CN110061109B - Porous GaN conductive DBR and preparation method thereof - Google Patents

Porous GaN conductive DBR and preparation method thereof Download PDF

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CN110061109B
CN110061109B CN201910342832.4A CN201910342832A CN110061109B CN 110061109 B CN110061109 B CN 110061109B CN 201910342832 A CN201910342832 A CN 201910342832A CN 110061109 B CN110061109 B CN 110061109B
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layer
gan
porous
porous gan
conductive dbr
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CN110061109A (en
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张宇
魏斌
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Shandong University
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Shandong University
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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
    • H01L33/10—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 light reflecting structure, e.g. semiconductor Bragg reflector
    • 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
    • H01L33/44—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 coatings, e.g. passivation layer or anti-reflective coating
    • H01L33/46—Reflective coating, e.g. dielectric Bragg reflector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S5/00—Semiconductor lasers
    • H01S5/10—Construction or shape of the optical resonator, e.g. extended or external cavity, coupled cavities, bent-guide, varying width, thickness or composition of the active region
    • H01S5/18—Surface-emitting [SE] lasers, e.g. having both horizontal and vertical cavities
    • H01S5/183—Surface-emitting [SE] lasers, e.g. having both horizontal and vertical cavities having only vertical cavities, e.g. vertical cavity surface-emitting lasers [VCSEL]
    • H01S5/18361—Structure of the reflectors, e.g. hybrid mirrors
    • H01S5/18363—Structure of the reflectors, e.g. hybrid mirrors comprising air layers
    • H01S5/18366—Membrane DBR, i.e. a movable DBR on top of the VCSEL

Abstract

The invention relates to a porous GaN conductive DBR and a preparation method thereof, comprising a substrate, a buffer layer, an unintended doped GaN layer, an n-type intentional doped gallium nitride layer and a porous GaN conductive DBR layer which are grown from bottom to top in sequence; the porous GaN conductive DBR layer is formed by alternately stacking a high-porosity porous GaN layer and a low-porosity porous GaN layer. The invention has no lattice mismatch problem, stable structure, and the porous GaN conductive DBR layer has the characteristics of high reflectivity, good conductivity and adjustable central wavelength.

Description

Porous GaN conductive DBR and preparation method thereof
Technical Field
The invention relates to a porous GaN conductive DBR and a preparation method thereof, belonging to the technical field of photoelectricity.
Background
The wide band gap III nitride semiconductor material has unique physical characteristics of wide band gap, capacity of covering infrared to ultraviolet band, powerful breakdown field, high temperature resistance, acid and alkali resistance, etc. and may be used widely in photoelectron, power electronic field, etc. in lighting, display, medical treatment, etc. With the continuous and deep research on gallium nitride materials and devices, gallium nitride optoelectronic devices must be applied to more optoelectronic fields, such as high-end lighting, optical communication, laser display, etc. Therefore, the technology which is simple and low in cost is developed by deeply researching the structural design of the prepared high-reflectivity conductive DBR, and the method has very important scientific significance and application value.
For nitride DBRs of AlN/GaN systems, the DBR cracks due to stress caused by lattice mismatching of the AlGaN/GaN DBR structure, and meanwhile, the conductivity of the AlGaN material is poor, so that the photoelectric performance of the device is affected. Although the AlInN and GaN can be lattice-matched by adjusting the ratio of Al and In the AlInN/GaN DBR, because the growth speed of AlInN is slow, and the refractive indexes of AlGaN, AlInN and GaN are relatively close, dozens of pairs of AlGaN/GaN with the thickness of 1/4 lambda are often needed, and a long growth time is needed, the DBR growth procedure is complex, the conditions are harsh, and the repetition rate is not high.
The highest reflectivity of the DBR with the GaN/Air structure prepared by etching the conductive GaN layer through the conductivity selective electrochemical etching technology is over 50 percent, but the DBR with the GaN/Air structure is unstable and non-conductive.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the porous GaN conductive DBR and the preparation method thereof, the problem of lattice mismatch is avoided, the structure is stable, and the porous GaN conductive DBR layer has the characteristics of high reflectivity, good conductivity and adjustable central wavelength.
Interpretation of terms:
dbr (distributed Bragg reflection), also called distributed Bragg mirror, is a periodic structure of two materials of different refractive index alternately arranged in ABAB fashion, each having an optical thickness of 1/4 times the central reflection wavelength.
The invention adopts the following technical scheme:
a porous GaN conductive DBR comprises a substrate, a buffer layer, an unintended doped GaN layer, an n-type intentionally doped gallium nitride layer and a porous GaN conductive DBR layer which are sequentially grown from bottom to top;
the porous GaN conductive DBR layer is formed by alternately stacking a high-porosity porous GaN layer and a low-porosity porous GaN layer, the period is preferably more than 5, the high porosity means the porosity is more than 30%, the low porosity means the porosity is less than 20% (including 0, namely no porosity), the pores are air pores (pores are formed by electrochemical corrosion after semiconductor doping, and are filled with air), and a certain refractive index difference is generated between the porous GaN layers due to the introduction of the air pores.
The reflectivity of the porous GaN conductive DBR layer near the luminous peak exceeds 50%, and the peak intensity, the full width at half maximum and the wavelength can be changed by adjusting the layer thickness and the periodicity, for example, the peak intensity can be increased and the full width at half maximum by increasing the (light and heavy doping) layer thickness and periodicity, the wavelength can be moved to the right, but the increase degree is different by changing different parameters, and the periodicity and the layer thickness can be designed according to requirements.
Preferably, the porous GaN conductive DBR layer includes 5 pairs or more of high-porosity porous GaN layers and low-porosity porous GaN layers alternately stacked.
Preferably, the dopant of the n-type doped GaN layer is silicon or germanium, and the doping concentration is 1 × 1018～5×1019cm-3Preferably 3X 1018cm-3。
Preferably, the high-porosity porous GaN layer and the low-porosity porous GaN layer are obtained by respectively etching the n-type heavily doped GaN layer and the n-type lightly doped GaN layer which are alternately stacked by adopting an electrochemical etching method, and the doping agent of the n-type lightly doped GaN layer and the n-type heavily doped GaN layer is silicon or germanium.
According to the invention, the alternating GaN layers with different high and low doping concentrations are adopted, and the porous GaN conductive DBR layer formed after corrosion has the characteristics of high reflectivity, good conductivity and adjustable central wavelength through selective electrochemical corrosion.
Preferably, the doping concentration of the n-type heavily doped GaN layer is 5 × 1018～1×1020cm-3Preferably 1X 1019cm-3The doping concentration of the n-type lightly doped GaN layer is 1 × 1016～5×1018cm-3Preferably 5X 1016cm-3。
Preferably, the porous GaN conductive DBR layer incorporates an indium or aluminum component, which may be GaN, AlGaN, InGaN, or AlInGaN.
Preferably, the aperture of the porous GaN conductive DBR layer is 1 nm-300 nm, and the aperture sizes of the high-porosity porous GaN layer and the low-porosity porous GaN layer are the same, and are all within the above range.
Preferably, the buffer layer is unintentionally doped with GaN or AlN.
Preferably, the substrate is sapphire, silicon carbide (SiC) or glass, and the structure of the substrate is a plane or a pattern.
A preparation method of a porous GaN conductive DBR comprises the following steps:
(1) growing a buffer layer and an unintended doped GaN layer on a substrate;
(2) growing an n-type doped GaN layer on the unintentionally doped GaN layer;
(3) growing more than 5 pairs of n-type heavily doped GaN layers and n-type lightly doped GaN layers which are alternately stacked on the n-type doped GaN layer;
(4) and corroding the n-type heavily doped GaN layer and the n-type lightly doped GaN layer which are alternately stacked by utilizing an electrochemical corrosion method to form the multi-period porous GaN conductive DBR with the overlapped high-porosity porous GaN layer and the low-porosity GaN layer. The invention is longitudinal corrosion, the n-type heavily doped GaN layer and the n-type lightly doped GaN layer are corroded to form holes, the preparation method is simple, the cost is reduced, and the higher the doping concentration is, the higher the hole forming rate is.
Preferably, selective electrochemical corrosion solution is adopted in the step (4) for corrosion, and a suitable selective electrochemical corrosion solution is selected according to different materials, wherein the selective electrochemical corrosion solution is weak acid, weak base or neutral salt solution, and is preferably sodium hydroxide, hydrochloric acid, sodium chloride or sodium nitrate and the like.
According to the invention, selective electrochemical corrosion is carried out in weak acid, weak base or neutral salt solution, air holes are selectively formed in more than 30% of the n-type heavily doped GaN layer, so that the effective refractive index of the material is changed, air holes are formed in less than 20% of the n-type lightly doped layer, and a certain refractive index difference is generated between the porous GaN layers due to the introduction of the air holes.
In the present invention, the details are not described in detail, and the present invention can be carried out by using the prior art.
The invention has the beneficial effects that:
the porous GaN conductive DBR can fundamentally solve the technical barrier of poor conductive performance of the GaN DBR structure. Through selective electrochemical corrosion of the periodic structure formed by alternately stacking the light doping layers and the heavy doping layers, high-porosity porous GaN can be selectively formed in the n-type heavy doping GaN layer, the effective refractive index of the material of the layer is greatly changed, the effective refractive index of the n-type light doping GaN layer is slightly changed (or is not changed), so that great refractive index difference is formed, the influence on the conductivity of the structure is small, and the conductive DBR formed by alternately stacking the high-porosity porous GaN layer and the low-porosity porous GaN layer is formed.
The porous GaN conductive DBR only needs to be doped with GaN with periodically modulated concentration, and the porous GaN conductive DBR structure is prepared by adopting selective electrochemical corrosion, so that the problem of lattice mismatch is avoided, the reflectivity can easily reach over 90 percent, the repeatability is high, the realization process is simple, and the practical application is facilitated. The porous GaN conductive DBR structure can achieve good conductivity by modulating the structural parameters and the preparation process of the high-porosity porous GaN layer and the low-porosity or non-porous GaN layer, effectively improves the performance of the GaN resonant cavity optoelectronic device, simplifies the preparation process, and can adjust the peak intensity, the half-height width and the wavelength by adjusting the thickness and the periodicity of each layer of the DBR, thereby meeting the design and the requirements of the field of optoelectronic technology on the optical device.
The invention is longitudinal corrosion, only needs epitaxial growth layer structure and then corrosion, the preparation method is simple, and the cost is reduced.
Drawings
FIG. 1 is a schematic structural diagram of a porous GaN conductive DBR of the invention;
FIG. 2 is a schematic view of a method for fabricating a porous GaN conductive DBR according to the invention;
FIG. 3 is a schematic cross-sectional Scanning Electron Microscope (SEM) magnification of 20 ten thousand times of the porous GaN conductive DBR structure of the invention;
FIG. 4 is a graph of the reflection spectrum and simulation results of FIG. 3;
FIG. 5 is a schematic diagram showing the variation of reflectivity with wavelength for different thicknesses of the porous GaN conductive DBR;
FIG. 6 is a schematic diagram showing the current-voltage variation of different porous GaN conductive DBR samples;
the GaN-based light-emitting diode comprises a substrate 10, a buffer layer 11, an unintended doped GaN layer 12, an intentional doped GaN-based layer 13-n type and a conductive DBR layer 14-porous GaN.
The specific implementation mode is as follows:
in order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific examples, but not limited thereto, and the present invention is not described in detail and is in accordance with the conventional techniques in the art.
Example 1:
a porous GaN conductive DBR, as shown in FIG. 1, comprises a substrate 10, a buffer layer 11, an unintentionally doped GaN layer 12, an n-type intentionally doped gallium nitride layer 13 and a porous GaN conductive DBR layer 14 which are grown in sequence from bottom to top;
the porous GaN conductive DBR layer 14 is formed by alternately stacking 15 pairs of high-void-ratio porous GaN layers having a void ratio of 52% and low-void-ratio porous GaN layers having a void ratio of 0 (i.e., no voids).
Example 2:
a porous GaN conductive DBR is constructed as in example 1, except that the n-type doped GaN layer 13 is doped with silicon at a concentration of 3 × 1018cm-3。
Example 3:
a porous GaN conductive DBR is structurally shown in embodiment 1, except that a high-porosity porous GaN layer and a low-porosity porous GaN layer are obtained by respectively etching an n-type heavily doped GaN layer and an n-type lightly doped GaN layer which are alternately stacked by adopting an electrochemical etching method, dopants of the n-type heavily doped GaN layer and the n-type heavily doped GaN layer are silicon, the higher doping concentration is, the higher porosity is, as shown in FIG. 3, which is a scanning electron microscope schematic diagram of a cross section of the porous GaN conductive DBR structure amplified by 20 ten thousand times, pores formed by the electrochemically etched n-type heavily doped GaN layer are more uniform, and the pore diameter is between 1nm and 300 nm; the un-etched GaN layer is an n-type lightly doped GaN layer, the two layers of materials have refractive index difference due to the introduction of air holes, and are alternately stacked to form the porous GaN conductive DBR layer 14, fig. 4 is a reflection spectrum and a simulation result diagram of fig. 3, the abscissa of which is wavelength, the ordinate is reflectivity, the solid line represents a simulation value, and the dotted line represents a measurement value, and it can be seen from the diagram that the porous GaN conductive DBR layer 14 reaches a reflectivity peak near 467nm and has a wider reflection band.
In this embodiment, the doping concentration of the n-type heavily doped GaN layer is 1 × 1019cm-3The doping concentration of the n-type lightly doped GaN layer is 5 multiplied by 1016cm-3。
Fig. 5 is a schematic diagram showing the change of the reflectivity with the wavelength under different thicknesses of the porous GaN conductive DBR, the abscissa is the wavelength, the ordinate is the reflectivity, the curves in the diagram are respectively 20nm for the original porous GaN conductive DBR layer and the porous GaN conductive DBR layer, 40nm for the porous GaN conductive DBR layer, and 60nm for the porous GaN conductive DBR layer from bottom to top, and it can be seen from the diagram that the peak intensity, the full width at half maximum, and the wavelength can be adjusted by adjusting the thickness or the number of cycles of the porous GaN conductive DBR layer 14.
Example 4:
a porous GaN conductive DBR is constructed as in example 1, except that the 14-pore diameter of the porous GaN conductive DBR layer is between 1 and 300 nm.
Example 5:
a porous GaN conductive DBR is constructed as shown in example 1, except that the buffer layer 11 is a low temperature GaN nucleation layer, the GaN nucleation layer is grown at low temperature by using high purity nitrogen as nitrogen source, trimethyl gallium or triethyl gallium as Ga source; the substrate 10 is sapphire.
Example 6:
a method for manufacturing a porous GaN conductive DBR, as shown in fig. 2, comprising the steps of:
(1) growing a buffer layer 11 and an unintentionally doped GaN layer 12 on a substrate 10;
(2) growing an n-type doped GaN layer 13 on the unintentionally doped GaN layer 12;
(3) growing 15 pairs of n-type heavily doped GaN layers and n-type lightly doped GaN layers which are alternately stacked on the n-type doped GaN layer 13;
(4) and corroding the n-type heavily doped GaN layer and the n-type lightly doped GaN layer which are alternately stacked by utilizing an electrochemical corrosion method to form the multi-period porous GaN conductive DBR with the overlapped high-porosity porous GaN layer and the low-porosity GaN layer. The invention is longitudinal corrosion, the n-type heavily doped GaN layer and the n-type lightly doped GaN layer are corroded to form holes, the preparation method is simple, the cost is reduced, and the higher the doping concentration is, the higher the hole forming rate is.
In the step (4), a selective electrochemical etching solution is adopted for etching, sodium nitrate is selected as the selective electrochemical etching solution in the embodiment, the aperture of the obtained porous GaN conductive DBR layer 14 is 1-300 nm, and the reflectivity near the luminescence peak is more than 90%.
Fig. 6 is a schematic diagram showing the current-voltage variation of different porous GaN conductive DBR samples, with the abscissa representing voltage and the ordinate representing current, and the legend at the upper left corner in the diagram sequentially shows from top to bottom: the voltage and current curves of the non-etched DBR sample, the DBR sample formed when the etching voltage is 15V, the DBR sample formed when the etching voltage is 18V and the DBR sample formed when the etching voltage is 22V can be seen from the graph, the current curve of the porous GaN conductive DBR formed after the selective electrochemical etching is not very different from the current curve of the non-etched DBR, namely the selective electrochemical etching has little influence on the conductivity of the structure.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (7)

1. A porous GaN conductive DBR is characterized by comprising a substrate, a buffer layer, an unintended doped GaN layer, an n-type intentional doped gallium nitride layer and a porous GaN conductive DBR layer which are sequentially grown from bottom to top;
the porous GaN conductive DBR layer is formed by alternately stacking a high-porosity porous GaN layer and a low-porosity porous GaN layer;
the porous GaN conductive DBR layer comprises more than 5 pairs of high-porosity porous GaN layers and low-porosity porous GaN layers which are alternately stacked, the porosity of the high-porosity porous GaN layers is more than 30%, and the porosity of the low-porosity porous GaN layers is 20%;
the high-porosity porous GaN layer and the low-porosity porous GaN layer are obtained by respectively corroding the n-type heavily doped GaN layer and the n-type lightly doped GaN layer which are alternately stacked by adopting an electrochemical corrosion method, and the doping agents of the n-type heavily doped GaN layer and the n-type lightly doped GaN layer are silicon or germanium;
the preparation method of the porous GaN conductive DBR comprises the following steps:
(1) growing a buffer layer and an unintended doped GaN layer on a substrate;
(2) growing an n-type doped GaN layer on the unintentionally doped GaN layer;
(3) growing more than 5 pairs of n-type heavily doped GaN layers and n-type lightly doped GaN layers which are alternately stacked on the n-type doped GaN layer;
(4) and performing longitudinal corrosion on the alternately stacked n-type lightly doped GaN layer and n-type heavily doped GaN layer by using an electrochemical corrosion method to form the multi-period porous GaN conductive DBR with overlapped high-porosity porous GaN layers and low-porosity GaN layers.
2. The porous GaN conductive DBR of claim 1, wherein the n-type doped GaN layer is doped with silicon or germanium at a concentration of 1 x 1018～5×1019cm-3。
3. The porous GaN conductive DBR of claim 1 wherein the pore size of the porous GaN conductive DBR layer is between 1nm and 300 nm.
4. The porous GaN conductive DBR of claim 1 wherein the buffer layer is unintentionally doped GaN or AlN.
5. The porous GaN conductive DBR of claim 1 wherein the substrate is sapphire, silicon carbide, or glass and the structure of the substrate is planar or patterned.
6. The porous GaN conductive DBR of claim 1 wherein step (4) is etched using a selective electrochemical etching solution that is a weak acid, weak base or neutral salt solution.
7. The porous GaN conductive DBR of claim 6, wherein the selective electrochemical etching solution is sodium hydroxide, hydrochloric acid, sodium chloride, or sodium nitrate.
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CN111433921B (en) * 2019-12-16 2023-08-15 厦门三安光电有限公司 Light-emitting diode
CN112002788A (en) * 2020-09-03 2020-11-27 中国科学院半导体研究所 III-nitride-based distributed Bragg reflector and preparation method thereof
CN112510129B (en) * 2020-11-10 2023-08-01 晶能光电股份有限公司 GaN-based vertical LED chip and preparation method thereof
CN117012874A (en) * 2022-04-27 2023-11-07 华为技术有限公司 Light-emitting chip, display module, electronic equipment and processing method of light-emitting chip

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WO2011094391A1 (en) * 2010-01-27 2011-08-04 Yale University Conductivity based selective etch for gan devices and applications thereof
CN106848016A (en) * 2017-04-06 2017-06-13 中国科学院半导体研究所 The preparation method of the porous DBR of GaN base
CN107895690A (en) * 2017-12-06 2018-04-10 肖之光 A kind of preparation method of large area, high reflectance gallium nitride/nanoporous gallium nitride distribution Bragg reflector

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011094391A1 (en) * 2010-01-27 2011-08-04 Yale University Conductivity based selective etch for gan devices and applications thereof
CN106848016A (en) * 2017-04-06 2017-06-13 中国科学院半导体研究所 The preparation method of the porous DBR of GaN base
CN107895690A (en) * 2017-12-06 2018-04-10 肖之光 A kind of preparation method of large area, high reflectance gallium nitride/nanoporous gallium nitride distribution Bragg reflector

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