CN106098890B - A kind of vertical structure nitrogen polar GaN base green LED chip and preparation method thereof based on carbon face SiC substrate - Google Patents

A kind of vertical structure nitrogen polar GaN base green LED chip and preparation method thereof based on carbon face SiC substrate Download PDF

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CN106098890B
CN106098890B CN201610445392.1A CN201610445392A CN106098890B CN 106098890 B CN106098890 B CN 106098890B CN 201610445392 A CN201610445392 A CN 201610445392A CN 106098890 B CN106098890 B CN 106098890B
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CN106098890A (en
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张源涛
邓高强
黄振
董鑫
马艳
张宝林
杜国同
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Shanghai Jiadan Electronic Information Co ltd
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吉林大学
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the 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 system
    • H01L33/32—Materials of the light emitting region containing only elements of group III and group V of the periodic system containing nitrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/005—Processes
    • H01L33/0062—Processes for devices with an active region comprising only III-V compounds
    • H01L33/0066—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/04—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction
    • H01L33/06—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the 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

Abstract

A kind of vertical structure nitrogen polar GaN base green light LED and preparation method thereof based on carbon face SiC substrate, belongs to light emitting semiconductor device field.It successively has the carbon face SiC substrate of angle of chamfer, n-Al by lower electrode layer, N-shapedx0Ga1‑x0N conductive buffer layer, n-GaN electronics provide layer, InGaN based quantum well active area, p-Alx1Ga1‑x1N electronic barrier layer, p-GaN hole injection layer and upper electrode layer are constituted.Using carbon face SiC as substrate, to obtain the polar GaN base green light LED device of nitrogen, compared with traditional gallium polar GaN device, nitrogen polarity LED structure designs the raising for being more advantageous to device efficiency.Polarized electric field in nitrogen polarity LED structure in electronic barrier layer is consistent with additional forward bias direction, facilitates the injection in hole, reduces the cut-in voltage of device.Meanwhile vertical structure LED can effectively avoid electric current congestion effect.The method of the present invention can obtain efficient GaN base green light LED, further promote the development of GaN base green light LED and its application.

Description

A kind of vertical structure nitrogen polar GaN base green LED chip based on carbon face SiC substrate And preparation method thereof
Technical field
The invention belongs to light emitting semiconductor device fields, and in particular to a kind of vertical structure nitrogen based on carbon face SiC substrate Polar GaN base green LED chip and preparation method thereof.
Background technique
GaN and its alloy cpd AlInGaN are important semiconductor material, have in terms of opto-electronic device extensive Using such as LED and LD.GaN base blue-ray LED based on Sapphire Substrate has been commercialized, and external quantum efficiency is up to 84%.So And the performance of GaN base green light LED but lags far behind, external quantum efficiency is less than 30%, and with the increase of electric current, efficiency meeting Decline sharply.Therefore, GaN base green light LED is increasingly becoming the research emphasis of scientific research personnel.What highly effective green light LED was difficult to obtain Main cause is that higher In content is needed in its Quantum well active district, the raising meeting of In content so that Quantum Well InGaN layer and The lattice mismatch that quantum builds GaN layer increases, so that stress suffered by Quantum Well increases, exacerbates the amount in Quantum Well Son limitation Stark effect, so that radiation recombination efficiency reduces.Furthermore low needed for the increase of lattice mismatch and high In component Temperature growth meeting is so that the defects of Quantum Well increases, to further decrease the performance of device.Green light LED can with blue-ray LED, Red-light LED makes more advanced white light for illumination LED together.Yttrium-aluminium-garnet (YAG) fluorescent powder is added to synthesize with traditional blue light White light LEDs compare, white light LEDs its colour rendering index that this method obtains is higher, at the same also can achieve higher light efficiency and Flexible Color control.However, generating dynamical white light with the mode of blend color, it is necessary to use high efficiency light source.Blue light and The performance of red-light LED is very significant, and peak power transformation efficiency is more than 81% and 70%.So realizing that efficient GaN base is green Light LED be it is vital, have important research significance.
Summary of the invention
The object of the invention is to be crystallized from epitaxial layer is improved in order to solve the problems, such as above-mentioned green LED low efficiency Quality, simplified device making technics and improvement device performance etc. comprehensively consider, in the carbon face SiC with angle of chamfer of N-shaped The nitrogen polar GaN base green light LED for having p-type AlGaN electronic barrier layer is developed on substrate.The GaN crystal of hexagonal wurtzite structure Belong to non-centrosymmetric structure, there are polar axis, that is, c-axis.Under the conditions of stressless, positive and negative charge center is not overlapped, and forms dipole Square.It, which mutually adds up, leads to polarization charge occur in plane of crystal, generates spontaneous polarity effect (i.e. along c-axis side along polar axis direction To), negative polarizing interfaces charge is in gallium face, and positive polarizing interfaces charge is in nitrogen face, so that polarized electric field is generated, direction of an electric field Along c axis direction.Polarized electric field can cause the inclination of energy band, and the transmission characteristic of carrier in device architecture is caused to change, from And influence the electricity of device, optical characteristics.Currently, most of GaN base LED be edge+c-axis [0001] direction carry out outside _ prolong, Its surface is (0001) face face Ji Jia, and this LED is referred to as gallium polarity LED.And edge-c-axis [0001] direction carries out extension, table Face is (0001) face face Ji Dan, can construct nitrogen polarity LED based on this extensional mode.It can generate and pass in nitrogen polarity LED structure System gallium polarity LED opposite polarized electric field enables it to the inclined direction of band and the inclination side of the energy band in gallium polarity LED structure To opposite (as shown in Figure 2), to raise the last one GaN barrier layer and p-AlGaN electronic blocking stratum boundary in nitrogen polarity LED structure Effective barrier height at face can effectively improve p-type AlGaN electronic barrier layer to the barrier effect of electronics, improve device Internal quantum efficiency and luminous efficiency.In addition, polarized electric field direction and additional forward direction in nitrogen polarity p-AlGaN electronic barrier layer Bias is identical, facilitates the injection in hole, reduces the cut-in voltage of device.
Designed by the present invention it is a kind of based on carbon face SiC substrate vertical structure nitrogen polar GaN base green light LED chip (see Attached drawing 1 and Detailed description of the invention), it is characterised in that: it is from bottom to up successively by the carbon face with angle of chamfer of lower electrode layer 8, n type SiC substrate 1, n-Alx0Ga1-x0N conductive buffer layer 2, n-GaN electronics provide layer 3, multiple quantum well active layer 4, p-Alx1Ga1-x1N Electronic barrier layer 5, p-GaN hole injection layer 6 and upper electrode layer 7 are constituted, wherein 0.2≤x0, x1≤0.4, electric current can it is upper, Perpendicular to epitaxial layer injection device between lower electrode；The present invention is used with the more matched n-SiC of GaN lattice as substrate 1, remote small In its lattice mismatch between Sapphire Substrate, is conducive to the quality for improving GaN epitaxial layer, reduces dislocation density, improve device Part internal quantum efficiency；Using the carbon face SiC substrate 1 for having angle of chamfer, to ensure to obtain the more smooth nitrogen polarity extension in surface Film (including n-GaN layer 3, multiple quantum well layer 4, p-Alx1Ga1-x1N layer 5, p-GaN layer 6).
A kind of vertical structure nitrogen polar GaN base green LED chip based on carbon face SiC substrate as described above, feature Be: the angle of chamfer of the carbon face SiC substrate 1 is 2~4 °.
A kind of vertical structure nitrogen polar GaN base green LED chip based on carbon face SiC substrate as described above, feature Be: n-GaN electronics provides layer 3 and prepares using two step temperature growth methods, i.e., first low temperature (850~980 DEG C) is in n- Alx0Ga1-x0The low-temperature gan layer of 100~200nm of epitaxial growth thickness on N conductive buffer layer 2, then increase temperature (1050~1150 DEG C) continue n-GaN layers of high temperature of 2~3 μ m-thick of epitaxial growth.
A kind of preparation side of the vertical structure nitrogen polar GaN base green LED chip based on carbon face SiC substrate as described above Method, its step are as follows:
(1) successively outer using MOCVD method in the carbon face SiC substrate in N-shaped with angle of chamfer (angle of chamfer is 2~4 °) Prolong growth n-Alx0Ga1-x0N conductive buffer layer 2 (50~100nm of thickness), N-shaped GaN electronics provide (the first low-temperature epitaxy growth of layer 3 The n-GaN of 100~200nm thickness, then high temperature epitaxy grow 2~3 μ m-thicks n-GaN), 4 (quantum of InGaN based quantum well active area Trap is by well layer Inx2Ga1-x2N and barrier layer GaN alternating growth composition, logarithm between 2~5 pairs, each well layer with a thickness of 2~ 4nm, each barrier layer with a thickness of 10~15nm, wherein 0.2≤x2≤0.3), p-Alx1Ga1-x1(the thickness 20 of N electronic barrier layer 5 ~30nm), p-GaN hole injection layer 6 (150~200nm of thickness), so that nitrogen polar GaN base green light LED knot be prepared Structure；Growth source is trimethyl aluminium, triethyl-gallium, trimethyl gallium and high-purity ammonia, and growth temperature is 710~1100 DEG C, growth pressure By force it is 100~400mbar, and carries out N-shaped and the doping of p type, doping concentration 10 respectively using silane and two luxuriant magnesium17~1020/ cm3；
(2) top electrode 7 (10~30nm of thickness) is prepared on p-GaN hole injection layer 6, has the carbon of angle of chamfer in N-shaped Face surface on back side of SiC substrate prepares lower electrode layer 8 (60~100nm of thickness)；Electrode material can be the pure metals such as Au, Ni or Ni- The binary alloy materials such as Au, Ti-Au, Zn-Au, Pt-Au are also possible to the ternarys such as Ti-Pt-Au, Ti-Ni-Au or Ni-Pt-Au Hot evaporation, electron beam evaporation plating or magnetically controlled sputter method can be used in alloy material, the method for preparing electrode.
Effect and benefit of the invention: the present invention uses carbon face SiC as substrate, to obtain the polar GaN base green light of nitrogen LED component, compared with traditional gallium polar GaN device, nitrogen polarity LED structure designs the raising for being more advantageous to device efficiency.? In nitrogen polarity LED structure, the polarized electric field direction and additional forward bias in Quantum Well are contrary, to weaken in Quantum Well Quantum confined stark effect, improve the internal quantum efficiency of device；Due to polarized electric field opposite in nitrogen polarity LED, quantum Effective potential barrier of 5 interface of trap active area 4 and electronic barrier layer is greatly improved, and the spilling of electronics can be preferably inhibited, into The internal quantum efficiency of one step raising device；In addition, polarized electric field in nitrogen polarity LED structure in electronic barrier layer 5 and it is additional just It is consistent to bias direction, facilitate the injection in hole, reduces the cut-in voltage of device.Meanwhile vertical structure LED can effectively be kept away Exempt from electric current congestion effect.The method of the present invention can obtain efficient GaN base green light LED, further promote GaN base green light LED Development and its application.The cut-in voltage of device prepared by the present invention is about 3V.
Detailed description of the invention
Fig. 1: the structural schematic diagram of nitrogen polar GaN based vertical structure green light LED of the present invention；
Fig. 2: nitrogen polarity LED (Fig. 2 a) and gallium polarity LED (Fig. 2 b) structure simulation energy band diagram under forward bias；
Fig. 3: the internal quantum efficiency that nitrogen polarity LED and gallium polarity LED structure obtain in simulation drawing 2 becomes with applied driving current The relation curve of change.
Fig. 4: nitrogen polarity LED prepared by the embodiment 1 luminous spectrogram under the injection of different electric currents；
It is identified in figure, 1 is the carbon face N-shaped SiC substrate of 4 degree of angles of chamfer, and 2 be n-AlGaN conductive buffer layer, and 3 be n-GaN Electronics provides layer, and 4 be InGaN based quantum well active area, and 5 be p-AlGaN electronic barrier layer, and 6 be p-GaN hole injection layer, and 7 are Upper electrode layer, 8 be lower electrode layer.
Specific embodiment
Specific embodiments of the present invention are described in detail below in conjunction with technical solution and attached drawing.
Embodiment 1:
1. using MOCVD method, primary property extension prepares nitrogen polarity in the N-shaped carbon face SiC substrate of 4 ° of bevelings of purchase GaN base blue green light LED structure, as shown in Figure 1.Specific structure is as follows: 4 ° chamfer N-shaped carbon face SiC (doping concentration be 9 × 1018/cm3) 1 n-Al is sequentially prepared on substrate0.3Ga0.7N conductive buffer layer 2 (thickness 100nm), n-GaN electronics provide the (thickness of layer 3 2 μm of degree, doping concentration are 3 × 1018/cm3, wherein the n-GaN of first extension 200nm low temperature, then to increase temperature epitaxial remaining 1.8 μm of thick n-GaN), InGaN based quantum well active area 4 (Quantum Well logarithm is 2 pairs, i.e. trap-base-trap-barrier layer structure, Barrier layer is GaN, thickness 13nm, well layer In0.23Ga0.77N, thickness 2.5nm；), p-Al0.3Ga0.75 (thickness of N electronic barrier layer 20nm, doping concentration are 3 × 1020/cm3), p-GaN hole injection layer 6 (thickness 150nm, doping concentration 3.8 × 1020/cm3)。 Growth source is trimethyl aluminium, triethyl-gallium, trimethyl gallium and high-purity ammonia, carries out N-shaped and p-type respectively using silane and two luxuriant magnesium Doping, 2 growth temperature of AlGaN conductive buffer layer are 1100 DEG C, reaction pressure 100mbar；N-GaN electronics provides the first of layer 3 Beginning low temperature and subsequent high temperature growth temperature are respectively 980 DEG C and 1080 DEG C, and reaction pressure is all 100mbar；InGaN based quantum well The reaction pressure of active area 4 is 400mbar, and furthermore the growth temperature of barrier layer GaN and well layer InGaN are respectively 830 DEG C and 710 ℃；P-AlGaN electronic barrier layer 5 and p-GaN hole injection layer 6 growth temperature is all 945 DEG C, and reaction pressure is respectively 100mbar and 150mbar.The specific growth parameter(s) of device layers is shown in Table 1.
2. upper and lower surfaces be respectively adopted hot evaporation method preparation Ni/Au electrode layer 10 (60nm, Ni layers of thickness with a thickness of 30nm, Au layers with a thickness of 30nm) and Ni electrode layer 11 (thickness 80nm), realize vertical structure nitrogen polar GaN base blue green light LED. The specific preparation process of electrode is shown in Table 2.
3. Fig. 2 (b) is the simulation energy band diagram of nitrogen polarity LED structure under forward bias in embodiment 1, Fig. 2 (a) is identical Under the conditions of gallium polarity LED structure simulation energy band diagram, the EBL in figure indicates p-AlGaN electronic barrier layer 5.It can from figure It arrives, the electronic blocking effective barrier height in nitrogen polarity LED structure is 1.11eV, hence it is evident that corresponding higher than in gallium polarity LED 0.25eV, therefore can be very good to inhibit the spilling of electronics, improve the internal quantum efficiency of device.In addition, p-AlGaN layers of nitrogen polarity Polarized electric field direction in 5 is identical as additional forward bias, facilitates the injection in hole, reduces the cut-in voltage of device.
4. Fig. 3 is that the obtained internal quantum efficiency of nitrogen polarity LED structure is bent with the relationship of driving current in simulation embodiment 1 Line, and provide the analog result of gallium polarity LED structure under identical structure.It can be found that the internal quantum efficiency of nitrogen polarity LED is remote The phenomenon that higher than gallium polarity LED, and its internal quantum efficiency is with the increase of driving current, and hardly generation efficiency declines.From Analog result can be seen that the superiority of the present invention program.
5. Fig. 4 show electricity of the nitrogen polar GaN base blue green light LED prepared in embodiment 1 under different driving electric current Photoluminescence spectrum, the cathode of the lower electrode connection DC power supply of device, top electrode connection are positive at this time.Emission wavelength is at 480nm All show bluish-green glow peak.
Table 1: each layer growth parameter(s) of vertical structure nitrogen polar GaN base blue green light LED
Table 1 is attached with: TMGa represents trimethyl gallium；TEGa represents triethyl-gallium；TMAl represents trimethyl aluminium；Cp2Mg is represented Two luxuriant magnesium； SiH4Represent silane；NH3Represent high-purity ammonia.
Table 2: device electrode preparation technology parameter
Lower electrode Ni Top electrode first layer Ni Second of Au of top electrode
Evaporation time (second) 80 30 20
Cavity pressure (Pascal) 1.3×10-3 1.3×10-3 1.3×10-3
Thickness (nanometer) 80 30 30

Claims (3)

1. a kind of vertical structure nitrogen polar GaN base green LED chip based on carbon face SiC substrate, from bottom to up successively under Electrode layer (8), the carbon face SiC substrate (1) for being 2~4 ° with angle of chamfer of N-shaped, n-Alx0Ga1-x0N conductive buffer layer (2), n- GaN electronics provides layer (3), multiple quantum well active layer (4), p-Alx1Ga1-x1N electronic barrier layer (5), p-GaN hole injection layer (6) it is constituted with upper electrode layer (7), wherein 0.2≤x0, x1≤0.4；It is characterized by: it is two layers that n-GaN electronics, which provides layer (3), Structure, i.e., low temperature n-GaN layers and high temperature n-GaN layers；InGaN based quantum well active layer (4) is by well layer Inx2Ga1-x2N and barrier layer GaN alternating growth composition, logarithm is between 2~5 pairs, 0.2≤x2≤0.3；And the chip is prepared by following steps,
(1) MOCVD method successively epitaxial growth n-Al is used in the carbon face SiC substrate (1) with angle of chamfer of N-shapedx0Ga1- x0N conductive buffer layer (2), N-shaped GaN electronics provide layer (3), InGaN based quantum well active layer (4), p-Alx1Ga1-x1The resistance of N electronics Barrier (5), p-GaN hole injection layer (6)；Growth temperature is 710~1100 DEG C, and growth pressure is 100~400mbar, and sharp N-shaped and p-type doping, doping concentration 10 are carried out respectively with silane and two luxuriant magnesium17~1020/cm3；Wherein, n-GaN electronics provides Layer (3) prepared using two step temperature growth methods, i.e., prior to 850~980 DEG C in n-Alx0Ga1-x0N conductive buffer layer (2) The low-temperature gan layer of upper 100~200nm of epitaxial growth thickness, then at 1050~1150 DEG C continue 2~3 μ m-thick of epitaxial growth height It is n-GaN layers warm；
(2) it is prepared on p-GaN hole injection layer (6) upper electrode layer (7), prepares lower electrode layer (8) in n-SiC substrate back, To which the vertical structure nitrogen polar GaN base green LED chip based on carbon face SiC substrate be prepared.
2. a kind of vertical structure nitrogen polar GaN base green LED chip based on carbon face SiC substrate as described in claim 1, It is characterized in that: n-Alx0Ga1-x0N conductive buffer layer (2) with a thickness of 50~100nm, n-GaN layers of low temperature with a thickness of 100~ 200nm, n-GaN layers of high temperature with a thickness of 2~3 μm, each well layer In in InGaN based quantum well active layer (4)x2Ga1-x2N's With a thickness of 2~4nm, each barrier layer GaN with a thickness of 10~15nm, p-Alx1Ga1-x1N electronic barrier layer (5) with a thickness of 20~ 30nm, p-GaN hole injection layer (6) with a thickness of 150~200nm, upper electrode layer (7) with a thickness of 30~120nm, lower electrode Layer (8) with a thickness of 60~100nm.
3. the vertical structure nitrogen polar GaN base green LED chip based on carbon face SiC substrate as described in claim 1, feature Be: the method for preparing upper electrode layer (7) and lower electrode layer (8) is hot evaporation, electron beam evaporation plating or magnetically controlled sputter method.
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