CN113675284B - Wide-band ultraviolet detector based on semi-polar superlattice structure and preparation method thereof - Google Patents

Wide-band ultraviolet detector based on semi-polar superlattice structure and preparation method thereof Download PDF

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CN113675284B
CN113675284B CN202110762359.2A CN202110762359A CN113675284B CN 113675284 B CN113675284 B CN 113675284B CN 202110762359 A CN202110762359 A CN 202110762359A CN 113675284 B CN113675284 B CN 113675284B
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徐峰
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Yangzhou University
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    • H01L31/03046—Inorganic materials including, apart from doping materials or other impurities, only AIIIBV compounds including ternary or quaternary compounds, e.g. GaAlAs, InGaAs, InGaAsP
    • H01L31/03048—Inorganic materials including, apart from doping materials or other impurities, only AIIIBV compounds including ternary or quaternary compounds, e.g. GaAlAs, InGaAs, InGaAsP comprising a nitride compounds, e.g. InGaN
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Abstract

The invention discloses a wide-band ultraviolet detector based on a semi-polar superlattice structure and a preparation method thereof, wherein the ultraviolet detector comprises a substrate, a film layer growing on the substrate, a mask layer deposited on the film layer, a light absorption layer growing on the mask layer and an electrode layer compounded on the light absorption layer; the light absorbing layer is a semi-polar AlInGaN superlattice material. The invention uses semi-polar Al with low defect density x Ga 1‑x N/In y Ga 1‑y The N superlattice structure is successfully applied to the ultraviolet detector absorption layer, and meanwhile, the metal Al and In metal element components x and y can be accurately regulated to ensure that the Al x In y Ga 1‑x‑y The band gap width of the N superlattice material is continuously adjustable within the range of 3.4-6.2 eV, and the corresponding response wavelength range is 200-365 nm. The ultraviolet detector can reduce the defect density and polarization effect of materials, and can effectively improve the collection efficiency of photo-generated carriers by combining a metal interdigital electrode process, and obviously improve the responsivity and response speed while reducing the dark current of the device.

Description

Wide-band ultraviolet detector based on semi-polar superlattice structure and preparation method thereof
Technical Field
The invention relates to a semiconductor device and a preparation method thereof, in particular to a wide-band ultraviolet detector based on a semi-polar superlattice structure and a preparation method thereof.
Background
The wide-band ultraviolet detection technology has extremely important application in the fields of ultraviolet communication, reconnaissance, early warning, environmental pollution monitoring and the like. AlGaN-based third-generation wide-bandgap semiconductor materials have been the preferred material system for preparing ultraviolet detectors due to the physical and chemical characteristics of high electron saturation speed, high breakdown electric field, high thermal conductivity, radiation resistance and the like. The detection wavelength can be continuously adjustable within the range of 200-365 nm by adjusting the material composition of AlGaN, and the method is very suitable for distinguishing and monitoring solar blind ultraviolet broadband under the background of visible light. AlGaN-based metal-semiconductor-metal (MSM) structure detectors are one of the most interesting ultraviolet detectors at present due to the advantages of small capacitance, simple structure, high responsivity, high ultraviolet detection ratio and the like.
Although the AlGaN ultraviolet detector has the advantages, high-density dislocation defects can be introduced into an AlGaN material based on lattice mismatch and thermal mismatch caused by heteroepitaxial growth, so that the Schottky barrier thickness is thinned, and defect-assisted tunneling current is formed, thereby increasing dark current of the detector.
Disclosure of Invention
The invention aims to: the invention aims to provide a wide-band ultraviolet detector based on a semi-polar superlattice structure, which has the advantages of high response speed, high detection efficiency, low dark current and good device performance; the invention further provides a preparation method of the wide-band ultraviolet detector based on the semi-polar superlattice structure.
The technical scheme is as follows: the wide-band ultraviolet detector based on the semi-polar superlattice structure comprises a substrate, a film layer growing on the substrate, a mask layer deposited on the film layer, a light absorption layer growing on the mask layer and an electrode layer compounded on the light absorption layer, wherein the substrate is provided with a plurality of light absorption layers; the light absorption layer is made of semi-polar AlInGaN superlattice material; alInGaN superlattice material is Al x Ga 1-x N/In y Ga 1-y The N superlattice structure, wherein the component x of Al changes in the interval from 0 to 1, the component y of in changes in the interval from 0 to 1, and x/y is 4.66.
Preferably, the substrate is a sapphire substrate or a silicon substrate.
Preferably, the film layer is a GaN film layer, the electrode layer is a Ni/Au double-layer MSM metal electrode layer, and the mask layer is SiO 2 Mask layer or Si 3 N 4 And (5) a mask layer.
Preferably, al x Ga 1-x N/In y Ga 1-y N superlattice structure contains N Al x Ga 1-x N sublayers and N In y Ga 1-y An N sub-layer; wherein Al is x Ga 1-x The N sub-layer is semi-polar crystal face with thickness not less than 0.1nm, in y Ga 1-y The N sub-layer is a semi-polar crystal face and has a thickness not less than 0.1nm.
Preferably, al x Ga 1-x N/In y Ga 1-y The number of periods of the superlattice structure of N is not less than 1.
Semi-polar Al x Ga 1-x N/In y Ga 1-y The N superlattice structure is formed by semi-polar Al x Ga 1-x N and In y Ga 1-y The N-super crystal lattice layer. Growth of Al x Ga 1-x N/In y Ga 1-y When the N superlattice structure is adopted, the components of each sublayer are shared by the upper layer and the lower layer, so that the AlInGaN superlattice material with the In-plane lattice constant between AlGaN and InGaN can be finally formed, and when the ratio of the metal element components x and y of Al and In is 4.66, the complete matching with the In-plane lattice constant of GaN can be realized.
Preferably, the band gap width of the AlInGaN superlattice material is adjustable within the range of 3.4-6.2 eV, and the response wavelength of the ultraviolet detector is 200-365 nm. By adjusting the metal element composition ratio x/y of Al and In, the adjustable range of the band gap width of the AlInGaN superlattice material is 3.4-6.2 eV, and the response wavelength of the corresponding ultraviolet detector is 200-365 nm.
The preparation method of the wide-band ultraviolet detector comprises the following steps:
(1) Epitaxially growing a thin film layer on a substrate by using a chemical vapor deposition method, or directly adopting a self-supporting substrate material with the thin film layer; then a mask layer is deposited on the film layer by utilizing a plasma enhanced chemical vapor deposition method;
(2) Forming a cross-shaped groove window along the semi-polar crystal direction of the film layer on the mask layer by utilizing photoetching and wet etching methods to expose the film layer;
(3) Performing secondary epitaxial growth on the film with the growth mask pattern by using a chemical vapor deposition method to obtain a semi-polar AlGaN/InGaN superlattice structure;
(4) And forming a metal electrode layer on the surface of the semi-polar AlGaN/InGaN superlattice structure by utilizing an electron beam evaporation method, and then performing rapid thermal annealing in a nitrogen atmosphere to form Schottky contact to obtain the ultraviolet detector.
Further, the chemical vapor deposition method in the step (1) and the step (3) is a metal organic chemical vapor deposition method based on a selective lateral epitaxy method.
Further, the substrate is a sapphire substrate and indium oxideOne or more of a tin substrate, a quartz substrate, and a magnesium oxide substrate; the film layer is a GaN film layer, the metal electrode layer is a Ni/Au double-layer MSM metal electrode layer, and the mask layer is SiO 2 Mask layer or Si 3 N 4 And (5) a mask layer.
The mask layer is SiO 2 Mask layer or Si 3 N 4 The mask layer is based on a selective transverse epitaxial growth quality transport mechanism, the type of the semi-polar surface is mainly based on the surface energy and the surface atomic stability of a crystal face, and when secondary epitaxial growth windows such as stripes, cross shapes and the like of the mask layer are along a specific semi-polar crystal direction of the GaN film layer, alGaN and InGaN superlattice sub-layer film materials with micro-surface morphology of semi-polar crystal faces can be obtained through growth.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages:
(1) The performance parameters of the ultraviolet detector reach the following indexes: (1) v-type defect density on superlattice material surface<4.6×105/cm 2 Surface roughness RMS<1nm; (2) the dark current of the detection device is lower than 1pA; (3) internal quantum efficiency of detector>80％；
(2) Dark current and photoconductive gain of the detection device are effectively reduced, and the AlGaN/InGaN superlattice structure can realize a lattice which is completely matched with the GaN layer, so that stress caused by lattice mismatch is effectively eliminated, and the gap filling factor of the growth mask layer is further optimized;
(3) The defect density of the material is reduced, and the selective lateral epitaxy process can deflect most dislocation lines by 90 degrees at a semi-polar interface, so that the dislocation density of the material is reduced.
Drawings
FIG. 1 is a schematic view of the structure of an ultraviolet detector in example 1;
fig. 2 is a schematic structural diagram of a semi-polar AlGaN/InGaN superlattice of example 1;
fig. 3 is a schematic structural diagram of AlGaN/InGaN superlattice in the ultraviolet detector of embodiment 1;
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings.
Example 1
1. Ultraviolet detector
As shown in fig. 1, a wide-band ultraviolet detector based on a semi-polar superlattice structure includes a substrate 1, a thin film layer 2 grown on the substrate 1, a mask layer 3 deposited on the thin film layer 2, a light absorbing layer 4 grown on the mask layer 3, and an electrode layer 5 composited on the light absorbing layer 4.
The substrate 1 is a sapphire substrate, the film layer 2 is a GaN film layer, and the mask layer 3 is SiO 2 The mask layer, the light absorption layer 4 is made of semi-polar AlGaN/InGaN superlattice material, and the electrode layer 5 is a Ni/Au double-layer MSM metal electrode layer.
As shown in fig. 2, the semi-polar AlGaN/InGaN superlattice structure is schematically shown, and the GaN thin film layer is sequentially formed by an InGaN layer 41, an AlGaN layer 42, an InGaN layer 43, an AlGaN layer 44, an InGaN layer 45, and an AlGaN layer 46. Fig. 2 only illustrates the structural relationship between the InGaN layer and the AlGaN layer, and the number of the InGaN layer and the AlGaN layer is more than the number of layers in the picture, and the AlGaN/InGaN superlattice structure includes n AlGaN sublayers and n InGaN sublayers.
As shown in fig. 3, the structure of AlGaN/InGaN superlattice in the ultraviolet detector is schematically shown, wherein the substrate 1 is a sapphire substrate, the thin film layer 2 is a GaN thin film layer, and the mask layer 3 is SiO 2 The mask layer and the light absorbing layer 4 are made of semi-polar AlGaN/InGaN superlattice materials, wherein the mask layer 3 blocks a large number of dislocation lines generated by heteroepitaxy, and meanwhile dislocation lines 6 extending upwards in a growth window area deflect at a semi-polar interface, so that the dislocation density of the materials is reduced.
2. The preparation method of the ultraviolet detector comprises the following steps:
(1) The chemical vapor deposition method adopts a planetary 4-inch metal organic chemical vapor deposition MOCVD preparation system, and utilizes the MOCVD system to epitaxially grow a GaN film layer on a sapphire substrate, wherein trimethylgallium (TMGa) is an MO growth source of gallium element; trimethylaluminum (TMAl) is an MO growth source of aluminum element and an MO growth source of trimethylindium (TMIn) indium element; the nitrogen source is ammonia (NH) 3 ) The method comprises the steps of carrying out a first treatment on the surface of the A silicon dioxide mask layer is then deposited on the GaN thin film layer using Plasma Enhanced Chemical Vapor Deposition (PECVD).
(2) A cross-shaped groove window along the semi-polar crystal direction of GaN is formed on the silicon dioxide mask layer by utilizing photoetching and wet etching methods, and the GaN film layer is exposed;
(3) Carrying out secondary MOCVD epitaxy on the GaN film with the growth mask pattern to obtain a semi-polar AlGaN/InGaN superlattice structure;
(4) And forming a Ni/Au double-layer MSM metal electrode through an electron beam evaporation process, and then performing rapid thermal annealing at 700 ℃ in a nitrogen atmosphere to form Schottky contact, thereby completing the preparation of the semi-polar AlGaN/InGaN superlattice structure MSM ultraviolet detection device.
Example 2
1. Ultraviolet detector
The substrate is a silicon substrate, the film layer is a GaN film layer, and the mask layer is Si 3 N 4 The mask layer, the light absorption layer is made of semi-polar AlGaN/InGaN superlattice material, and the electrode layer is a Ni/Au double-layer MSM metal electrode layer.
2. The preparation method of the ultraviolet detector comprises the following steps:
(1) The chemical vapor deposition method adopts a planetary 4-inch metal organic chemical vapor deposition MOCVD preparation system, and utilizes the MOCVD system to epitaxially grow a GaN film layer on a silicon substrate, wherein trimethylgallium (TMGa) is an MO growth source of gallium element; trimethylaluminum (TMAl) is an MO growth source of aluminum element and an MO growth source of trimethylindium (TMIn) indium element; the nitrogen source is ammonia (NH) 3 ) The method comprises the steps of carrying out a first treatment on the surface of the Then depositing Si on the GaN film layer by Plasma Enhanced Chemical Vapor Deposition (PECVD) 3 N 4 And (5) a mask layer.
(2) Si in a wet etching method by utilizing photoetching 3 N 4 A cross-shaped groove window along the semi-polar crystal direction of GaN is formed on the mask layer, and the GaN film layer is exposed;
(3) Carrying out secondary MOCVD epitaxy on the GaN film with the growth mask pattern to obtain a semi-polar AlGaN/InGaN superlattice structure;
(4) And forming a Ni/Au double-layer MSM metal electrode through an electron beam evaporation process, and then performing rapid thermal annealing at 700 ℃ in a nitrogen atmosphere to form Schottky contact, thereby completing the preparation of the semi-polar AlGaN/InGaN superlattice structure MSM ultraviolet detection device.
The MOCVD selective lateral epitaxy process in the embodiment utilizes silicon dioxide (or silicon nitride and the like) with a cross-shaped groove structure as a growth mask layer, the growth mask blocks a large number of dislocation lines generated by heteroepitaxy, meanwhile, dislocation lines extending upwards in a growth window area deflect at a semi-polar interface to reduce density, and furthermore, the AlGaN/InGaN superlattice structure which is optimally designed in the invention can realize lattice matching with a GaN film layer, so that stress caused by lattice mismatch is effectively eliminated, and finally, the number of surface defects of the semi-polar AlGaN/InGaN superlattice structure is greatly reduced, thereby effectively reducing dark current and gain of a deep ultraviolet detection device.
The invention uses semi-polar Al with low defect density x Ga 1-x N/In y Ga 1-y The N superlattice structure is successfully applied to the ultraviolet detector absorption layer, and meanwhile, the metal Al and In metal element components x and y can be accurately regulated to ensure that the Al x In y Ga 1-x-y The band gap width of the N superlattice material is continuously adjustable within the range of 3.4-6.2 eV, and the corresponding response wavelength range is 200-365 nm.
Wherein Al is x In y Ga 1-x-y Band gap width E of N material g The solution can be found as follows:
in AlGaN and InGaN materials, respective energy band bending parameters b AlGaN 、b InGaN Respectively taking 0.7eV and 2.1eV, and obtaining b through secondary approximation xy ≈1eV。
The invention is reasonably designed with semi-polar Al x Ga 1-x N/In y Ga 1-y The N superlattice structure wide-band ultraviolet detector can reduce the material defect density and polarization effect, and can effectively improve the collection efficiency of photo-generated carriers by combining a metal interdigital structure electrode process, and remarkably improve the responsivity and response speed while reducing the dark current of the device.

Claims (9)

1. The wide-band ultraviolet detector based on the semi-polar superlattice structure is characterized by comprising a substrate, a film layer growing on the substrate, a mask layer deposited on the film layer, a light absorption layer growing on the mask layer and an electrode layer compounded on the light absorption layer; the film layer is a GaN film layer; the light absorption layer is made of semi-polar AlInGaN superlattice material; the AlInGaN superlattice material is Al x Ga 1-x N/In y Ga 1-y N-superlattice structure in which the composition of AlxA composition of in with a variation interval of 0 to 1yThe change interval is 0 to 1, andx/y4.66.
2. The broad band ultraviolet detector based on semi-polar superlattice structure as defined in claim 1, wherein the substrate is a sapphire substrate or a silicon substrate.
3. The broad band ultraviolet detector based on semi-polar superlattice structure as defined in claim 1, wherein said electrode layer is a Ni/Au double-layer MSM metal electrode layer, and said mask layer is SiO 2 Mask layer or Si 3 N 4 And (5) a mask layer.
4. The broad band ultraviolet detector based on semi-polar superlattice structure as defined in claim 1, wherein Al x Ga 1-x N/In y Ga 1-y N superlattice structure contains N Al x Ga 1-x N sublayers and N In y Ga 1-y An N sub-layer; wherein Al is x Ga 1-x The N sub-layer is semi-polar crystal face with thickness not less than 0.1nm, in y Ga 1-y The N sub-layer is a semi-polar crystal face and has a thickness not less than 0.1nm.
5. The broad band ultraviolet detector based on semi-polar superlattice structure as defined in claim 1, wherein Al x Ga 1-x N/In y Ga 1-y The number of periods of the superlattice structure of N is not less than 1.
6. The broad band ultraviolet detector based on semi-polar superlattice structure as in any one of claims 1-5, wherein the AlInGaN superlattice material has a band gap width adjustable in a range of 3.4-6.2 eV, and the response wavelength of the ultraviolet detector is 200-365 nm.
7. The preparation method of the wide-band ultraviolet detector based on the semi-polar superlattice structure is characterized in that the wide-band ultraviolet detector based on the semi-polar superlattice structure comprises a substrate, a film layer growing on the substrate, a mask layer deposited on the film layer, a light absorption layer growing on the mask layer and an electrode layer compounded on the light absorption layer; the film layer is a GaN film layer; the light absorption layer is made of semi-polar AlInGaN superlattice material; the AlInGaN superlattice material is Al x Ga 1-x N/In y Ga 1-y N-superlattice structure in which the composition of AlxA composition of in with a variation interval of 0 to 1yThe change interval is 0 to 1, andx/y4.66;
the method comprises the following steps:
(1) Epitaxially growing a thin film layer on a substrate by using a chemical vapor deposition method, or directly adopting a self-supporting substrate material with the thin film layer; then a mask layer is deposited on the film layer by utilizing a plasma enhanced chemical vapor deposition method;
(2) Forming a cross-shaped groove window along the semi-polar crystal direction of the film layer on the mask layer by utilizing photoetching and wet etching methods to expose the film layer;
(3) Performing secondary epitaxial growth on the film with the growth mask pattern by using a chemical vapor deposition method to obtain a semi-polar AlGaN/InGaN superlattice structure;
(4) And forming a metal electrode layer on the surface of the semi-polar AlGaN/InGaN superlattice structure by utilizing an electron beam evaporation method, and then performing rapid thermal annealing in a nitrogen atmosphere to form Schottky contact to obtain the ultraviolet detector.
8. The method of claim 7, wherein the chemical vapor deposition method in step (1) and step (3) is a metal organic chemical vapor deposition method based on a selective lateral epitaxy method.
9. The method for manufacturing a wide-band ultraviolet detector based on a semi-polar superlattice structure as defined in claim 7, wherein the substrate is a sapphire substrate or a silicon substrate; the film layer is a GaN film layer, the metal electrode layer is a Ni/Au double-layer MSM metal electrode layer, and the mask layer is SiO 2 Mask layer or Si 3 N 4 And (5) a mask layer.
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CN110880533A (en) * 2018-09-06 2020-03-13 中国科学院苏州纳米技术与纳米仿生研究所 Heterojunction based on superlattice structure, enhanced HEMT device and manufacturing method thereof
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CN1347581A (en) * 1999-03-26 2002-05-01 松下电器产业株式会社 Semiconductor structures having strain compensated layer and method of fabrication
CN105742415A (en) * 2016-03-01 2016-07-06 聚灿光电科技股份有限公司 Ultraviolet GaN-based LED epitaxy structure and manufacturing method thereof
CN110880533A (en) * 2018-09-06 2020-03-13 中国科学院苏州纳米技术与纳米仿生研究所 Heterojunction based on superlattice structure, enhanced HEMT device and manufacturing method thereof
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