CN109119508B - Back incidence solar blind ultraviolet detector and preparation method thereof - Google Patents
Back incidence solar blind ultraviolet detector and preparation method thereof Download PDFInfo
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- CN109119508B CN109119508B CN201810897294.0A CN201810897294A CN109119508B CN 109119508 B CN109119508 B CN 109119508B CN 201810897294 A CN201810897294 A CN 201810897294A CN 109119508 B CN109119508 B CN 109119508B
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
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- 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 back incidence solar blind ultraviolet detector and a preparation method thereof, wherein a back incidence structure is adopted, and the device comprises: the invention aims to solve the problems that an AlGaN-based p-i-n junction ultraviolet detector is low in p-type doping efficiency, thin film cracks, an epitaxial structure needs to be optimized, the crystal quality is low and the like.
Description
Technical Field
The invention relates to the field of photoelectric detectors, in particular to a back incidence solar blind ultraviolet detector and a preparation method thereof.
Background
The solar blind ultraviolet detector can detect ultraviolet light and convert the detected ultraviolet light into an easily identifiable electric signal for transmission. The solar blind ultraviolet detector has the advantages of high quantum efficiency, high sensitivity, stable performance, low background noise, difficult interference of radiation, chemistry and the like, wide detection range and the like, is widely applied to a plurality of military and civil fields such as missile guidance, early warning, fire alarm, communication, solar astronomical research and the like at present, and particularly has the advantages of high detection sensitivity and high precision in places with weak ultraviolet signals.
In the existing solar blind ultraviolet detector preparation technology, the preparation materials mainly comprise three types of 4H-SiC, mgZnO, gaN/AlGaN, and different solar blind ultraviolet detectors prepared from the three types of materials have advantages and disadvantages. The 4H-SiC type solar blind ultraviolet detector has high melting point and good heat conduction performance, is suitable for working at high temperature and high energy, but has the defects of low quantum efficiency and unadjustable band gap; the MgZnO solar blind ultraviolet detector has the advantages of single crystal substrate matching, no toxicity or harm, simple synthesis, low cost, high electronic saturation and drift speed, wide band gap, adjustability and the like, but lacks a packaging technology corresponding to the MgZnO solar blind ultraviolet detector at present; the GaN/AlGaN solar blind ultraviolet detector has the advantages of stable chemical property, difficult radiation interference, adjustable band gap by doping Al, good detection performance, high response speed, high growth temperature, difficult substrate matching and the like.
Related technology for preparing a solar blind ultraviolet detector is developed to date, gaN/AlGaN is the best preparation material at present, and is most widely applied to ultraviolet detectors with wide band gaps. In AlGaN-based p-i-n junction UV detectors, the p-region increases the sensitivity to UV light, making it easier for the i-layer to be absorbed and excited electron-hole pairs to form carriers and to transit in a short time. The p-i-n junction of the detector can greatly improve the detection capability, generate more carriers and accelerate the carrier speed, the i layer enables the matrix material not to influence the breakdown voltage any more, and the responsivity, the response time and the quantum efficiency of the device are improved. Although AlGaN-based p-i-n junction uv detectors have many advantages, there are also some disadvantages: when Al ions are injected to prepare AlGaN with high Al composition, the AlGaN can collide with the sapphire substrate, so that the crystal lattice is damaged and thermally mismatched, and high dislocation density and film cracks are caused; the p-type doping is not efficient.
Disclosure of Invention
The invention aims to solve the problems of low p-type doping efficiency, film cracks, to-be-optimized epitaxial structure and low crystal quality of an AlGaN-based p-i-n junction ultraviolet detector, and provides a back incidence solar blind ultraviolet detector with low dark current, higher quantum efficiency, better inhibition ratio, higher detection rate and better performance and a preparation method thereof.
The invention adopts the technical scheme that: a back-incident solar blind ultraviolet detector comprising: the semiconductor device comprises a substrate, a buffer layer, a stress release layer, an n-type ohmic contact layer, an n-type transition layer, an i-type light absorption layer, a p-type doping layer, a p-type transition layer, a p-type ohmic contact layer, a protective layer, an n-type electrode and a p-type electrode;
the substrate is a sapphire substrate and is positioned at the lowest part of each layer;
the buffer layer is a high-temperature AlN layer with the thickness of 350nm and is used for controlling stress accumulation and preventing the cracking of the film and is positioned on the substrate;
the stress release layer is AlN/Al 0.6 Ga 0.4 An N-superlattice layer, which is used for reducing dislocation density of the epitaxial structure and is positioned above the buffer layer;
the n-type ohmic contact layer is made of Al doped with Si 0.6 Ga 0.4 N is formed, the thickness of the N is 550nm, and the N is positioned on the stress release layer;
the n-type transition layer is made of Al x Ga 1-x The Al component of the layer is changed from 0.6 of the N-type ohmic contact layer to 0.45 of the i-type light absorption layer, the layer avoids abrupt change of the Al component, improves the carrier collection rate, and is positioned on the N-type ohmic contact layer;
the i-type light absorption layer has a thickness of 200nm and is formed by undoped Al 0.45 Ga 0.55 N is arranged on the N-type transition layer;
the thickness of the p-type doped layer is 75nm, and the p-type doped layer is formed by Al doped with Mg 0.45 Ga 0.55 N is arranged on the i-type light absorption layer;
the p-type transition layer is made of Al doped with Mg x Ga 1-x The Al component gradually decreases from 0.45 to 0, gradually decreases from the direction close to the p-type doped layer to the p-type ohmic contact layer, and is 25nm thick and is positioned on the p-type doped layer;
the p-type ohmic contact layer is 50nm thick and is formed by doping GaN with Mg and is positioned on the p-type transition layer;
the protective layer is SiO 2 The layer is 200nm thick and covers the parts outside the two electrodes on the upper surface of the whole device;
the n-type electrode is annular and is positioned on the edge of the n-type ohmic contact layer;
the p-type electrode is positioned on the p-type ohmic contact layer.
The preparation method of the back incidence solar blind ultraviolet detector comprises the following steps:
cleaning a substrate epitaxial wafer: soaking the epitaxial wafer in acetone, simultaneously using ultrasonic for cleaning for 10 minutes, then using alcohol for soaking and ultrasonic for cleaning for 10 minutes, then deionizing and cleaning organic matters adsorbed on the epitaxial wafer, soaking the epitaxial wafer in hydrochloric acid solution for 5 minutes, and then deionizing and flushing.
Manufacturing a buffer layer and a stress release layer: on the substrate, a buffer layer is epitaxially grown at 1100 ℃ by using a metal organic chemical vapor deposition method, and then a stress release layer is epitaxially grown on the buffer layer at 1200 ℃ and a III/V flow ratio of 1000 and a reaction chamber pressure of between 10Pa and 15 Pa.
Manufacturing an n-type ohmic contact layer: and growing and forming an n-type ohmic contact layer on the stress release layer by adopting a metal organic compound chemical vapor deposition method.
And (3) manufacturing a transition layer: al ions are injected for multiple times, al ions are injected into the transition layer at different energy and dosage according to the requirement, the injection condition of the Al ions is gradually and slowly changed, the content of Al components at different positions in the n-type transition layer and the p-type transition layer is further changed, the Al components are slowly changed, the gradient of the Al components is reduced, the injection times are 5 to 10 times according to the requirement, the injection energy is 10keV to 100keV, and the injection dosage is 2 multiplied by 10 13 ions/cm 2 Up to 1X 10 14 ions/cm 2 And respectively growing an n-type transition layer and a p-type transition layer on the n-type ohmic contact layer and the p-type doped layer.
Manufacturing an i-type light absorption layer and a p-type doping layer: and an i-type light absorption layer and a p-type doping layer are formed on the n-type transition layer by adopting a metal organic compound chemical vapor deposition method.
And (3) manufacturing a p-type ohmic contact layer: and growing a p-type ohmic contact layer on the p-type transition layer by using a metal organic compound chemical vapor deposition method.
Manufacturing a protective layer: device SiO using plasma enhanced chemical vapor deposition 2 Preparation of protective layer with passivation and lifting functionsHigh device performance reliability.
And (5) etching a table top: ICP process is adopted, the ICP power is 300W, the RF power is 100W, and Cl 2 /BCl 3 The flow ratio is 0.8 (ml/s)/0.1 (ml/s) under the standard state, siO 2 The mask, cavity pressure is 12 to 15Pa, and the device is treated by boiling potassium hydroxide solution after etching to reduce adverse effect caused by etching.
Manufacturing an electrode: the n-type electrode is Ti/Al/Ni/Au alloy, the p-type electrode is Ni/Au double-layer metal, the protection layer covering partial areas on the n-type ohmic contact layer and the p-type ohmic contact layer is removed by photoetching and electron beam evaporation methods, so that positions for installing the n-type electrode and the p-type electrode are left, the n-type electrode and the p-type electrode are formed by depositing corresponding positions respectively by electron beam evaporation and deposition, and finally the n-type electrode and the p-type electrode are annealed rapidly in nitrogen at 700 ℃ for 1min.
The invention has the beneficial effects that: (1) The presence of the buffer layer allows the film cracking to be suppressed to some extent. (2) The back incidence structure avoids the problem of low doping efficiency of the p-type layer, and the p-type ohmic contact layer with lower resistance can be manufactured by thicker metal. (3) The presence of the stress relief layer allows dislocation density in the epitaxial structure to be controlled. (4) The electrode connection is more stable and reliable, and the resistance of the two electrodes is greatly reduced by carrying out rapid degradation treatment on the electrodes. (5) The low Al composition gradient of the two transition layers improves device performance.
Drawings
FIG. 1 is a schematic cross-sectional view of the present invention.
Fig. 2 is a schematic top view of the present invention.
In the figure: 1-substrate, 2-buffer layer, 3-stress releasing layer, 4-n type ohmic contact layer, 5-n type transition layer, 6-i type light absorbing layer, 7-p type doped layer, 8-p type transition layer, 9-p type ohmic contact layer, 10-protective layer, 11-n type electrode, 12-p type electrode.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings.
The invention adopts a back incidence structure, as shown in fig. 1, the device of the invention comprises:the semiconductor device comprises a substrate (1), a buffer layer (2), a stress release layer (3), an n-type ohmic contact layer (4), an n-type transition layer (5), an i-type light absorption layer (6), a p-type doping layer (7), a p-type transition layer (8), a p-type ohmic contact layer (9), a protective layer (10), an n-type electrode (11) and a p-type electrode (12), wherein the substrate (1) is a sapphire substrate and is positioned at the lowest part of each layer; the buffer layer (2) is a high-temperature AlN layer with the thickness of 350nm and is used for controlling stress accumulation and preventing the cracking of the film and is positioned on the substrate (1); the stress release layer (3) is AlN/Al 0.6 Ga 0.4 An N-superlattice layer, which serves to reduce the dislocation density of the epitaxial structure, above the buffer layer (2); the n-type ohmic contact layer (4) is made of Al doped with Si 0.6 Ga 0.4 N is formed, the thickness of the N is 550nm, and the N is positioned on the stress release layer (3); the n-type transition layer (5) is made of Al x Ga 1-x N is formed, the thickness is 20nm, the Al component of the layer is changed, the N-type ohmic contact layer (4) is gradually changed from 0.6 to 0.45 of the i-type light absorption layer (6), the layer avoids abrupt change of the Al component, the carrier collection rate is improved, and the layer is positioned above the N-type ohmic contact layer (4); the i-type light absorbing layer (6) is 200nm thick and is made of undoped Al 0.45 Ga 0.55 N is arranged on the N-type transition layer (5); the p-type doped layer (7) is Al doped with Mg 0.45 Ga 0.55 An N layer with the thickness of 75nm and positioned on the i-type light absorption layer (6); the p-type transition layer (8) is made of Al doped with Mg x Ga 1-x The Al component gradually decreases to 0 from 0.45 and is 25nm thick and is positioned on the p-type doped layer (7); the p-type ohmic contact layer (9) is 50nm thick and is formed by Mg-doped GaN and is positioned on the p-type transition layer (8); the protective layer (10) is SiO 2 A layer with the thickness of 200nm covering the whole upper surface of the device except the n-type electrode (11) and the p-type electrode (12); the n-type electrode (11) is annular and is positioned on the edge of the n-type ohmic contact layer (4); the p-type electrode (12) is positioned on the p-type ohmic contact layer (9).
The preparation method is partially the same as the conventional preparation method, but other parts are optimized:
the preparation process comprises the following steps: the substrate (1) epitaxial wafer cleaning, the manufacture of a buffer layer (2) and a stress release layer (3), the manufacture of an n-type ohmic contact layer (4), the manufacture of a transition layer, the manufacture of an i-type light absorption layer (6) and a p-type doping layer (7), the manufacture of a p-type ohmic contact layer (9), the manufacture of a protection layer (10), the mesa etching and the manufacture of an electrode, wherein the processes of the substrate (1) epitaxial wafer cleaning, the manufacture of the transition layer, the preparation of the protection layer, the mesa etching, the preparation of the electrode and the preparation of the transition layer are optimized in the invention.
Cleaning an epitaxial wafer of a substrate (1): soaking the epitaxial wafer in acetone, simultaneously using ultrasonic for cleaning for 10 minutes, then using alcohol for soaking and ultrasonic for cleaning for 10 minutes, then deionizing and cleaning organic matters adsorbed on the epitaxial wafer, soaking the epitaxial wafer in hydrochloric acid solution for 5 minutes, and then deionizing and flushing.
Manufacturing a buffer layer (2) and a stress release layer (3): on the substrate (1), a buffer layer (2) is epitaxially grown by a metal organic chemical vapor deposition method at a high temperature of 1100 ℃, and then a stress release layer (3) is epitaxially grown on an epitaxial wafer at 1200 ℃ and a III/V flow ratio of 1000 and a reaction chamber pressure of between 10Pa and 15 Pa.
Manufacturing an n-type ohmic contact layer (4): and growing an n-type ohmic contact layer (4) on the stress release layer (3) by adopting a metal organic compound chemical vapor deposition method.
And (3) manufacturing a transition layer: al ions are injected for multiple times, each time, the Al ions are injected into the transition layer according to the requirement, the injection condition of the Al ions is gradually and slowly changed, and then the content of Al components at different positions in the n-type transition layer (5) and the p-type transition layer (8) is changed, so that the Al components are slowly changed, the change gradient of the Al components is reduced, the injection times are 5-10 times according to the requirement, the injection energy is 10keV to 100keV, and the injection dosage is 2 multiplied by 10 13 ions/cm 2 Up to 1X 10 14 ions/cm 2 And respectively growing an n-type transition layer (5) and a p-type transition layer (8) on the n-type ohmic contact layer (4) and the p-type doped layer (7).
Manufacturing an i-type light absorption layer (6) and a p-type doping layer (7): and an i-type light absorption layer (6) and a p-type doped layer (7) are sequentially grown on the n-type transition layer (5) by adopting a metal organic compound chemical vapor deposition method.
Manufacturing a p-type ohmic contact layer (9): and forming a p-type ohmic contact layer (9) on the p-type transition layer (8) by using a metal organic chemical vapor deposition method.
Manufacturing a protective layer (10): device SiO using Plasma Enhanced Chemical Vapor Deposition (PECVD) 2 The preparation of the protective layer (10) has the functions of passivation and improving the performance reliability of the device.
And (5) etching a table top: ICP process is adopted, the ICP power is 300W, the RF power is 100W, and Cl 2 /BCl 3 The flow ratio is 0.8 (ml/s)/0.1 (ml/s) under the standard state, siO 2 And the pressure of the cavity is 12-15Pa, and the device is treated by using boiling potassium hydroxide solution after etching so as to reduce adverse effects caused by etching.
Manufacturing an electrode: the n-type electrode (11) is Ti/Al/Ni/Au series alloy, the p-type electrode (12) is Ni/Au series double-layer metal, a protective layer (10) covering partial areas on the n-type ohmic contact layer (4) and the p-type ohmic contact layer (9) is removed by utilizing a photoetching and electron beam evaporation method, positions for installing the n-type electrode (11) and the p-type electrode (12) are reserved, the n-type electrode (11) and the p-type electrode (12) are formed by utilizing electron beam evaporation deposition at corresponding positions respectively, and finally the n-type electrode and the p-type electrode (12) are annealed rapidly in nitrogen at 700 ℃ for 1min.
Claims (10)
1. A back-incident solar blind ultraviolet detector comprising: the semiconductor device comprises a substrate (1), a buffer layer (2), a stress release layer (3), an n-type ohmic contact layer (4), an n-type transition layer (5), an i-type light absorption layer (6), a p-type doping layer (7), a p-type transition layer (8), a p-type ohmic contact layer (9), a protective layer (10), an n-type electrode (11) and a p-type electrode (12), wherein the substrate (1) is a sapphire substrate and is positioned at the lowest part of each layer; the buffer layer (2) is a high-temperature AlN layer and is positioned on the substrate (1); the stress release layer (3) is AlN/Al 0.6 Ga 0.4 The N superlattice layer is positioned above the buffer layer (2); the n-type ohmic contact layer (4) is made of Al doped with Si 0.6 Ga 0.4 N is arranged on the stress release layer (3); the n-type transition layer (5) is made of Al x Ga 1-x N, which is located above the N-type ohmic contact layer (4); the i-shaped light absorberThe receiving layer (6) is made of undoped Al 0.45 Ga 0.55 N is arranged on the N-type transition layer (5); the p-type doped layer (7) is made of Al doped with Mg 0.45 Ga 0.55 N is arranged on the i-type light absorption layer (6); the p-type transition layer (8) is formed by AlGaN doped with Mg and is positioned above the p-type doped layer (7); the p-type ohmic contact layer (9) is formed by Mg-doped GaN and is positioned on the p-type transition layer (8); the protective layer (10) is SiO 2 A layer covering the entire upper surface of the device except for the n-type electrode (11) and the p-type electrode (12); the n-type electrode (11) is annular and is positioned on the edge of the n-type ohmic contact layer (4); the p-type electrode (12) is positioned on the p-type ohmic contact layer (9).
2. The back-entry solar blind ultraviolet detector according to claim 1, wherein: the thickness of the buffer layer (2) is 350nm.
3. The back-entry solar blind ultraviolet detector according to claim 1, wherein: the thickness of the n-type ohmic contact layer (4) is 550nm.
4. The back-entry solar blind ultraviolet detector according to claim 1, wherein: the n-type transition layer (5) is 20nm thick, and the Al composition of the layer is changed from 0.6 of the n-type ohmic contact layer (4) to 0.45 of the i-type light absorption layer (6).
5. A back-entry solar blind ultraviolet detector according to claim 1 or 4, wherein: the i-type light absorption layer (6) is 200nm thick.
6. The back-entry solar blind ultraviolet detector according to claim 1, wherein: the p-type doped layer (7) is 75nm thick.
7. The back-entry solar blind ultraviolet detector according to claim 1, wherein: the Al component of the p-type transition layer (8) gradually decreases from 0.45 to 0, and gradually decreases from the position close to the p-type doped layer (7) to the p-type ohmic contact layer (9) and is 25nm thick.
8. The back-entry solar blind ultraviolet detector according to claim 1, wherein: the p-type ohmic contact layer (9) is 50nm thick.
9. The back-entry solar blind ultraviolet detector according to claim 1, wherein: the protective layer (10) is 200nm thick.
10. A preparation method of a back incidence solar blind ultraviolet detector is characterized by comprising the following steps of:
cleaning an epitaxial wafer of a substrate (1): soaking an epitaxial wafer in acetone, simultaneously using ultrasonic for cleaning for 10 minutes, then using alcohol for soaking and ultrasonic for cleaning for 10 minutes, then deionizing and cleaning organic matters adsorbed on the epitaxial wafer, soaking the epitaxial wafer in hydrochloric acid solution for 5 minutes, and then deionizing and flushing;
manufacturing a buffer layer (2) and a stress release layer (3): epitaxially growing a buffer layer (2) on a substrate (1) by using a metal organic chemical vapor deposition method at a high temperature of 1100 ℃, and epitaxially growing a stress release layer (3) on the buffer layer (2) at a III/V flow ratio of 1200 ℃ and a reaction cavity pressure of between 10Pa and 15 Pa;
manufacturing an n-type ohmic contact layer (4): forming an n-type ohmic contact layer (4) on the stress release layer (3) by adopting a metal organic compound chemical vapor deposition method;
and (3) manufacturing a transition layer: al ions are injected for multiple times, each time, the Al ions are injected into the transition layer according to the requirement, the injection condition of the Al ions is gradually and slowly changed, and then the content of Al components at different positions in the n-type transition layer (5) and the p-type transition layer (8) is changed, so that the Al components are slowly changed, the change gradient of the Al components is reduced, the injection times are 5 to 10 times according to the requirement, the injection energy is 10keV to 100keV, and the injection dosage is 2 multiplied by 10 13 ions/cm 2 Up to 1X 10 14 ions/cm 2 An n-type transition layer (5) and a p-type transition layer (8) are respectively formed on the n-type ohmic contact layer (4) and the p-type doped layer (7) in a growing mode;
manufacturing an i-type light absorption layer (6) and a p-type doping layer (7): an i-type light absorption layer (6) and a p-type doping layer (7) are formed on the n-type transition layer (5) by adopting a metal organic compound chemical vapor deposition method in sequence;
manufacturing a p-type ohmic contact layer (9): forming a p-type ohmic contact layer (9) on the p-type transition layer (8) by using a metal organic compound chemical vapor deposition method;
manufacturing a protective layer (10): device SiO using plasma enhanced chemical vapor deposition 2 The preparation of the protective layer (10) has the functions of passivation and improving the performance reliability of the device;
and (5) etching a table top: ICP process is adopted, the ICP power is 300W, the RF power is 100W, and Cl 2 / BCl 3 The flow ratio is 0.8 (ml/s)/0.1 (ml/s) under the standard state, siO 2 A mask, wherein the cavity pressure is 12Pa to 15Pa, and the device is treated by using boiling potassium hydroxide solution after etching so as to reduce adverse effects caused by etching;
manufacturing an electrode: the n-type electrode (11) is Ti/Al/Ni/Au series alloy, the p-type electrode (12) is Ni/Au series double-layer metal, a protective layer (10) covering partial areas on the n-type ohmic contact layer (4) and the p-type ohmic contact layer (9) is removed by utilizing a photoetching and electron beam evaporation method, positions for installing the n-type electrode (11) and the p-type electrode (12) are reserved, the n-type electrode (11) and the p-type electrode (12) are formed by utilizing electron beam evaporation deposition at corresponding positions respectively, and finally the n-type electrode and the p-type electrode (12) are annealed rapidly in nitrogen at 700 ℃ for 1min.
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| CN111933748A (en) * | 2020-07-22 | 2020-11-13 | 中国电子科技集团公司第十三研究所 | Back-incident solar blind ultraviolet detector and manufacturing method thereof |
| CN112018210B (en) * | 2020-09-18 | 2022-05-17 | 南京冠鼎光电科技有限公司 | Polarization-enhanced narrow-band AlGaNp-i-n type ultraviolet detector and preparation method thereof |
| CN113964224B (en) * | 2021-12-22 | 2022-04-01 | 至芯半导体(杭州)有限公司 | Semiconductor ultraviolet detector chip and epitaxial structure thereof |
| CN114068741B (en) * | 2022-01-17 | 2022-04-19 | 至善时代智能科技(北京)有限公司 | Ultraviolet detector chip |
| CN117334776B (en) * | 2023-09-05 | 2024-05-14 | 武汉敏芯半导体股份有限公司 | Photoelectric detector based on periodic strain and manufacturing method thereof |
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