CN116960226A - Photoelectric detector for low-temperature methane detection and preparation method thereof - Google Patents

Photoelectric detector for low-temperature methane detection and preparation method thereof Download PDF

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Publication number
CN116960226A
CN116960226A CN202311115515.1A CN202311115515A CN116960226A CN 116960226 A CN116960226 A CN 116960226A CN 202311115515 A CN202311115515 A CN 202311115515A CN 116960226 A CN116960226 A CN 116960226A
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inasp
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朱岩
杨志茂
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Jiangsu Tuowei Optoelectronic Technology Co ltd
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Jiangsu Tuowei Optoelectronic Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • 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
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/184—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP
    • H01L31/1844—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP comprising ternary or quaternary compounds, e.g. Ga Al As, In Ga As P
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • 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
    • H01L31/02—Details
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • 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
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    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • 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 potential barriers, e.g. phototransistors
    • H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
    • H01L31/102—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier
    • H01L31/105—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier the potential barrier being of the PIN type

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Abstract

The invention discloses a photoelectric detector for detecting low-temperature methane and a preparation method thereof.

Description

Photoelectric detector for low-temperature methane detection and preparation method thereof
Technical Field
The invention relates to the technical field of photoelectric detectors, in particular to a photoelectric detector for detecting low-temperature methane and a preparation method thereof.
Background
Compared with the traditional electrochemical method, the system cost can be greatly reduced by utilizing the laser spectroscopy (TDLS) to detect methane. Methane has a strong absorption for 1654nm laser light, and thus a photodetector for methane detection needs to have a strong responsivity for 1654nm laser light in a wide temperature interval. The In composition of a conventional InGaAs PIN detector was 53% and the InGaAs absorber layer was lattice matched to the InP substrate. This helps to reduce dislocations in the absorber layer and thus reduce dark current in the device. The room temperature cut-off wavelength of a conventional InGaAs PIN detector is about 1700nm. The cut-off wavelength of the detector decreases with decreasing temperature, and at low temperature (-40 ℃) the cut-off wavelength decreases to 1650nm, thus the absorption of 1654nm laser light decreases substantially.
Therefore, improvements are needed to conventional InGaAs PIN photodetectors to ensure that they are more responsive to 1654nm light over a wide temperature range (-40-85 ℃).
Disclosure of Invention
In order to solve the defects of the technical scheme, the invention aims to provide a preparation method of a photoelectric detector for detecting low-temperature methane.
Another object of the present invention is to provide a photodetector for low-temperature methane detection prepared by the above preparation method.
The aim of the invention is achieved by the following technical scheme.
The preparation method of the photoelectric detector for detecting the low-temperature methane comprises the following steps:
step one: an N-type InP buffer layer, an N-type InAsP metamorphic buffer layer, an unintended doped InGaAs absorption layer and an unintended doped InAsP cover layer are sequentially grown on an N-type InP substrate by utilizing a deposition mode of MOCVD or MBE;
step two: depositing a SiN film on the upper surface of the unintentionally doped InAsP cover layer by utilizing a PECVD deposition mode;
step three: forming a Zn diffusion window pattern on the surface of the SiN film by using photoresist, removing the SiN film on the Zn diffusion window pattern by using an etching method, exposing the lower unintentional doping InAsP cover layer, and removing the photoresist after etching to form a Zn diffusion window;
step four: performing Zn diffusion in the Zn diffusion window area by using MOCVD or a furnace tube method to form a P-type Zn diffusion area, wherein the Zn diffusion area comprises an unintended doping InAsP cover layer and an unintended doping InGaAs absorption layer;
step five: depositing SiN antireflection films on all exposed upper surfaces by utilizing a PECVD (plasma enhanced chemical vapor deposition) deposition mode;
step six: forming a VIA hole pattern on the SiN film above the P-type Zn diffusion area by using photoresist, removing the SiN film on the VIA hole pattern by using an etching method to obtain a VIA hole, exposing the P-type Zn diffusion area below, removing the photoresist after etching is finished, and forming a metal contact hole on the upper surface of the P-type Zn diffusion area;
step seven: forming a P metal pattern above the VIA hole by using photoresist, evaporating metal by using electron beam evaporation or magnetron sputtering, performing metal stripping, and annealing to obtain a P metal electrode, wherein the upper surface contact of the P metal electrode and a P type Zn diffusion area is ohmic contact;
step eight: thinning and polishing the back surface of the N-type InP substrate;
step nine: and preparing an N metal electrode on the back surface of the N-type InP substrate by utilizing an electron beam evaporation or magnetron sputtering method, and annealing to form ohmic contact.
In the above technical scheme, in the first step, the thickness of the N-type InP buffer layer is 0.5-2 μm, and the doping concentration is 1×10 17 /cm 3 ～2×10 18 /cm 3 。
In the above technical solution, in the first step, the N-type InAsP graded buffer layer is one or more layers, the number of layers is greater than or equal to 1 and less than or equal to 10, the lattice constant at the bottom is the same As that of the N-type InP buffer layer, the lattice constant at the top is the same As that of the unintentional InGaAs absorption layer, the As component is gradually increased from bottom to top, the P component is gradually decreased, the lattice mismatch between the lowest-layer InAsP graded buffer layer and the InP substrate is not higher than 0.5%, the lattice mismatch between every 2 InAsP graded buffer layers is not higher than 0.25%, and the thickness of each layer is 0.1-2 μm.
In the above technical solution, in the first step, the In component In the unintentionally doped InGaAs absorbing layer is greater than 53%, the wavelength of fluorescence (PL) at room temperature is greater than or equal to 1710nm, the wavelength of cutoff at room temperature is greater than 1740nm, and the responsivity to 1654nm light at-40 ℃ is not less than 0.5A/W, and the lattice constant of the unintentionally doped InGaAs absorbing layer is matched with the lattice constant of the uppermost layer of the N-type InAsP graded buffer layer, and the thickness of the unintentionally doped InGaAs absorbing layer is 1-5 μm.
In the above technical scheme, in the first step, the lattice constant of the unintentionally doped InAsP cap layer is matched with that of the unintentionally doped InGaAs absorption layer, the thickness of the unintentionally doped InAsP cap layer is 0.5-5 μm, the unintentionally doped InAsP cap layer is used for forming an active region in the subsequent Zn diffusion process, and a window layer with a high band gap is provided, so that the surface recombination current is reduced, and the dark current of the whole detector is reduced.
In the above technical solution, in the second step, the thickness of the SiN film is 100-500 nm.
In the above technical scheme, in the third step, the Zn diffusion window is circular or square, and its diameter or side length is 10-5000 μm.
In the above technical solution, in the fourth step, the P-type Zn diffusion region sequentially goes from the upper surface of the unintentionally doped InAsP cap layer to the unintentionally doped InGaAs absorption layer from top to bottom, where the thickness of the unintentionally doped InGaAs absorption layer is 0.1-0.5 μm.
In the above technical scheme, in the fifth step, the reflectance of the SiN anti-reflection film for 1654nm wavelength light is 70% or more.
In the above technical solution, in the eighth step, the thickness of the semi-insulating InP substrate after thinning and polishing is 50-200 μm.
The photoelectric detector for detecting the low-temperature methane is obtained by the preparation method.
The invention has the advantages and beneficial effects that:
1. the invention aims to provide a 1654nm reinforced InGaAs PIN photoelectric detector for low-temperature methane detection and a preparation method thereof. According to the invention, one or more InAsP (indium gallium arsenide) metamorphic buffer layers are introduced, so that the lattice constant of InP is expanded, and a virtual substrate is formed at the top of the InAsP metamorphic buffer layers, so that the InGaAs absorption layer with high quality and high In component can be grown on the InAsP metamorphic buffer layers, and the cut-off wavelength In low-temperature detection is improved.
2. The In component In the unintentionally doped InGaAs absorption layer of the detector is more than 53%, and the fluorescence (PL) wavelength at room temperature is more than or equal to 1710nm. The room temperature cut-off wavelength is ensured to be larger than 1740nm, the responsivity of the detector for 1654nm light at-40 ℃ is ensured to be not lower than 0.5A/W, and the responsivity of the detector under the low temperature condition is improved.
3. The function of the unintentionally doped InAsP cover layer is to form an active region for a subsequent Zn diffusion process and provide a window layer with a high band gap, so that the surface recombination current is reduced, and the dark current of the whole device is reduced. The lattice constant of the unintentionally doped InAsP cap layer is matched to the unintentionally doped InGaAs absorber layer.
4. The In component of the unintentionally doped InGaAs absorber layer of the detector of the invention is greater than 53% and therefore the InGaAs absorber layer material is lattice mismatched to the InP substrate. If InGaAs material with an In composition higher than 53% is grown directly on an InP substrate, it causes a very high dislocation density In the InGaAs absorber layer, resulting In a high dark current of the detector. The InAsP metamorphic buffer layer is introduced, so that lattice mismatch between InP and InGaAs absorption layers is improved, a better virtual substrate is provided for the unintentionally doped InGaAs absorption layers, dark current of the detector is reduced, and performance of the detector is improved.
Drawings
Fig. 1 is a schematic flow chart of step one-step four in embodiment 1 of the present invention.
Fig. 2 is a schematic flow chart of steps five to six in embodiment 1 of the present invention.
Fig. 3 is a flow chart of step seven of embodiment 1 of the present invention.
Fig. 4 is a schematic flow chart of steps eight to nine in embodiment 1 of the present invention.
FIG. 5 shows the response and temperature of the photodetector obtained in example 1 of the present invention to 1654nm light.
Wherein, the liquid crystal display device comprises a liquid crystal display device,
1: an N-type InP substrate, a semiconductor device, a semiconductor,
2: an N-type InP buffer layer,
3: an N-type InAsP graded buffer layer,
4: the InGaAs absorber layer is unintentionally doped,
5: the InAsP cap layer is unintentionally doped,
6: a thin film of SiN,
7: a Zn diffusion window is provided in the substrate,
8: a P-type Zn diffusion region,
9: siN reduction the reverse-flow film is arranged on the surface of the substrate,
10: the holes of the VIA are arranged on the holes,
11: a P metal electrode, wherein the P metal electrode,
12: n metal electrode.
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments.
Example 1
As shown in fig. 1-4, a method for preparing a photoelectric detector for detecting low-temperature methane comprises the following steps:
step one: an N-type InP buffer layer 2, an N-type InAsP metamorphic buffer layer 3, an unintentionally doped InGaAs absorption layer 4 and an unintentionally doped InAsP cover layer 5 are sequentially grown on an N-type InP substrate 1 by utilizing a deposition mode of MOCVD or MBE, wherein the thickness of the N-type InP buffer layer 2 is 1 mu m, and the doping concentration is 1 multiplied by 10 18 /cm 3 The method has the function of better matching the lattice constant difference caused by different growth conditions between epitaxial layer materials on the N-type InP substrate 1 and the N-type InP buffer layer 2, so as to ensure the growth quality of the epitaxial layer; the number of the N-type InAsP graded buffer layer 3 is one, and the thickness is 1 μm. Wherein, the composition of As is 7%, the lattice mismatch with the N-type InP substrate 1 is 0.23%, the lattice constant of InP is expanded by introducing an InAsP metamorphic buffer layer, a virtual substrate is formed on the top of the InAsP metamorphic buffer layer, thereby the growth of an InGaAs absorbing layer with high quality and high In composition can be carried out on the virtual substrate, and the dark current of the device is reduced; the thickness of the unintended doped InGaAs absorption layer 4 is 5 mu m, the In component is 58%, the layer is a photo-generated carrier generation layer, the room temperature fluorescence (PL) wavelength is 1770nm, the cut-off wavelength of the detector is expanded, the room temperature cut-off wavelength is more than 1740nm, the responsivity of the unintended doped InGaAs absorption layer to 1654nm light is not lower than 0.5A/W at-40 ℃, and the lattice constant of the unintended doped InGaAs absorption layer is matched with the lattice constant of the uppermost layer of the N-type InAsP metamorphic buffer layer 3; lattice constant of the unintentionally doped InAsP cap layer 5 matches the unintentionally doped InGaAs absorber layerMatching. The thickness of the InAsP cover layer 5 which is not intentionally doped is 1 mu m, the As component is 7%, the InAsP cover layer which is not intentionally doped is used for forming an active region (P-type diffusion region) by a subsequent Zn diffusion process, a window layer with a high band gap is provided, the surface composite current is reduced, and the dark current of the whole detector is reduced;
step two: depositing a SiN film 6 on the upper surface of the unintentionally doped InAsP cover layer 5 by utilizing a PECVD (plasma enhanced chemical vapor deposition) deposition mode, wherein the thickness of the SiN film 6 is 100nm;
step three: forming a Zn diffusion window pattern on the surface of the SiN film 6 by using photoresist, removing the SiN film 6 on the Zn diffusion window pattern by using an etching method, exposing the lower unintentional doping InAsP cover layer 5, removing the photoresist after etching is finished, and forming a Zn diffusion window 7, wherein the Zn diffusion window 7 is circular, and the diameter of the Zn diffusion window 7 is 1000 mu m;
step four: carrying out Zn diffusion in the Zn diffusion window 7 area by using MOCVD or a furnace tube method to form a P-type Zn diffusion area 8, wherein the Zn diffusion area comprises an unintentional doping InAsP cover layer 5 and a part of unintentional doping InGaAs absorption layer 4, and the Zn diffusion depth enters the position of 0.2 mu m of the InGaAs absorption layer;
step five: depositing SiN antireflection films 9 on all exposed upper surfaces by utilizing a PECVD (plasma enhanced chemical vapor deposition) deposition mode, wherein the reflectivity of the SiN antireflection films 9 for 1654nm wavelength light is 95%;
step six: forming a VIA hole pattern on the SiN film 6 above the P-type Zn diffusion area 8 by using photoresist, removing the SiN film 6 on the VIA hole pattern by using an etching method to obtain a VIA hole 10, exposing the P-type Zn diffusion area 8 below, removing the photoresist after etching, and forming a metal contact hole on the upper surface of the P-type Zn diffusion area 8, wherein the VIA hole 10 is in a circular shape, the ring width is 10 mu m, and the distance between the outer edge of the VIA hole 10 and the edge of the Zn diffusion area 8 is 5 mu m;
step seven: forming a P metal pattern above the VIA hole 10 by using photoresist, evaporating metal by using electron beam evaporation or magnetron sputtering, performing metal stripping, and annealing to obtain a P metal electrode 11, wherein the P metal electrode 11 is in ohmic contact with the upper surface of the P type Zn diffusion region 8;
step eight: thinning and polishing are carried out on the back surface of the N-type InP substrate 1, and the thickness of the N-type InP substrate 1 after thinning and polishing is 150 mu m;
step nine: an N metal electrode 12 is prepared on the back surface of the N InP substrate 1 by an electron beam evaporation method, and is annealed to form an ohmic contact.
FIG. 5 shows the relationship between the responsivity of the photodetector of the present invention and the prior art photodetector (Infornix IFY15P1000-R1 series) and the temperature, from which it can be seen that the responsivity of the photodetector of the present invention with respect to 1654nm light remains very high at low temperature, whereas the responsivity of the prior art photodetector with respect to 1654nm light at-40℃is greatly reduced with respect to room temperature.
The foregoing has described exemplary embodiments of the invention, it being understood that any simple variations, modifications, or other equivalent arrangements which would not unduly obscure the invention may be made by those skilled in the art without departing from the spirit of the invention.

Claims (10)

1. The preparation method of the photoelectric detector for detecting the low-temperature methane is characterized by comprising the following steps of:
step one: an N-type InP buffer layer, an N-type InAsP metamorphic buffer layer, an unintended doped InGaAs absorption layer and an unintended doped InAsP cover layer are sequentially grown on an N-type InP substrate by utilizing a deposition mode of MOCVD or MBE;
step two: depositing a SiN film on the upper surface of the unintentionally doped InAsP cover layer by utilizing a PECVD deposition mode;
step three: forming a Zn diffusion window pattern on the surface of the SiN film by using photoresist, removing the SiN film on the Zn diffusion window pattern by using an etching method, exposing the lower unintentional doping InAsP cover layer, and removing the photoresist after etching to form a Zn diffusion window;
step four: performing Zn diffusion in the Zn diffusion window area by using MOCVD or a furnace tube method to form a P-type Zn diffusion area, wherein the Zn diffusion area comprises an unintended doping InAsP cover layer and an unintended doping InGaAs absorption layer;
step five: depositing SiN antireflection films on all exposed upper surfaces by utilizing a PECVD (plasma enhanced chemical vapor deposition) deposition mode;
step six: forming a VIA hole pattern on the SiN film above the P-type Zn diffusion area by using photoresist, removing the SiN film on the VIA hole pattern by using an etching method to obtain a VIA hole, exposing the P-type Zn diffusion area below, removing the photoresist after etching is finished, and forming a metal contact hole on the upper surface of the P-type Zn diffusion area;
step seven: forming a P metal pattern above the VIA hole by using photoresist, evaporating metal by using electron beam evaporation or magnetron sputtering, performing metal stripping, and annealing to obtain a P metal electrode, wherein the upper surface contact of the P metal electrode and a P type Zn diffusion area is ohmic contact;
step eight: thinning and polishing the back surface of the N-type InP substrate;
step nine: and preparing an N metal electrode on the back surface of the N-type InP substrate by utilizing an electron beam evaporation or magnetron sputtering method, and annealing to form ohmic contact.
2. The method according to claim 1, wherein in the first step, the N-type InP buffer layer has a thickness of 0.5 to 2 μm and a doping concentration of 1 x 10 17 /cm 3 ～2×10 18 /cm 3 ；
The N-type InAsP graded buffer layer is one or more layers, the number of layers is more than or equal to 1 and less than or equal to 10, the lattice constant at the bottom is the same As that of the N-type InP buffer layer, the lattice constant at the top is the same As that of the unintentional doped InGaAs absorption layer, the As component is gradually increased from bottom to top, the P component is gradually reduced, the lattice mismatch between the lowest InAsP graded buffer layer and the InP substrate is not higher than 0.5%, the lattice mismatch between every 2 InAsP graded buffer layers is not higher than 0.25%, and the thickness of each layer is 0.1-2 mu m.
3. The method of manufacturing according to claim 1, wherein In the first step, the In component In the unintentionally doped InGaAs absorbing layer is greater than 53%, the room temperature fluorescence wavelength is greater than or equal to 1710nm, the room temperature cutoff wavelength is greater than 1740nm, and the responsivity to 1654nm light at-40 ℃ is not less than 0.5A/W, the lattice constant of the unintentionally doped InGaAs absorbing layer is matched with the lattice constant of the uppermost layer of the N-type InAsP-type graded buffer layer, and the thickness of the unintentionally doped InGaAs absorbing layer is 1-5 μm.
4. The method of claim 1 wherein in step one, the lattice constant of the unintentionally doped InAsP cap layer is matched to the unintentionally doped InGaAs absorber layer, the unintentionally doped InAsP cap layer has a thickness of 0.5-5 μm, the unintentionally doped InAsP cap layer is used in a subsequent Zn diffusion process to form an active region and provide a high bandgap window layer, reducing surface recombination current and reducing dark current in the detector as a whole.
5. The method according to claim 1, wherein in the second step, the SiN film has a thickness of 100 to 500nm.
6. The method according to claim 1, wherein in the third step, the Zn diffusion window is round or square, and the diameter or side length thereof is 10 to 5000. Mu.m.
7. The method of claim 1, wherein in step four, the P-type Zn diffusion region is sequentially from the upper surface of the unintentionally doped InAsP cap layer to the unintentionally doped InGaAs absorber layer from top to bottom, wherein the thickness of the unintentionally doped InGaAs absorber layer is 0.1 to 0.5 μm.
8. The method according to claim 1, wherein in the fifth step, the SiN antireflection film has a reflectance of 70% or more with respect to a 1654nm wavelength light.
9. The method according to claim 1, wherein in the eighth step, the thickness of the semi-insulating InP substrate after thinning and polishing is 50 to 200 μm.
10. A photodetector for low temperature methane detection obtained by the production method according to any one of claims 1 to 9.
CN202311115515.1A 2023-08-31 2023-08-31 Photoelectric detector for low-temperature methane detection and preparation method thereof Pending CN116960226A (en)

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