CN110797430A - Monolithic dual band integrated sensor and method of making same - Google Patents
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
- H01L31/10—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors characterised by at least one potential-jump barrier or surface barrier, e.g. phototransistors
- H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
- H01L31/1013—Devices sensitive to infrared, visible or ultraviolet radiation devices sensitive to two or more wavelengths, e.g. multi-spectrum radiation detection devices
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- H—ELECTRICITY
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- H—ELECTRICITY
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Abstract
A monolithic dual-band integrated sensor and a preparation method thereof relate to the technical field of sensors and solve the problems of difficult integration, weak infrared detection performance and complex structure in the prior art. The preparation method comprises the steps of growing or preparing the self-supporting gallium nitride single crystal material, the buffer layer, the two-dimensional nitride thin film layer and the infrared sensor electrode in sequence; preparing a first ultraviolet sensor electrode and a second ultraviolet sensor electrode on a self-supporting gallium nitride single crystal material, and annealing. The preparation method is novel and simple, and the prepared dual-waveband sensor is simple in structure and obvious in dual-waveband detection effect.
Description
Technical Field
The invention relates to the technical field of sensors, in particular to a monolithic dual-band integrated sensor and a preparation method thereof.
Background
The ultraviolet-infrared dual-band detection technology has very important application value in the aspects of fire, weather, military detection and the like. By adopting ultraviolet-infrared double-color detection, the identification probability of the detected target can be greatly improved. The ultraviolet sensor is taken as a core device of an ultraviolet detection technology, and receives high attention and intensive research at home and abroad for several years. The ultraviolet sensor is mainly applied to military fields such as ultraviolet alarm, ultraviolet communication and ultraviolet guidance in the early stage, and then the ultraviolet sensor is gradually cured and civilized and is gradually and slowly applied to other fields such as ultraviolet disinfection, fire detection, ultraviolet curing and polymerization, biomedicine, spectral analysis and particle detection. First-generation and second-generation semiconductors such as Si and GaAs can be used for manufacturing ultraviolet sensors, but the characteristics and the use of the device are greatly limited due to the characteristics of small forbidden band width, large long-wave cut-off wavelength of the device, low maximum working temperature and the like, and the limitation is particularly prominent particularly under severe environments such as high temperature, sunlight irradiation and the like. The third-generation semiconductor GaN with the forbidden bandwidth larger than 2.2eV has the advantages of forbidden bandwidth, high critical breakdown electric field, high electron saturation velocity, high thermal conductivity, strong radiation resistance and the like, so that the defects of the first-generation semiconductor ultraviolet sensor and the second-generation semiconductor ultraviolet sensor are well overcome, and the third-generation semiconductor GaN becomes a main material for manufacturing the ultraviolet sensors at present. GaN avoids the use of complex filtering systems in Si sensors and solves the disadvantage of Si sensors that photogenerated carriers recombine at the sensor surface. The GaN-based sensor is a semiconductor all-solid-state sensor, has the advantages of small volume and low power consumption, and effectively overcomes the defects that a photomultiplier needs a large power supply and a cathode for refrigeration and the like. The radiation resistance is strong, and the sensor can work in severe environments such as high altitude and the like, which cannot be realized by a Si sensor and a photomultiplier.
Infrared photoelectric sensors are widely used in various fields such as fire alarm control systems, night vision systems, environmental detection, unmanned driving, food safety, and the like. Such as induction faucets, induction doors and lamps, mineral resource exploration, non-destructive inspection, gas analysis, infrared imaging, fire warning, infrared precision guidance, aerial detection, and meteorological satellites, among other applications. The infrared photoelectric detection is always a focus of people, and at present, germanium, silicon, indium arsenide, indium phosphide and the like are provided with infrared band sensors. However, the semiconductor material and the process are complex to prepare and high in cost. The photoresponse cutoff waveband of silicon is 1100nm, and a single silicon is difficult to realize the optical sensor with an infrared communication waveband. How to integrate a communication waveband photoelectric sensor on a silicon substrate is a great problem faced by the related field. Indium arsenide, indium phosphide and silicon epitaxially grown on a silicon substrate have a large lattice mismatch problem, and are complex in flow and high in process cost.
The infrared-ultraviolet bicolor integrated sensor integrates an infrared sensor and an ultraviolet sensor together. In recent years, the infrared-ultraviolet integrated double-color detection technology has been developed greatly at home and abroad, and particularly in recent years, the wide bandgap semiconductor epitaxial growth technology is mature day by day, and the epitaxial growth of high-crystal-quality materials promotes the development of sensors. However, the current infrared-ultraviolet two-color integrated sensor is still not well popularized, wherein the problems of difficult integration of an infrared-ultraviolet photosensitive material or a detection system, weak detection performance of an infrared detection system after an integrated device, complex structure of the two-color integrated sensor and the like caused by lattice mismatch become main reasons for limiting the development of the two-color integrated sensor.
Disclosure of Invention
The invention provides a monolithic dual-waveband integrated sensor and a preparation method thereof, aiming at solving the problems of difficult integration of an infrared-ultraviolet photosensitive material or a detection system, weak detection performance of an infrared detection system behind an integrated device and complex structure of a bicolor integrated detector caused by lattice mismatch.
The technical scheme adopted by the invention for solving the technical problem is as follows:
the monolithic dual-band integrated sensor comprises a self-supporting gallium nitride single crystal material, a buffer layer, a two-dimensional nitride thin film layer, an infrared sensor electrode, a first ultraviolet sensor electrode and a second ultraviolet sensor electrode; the buffer layer, the first ultraviolet sensor electrode and the second ultraviolet sensor electrode are all prepared on the upper surface of the self-supporting gallium nitride single crystal material; the two-dimensional nitride film layer is prepared on the upper surface of the buffer layer, the infrared sensor electrode is prepared on the upper surface of the two-dimensional nitride film layer, and the buffer layer and the two-dimensional nitride film layer are both positioned between the first ultraviolet sensor electrode and the second ultraviolet sensor electrode.
A method of making a monolithic dual band integrated sensor comprising the steps of:
step one, growing a self-supporting gallium nitride single crystal material;
growing a buffer layer on the self-supporting gallium nitride single crystal material;
growing a two-dimensional nitride film layer on the buffer layer;
preparing an infrared sensor electrode on the two-dimensional nitride film layer;
preparing a first ultraviolet sensor electrode and a second ultraviolet sensor electrode on the self-supporting gallium nitride single crystal material;
and step six, annealing the electrode.
The invention has the beneficial effects that:
1. the infrared sensor part of the monolithic dual-waveband integrated sensor is based on the mechanism that a two-dimensional nitride film layer and infrared light generate phonon excimer resonance, and the ultraviolet sensor part is based on the transition mechanism that forbidden band width is an ultraviolet waveband, and the infrared-ultraviolet dual-color sensor is realized by utilizing the phonon excimer resonance and the forbidden band width. The monolithic dual-band integrated sensor realizes the detection of homogeneous gallium nitride-based infrared-ultraviolet dual-color dual-band, has lattice matching, excellent infrared light detection performance, obvious infrared-ultraviolet dual-band detection sensing effect, simple structure, easy integration, wide development and application prospect and the like.
2. The monolithic dual-band integrated sensor has the advantages of novel preparation method, simple process, obvious dual-band detection effect, wide development and application prospect and the like.
3. The invention provides a new method for realizing a homogenous gallium nitride-based infrared-ultraviolet dual-band sensor by utilizing phonon excimer resonance and forbidden bandwidth, and provides a new way for realizing infrared band detection by gallium nitride.
Drawings
FIG. 1 is a schematic structural diagram of a monolithic dual band integrated sensor of the present invention.
FIG. 2 is a flow chart of a method of making a monolithic dual band integrated sensor of the present invention.
In the figure: 1. the self-supporting gallium nitride single crystal material comprises a self-supporting gallium nitride single crystal material body, 2, a buffer layer, 3, a two-dimensional nitride thin film layer, 4, an infrared sensor electrode, 5, a first ultraviolet sensor electrode, 6 and a second ultraviolet sensor electrode.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
The monolithic dual-band integrated sensor comprises a self-supporting gallium nitride single crystal material 1, a buffer layer 2, a two-dimensional nitride thin-film layer 3, an infrared sensor electrode 4, a first ultraviolet sensor electrode 5 and a second ultraviolet sensor electrode 6.
Structure of monolithic dual band integrated sensor fig. 1, a buffer layer 2, a first uv sensor electrode 5 and a second uv sensor electrode 6 are all fabricated on a self-supporting gallium nitride single crystal material 1. The buffer layer 2 is positioned on the upper surface of the self-supporting gallium nitride single crystal material 1, the two-dimensional nitride thin film layer 3 is positioned on the buffer layer 2, the first ultraviolet sensor electrode 5 is positioned on the upper surface of the self-supporting gallium nitride single crystal material 1, and the second ultraviolet sensor electrode 6 is positioned on the upper surface of the self-supporting gallium nitride single crystal material 1. The buffer layer 2 and the two-dimensional nitride thin-film layer 3 are both located between the first ultraviolet sensor electrode 5 and the second ultraviolet sensor electrode 6. The infrared sensor electrode 4 is located on the two-dimensional nitride thin-film layer 3. The infrared sensor electrode 4 is not in direct contact with the first ultraviolet sensor electrode 5, nor is the infrared sensor electrode 4 in direct contact with the second ultraviolet sensor electrode 6.
The self-supporting gallium nitride single crystal material 1 is a wide bandgap semiconductor material. The growth method of the self-supporting gallium nitride single crystal material 1 mainly comprises Hydride Vapor Phase Epitaxy (HVPE) and NH3And a molten Ga vapor transport method, a czochralski method, and the like.
The buffer layer 2 mainly adopts AlN, namely AlN is used as a buffer filter layer for absorbing ultraviolet light, namely an AlN blocking layer is inserted between an infrared wave band and an ultraviolet wave band, so that the ultraviolet wave band in incident light can be absorbed and filtered by the AlN, the ultraviolet wave band is prevented from entering, and the residual infrared wave band passes through. The buffer layer 2 is grown mainly by Metal Organic Chemical Vapor Deposition (MOCVD).
The two-dimensional nitride thin-film layer 3 is two-dimensional GaN. The two-dimensional GaN is a brand-new two-dimensional material, a GaN two-dimensional film is epitaxially grown on a homogeneous GaN substrate, and the film is matched in crystal lattice, few in defects and good in surface state. The two-dimensional GaN quantum size effect is obvious, the interaction of the 2s state and the 2p state of N is enhanced, the energy bands are overlapped, and the good conductive characteristic is presented. The two-dimensional nitride film layer 3 can generate phonon excimer resonance with infrared light, the film is electrified, a strong electric field is applied to the surface of the nitride, infrared photons propagating on the surface of the film are coupled and polarized with the phonons under the action of the electric field to generate resonance, and new waves are generated after the coupling and can be represented by electric signals, so that the detection of the infrared light is realized. A two-dimensional nitride film layer 3 is homoepitaxially grown on the self-supporting gallium nitride single crystal material 1, and the epitaxial growth and lattice matching reduce the defect density and improve the film quality. The two-dimensional nitride thin-film layer 3 is grown by chemical vapor deposition (cvd) or Metal Organic Chemical Vapor Deposition (MOCVD). In the method for preparing the two-dimensional gallium nitride film in the embodiment, urea is used as a nitrogen source, and liquid metal gallium is used as a gallium source for chemical vapor deposition.
The infrared sensor electrode 4 is of a metal-semiconductor-metal structure, an ohmic structure or a schottky structure, and can be selected as required. The infrared sensor electrode 4 is prepared by the existing preparation method. For example, Ti/Al and Ti/Au form an ohmic structure, and Ni/Au and Pt form a Schottky structure.
The first ultraviolet sensor electrode 5 adopts a metal-semiconductor-metal structure, an ohmic structure or a schottky structure,
the second ultraviolet sensor electrode 6 is of a metal-semiconductor-metal structure, an ohmic structure or a schottky structure, and can be selected as required. The first ultraviolet sensor electrode 5 and the second ultraviolet sensor electrode 6 are prepared by an existing preparation method. Wherein the ultraviolet sensor and the infrared sensor share a first ultraviolet sensor electrode 5. The first ultraviolet sensor electrode 5 is grounded and then the second ultraviolet sensor electrode 6 and the infrared sensor electrode 4 are simultaneously biased so that the ultraviolet sensor and the infrared sensor can simultaneously operate.
The infrared sensor part of the monolithic dual-waveband integrated sensor is based on the mechanism that the two-dimensional nitride film layer 3 and infrared light generate phonon excimer resonance, and the ultraviolet sensor part is based on the transition mechanism that forbidden band width is an ultraviolet waveband, and the infrared-ultraviolet dual-color sensor is realized by utilizing the phonon excimer resonance and the forbidden band width. The monolithic dual-band integrated sensor realizes the detection of homogeneous gallium nitride-based infrared-ultraviolet dual-color dual-band, has lattice matching, excellent infrared light detection performance, obvious infrared-ultraviolet dual-band detection sensing effect, simple structure, easy integration, wide development and application prospect and the like.
As shown in fig. 2, the method for manufacturing a monolithic dual band integrated sensor of the present invention mainly comprises the following steps:
step one, growing a self-supporting gallium nitride single crystal material 1;
secondly, growing a buffer layer 2 on the self-supporting gallium nitride single crystal material 1;
growing a two-dimensional nitride film layer 3 on the buffer layer 2;
fourthly, preparing an infrared sensor electrode 4 on the two-dimensional nitride film layer 3;
preparing a first ultraviolet sensor electrode 5 and a second ultraviolet sensor electrode 6 on the self-supporting gallium nitride single crystal material 1;
and step six, annealing the electrode.
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The buffer layer 2 of the monolithic dual-band integrated sensor is made of AlN, and the two-dimensional nitride thin film layer 3 is made of two-dimensional GaN. The preparation method of the embodiment specifically comprises the following steps:
(1) growing a self-supporting gallium nitride single crystal material 1: firstly, the sapphire substrate is nitrided into AlN or AlN-Al2O3The thin layer promotes nucleation, or a GaN thin layer is deposited at low temperature by using a Metal Organic Chemical Vapor Deposition (MOCVD) method to be used as a buffer thin layer, so that the quality of the epitaxial thin film is improved. Growing high-quality GaN monocrystal on the nitride layer or GaN thin layer by Hydride Vapor Phase Epitaxy (HVPE), reacting HCl gas with liquid metal Ga to produce GaCl, and reacting GaCl with NH3And reacting to generate GaN. And finally, removing the sapphire substrate by adopting a laser lift-off technology to obtain the self-supporting gallium nitride single crystal material 1 with the thickness of 450 mu m.
(2) And (3) growing a buffer layer 2: trimethyl aluminum (TMA) is used as an aluminum source, ammonia gas (NH3) is used as a nitrogen source, and an AlN layer with the thickness of 2-3nm is grown on the self-supporting gallium nitride single crystal material 1 by using an MOCVD method, wherein the AlN layer is the buffer layer 2.
(3) Growing the two-dimensional nitride thin film layer 3: urea is used as a nitrogen source, liquid metal gallium is used as a gallium source to carry out chemical vapor deposition, and a two-dimensional gallium nitride film layer with the thickness of 4-8nm is deposited on the buffer layer 2.
(4) Preparing an infrared sensor electrode 4: utilizing photoetching technology to obtain a metal-semiconductor-metal sensor mask pattern; preparing an infrared sensor electrode 4 on the two-dimensional nitride thin film layer 3 obtained in the step (3) through vacuum evaporation or electron beam evaporation to prepare a metal-semiconductor-metal structure sensor; the photoresist is then washed off using the Lift off technique, and the solution used can be either NMP (N-methylpyrrolidone) or acetone. The electrode material is a metal material capable of forming Schottky contact or ohmic contact with the two-dimensional nitride thin film layer 3, such as Ti (15nm)/Al (150-200nm), Ti (15nm)/Au (150-200nm) to form an ohmic structure, Ni (15nm)/Au (150-200nm), Pt (150-200nm) to form a Schottky structure.
(5) Preparing an ultraviolet sensor electrode: shielding the middle two-dimensional gallium nitride thin film layer part by using photoresist by using a photoetching technology, etching at two ends (the left end and the right end corresponding to the figure 1) of the two-dimensional gallium nitride thin film layer by using a plasma etching technology (ICP) until the self-supporting gallium nitride single crystal material 1 is exposed, then arranging a first ultraviolet sensor electrode 5 and a second ultraviolet sensor electrode 6 on the exposed self-supporting gallium nitride single crystal material 1 by using a vacuum evaporation method or an electron beam evaporation method, and at the moment, keeping the buffer layer 2 and the two-dimensional nitride thin film layer 3 between the first ultraviolet sensor electrode 5 and the second ultraviolet sensor electrode 6; the photoresist is then washed off using the Lift off technique, and the solution used can be either NMP or acetone. The materials of the prepared first ultraviolet sensor electrode 5 and the second ultraviolet sensor electrode 6 both adopt metal materials which can form Schottky contact or ohmic contact with the self-supporting gallium nitride single crystal material 1, such as Ti (15nm)/Al (150-200nm) and Ti (15nm)/Au (150-200nm) to form an ohmic structure, and Ni (15nm)/Au (150-200nm) and Pt (150-200nm) to form a Schottky structure.
(6) And (4) carrying out electrode annealing on the device obtained in the step (5) in a rapid heating annealing furnace. In N2Annealing at 400-600 ℃ for 5-10 minutes. And after the electrode is annealed, the preparation of the monolithic dual-band integrated sensor is finished.
The preparation method is novel and simple in process, and the prepared monolithic dual-band integrated sensor has an obvious dual-band detection effect and has the advantages of wide development and application prospects and the like.
According to the invention, infrared light is detected by utilizing two-dimensional nitride film infrared phonon excimer resonance, the two-dimensional nitride film layer 3 detects an infrared band, the self-supporting gallium nitride monocrystal material 1 detects an ultraviolet band, the infrared-ultraviolet band can be detected simultaneously, and the problem that gallium nitride infrared band detection and gallium nitride infrared-ultraviolet band double-color integrated detection cannot be realized at present is solved. The invention provides a new method for realizing a homogenous gallium nitride-based infrared-ultraviolet dual-band sensor by utilizing phonon excimer resonance and forbidden bandwidth, and provides a new way for realizing infrared band detection by gallium nitride.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. The monolithic dual-band integrated sensor is characterized by comprising a self-supporting gallium nitride single crystal material (1), a buffer layer (2), a two-dimensional nitride thin film layer (3), an infrared sensor electrode (4), a first ultraviolet sensor electrode (5) and a second ultraviolet sensor electrode (6); the buffer layer (2), the first ultraviolet sensor electrode (5) and the second ultraviolet sensor electrode (6) are all prepared on the upper surface of the self-supporting gallium nitride single crystal material (1); the two-dimensional nitride film layer (3) is prepared on the upper surface of the buffer layer (2), the infrared sensor electrode (4) is prepared on the upper surface of the two-dimensional nitride film layer (3), and the buffer layer (2) and the two-dimensional nitride film layer (3) are both positioned between the first ultraviolet sensor electrode (5) and the second ultraviolet sensor electrode (6).
2. The monolithic dual band integrated sensor according to claim 1, wherein the buffer layer (2) is of AlN.
3. The monolithic dual band integrated sensor according to claim 1, wherein the two-dimensional nitride thin film layer (3) is two-dimensional GaN.
4. The monolithic dual band integrated sensor according to claim 1, wherein the infrared sensor electrode (4), the first ultraviolet sensor electrode (5) and the second ultraviolet sensor electrode (6) all employ a metal-semiconductor-metal structure, an ohmic structure or a schottky structure.
5. A method of making the monolithic dual band integrated sensor of any of claims 1-4, comprising the steps of:
step one, growing a self-supporting gallium nitride single crystal material (1);
secondly, growing a buffer layer (2) on the self-supporting gallium nitride single crystal material (1);
growing a two-dimensional nitride film layer (3) on the buffer layer (2);
fourthly, preparing an infrared sensor electrode (4) on the two-dimensional nitride film layer (3);
preparing a first ultraviolet sensor electrode (5) and a second ultraviolet sensor electrode (6) on the self-supporting gallium nitride single crystal material (1);
and step six, annealing the electrode.
6. The method of claim 5, wherein in step one, hydride vapor phase epitaxy, NH, is used3And growing the self-supporting gallium nitride single crystal material (1) by a molten Ga gas phase transmission method or a pulling method.
7. The method of manufacturing a monolithic dual band integrated sensor as claimed in claim 6, wherein said step one specific process is: firstly, nitriding a sapphire substrate to generate a nitrided layer on the sapphire substrate, or depositing a GaN thin layer on the sapphire substrate at a low temperature by using an organic metal chemical vapor deposition method; then, growing a GaN monocrystal on the nitride layer or the GaN thin layer by a hydride vapor phase epitaxy method; and finally, removing the sapphire substrate by adopting a laser lift-off technology to obtain the self-supporting gallium nitride single crystal material (1).
8. The method for manufacturing a monolithic dual band integrated sensor according to claim 5, wherein in step two, the buffer layer (2) is manufactured by metal organic chemical vapor deposition.
9. The method of claim 5, wherein the step three is a step of fabricating the two-dimensional nitride thin film layer (3) by chemical vapor deposition or metal organic chemical vapor deposition.
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