CN113241386A - Silicon-doped gallium blocking impurity band medium-long wave infrared detector and preparation method thereof - Google Patents
Silicon-doped gallium blocking impurity band medium-long wave infrared detector and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a silicon-doped gallium blocking impurity band medium-long wave infrared detector and a preparation method thereof. The device comprises a substrate, a negative electrode contact layer, an absorption layer, a barrier layer and a dielectric layer from bottom to top, wherein a positive electrode contact area is positioned on the left side of the barrier layer and embedded in the barrier layer, a positive electrode is positioned above the positive electrode contact area, and the negative electrode is deep into the substrate along the side wall of a V-shaped hole. The preparation steps are that a negative electrode contact layer, an absorption layer and a barrier layer are grown by a molecular beam epitaxy method, a positive electrode contact area is prepared by an ion implantation process, positive and negative electrodes are prepared by photoetching, etching and an electron beam evaporation process, and finally silicon nitride in a photosensitive area is etched to finish the preparation of the device. The gallium doped silicon is used as a medium-long wave infrared absorption layer, the intrinsic silicon is used as a blocking layer to inhibit dark current, and high-performance detection of medium-long wave infrared is realized. The invention is characterized in that the gallium impurity energy level with relatively deep energy level position is constructed, the manufacturing process is simple, and the working temperature is high.
Description
Technical Field
The invention designs a silicon-doped gallium blocking impurity band medium-long wave infrared detector and a preparation method thereof. The device specifically comprises a device for realizing high-performance detection of medium-and-long-wave infrared radiation by using a molecular beam epitaxial silicon gallium-doped material as a medium-and-long-wave infrared absorption layer and using intrinsic silicon as a barrier layer to inhibit dark current.
Background
Medium-long wave infrared (5-14 μm) is one of the important atmospheric windows in infrared photonics research. The target spontaneous radiation wave band at normal temperature has energy matching with the energy required by the change of the vibration dipole moment of the organic molecules, and contains important 'fingerprint' information of the biomolecules. Therefore, the method plays an important role in the fields of military, life science, industrial monitoring and the like for detecting and decoding the long-wave infrared. However, the electromagnetic radiation energy corresponding to the long-wave infrared is extremely low, and the semiconductor detection material with the energy band width near 0.1eV is required based on the photoelectric effect, which is a very difficult task for the growth process control of the material. In addition, due to the small forbidden bandwidth of the material, any defect, dislocation, surface treatment and the like can increase the leakage current of the device, reduce the signal-to-noise ratio of the device, and greatly limit the performance of the long-wave infrared photoelectric detector.
The extrinsic silicon-based very long wave infrared detector has the advantages of longer detection wavelength, lower dark current and higher signal-to-noise ratio based on an impurity band transition mechanism. It has been proved that the detection of 40 μm ultra-long wave infrared can be realized, and the quantum efficiency can reach more than 80% by controlling the concentration of the doping element. Typically operating at liquid helium temperatures, very low dark current levels (<0.1e/s/pixel) can be achieved. Based on a mature silicon process platform, the silicon-based very-long-wave infrared focal plane detector has wide prospects.
Disclosure of Invention
The invention provides a silicon-doped gallium blocking medium-long wave infrared detector in an impurity band and a preparation method thereof.
The structure of the detector is as follows: epitaxially growing a negative electrode contact layer 2 on a substrate 1, epitaxially growing an absorption layer 3 and a barrier layer 4 on the negative electrode contact layer 2, injecting a positive electrode contact region 5 in the left partial region of the barrier layer 4, chemically etching a V-shaped hole until the negative electrode contact layer 2 is exposed, preparing a positive electrode 6 and a negative electrode 7, and forming a dielectric layer 8 between the positive electrode 6 and the negative electrode 7 and the upper surface of the barrier layer 4.
The substrate 1 is high-conductivity silicon;
the negative electrode contact layer 2 and the positive electrode contact layer 5 are doped with phosphorus ions with the doping concentration of 8 multiplied by 1014cm-2；
The absorption layer 3 is doped with gallium ions with the doping concentration of 1 multiplied by 1016～1×1018cm-3The thickness is 20-30 μm;
the barrier layer 4 is intrinsic silicon and has the thickness of 5-10 mu m;
the positive electrode 6 and the negative electrode 7 are titanium-aluminum composite metal films, titanium is on the lower layer and has the thickness of 20nm, and aluminum is on the upper layer and has the thickness of 600 nm.
The dielectric layer 8 is silicon nitride and has a thickness of 200 nm.
The preparation method of the silicon-doped gallium blocking impurity band medium-long wave infrared detector comprises the following steps:
1) epitaxially growing a negative electrode contact layer 2, an absorption layer 3 and a barrier layer 4 on a substrate 1 by a molecular beam epitaxy method;
2) growing a silicon nitride mask by a plasma enhanced chemical vapor deposition method, patterning the silicon nitride mask, etching silicon nitride by reactive ions to open a positive electrode contact hole, and performing rapid annealing activation after ion implantation to form a positive electrode contact region 5;
3) etching the silicon nitride by reactive ions to open the negative electrode contact hole, and performing wet etching until the negative electrode contact layer 2 is exposed;
4) after the negative electrode contact layer 2 and the positive electrode contact region 5 are exposed by photoetching, the positive electrode 6 and the negative electrode 7 are evaporated by electron beams and annealed to form good ohmic contact.
5) And removing the silicon nitride in the photosensitive area by adopting a reactive ion etching process, and reserving the dielectric layer 8 between the positive electrode 6 and the negative electrode 7 and the upper surface of the barrier layer 4.
Compared with the prior art, the invention has the following beneficial effects:
1. the gallium-doped silicon absorption layer is epitaxially grown by adopting a molecular beam epitaxy method, so that the thickness of the grown absorption layer can be conveniently controlled and the doping concentration can be conveniently adjusted, the absorption efficiency of the absorption layer on medium-long wave infrared radiation and the response rate of a device are improved, meanwhile, the damage caused by preparing materials by using other methods such as ion implantation and the like is avoided, and the dark current is reduced;
2. the mode of collecting the negative electrode with the V-shaped hole is adopted, so that the distance between the positive electrode and the negative electrode is reduced, the electric field is uniformly distributed, the collection capability of photon-generated carriers is enhanced, and the sensitivity of the detector is improved. And meanwhile, the V-shaped hole is processed by wet etching, so that the preparation process of the groove area is simplified, and the cost is reduced.
Drawings
FIG. 1 is a schematic structural cross-sectional view of a silicon-doped gallium-blocking impurity band medium-long wave infrared detector. Wherein 1 is a substrate, 2 is a negative electrode contact layer, 3 is an absorption layer, 4 is a barrier layer, 5 is a positive electrode contact region, 6 is a positive electrode, 7 is a negative electrode, and 8 is a dielectric layer;
FIG. 2 is a flow chart of a process for manufacturing a silicon-doped gallium-blocking mid-wavelength infrared detector in an impurity band;
FIG. 3 is a comparison of absorption spectra of a long-wave infrared detector and an intrinsic silicon device in a gallium-doped silicon blocking impurity band.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings in which:
the invention develops a preparation method of a silicon-doped gallium blocking impurity band medium-long wave infrared detector, which realizes the absorption of low-energy medium-long wave infrared radiation by utilizing the transition from valence band electrons to the impurity energy level of gallium atoms, and in addition, utilizes intrinsic silicon as a blocking layer to inhibit the jump conductance of the impurity band, reduce the dark current of a device and realize the high-performance detection of medium-long wave infrared radiation.
The method comprises the following specific steps:
1. molecular beam epitaxial growth of the negative electrode contact layer 2, the absorption layer 3 and the barrier layer 4: growing a negative electrode contact layer 2 on a high-conductivity silicon substrate 1 by adopting a molecular beam epitaxy process, doping phosphorus ions with the doping concentration of 8 multiplied by 1014cm-2Epitaxially growing an absorption layer 3 doped with gallium ions at a concentration of 1X 10 on the negative electrode contact layer 216～1×1018cm-3The thickness is 20-30 mu m, the intrinsic silicon barrier layer 4 is epitaxially grown on the silicon absorption layer 3, no impurity ions are intentionally doped, and the growth thickness is 5-10 mu m;
2. ultrasonic cleaning: rinsing in a trichloroethylene solution for 5 minutes, rinsing with acetone for 5 minutes, rinsing with isopropanol for 5 minutes, cleaning with deionized water for 3 minutes, baking in a 65 ℃ oven for 15 minutes, drying, and observing whether the cleaning is clean, whether cracks exist or not under a microscope;
3. first photoetching: spin-coating positive photoresist AZ5214 on the surface of the intrinsic silicon barrier layer 4, wherein the thickness of the positive photoresist AZ5214 is 1.5 mu m, the positive photoresist AZ is baked at the temperature of 95 ℃ for 90 seconds, exposed for 6.5 seconds, developed for 45 seconds, washed by deionized water and dried by nitrogen gas to form a photoetching mark area window;
4. hardening the film: and (3) hardening the photoresist AZ5214 at the hardening temperature of 110 ℃ for 10 minutes to improve the adhesion and the mask protection capability of the photoresist AZ 5214.
5. Forming a mark layer by ion beam etching: forming a 100nm photoetching mark by using an argon plasma etching process for photoetching process alignment in subsequent steps;
6. removing the photoresist: removing the photoresist by using acetone, ultrasonically cleaning for 10 minutes by using isopropanol, flushing by using deionized water, and drying by using nitrogen;
7. removing photoresist by using plasma: further removing the residual photoresist basement membrane after exposure and development by adopting an argon plasma photoresist removing process with the power of 200W for 180 seconds;
8. depositing a silicon nitride mask: depositing a silicon nitride mask on the upper surface of the intrinsic silicon barrier layer 4 by adopting a plasma enhanced chemical vapor deposition process, wherein the deposition thickness is 200 nm;
9. and (3) second photoetching: spin coating positive glue AZ5214 with the thickness of 1.5 μm on the surface of the silicon nitride, baking at 95 ℃ for 90 seconds, exposing for 6.5 seconds, developing for 45 seconds, washing with deionized water, and blow-drying with nitrogen to form a positive electrode etching window;
10. hardening the film: and (3) hardening the photoresist AZ5214 at the hardening temperature of 110 ℃ for 90 seconds to improve the adhesion and the mask protection capability of the photoresist AZ 5214.
11. Reactive ion etching: etching the silicon nitride passivation layer by adopting a reactive ion etching process, wherein the etching depth is 200nm, and part of the intrinsic silicon barrier layer is exposed;
12. ion implantation: implanting phosphorus ions into the high-purity silicon barrier layer by ion implantation process with implantation energy of 50keV and implantation dosage of 8 × 1014cm-2The injection angle is 7 degrees;
13. removing the photoresist: removing the photoresist by using acetone, ultrasonically cleaning for 10 minutes by using isopropanol, flushing by using deionized water, and drying by using nitrogen;
14. removing photoresist by using plasma: further removing the residual photoresist basement membrane after exposure and development by adopting an argon plasma photoresist removing process with the power of 200W for 180 seconds;
15. and (3) rapid thermal annealing: in a nitrogen atmosphere, a rapid thermal annealing process is adopted, the temperature rising and reducing rate is 90 ℃/s, the annealing temperature is 950 ℃, the annealing temperature holding time is 30 seconds, injected ions are activated, and crystal lattice damage is repaired to form a positive electrode contact area 5;
16. reactive ion etching: etching the silicon nitride passivation layer by adopting a reactive ion etching process, wherein the etching depth is 200nm, and removing the silicon nitride mask deposited in the front;
17. depositing a silicon nitride passivation layer: growing a new silicon nitride passivation layer by plasma enhanced chemical vapor deposition, wherein the thickness of the passivation layer is 200nm, and the passivation layer protects the ion injection layer and prevents the ion injection layer from being corroded;
18. and (3) third photoetching: spin coating positive glue AZ5214 on the surface of the device, wherein the thickness is 1.5 mu m, pre-baking is carried out for 90s exposure for 6.5 s at 95 ℃, development is carried out for 45 s, deionized water is used for washing, and nitrogen is used for blow-drying to form a corrosion area window;
19. hardening the film: hardening the photoresist AZ5214 at 110 ℃ for 90 seconds to improve the adhesion and the etching resistance of the photoresist AZ 5214;
20. reactive ion etching: etching the silicon nitride passivation layer by adopting a reactive ion etching process, wherein the etching depth is 200 nm;
21. wet etching: KOH is adopted: h2Heating the O-1: 1 solution in a water bath at 85 ℃, and corroding at the speed of about 1 mu m/min until the negative electrode contact layer 2 is exposed, wherein the corrosion depth is 11 mu m;
22. removing the photoresist: removing the photoresist by using acetone, ultrasonically cleaning for 10 minutes by using isopropanol, flushing by using deionized water, and drying by using nitrogen;
23. removing photoresist by using plasma: further removing the residual photoresist basement membrane after exposure and development by adopting an argon plasma photoresist removing process with the power of 200W for 180 seconds;
24. fourth photoetching: spin coating positive glue AZ5214 on the surface of the device, wherein the thickness of the positive glue is 2 microns, baking is carried out at 95 ℃ for 90 seconds, exposure is carried out for 6.5 seconds, development is carried out for 45 seconds, deionized water is used for washing, and nitrogen is used for drying;
25. hardening the film: hardening the photoresist AZ5214 at 110 ℃ for 90 seconds to improve the adhesion and the etching resistance of the photoresist AZ 5214;
26. reactive ion etching: etching the silicon nitride passivation layer by adopting a reactive ion etching process, wherein the etching depth is more than 200nm, and the positive electrode contact area 5 is exposed;
27. removing the photoresist: removing the photoresist by using acetone, ultrasonically cleaning for 10 minutes by using isopropanol, flushing by using deionized water, and drying by using nitrogen;
28. removing photoresist by using plasma: further removing the residual photoresist basement membrane after exposure and development by adopting an argon plasma photoresist removing process with the power of 200W for 180 seconds;
29. fifth photoetching: sequentially and rotatably coating photoresist LOR10A and photoresist AZ5214 with the thickness of 6 microns on the surface of the device by adopting a double-layer photoresist photoetching process, baking at 95 ℃ for 90 seconds, exposing for 6.5 seconds, developing for 45 seconds, washing with deionized water, and drying by nitrogen;
30. hardening the film: hardening photoresist LOR10A + AZ5214 at 110 deg.C for 3 min to improve its adhesion and etching resistance;
31. electron beam evaporation of positive and negative electrodes: evaporating electrode by electron beam lithography process with vacuum degree of 5 × 10-4Pa, the evaporation rate is 1nm/s, and the method comprises the steps of sequentially evaporating titanium and aluminum metal films from bottom to top, wherein the evaporation thicknesses are respectively 20nm and 600nm, so that a positive electrode 6 and a negative electrode 7 are obtained;
32. stripping: stripping with acetone, carrying out water bath at 80 ℃ for 30 minutes, carrying out ultrasonic cleaning for 5 minutes, carrying out ultrasonic cleaning with isopropanol for 5 minutes, soaking with 2.38% tetramethyl ammonium hydroxide solution for 30 seconds, washing with deionized water, and drying with nitrogen; (HMP solution can be used if stripping is incomplete, temperature 150 ℃ or higher.)
33. And annealing the positive electrode and the negative electrode: in a nitrogen atmosphere, the annealing temperature is 450 ℃, and the annealing temperature holding time is 30 minutes, so that the electrode forms good ohmic contact;
34. and sixth photoetching: spin-coating a photoresist AZ5214 on the surface of the device, wherein the thickness of the photoresist AZ5214 is 1.5 mu m, baking the photoresist at 95 ℃ for 90 seconds, exposing the photoresist for 6.5 seconds, developing the photoresist for 45 seconds, flushing the photoresist with deionized water, and drying the photoresist with nitrogen;
35. hardening the film: hardening the photoresist AZ5214 at 110 ℃ for 90 seconds to improve the adhesion and the etching resistance of the photoresist AZ 5214;
36. removing the silicon nitride passivation layer of the photosensitive area: etching the silicon nitride passivation layer by adopting a reactive ion etching process, wherein the etching depth is more than 200 nm;
37. cleaning: rinsing with acetone for 5 minutes, rinsing with isopropanol for 5 minutes, rinsing with absolute ethyl alcohol for 5 minutes, cleaning with deionized water for 3 minutes, and drying with a nitrogen gun, thereby completing the preparation of the device.
FIG. 3 is a comparison graph of absorption spectra of a long-wave infrared detector and an intrinsic silicon device in a silicon-doped gallium blocking impurity band, wherein the silicon-doped gallium material has large absorption to radiation of a wave band of 5-15 μm;
the three device parameters were as follows: the gallium ion doping concentration of the absorption layer 3 is 1 × 10 of the left boundary value16The thickness is 20 μm at the left boundary value, and the thickness of the barrier layer 4 is 5 μm at the left boundary value; the gallium ion doping concentration of the absorption layer 3 is 1 × 10 at the right boundary value18The thickness is 30 μm at the right boundary value, and the thickness of the barrier layer 4 is 10 μm at the right boundary value; the gallium ion doping concentration of the absorption layer 3 is an intermediate value of 1 × 1018The thickness is 30 μm at the middle, and the thickness of the barrier layer 4 is 10 μm at the middle; the three devices have stable performance and show obvious absorption to radiation of a wave band of 5-15 mu m.
The result shows that the detector based on the silicon-doped gallium-blocking impurity band structure is reasonable and effective in realizing the method for detecting the medium-long wave infrared radiation with high performance.
Claims (8)
1. The utility model provides a silicon mixes gallium and blocks medium-long wave infrared detector in impurity band which characterized in that, the device is from bottom to top in proper order: the device comprises a substrate (1), a negative electrode contact layer (2), an absorption layer (3), a barrier layer (4) and a dielectric layer (8), wherein the dielectric layer (8) covers half of the barrier layer (4), a positive electrode contact region (5) is positioned on the left side of the barrier layer (4) and embedded into the barrier layer, a positive electrode (6) is positioned on the positive electrode contact region (5) and forms ohmic contact with the positive electrode contact region and the positive electrode contact region, and a negative electrode (7) is deep into the substrate (1) along the side wall of a V-shaped hole and forms ohmic contact with the negative electrode contact layer (2). Wherein.
2. The silicon-doped gallium-blocking impurity band mid-wavelength infrared detector of claim 1, characterized in that: the substrate (1) is made of high-conductivity silicon.
3. The silicon-doped gallium-blocking impurity band mid-wavelength infrared detector of claim 1, characterized in that: the negative electrode contact layer (2) and the positive electrode contact region (5) are doped with phosphorus ions with the doping concentration of 8 multiplied by 1014cm-2。
4. The silicon-doped gallium-blocking impurity band mid-wavelength infrared detector of claim 1, characterized in that: the absorption layer (3) is doped with gallium ions with the doping concentration of 1 multiplied by 1016～1×1018cm-3The thickness is 20 to 30 μm.
5. The silicon-doped gallium-blocking impurity band mid-wavelength infrared detector of claim 1, characterized in that: the barrier layer (4) is intrinsic silicon and has a thickness of 5-10 mu m.
6. The silicon-doped gallium-blocking impurity band mid-wavelength infrared detector of claim 1, characterized in that: the positive electrode (6) and the negative electrode (7) are titanium-aluminum composite metal films, titanium is arranged at the lower layer and has the thickness of 20nm, aluminum is arranged at the upper layer and has the thickness of 600nm
7. The silicon-doped gallium-blocking impurity band mid-wavelength infrared detector of claim 1, characterized in that: the dielectric layer (8) is silicon nitride and has a thickness of 200 nm.
8. A method of manufacturing a silicon-doped gallium-blocking mid-wavelength infrared detector of claim 1, characterized in that the method comprises the following steps:
1) epitaxially growing a negative electrode contact layer (2), an absorption layer (3) and a barrier layer (4) on a substrate (1) by a molecular beam epitaxy method;
2) growing a silicon nitride mask by a plasma enhanced chemical vapor deposition method, patterning the silicon nitride mask, etching silicon nitride by reactive ions to open a positive electrode contact hole, and performing rapid annealing activation after ion implantation to form a positive electrode contact region (5);
3) reactive ion etching silicon nitride to open a negative electrode contact hole, and wet etching until the negative electrode contact layer (2) is exposed;
4) after a negative electrode contact layer (2) and a positive electrode contact region (5) are exposed by photoetching, an electron beam is used for evaporating a positive electrode (6) and a negative electrode (7), and annealing is carried out to form good ohmic contact;
and removing the silicon nitride in the photosensitive area by adopting a reactive ion etching process, and reserving the dielectric layer (8) between the positive electrode (6) and the negative electrode (7) and the upper surface of the barrier layer (4).
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110409635.7A CN113241386A (en) | 2021-04-16 | 2021-04-16 | Silicon-doped gallium blocking impurity band medium-long wave infrared detector and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110409635.7A CN113241386A (en) | 2021-04-16 | 2021-04-16 | Silicon-doped gallium blocking impurity band medium-long wave infrared detector and preparation method thereof |
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