CN110137277B - Nonpolar self-supporting GaN-based pin ultraviolet photoelectric detector and preparation method thereof - Google Patents

Nonpolar self-supporting GaN-based pin ultraviolet photoelectric detector and preparation method thereof Download PDF

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CN110137277B
CN110137277B CN201910281833.2A CN201910281833A CN110137277B CN 110137277 B CN110137277 B CN 110137277B CN 201910281833 A CN201910281833 A CN 201910281833A CN 110137277 B CN110137277 B CN 110137277B
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尹以安
李锴
曾妮
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Jiangsu Third Generation Semiconductor Research Institute Co Ltd
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South China Normal University
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Abstract

The invention discloses a nonpolar self-supporting GaN-based pin ultraviolet photoelectric detector and a preparation method thereof, wherein the detector comprises a nonpolar self-supporting GaN substrate, an n-type GaN layer and an n-type Alx1Ga1‑x1N graded layer, intrinsic Alx2Ga1‑x2N-layer, p-type Aly1Ga1‑y1N/Aly2Ga1‑y2The N superlattice layer and the p-type GaN cover layer are sequentially arranged from bottom to top; the back surface of the nonpolar self-supporting GaN substrate is connected with an n-type ohmic electrode; the upper surface of the p-type GaN cover layer is connected with the p-type ohmic electrode. The detector solves the problems of large polarization electric field, lattice mismatch between an epitaxial layer and a substrate, difficult p-type doping and uneven internal electric field, and simplifies the preparation process of the ultraviolet photoelectric detector chip.

Description

Nonpolar self-supporting GaN-based pin ultraviolet photoelectric detector and preparation method thereof
Technical Field
The invention relates to the technical field of semiconductor devices, in particular to a nonpolar self-supporting GaN-based pin ultraviolet photoelectric detector and a preparation method thereof.
Background
The ultraviolet detection technology is a novel photoelectric detection technology, is widely applied to the fields of accurate guidance, ultraviolet high-confidentiality communication and the like in national defense and military, and is applied to environmental pollution monitoring, biological analysis, astronomy, flame detection and the like in a civil direction. Gallium nitride (GaN) and series materials thereof are used as third-generation semiconductors, have the advantages of large forbidden bandwidth and wide spectral range, and have great application value in the field of photoelectronics. The GaN-based ternary alloy AlGaN belongs to a direct band gap semiconductor, the band gap can continuously change along with the Al component from 3.4eV to 6.2eV, the corresponding peak response wavelength range of the band gap is 200 nm-365 nm, and the peak response wavelength range just covers a solar spectrum blind area (220-290 nm) generated by absorbing ultraviolet light by an ozone layer, so that the AlGaN is one of ideal materials for manufacturing a solar blind ultraviolet detector.
At present, AlGaN/GaN ultraviolet photodetectors still have problems, for example, the AlGaN material with high Al component has strong polarization, which affects the external quantum efficiency of the device and reduces the responsivity of the ultraviolet detector; larger lattice mismatch exists between the AlGaN epitaxial layer and the sapphire substrate, and the corresponding photoelectric detector epitaxial structure has high dislocation density, so that the dark current of the device can be increased; the P-type dopant Mg has a large activation energy in the AlGaN material having a high Al composition, and it is difficult to obtain P-type AlGaN having a high concentration. In addition, when the detection device works in a reverse bias mode, an uneven electric field exists inside the detection device, and collection of photon-generated carriers is not facilitated; and the area with high electric field density is easy to break down when the device works at high voltage, so that the device is broken down and damaged. The above problems limit its application to some extent.
The nonpolar self-supporting GaN substrate is widely concerned at present, and has a very good application prospect in the aspects of preparing LEDs, photoelectric detectors and power devices. Compared with the sapphire substrate commonly used in the ultraviolet photoelectric detector in recent years, the nonpolar self-supporting GaN substrate has great advantages. First, direct epitaxy of GaN layers on nonpolar free-standing GaN substrates is a lattice matched growth that enables high quality epitaxial materials with low defect densities to be obtained. Second, compared to sapphire substrates, nonpolar self-supporting GaN substrates have good electrical conductivity, which can enhance the heat dissipation of the uv photodetector. And thirdly, the nonpolar self-supporting GaN substrate has good conductivity, and an electrode can be evaporated on the back surface of the substrate, so that two ohmic contacts are arranged on different sides of the substrate, thereby realizing a vertical conduction structure and avoiding the breakdown and damage of a device caused by current gathering in one region. The high potential barrier of the pin ultraviolet photoelectric detector enables the dark current of the pin ultraviolet photoelectric detector to be lower, the pin ultraviolet photoelectric detector can work under low bias, the response speed is high, the high impedance is suitable for a focal plane array reading circuit, and therefore the pin ultraviolet photoelectric detector is superior to ultraviolet photoelectric detectors with other structures in performance. In order to better solve the problems, a nonpolar self-supporting GaN-based pin ultraviolet photoelectric detector and a preparation method are provided.
Disclosure of Invention
In order to solve the defects of the prior art, the present invention provides a pin ultraviolet photodetector based on a nonpolar self-supporting GaN substrate and a method for manufacturing the same, so as to solve the problems of large polarization electric field, lattice mismatch between an epitaxial layer and the substrate, difficult p-type doping, and uneven internal electric field in the background art, and simplify the manufacturing process of the ultraviolet photodetector chip.
To achieve the above object, the present invention provides the following solutions.
The invention provides a nonpolar self-supporting GaN-based pin ultraviolet photoelectric detector which comprises a nonpolar self-supporting GaN substrate, an n-type GaN layer and an n-type Alx1Ga1-x1N graded layer, intrinsic Alx2Ga1-x2N-layer, p-type Aly1Ga1-y1N/Aly2Ga1-y2The N-type GaN-based super-lattice thin film transistor comprises an N-type super-lattice layer, a p-type GaN cover layer, an N-type ohmic electrode and a p-type ohmic electrode; the n-type GaN layer and the n-type Al layerx1Ga1-x1N graded layer, intrinsic Alx2Ga1-x2N-layer, p-type Aly1Ga1-y1N/Aly2Ga1-y2The N superlattice layer and the p-type GaN cover layer are sequentially arranged on the front surface of the nonpolar self-supporting GaN substrate from bottom to top; the back surface of the nonpolar self-supporting GaN substrate is connected with an n-type ohmic electrode; the upper surface of the p-type GaN cover layer is connected with the p-type ohmic electrode.
Preferably, the thickness of the nonpolar self-supporting GaN substrate is 300-500 μm.
Preferably, the thickness of the n-type GaN layer is 100-250 nm.
Preferably, the n-type Alx1Ga1-x1The Al component x1 of the N gradual change layer linearly increases according to a uniform gradient from bottom to top, the Al component of the lowest layer is 0, the Al component of the uppermost layer is 0.3-0.4, and the N type Alx1Ga1-x1The total thickness of the N gradient layer is 100-350 nm.
Preferably, the intrinsic Alx2Ga1-x2The thickness of the N layer is 250-350 nm, and x2 meets the condition that x2 is more than or equal to x 1.
Preferably, the p-type Aly1Ga1-y1N/Aly2Ga1-y2Al in N superlattice layery1Ga1-y1N layer and Aly2Ga1-y2N layers grow alternately and are repeated for 1-10 periods, and in each period, Al is addedy1Ga1-y1The thickness of the N layer is 1-20 nm, and Aly2Ga1-y2The thickness of the N layer is 1-20 nm, and Aly1Ga1-y1N layer constituting a potential barrier, Aly2Ga1-y2The N layer forms a potential well, the width of the potential barrier or the potential well is 1-100 nm, and y1 and y2 satisfy that y1 is larger than y2 and is larger than or equal to x 2.
Preferably, the thickness of the p-type GaN cover layer is 20-40 nm.
Preferably, the n-type ohmic electrode is a Ti/Al/Ni/Au alloy electrode.
Preferably, the p-type ohmic electrode is a Ni/Au alloy electrode.
The invention also provides a preparation method of the nonpolar self-supporting GaN-based pin ultraviolet photodetector, which comprises the following preparation steps:
(1) utilizing hydride chemical vapor deposition to deposit a nonpolar self-supporting GaN substrate, the substrate having a room temperature resistivity of less than 0.05 Ω -cm;
(2) adopts MOCVD method, trimethyl gallium TMGa is used as gallium source, high purity NH3As ammonia source, an n-type GaN layer with a doping concentration of 5 × 10 is grown on the front surface of the nonpolar self-supporting GaN substrate18～1×1019cm-3；
(3) Growing n-type Al with gradually changed Al component on the n-type GaN layer by Al ion implantationx1Ga1-x1A graded N layer with a doping concentration of 5 × 1018～1×1019cm-3The Al component x1 gradually increases from bottom to top, the Al component at the lowest layer is 0, the Al component at the uppermost layer is 0.3-0.4, and the n-type Al isx1Ga1-x1The N gradient layers grow 5-10 layers in total;
(4) in n-type Alx1Ga1-x1Growing a layer of unintentionally doped intrinsic Al on the N-graded layerx2Ga1-x2N layers;
(5) in intrinsic Alx2Ga1-x2Growing p-type Al on the N layer by MOCVD methody1Ga1-y1N/Aly2Ga1-y2N superlattice layer with doping concentration of 1 × 1018～5×1018cm-3；
(6) In p-type Aly1Ga1-y1N/Aly2Ga1-y2A p-type GaN cover layer with the doping concentration of 1 × 10 is grown on the N superlattice layer18～5×1018cm-3；
(7) Manufacturing an ohmic contact N-type electrode by electron beam evaporation, thinning the nonpolar self-supporting GaN substrate to 100-150 mu m, evaporating an N-type ohmic electrode on the back of the nonpolar self-supporting GaN substrate, wherein the N-type ohmic electrode is a Ti/Al/Ni/Au alloy electrode, and evaporating N at 850-900 ℃ after evaporation2Annealing for 2-3 minutes in the environment;
(8) manufacturing a p-type electrode in ohmic contact by electron beam excitation, evaporating the p-type ohmic electrode on a p-type GaN cover layer, wherein the p-type ohmic electrode is a Ni/Au alloy electrode, and evaporating the N-type ohmic electrode at 600-700 ℃ after evaporation2Annealing for 3-5 minutes in the environment.
Compared with the prior art, the invention has the following beneficial effects:
the non-polar self-supporting GaN substrate is relied on to reduce the lattice mismatch with the epitaxial layer, so that the dark current is reduced, the recombination center generated in the device is reduced, the quantum efficiency of the device is improved, the vertical conduction structure is realized by evaporating the ohmic electrode on the back surface of the substrate, the internal electric field is more uniform, the heat dissipation performance of the device is enhanced, and the risk of breakdown and damage of the device is reduced. By means of n-type Alx1Ga1-x1The N gradual change layer enables the conduction band order of a heterogeneous interface to be relaxed, and intrinsic Al is reducedx2Ga1-x2Lattice mismatch between the N layer and the N-type GaN layer reduces a polarization electric field, and improves collection efficiency of photon-generated carriers, thereby improving responsivity of the ultraviolet detector. The activation energy of p-type doped Mg is reduced by depending on the superlattice, and the ionization rate of Mg element is improved, so that the p-type doping concentration is improved.
Drawings
Fig. 1 is a schematic diagram of a nonpolar self-supporting GaN-based pin ultraviolet photodetector provided by an embodiment.
Detailed Description
The following further describes the practice of the present invention in conjunction with the drawings and examples, but the practice and protection of the present invention is not limited thereto.
The invention provides a nonpolar self-supporting GaN-based pin ultraviolet photodetector. Referring to FIG. 1, the detector includes a nonpolar free-standing GaN substrate 101, an n-type GaN layer 102, and n-type Alx1Ga1-x1N graded layer 103, intrinsic Al0.4Ga0.6 N layer 104, p-type Al0.45Ga0.55N/Al0.4Ga0.6An N-superlattice layer 105, a p-type GaN cap layer 106, an N-type ohmic electrode 107 and a p-type ohmic electrode 108. Wherein the thickness of the nonpolar self-supporting GaN substrate 101 is 300 μm; an n-type GaN layer 102 with a thickness of 100nm and a doping concentration of 5 × 10 is disposed on the front surface of the nonpolar self-supporting GaN substrate 10118cm-3(ii) a n type Alx1Ga1-x1An N graded layer 103 with a thickness of 100nm and a doping concentration of 5 × 10 is disposed on the N-type GaN layer 10218cm-3(ii) a n type Alx1Ga1-x1The Al component of the N-graded layer 103 gradually increases from bottom to top, and the N-type Alx1Ga1-x1The N gradual change layer 103 grows 5 layers together, and the Al component x1 of each layer from bottom to top is 0, 0.1, 0.2, 0.3 and 0.4 respectively; intrinsic Al0.4Ga0.6N layer 104 on N-type Alx1Ga1-x1The thickness of the N gradual change layer 103 is 350 nm; p type Al0.45Ga0.55N/Al0.4Ga0.6The N-superlattice layer 105 is located on the intrinsic Al0.4Ga0.6On the N layer 104, the p-type Aly1Ga1-y1N/Aly2Ga1-y2Al in N-superlattice layer 105y1Ga1-y1N layer and Aly2Ga1-y2N layers were grown alternately and repeated for 10 cycles, Al in each cycle0.4Ga0.6The thickness of the N layer is 4nm, Al0.45Ga0.55The thickness of the N layer is 4nm, Aly1Ga1-y1N layer constituting a potential barrier, Aly2Ga1-y2The N layers form a potential well, the width of the potential barrier or the potential well is 10nm, and the doping concentration is 3 multiplied by 1018cm-3；
The p-type GaN cap layer 106 is located on the p-type Al0.45Ga0.55N/Al0.4Ga0.6A 30nm thick N-type superlattice layer 105 with a doping concentration of 3 × 1018cm-3(ii) a The n-type ohmic electrode 107 is positioned on the back surface of the thinned nonpolar self-supporting GaN substrate 101, the n-type ohmic electrode 107 is a Ti/Al/Ni/Au alloy electrode, and the thicknesses of Ti, Al, Ni and Au in the Ti/Al/Ni/Au alloy electrode are respectively 20nm, 120nm, 20nm and 200 nm; the p-type ohmic electrode 108 is positioned on the p-type GaN cover layer 106, the p-type ohmic electrode 108 is a Ni/Au alloy electrode, and the thickness of a Ni layer and the thickness of an Au layer in the Ni/Au alloy electrode are respectively 20nm and 200 nm.
The embodiment also provides a preparation method of the nonpolar self-supporting GaN-based pin ultraviolet photodetector, which comprises the following preparation steps:
(1) using hydride chemical vapor deposition of a nonpolar free standing GaN substrate 101 having a room temperature resistivity of less than 0.05 Ω -cm;
(2) adopts MOCVD method, trimethyl gallium TMGa is used as gallium source, high purity NH3As an ammonia source, an n-type GaN layer 102 with a doping concentration of 5X 10 was grown on the front surface of the nonpolar self-supporting GaN substrate 10118cm-3；
(3) Growing n-type Al with gradually changed Al components on the n-type GaN layer 102 by multiple Al ion implantations with different energies and dosagesx1Ga1-x1A graded N layer 103 with a doping concentration of 5 × 1018cm-3Said n-type Alx1Ga1-x1The N gradual change layer 103 grows 5 layers together, and the Al component x1 of each layer from bottom to top is 0, 0.1, 0.2, 0.3 and 0.4 respectively;
(4) in n-type Alx1Ga1-x1Growing a layer of unintentionally doped intrinsic Al on the N-graded layer 1030.4Ga0.6An N layer 104;
(5) in intrinsic Al0.4Ga0.6Growing p-type Al on the N layer 104 by MOCVD method0.45Ga0.55N/Al0.4Ga0.6An N-type superlattice layer 105 with a doping concentration of 3 × 1018cm-3；
(6) In p-type Al0.45Ga0.55N/Al0.4Ga0.6A p-type GaN cap layer 106 with a doping concentration of 3 × 10 is grown on the N-type superlattice layer 10518cm-3；
(7) Will be notThinning the polar self-supporting GaN substrate 101 to 100 mu m, evaporating an N-type ohmic electrode 107 on the back surface of the thinned nonpolar self-supporting GaN substrate 101, wherein the N-type ohmic electrode 107 is a Ti/Al/Ni/Au alloy electrode, and evaporating N at 850 ℃ after evaporation2Annealing for 2 minutes under the environment;
(8) evaporating a p-type ohmic electrode 108 on the p-type GaN capping layer 106, wherein the p-type ohmic electrode 108 is a Ni/Au alloy electrode, and evaporating N at 600 DEG after evaporation2Anneal for 3 minutes at ambient.
The invention reduces lattice mismatch with the epitaxial layer by depending on the nonpolar self-supporting GaN substrate, thereby reducing dark current, reducing recombination centers generated in the device, improving the quantum efficiency of the device, realizing a vertical conduction structure by evaporating the ohmic electrode on the back of the substrate, enabling an internal electric field to be more uniform, enhancing the heat dissipation performance of the device and reducing the risk of breakdown and damage of the device. By means of n-type Alx1Ga1-x1The N gradual change layer enables the conduction band order of a heterogeneous interface to be relaxed, and intrinsic Al is reducedx2Ga1-x2Lattice mismatch between the N layer and the N-type GaN layer reduces a polarization electric field, and improves collection efficiency of photon-generated carriers, thereby improving responsivity of the ultraviolet detector. The activation energy of p-type doped Mg is reduced by depending on the superlattice, and the ionization rate of Mg element is improved, so that the p-type doping concentration is improved.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (10)

1. The nonpolar self-supporting GaN-based pin ultraviolet photoelectric detector is characterized by comprising a nonpolar self-supporting GaN substrate (101), an n-type GaN layer (102), and an n-type Alx1Ga1-x1N graded layer (103), intrinsic Alx2Ga1-x2N layer (104), p-type Aly1Ga1- y1N/Aly2Ga1-y2An N superlattice layer (105), a p-type GaN cover layer (106), an N-type ohmic electrode (107) and a p-type ohmic electrode (108); the n typeGaN layer (102), n-type Alx1Ga1-x1N graded layer (103), intrinsic Alx2Ga1-x2N layer (104), p-type Aly1Ga1-y1N/Aly2Ga1-y2The N superlattice layer (105) and the p-type GaN cover layer (106) are sequentially arranged on the front surface of the nonpolar self-supporting GaN substrate (101) from bottom to top; the back surface of the nonpolar self-supporting GaN substrate (101) is connected with an n-type ohmic electrode (107); the upper surface of the p-type GaN capping layer (106) is connected with a p-type ohmic electrode (108).
2. The nonpolar self-supporting GaN-based pin ultraviolet photodetector according to claim 1, characterized in that the thickness of the nonpolar self-supporting GaN substrate (101) is 300-500 μm.
3. The non-polar self-supporting GaN-based pin ultraviolet photodetector of claim 1, wherein the thickness of the n-type GaN layer (102) is 100-250 nm.
4. The nonpolar self-supporting GaN-based pin ultraviolet photodetector of claim 1, wherein the n-type Al isx1Ga1-x1The Al component x1 of the N gradual change layer (103) is linearly increased according to a uniform gradient from bottom to top, the Al component at the lowest layer is 0, the Al component at the uppermost layer is 0.3-0.4, and N-type Alx1Ga1-x1The total thickness of the N-graded layer (103) is 100 to 350 nm.
5. The nonpolar self-supporting GaN-based pin ultraviolet photodetector of claim 1, wherein the intrinsic Al isx2Ga1-x2The thickness of the N layer (104) is 250-350 nm, and x2 meets the condition that x2 is more than or equal to x 1.
6. The nonpolar self-supporting GaN-based pin ultraviolet photodetector of claim 1, wherein the p-type Al isy1Ga1-y1N/Aly2Ga1-y2Al in the N-superlattice layer (105)y1Ga1-y1N layer and Aly2Ga1-y2N layers grow alternately and are repeated for 1-10 periodsIn each cycle, Aly1Ga1-y1The thickness of the N layer is 1-20 nm, and Aly2Ga1-y2The thickness of the N layer is 1-20 nm, and Aly1Ga1-y1N layer constituting a potential barrier, Aly2Ga1-y2The N layer forms a potential well, the width of the potential barrier or the potential well is 1-100 nm, and y1 and y2 satisfy that y1 is larger than y2 and is larger than or equal to x 2.
7. The nonpolar self-supporting GaN-based pin ultraviolet photodetector of claim 1, wherein the thickness of the p-type GaN cap layer (106) is 20-40 nm.
8. The non-polar self-supporting GaN-based pin ultraviolet photodetector of claim 1, characterized in that the n-type ohmic electrode (107) is a Ti/Al/Ni/Au alloy electrode.
9. The non-polar self-supporting GaN-based pin ultraviolet photodetector of claim 1, characterized in that the p-type ohmic electrode (108) is a Ni/Au alloy electrode.
10. A method of manufacturing a non-polar self-supporting GaN-based pin ultraviolet photodetector according to any of claims 1 to 9, comprising the steps of:
(1) using hydride chemical vapor deposition of a nonpolar free standing GaN substrate (101) having a room temperature resistivity of less than 0.05 Ω -cm;
(2) adopts MOCVD method, trimethyl gallium TMGa is used as gallium source, high purity NH3As an ammonia source, an n-type GaN layer (102) is grown on the front surface of the nonpolar self-supporting GaN substrate (101) with a doping concentration of 5 × 1018～1×1019cm-3；
(3) Growing n-type Al with x1 gradually changed on the n-type GaN layer (102) by Al ion implantationx1Ga1-x1A N graded layer (103) with a doping concentration of 5 × 1018～1×1019cm-3The Al component x1 gradually increases along the direction from bottom to top, the Al component at the lowest layer is 0, the Al component at the uppermost layer is 0.3-0.4, and the n-type Alx1Ga1-x1The N gradual change layers (103) grow 5-10 layers together;
(4) in n-type Alx1Ga1-x1Growing an unintentionally doped intrinsic Al layer on the N graded layer (103)x2Ga1-x2An N layer (104);
(5) in intrinsic Alx2Ga1-x2Growing p-type Al on the N layer (104) by adopting an MOCVD methody1Ga1-y1N/Aly2Ga1-y2An N-type superlattice layer (105) with a doping concentration of 1 × 1018～5×1018cm-3；
(6) In p-type Aly1Ga1-y1N/Aly2Ga1-y2A p-type GaN cover layer (106) is grown on the N superlattice layer (105) with the doping concentration of 1 × 1018～5×1018cm-3；
(7) Thinning the nonpolar self-supporting GaN substrate (101) to 100-150 mu m, evaporating an N-type ohmic electrode (107) on the back surface of the thinned nonpolar self-supporting GaN substrate (101), wherein the N-type ohmic electrode (107) is a Ti/Al/Ni/Au alloy electrode, and evaporating N at 850-900 ℃ after evaporation2Annealing for 2-3 minutes in the environment;
(8) evaporating a p-type ohmic electrode (108) on the p-type GaN capping layer (106), wherein the p-type ohmic electrode (108) is a Ni/Au alloy electrode, and evaporating N at 600-700 ℃ after evaporation2Annealing for 3-5 minutes in the environment.
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