obtains the vertical structure ultraviolet LED.
Wherein, substrate used is transparent, the conductive and small β-Ga of AlGaN lattice mismatches2O3Substrate.
Preferably, epitaxial growth is carried out using metal organic chemical vapor deposition (MOCVD) method in step A~F, with
Grow the AlN buffer layers, AlGaN stress release layers, N-shaped AlGaN layer, multi-quantum well active region, p-type AlGaN layer, p-type
GaN layer.
Preferably, needing to carry out thermal anneal process, hot annealing conditions to substrate before growing AIN buffer layer in step A
Further preferably 950 DEG C, N2Atmosphere, anneal 3min.
Preferably, in step A when growing low temperature AlN buffer layers, the thickness of the AlN nucleating layers is 2~50nm；It is described
The formation condition of low temperature AI N buffer layers is：480~650 DEG C, N2Atmosphere grows 3min.
Preferably, the thickness of the AlGaN stress release layers grown in step B be 1~2 μm, Al components from 100% to
55% gradual change.
Preferably, in step D when preparing multi-quantum well luminescence layer, first growing n-type AlGaN layer, regrowth Quantum Well
Luminescent layer；The thickness of the N-shaped AlGaN layer is 1~3 μm；The trap of the mqw light emitting layer and base are AlGaN.
Preferably, the thickness of the p-type AlGaN layer formed in step E is 50~100nm.
Preferably, the thickness of the p-type GaN layer formed in step F is 20~100nm.
Preferably, grown in step 1 the AlN nucleating layers formed when the low temperature AI N buffer layers thickness be 2~
50nm；
Preferably, the formation condition of the buffer layer of low temperature AI N described in step 1 is：480~650 DEG C, N2Atmosphere, growth
3min。
Preferably, p-electrode is prepared on mirror layer in step H, in β-Ga2O3N-electrode is prepared on substrate floor.
The invention also discloses it is a kind of according to above-mentioned preparation method be prepared based on Ga2O3The vertical structure of substrate is purple
The wave-length coverage of outer LED, the ultraviolet light which sends out are 270~400nm.
Below in conjunction with the accompanying drawings, explanation is further elaborated to technical scheme of the present invention by specific embodiment.
Fig. 1 is the present invention based on Ga2O3The structural schematic diagram of the vertical structure ultraviolet LED of substrate, as shown in Figure 1, from upper
It is as follows to lower each layer function：
β-Ga2O3Due to have the characteristics that light transmittance high, good conductivity and with AlGaN lattice mismatches it is small, in MOCVD epitaxy
Substrate supports are provided during growing nitride film, necessary condition are provided for extension high quality AlGaN films, in device
It, can be as the photosphere that goes out of vertical structure ultraviolet LED, the ultraviolet light of ultraviolet LED due to high light transmittance in preparation process
Output waveband is 270~400nm.
Make a living long high quality AlGaN films of low temperature AI N buffer layers provide nucleating point；Effectively improving AlGaN epitaxial films
Ga is effectively prevented while quality2O3Substrate and H2Haptoreaction, it is therefore prevented that H in AlGaN growth courses2To Ga2O3Substrate
Etching.
N-shaped AlGaN layer, multi-quantum well luminescence layer, p-type AlGaN layer are main light emitting functional layers.
P-type GaN layer can effectively improve hole injection fluence.
Fig. 2 is the flow chart of preparation method according to an embodiment of the invention, is included the following steps：
Step 1：Take β-Ga2O3Substrate is put into the solution that sulfuric acid, hydrogen peroxide are prepared according to 3: 1 volume ratio, cleaning lining
Bottom surface.Substrate after cleaning is put into MOCVD device and carries out the high temperature anneal, actual conditions are 950 DEG C, N2Atmosphere,
Anneal 3min；
Step 2：The thickness of growing low temperature AlN buffer layers on substrate, nucleating layer is 2~50nm.Specific experiment condition is
N2Atmosphere, grows 3min by 480 DEG C~650 DEG C；
Step 3：AlGaN stress release layers are grown on AlN buffer layers, thickness is 1~2 μm；
Step 4：The growing n-type AlGaN layer on AlGaN stress release layers, thickness are 1~3 μm, wherein N-shaped AlGaN layer
It is obtained using doped chemical Si；
Step 5：Multi-quantum well luminescence layer is grown in N-shaped AlGaN layer；The trap of mqw light emitting layer and base are AlGaN；
Step 6：P-type AlGaN layer is grown in multi-quantum well luminescence layer, thickness is 50~100nm；
Step 7：P-type GaN layer is grown in p-type AlGaN layer, thickness is 20~100nm；
Step 8：Speculum is prepared in p-type GaN layer, makes the higher β-Ga of light transmittance2O3Substrate is as light-emitting surface；Reflection
Mirror is using conventional material preparation, such as silver, aluminium plated film；
Step 9：In speculum and Ga2O3Substrate floor prepares p/n electrodes respectively, completes the making of device.
By test detect, find the present invention based on Ga2O3The vertical structure ultraviolet LED of substrate has following performance：Hair
The deep ultraviolet LED of optical wavelength 320nm, Injection Current have no saturation at 500mA, and upside-down mounting deep ultraviolet LED on traditional sapphire
Reach saturation in 100mA, it is shown that good transmission performance is suitble to work under high current.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical solution and advantageous effect
Describe in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in the protection of the present invention
Within the scope of.
Claims (10)
1. one kind being based on Ga2O3The preparation method of the vertical structure ultraviolet LED of substrate, which is characterized in that include the following steps：
Step 1：In β-Ga2O3Grown low temperature AI N buffer layers；
Step 2：AlGaN stress release layers are grown on low temperature AI N buffer layers；
Step 3：The growing n-type AlGaN layer on AlGaN stress release layers；
Step 4：Multi-quantum well luminescence layer is grown in N-shaped AlGaN layer；
Step 5：P-type AlGaN layer is grown in multi-quantum well luminescence layer；
Step 6：P-type GaN layer is grown in p-type AlGaN layer；
Step 7：Mirror layer is prepared in p-type GaN layer；
Step 8：P-electrode and n-electrode are prepared, is obtained described based on Ga2O3The vertical structure ultraviolet LED of substrate.
2. preparation method according to claim 1, which is characterized in that be all made of Metallo-Organic Chemical Vapor in step 1~5
Sedimentation carries out epitaxial growth, to grow low temperature AI N buffer layers, AlGaN stress release layers, N-shaped AlGaN layer, multiple quantum wells
The active area of luminescent layer, p-type AlGaN layer, p-type GaN layer.
3. preparation method according to claim 1, which is characterized in that before growing the low temperature AI N buffer layers in step 1
It needs to carry out thermal anneal process to substrate；Hot annealing conditions are preferably：950 DEG C, N2Atmosphere, anneal 3min；
Preferably, the thickness for growing the AlN nucleating layers formed when the low temperature AI N buffer layers in step 1 is 2~50nm；
Preferably, the formation condition of the buffer layer of low temperature A1N described in step 1 is：480~650 DEG C, N2Atmosphere grows 3min.
4. preparation method according to claim 1, which is characterized in that the AlGaN stress release layers formed in step 2
Thickness be 1~2 μm；
Preferably, the AlGaN stress release layers are content gradually variationals, wherein from 100% to 55% gradual change of Al components.
5. preparation method according to claim 1, which is characterized in that the thickness of N-shaped AlGaN layer described in step 3 be 1~
3μm；
Preferably, the trap of mqw light emitting layer described in step 4 and base material therefor are AlGaN.
6. preparation method according to claim 1, which is characterized in that the thickness of the p-type AlGaN layer formed in step 5
Degree is 50~100nm.
7. preparation method according to claim 1, which is characterized in that the thickness of the p-type GaN layer formed in step 6
For 20~100nm.
8. preparation method according to claim 1, which is characterized in that p-electrode is prepared in step 8 on mirror layer,
β-Ga2O3N-electrode is prepared on substrate floor.
9. the preparation method according to claim 1 to 8 any one be prepared based on Ga2O3The vertical structure of substrate
Ultraviolet LED.
10. the ultraviolet wavelength range of the vertical structure ultraviolet LED according to claim, transmitting is 270nm-400nm.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109301044A (en) * | 2018-10-15 | 2019-02-01 | 华中科技大学鄂州工业技术研究院 | Deep ultraviolet LED vertical chip based on the positive assembling structure of n-type doping gallium oxide |
| CN110931606A (en) * | 2019-12-20 | 2020-03-27 | 深圳第三代半导体研究院 | Vertical light emitting diode and manufacturing method thereof |
| CN111739988A (en) * | 2020-06-29 | 2020-10-02 | 山东大学 | Vertical-structure broadband near-infrared LED and preparation method thereof |
| CN112310255A (en) * | 2020-11-04 | 2021-02-02 | 山西中科潞安紫外光电科技有限公司 | Deep ultraviolet light-emitting diode with vertical structure and preparation method thereof |
| CN115548177A (en) * | 2022-10-12 | 2022-12-30 | 深圳大学 | Deep ultraviolet light-emitting diode and preparation method thereof |
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| CN109301044A (en) * | 2018-10-15 | 2019-02-01 | 华中科技大学鄂州工业技术研究院 | Deep ultraviolet LED vertical chip based on the positive assembling structure of n-type doping gallium oxide |
| CN110931606A (en) * | 2019-12-20 | 2020-03-27 | 深圳第三代半导体研究院 | Vertical light emitting diode and manufacturing method thereof |
| CN111739988A (en) * | 2020-06-29 | 2020-10-02 | 山东大学 | Vertical-structure broadband near-infrared LED and preparation method thereof |
| CN111739988B (en) * | 2020-06-29 | 2021-11-12 | 山东大学 | Vertical-structure broadband near-infrared LED and preparation method thereof |
| CN112310255A (en) * | 2020-11-04 | 2021-02-02 | 山西中科潞安紫外光电科技有限公司 | Deep ultraviolet light-emitting diode with vertical structure and preparation method thereof |
| CN115548177A (en) * | 2022-10-12 | 2022-12-30 | 深圳大学 | Deep ultraviolet light-emitting diode and preparation method thereof |
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