CN116678496A - Preparation method of photoelectrochemistry type weak light detection film - Google Patents
Preparation method of photoelectrochemistry type weak light detection film Download PDFInfo
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- 238000001514 detection method Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 61
- 239000010703 silicon Substances 0.000 claims abstract description 61
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000005530 etching Methods 0.000 claims abstract description 57
- 239000000758 substrate Substances 0.000 claims abstract description 37
- 238000004528 spin coating Methods 0.000 claims abstract description 36
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- 238000005191 phase separation Methods 0.000 claims abstract description 20
- 238000005516 engineering process Methods 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 238000005566 electron beam evaporation Methods 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 238000001020 plasma etching Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 54
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 34
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 26
- 239000004793 Polystyrene Substances 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 19
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 19
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 17
- 229920002223 polystyrene Polymers 0.000 claims description 17
- 238000000151 deposition Methods 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 210000002381 plasma Anatomy 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 12
- 230000008021 deposition Effects 0.000 claims description 12
- 238000007747 plating Methods 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- 229920001486 SU-8 photoresist Polymers 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- YTAHJIFKAKIKAV-XNMGPUDCSA-N [(1R)-3-morpholin-4-yl-1-phenylpropyl] N-[(3S)-2-oxo-5-phenyl-1,3-dihydro-1,4-benzodiazepin-3-yl]carbamate Chemical compound O=C1[C@H](N=C(C2=C(N1)C=CC=C2)C1=CC=CC=C1)NC(O[C@H](CCN1CCOCC1)C1=CC=CC=C1)=O YTAHJIFKAKIKAV-XNMGPUDCSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 3
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 2
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000010894 electron beam technology Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims description 2
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- 238000010025 steaming Methods 0.000 claims description 2
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 238000010301 surface-oxidation reaction Methods 0.000 abstract 1
- 235000012431 wafers Nutrition 0.000 description 35
- 210000004027 cell Anatomy 0.000 description 15
- 229920002959 polymer blend Polymers 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 229920003255 poly(phenylsilsesquioxane) Polymers 0.000 description 6
- 229910021607 Silver chloride Inorganic materials 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 5
- 239000002052 molecular layer Substances 0.000 description 4
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- 239000007787 solid Substances 0.000 description 4
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- 238000000926 separation method Methods 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
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- 229920002521 macromolecule Polymers 0.000 description 1
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- 230000004297 night vision Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J1/00—Photometry, e.g. photographic exposure meter
- G01J1/42—Photometry, e.g. photographic exposure meter using electric radiation detectors
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Weting (AREA)
Abstract
The invention provides a preparation method of a photoelectrochemical weak light detection film, which comprises the following steps: the preparation method comprises the steps of performing pretreatment on a silicon wafer substrate, removing a surface silicon dioxide layer, spin-coating a high polymer layer on the surface of the silicon wafer substrate, coating a phase separation blending film, performing selective etching through a reactive ion etching technology to obtain a nanoscale template, performing pretreatment on the template to remove the silicon dioxide layer generated by surface oxidation, performing electron beam evaporation technology on the template to evaporate a catalyst film, and then using an organic solvent to selectively remove the template to obtain the discontinuous photoelectrochemical weak light detection film. The light detection film provided by the invention has high responsivity and high sensitivity to weak light, and simultaneously has the advantages of simple preparation method, stable performance, mass production and the like. The invention creatively applies the pinch-off effect to the research of the photoelectrochemical photodetection film, and has very important significance.
Description
Technical Field
The invention relates to the technical field of photoelectric detection devices, in particular to a preparation method of a photoelectrochemical weak light detection film based on pinch-off effect.
Background
The weak light imaging technology has been widely used in the fields of night vision, biological and chemical sensing, automobile driving assistance systems, and the like, and therefore, research on weak light detection has been receiving a great deal of attention in recent years.
With conventional solid state photodetectors, optical signal detection involves semiconductor carriers generated by the photoelectric effect, carrier transfer to electrodes, carrier collection, and the like. Wherein, the long transmission path from the semiconductor to the electrode causes serious electron-hole carrier recombination effect during carrier transmission and collection, resulting in reduced photocurrent density and sensitivity, thereby being unfavorable for weak light detection of intrinsic few photoelectrons. By increasing the light utilization by using the plasmon effect (patent CN 110556478A) or quantum dots (patent CN113328006 a), and by promoting the charge separation by heterostructures, the photocurrent density of solid palladium is increased, however heterostructures still rely on high voltages for charge separation with high energy consumption. In addition, conventional solid state photodetectors are also limited by the solid state operating environment.
Currently, emerging photoelectrochemical photodetectors can immediately consume photogenerated carriers on the semiconductor surface and reduce charge recombination by coordinating the traditional photoelectrochemical effect with a surface electrolyte assisted chemical reaction, thereby achieving lower applied voltages, greater photocurrent densities, higher responsivity, higher sensitivity, and freedom and viable manufacturing processes suitable for liquid states, etc., as in patent CN108975289a. Although photoelectrochemical type photodetectors provide higher charge separation efficiency, they still suffer from low photocurrent density, low responsivity, and efficacy at ultra-low light intensities for weak light detection with small amounts of photoelectrons. Therefore, further reduction of surface carrier recombination of the photoelectrochemical type photodetector is expected to obtain effective weak light detection.
Disclosure of Invention
The invention aims to solve the technical problems and provides a weak light detection film with excellent photoelectric detection performance.
The technical scheme of the invention is as follows: a preparation method of a photoelectrochemistry type weak light detection film comprises the following specific steps:
a) Etching the surface of the silicon wafer by acid;
b) Preparing an organic solution containing no silicon polymer;
c) Spin-coating an organic solution without a silicon polymer on the surface of a silicon wafer substrate, and curing to obtain a polymer layer without silicon;
d) Depositing a layer of SiO on the polymer layer without silicon 2 A film;
e) Dissolving polystyrene and polyphenyl silsesquioxane in an organic solvent, and performing ultrasonic treatment to form a blending phase separation solution;
f) Spin-coating the solution on the substrate to obtain a phase separation blend film;
g) Selectively etching the separated blend film by utilizing a reactive ion etching technology to form a discontinuous film structure template on the surface of the silicon wafer substrate;
h) Etching the surface of the template by acid;
i) Evaporating a layer of metal nickel catalyst film on the surface of the template by utilizing an electron beam evaporation technology;
j) After the ultrasonic lift-off treatment by using an organic solvent, a discontinuous photoelectrochemical weak light detection film is obtained.
Preferably the acid in step a) is hydrofluoric acid or an aqueous solution of hydrochloric acid; the mass concentration of the solution is 20-40%; the treatment time is 1-3min.
Preferably, the organic solution which does not contain the silicon macromolecule in the step b) is cyclohexanone solution of SU-8 photoresist or chlorobenzene solution of polymethyl methacrylate; the mass concentration of the organic solution without the silicon polymer is 3-10%; the rotating speed of the spin coating in the step c) is 1000-4000 rpm, and the spin coating time is 40-60s; the curing process in step c) is: when the cyclohexanone solution of the SU-8 photoresist is spin-coated, the ultraviolet irradiation is carried out for 5-7min, and the heat treatment is carried out for 5-10min at 120-130 ℃ to finish the solidification; after spin-coating the chlorobenzene solution of polymethyl methacrylate, drying and curing at 80-90 ℃ for 1-3min; the thickness of the obtained polymer layer without silicon is 100-500nm.
Preferably the deposition of SiO as described in step d) 2 Of layers ofThe method is plasma enhanced chemical vapor deposition (OxFORD P80 PECVD) technology, deposited SiO 2 The layer thickness is 15-40nm.
Preferably, the organic solvent in step e) is toluene or chlorobenzene; the mass ratio of the polystyrene to the polyphenyl silsesquioxane is (1-5): 1, a step of; the mass total concentration of the solution is 2-6%;
preferably, in the step f), the spin coating rotating speed is 2000-4000 rpm, and the spin coating time is 40-60s;
preferably, the reactive ion etching apparatus in step g) is a ULVAC ICPRIE etcher; the selective etching process comprises the following steps: firstly using O 2 Removing part of the continuous phase of the polystyrene by plasma etching to form a polyphenyl silsesquioxane dispersed phase of the nano column, wherein the etching time is 250-350s; then O is used 2 /CHF 3 Partially removing the polyphenyl silsesquioxane adhered together at the bottom of the nano column by mixed gas etching, wherein the etching time is 45-100s; then using this as mask, using CF continuously 4 /CHF 3 Etching SiO downward by mixed gas 2 Etching the layer for 90-210s, and then using O 2 Etching the silicon-free polymer layer downwards by using plasma for 100-400s; the flow rate of the plasmas is 10-30sccm, and the power is 35-40W.
Preferably, the acid in the step h) is hydrofluoric acid or dilute aqueous solution of hydrochloric acid, and the mass concentration of the acid is 20-40%; the treatment time is 1-3min.
The electron beam evaporation process described in step i) is preferably as follows: deflating the film plating instrument to break the vacuum state, clamping the template on the sample stage, adding metal nickel steaming material into the lower tungsten crucible, vacuumizing until the vacuum degree is 1-5 x 10 -3 Pa, turning on high voltage electron beam, evaporating 1-5nm metal nickel layer, and coating at the rate of
Preferably, the organic solvent in the step j) is acetone or toluene, and the ultrasonic time is 5-30min; the duty ratio of the discontinuous photoelectrochemical type weak light detection film obtained in the step j) is 4.9-90.1%.
The beneficial effects are that:
the photoelectric chemical weak light detection film based on the pinch-off effect provided by the invention has the advantages that the adopted silicon substrate has a narrower band gap and a wider response spectrum, the pinch-off effect caused by discontinuous metallic nickel accelerates the consumption of photo-generated carriers on the surface of a semiconductor, reduces charge recombination, amplifies the response of an electrode to weak light, and therefore has lower applied voltage, larger photocurrent density, higher response and higher sensitivity; in addition, the preparation process is simple, is suitable for batch application, and has wide application prospect.
Drawings
FIG. 1 is a flow chart of the preparation of a discontinuous nano metallic nickel film of the present invention; wherein: 1-silicon wafer substrate, 2-high molecular layer, 3-SiO 2 A layer, a 4-PPSQ nano column, a 5-PS+PPSQ interweaved structure and a 6-metallic nickel film; (a) Is a silicon-free polymer layer and SiO on a silicon wafer substrate 2 Schematic representation of the film; (b) To be at SiO 2 A schematic diagram of spin-coating phase-separated blend film on the film; (c) A schematic diagram of a discontinuous film structure template on the surface of a silicon wafer substrate after selectively etching the phase-separated blend film by utilizing reactive ion etching; (d) Evaporating a layer of metal nickel catalyst film on the surface of the template; (e) Is a schematic diagram of discontinuous metallic nickel catalyst film obtained after ultrasonic lift-off treatment with organic solvent;
FIG. 2 is an SEM image of a phase separated template of the nanopores produced in example 1;
FIG. 3 is an SEM image of a discontinuous nano-nickel film prepared in example 1;
FIG. 4 is an SEM image of a phase separated template of the nanopores produced in example 2;
FIG. 5 is an SEM image of a discontinuous nano-nickel film prepared in example 2.
Detailed Description
The following detailed description of the invention is provided in connection with the accompanying drawings, and it is evident that the described embodiments are some, but not all, examples of the invention.
The basic preparation flow of the discontinuous nano metallic nickel film of the examples 1-5 of the present invention is shown in FIG. 1.
Example 1
Acid etching of silicon wafers: treating the silicon wafer by using hydrofluoric acid diluted water solution with the mass concentration of 20 percent for 3 minutes;
preparing a polymethyl methacrylate polymer layer on the surface of a silicon wafer: preparing polymethyl methacrylate solution with the mass fraction of 10% by taking chlorobenzene as a solvent, spin-coating on a silicon substrate at the rotating speed of 1000 revolutions per minute for 60s, and performing heat treatment at 90 ℃ for 3min to finish curing, wherein the thickness of the polymethyl methacrylate is 500nm;
deposition of SiO 2 Layer (c): deposition of SiO on polymer layer by chemical vapor deposition technique 2 A layer having a thickness of 15nm;
preparing a phase separation structural film: spin-coating a polystyrene and polyphenyl silsesquioxane polymer blend and a solution on the substrate, wherein the mass ratio of the polystyrene to the polyphenyl silsesquioxane is 1:1, the total solution concentration is 6%, the solvent is toluene, the spin-coating rate of the polymer blend solution is 2000 revolutions per minute, and the spin-coating time is 40s;
and (3) selective etching: by O 2 Plasma (30 sccm, 35W) etching for 250s, removing the polystyrene continuous phase, then using O 2 /CHF 3 Etching with mixed gas (20 sccm/20sccm, 40W) for 45s, partially removing the residual polyphenyl silsesquioxane adhered together at the bottom of the nanometer column, forming a film with nanometer holes on the silicon wafer substrate, and continuing using CF with the film as mask 4 /CHF 3 Etching the mixed gas downwards for 90s to remove SiO in the holes 2 Layer, reuse of O 2 Etching downwards by plasma (10 sccm, 35W) for 400s to remove the polymethyl methacrylate polymer layer below the hole, so as to obtain a nano-pore phase separation template, as shown in figure 2;
acid etching of silicon wafers: treating the sample with 20% hydrofluoric acid diluted water solution for 3min;
coating: plating a 1nm metal nickel film on the substrate by utilizing an electron beam evaporation technology, wherein the plating rate is thatVacuum degree is 1 x 10 when coating film -3 Pa；
Lifting: removing phase separation hole templates on a silicon wafer substrate by ultrasonic lifting of acetone, wherein the ultrasonic time is 30min, and discontinuous distribution of metallic nickel is obtained, and the duty ratio is 4.9%, as shown in figure 3;
and encapsulating the sample by silica gel to prepare a small electrode serving as a working electrode for standby. Providing a counter electrode and a reference electrode, injecting electrolyte into the electrolytic cell, and assembling the electrolytic cell into a three-electrode system electrolytic cell to obtain the optical detector. At an incident light intensity of 1W/m 2 Under the irradiation of incident light, the bias voltage of 1.0V vs. Ag/AgCl is applied to the electrode, the photoresponsivity can reach the magnitude of 3100mA/W, the response speed is higher, and the magnitude of ms can be reached.
Example 2
Acid etching of silicon wafers: treating the silicon wafer with 30% hydrofluoric acid diluted water solution for 2min;
preparing a polymethyl methacrylate polymer layer on the surface of a silicon wafer: preparing polymethyl methacrylate solution with the mass fraction of 5% by taking chlorobenzene as a solvent, spin-coating on a silicon substrate at the rotating speed of 2000 rpm for 50s, and performing heat treatment at 85 ℃ for 2min to finish curing, wherein the thickness of the polymethyl methacrylate is 200nm;
deposition of SiO 2 Layer (c): deposition of SiO on polymer layer by chemical vapor deposition technique 2 A layer having a thickness of 20nm;
preparing a phase separation structural film: spin-coating a polystyrene and polyphenyl silsesquioxane polymer blend and a solution on the substrate, wherein the mass ratio of the polystyrene to the polyphenyl silsesquioxane is 2:1, the total solution concentration is 5%, the solvent is toluene, the spin-coating rate of the polymer blend solution is 3000 rpm, and the spin-coating time is 50s;
and (3) selective etching: by O 2 Plasma (10 sccm, 35W) etching for 320s, removing polystyrene continuous phase, then using O 2 /CHF 3 Etching with mixed gas (20 sccm/20sccm, 40W) for 55s, and partially removing the polyphenyl silsesquioxane remaining on the bottom of the nano-pillarsForming nanometer hole film on silicon chip substrate, masking with the film, and using CF continuously 4 /CHF 3 Etching the mixed gas downwards for 105s to remove SiO in the holes 2 Layer, reuse of O 2 Downward etching by plasma (10 sccm, 35W) for 150s to remove the polymethyl methacrylate polymer layer below the hole, so as to obtain a nano-pore phase separation template, as shown in figure 4;
acid etching of silicon wafers: treating the sample with 30% hydrofluoric acid diluted water solution for 2min;
coating: plating a 2nm metal nickel film on the substrate by utilizing an electron beam evaporation technology, wherein the plating rate is thatVacuum degree is 2 x 10 when coating film -3 Pa；
Lifting: removing phase separation hole templates on the silicon wafer substrate by ultrasonic lifting of acetone for 20min to obtain discontinuous distribution metal nickel with a duty ratio of 35.9%, as shown in figure 5;
and encapsulating the sample by silica gel to prepare a small electrode serving as a working electrode for standby. Providing a counter electrode and a reference electrode, injecting electrolyte into the electrolytic cell, and assembling the electrolytic cell into a three-electrode system electrolytic cell to obtain the optical detector. At an incident light intensity of 1W/m 2 Under the irradiation of incident light, a voltage of 1.0V vs. Ag/AgCl is applied to the working electrode, the photoresponsivity can reach the order of 107A/W, the response speed is higher, and the response speed can reach the order of ms.
Example 3
Acid etching of silicon wafers: treating the silicon wafer by using a hydrochloric acid diluted water solution with the mass concentration of 40% for 1min;
preparing a high molecular layer on the surface of a silicon wafer: and (3) preparing a SU-8 photoresist solution with the mass fraction of 3% by taking cyclohexanone as a solvent, spin-coating on a silicon substrate at the rotating speed of 4000 revolutions per minute for 40s, and carrying out ultraviolet irradiation for 5min and heat treatment at 120 ℃ for 5min to finish curing. The thickness of the SU-8 photoresist is 100nm
Deposition of SiO 2 Layer (c): deposition of SiO on polymer layer by chemical vapor deposition technique 2 A layer having a thickness of 40nm;
preparing a phase separation structural film: spin-coating a polystyrene and polyphenyl silsesquioxane polymer blend and a solution on the substrate, wherein the mass ratio of the polystyrene to the polyphenyl silsesquioxane is 5:1, the total solution concentration is 2%, the solvent is chlorobenzene, the spin-coating rate of the polymer blend solution is 4000 revolutions per minute, and the spin-coating time is 60s;
and (3) selective etching: by O 2 Plasma (10 sccm, 35W) etching for 300s, removing polystyrene continuous phase, then using O 2 /CHF 3 Etching with mixed gas (20 sccm/20sccm, 40W) for 45s, partially removing the residual polyphenyl silsesquioxane adhered together at the bottom of the nanometer column, forming a film with nanometer holes on the silicon wafer substrate, and continuing using CF with the film as mask 4 /CHF 3 Etching 210s downward by mixed gas to remove SiO in the holes 2 Layer, reuse of O 2 Etching downwards by plasma (30 sccm, 35W) for 100s to remove the polymethyl methacrylate polymer layer below the holes, so as to obtain a nano-pore phase separation template;
acid etching of silicon wafers: treating the sample with 40% hydrofluoric acid diluted water solution for 1min;
coating: plating a 5nm metal nickel film on the substrate by utilizing an electron beam evaporation technology, wherein the plating rate is thatVacuum degree is 5 x 10 when coating film -3 Pa；
Lifting: removing a phase separation hole template on the silicon wafer substrate by using toluene ultrasonic lifting, wherein the ultrasonic time is 30min, and the discontinuous distribution metal nickel is obtained, and the duty ratio is 28.8%;
packaging the small electrode: and encapsulating the sample by silica gel to prepare a small electrode serving as a working electrode for standby. Providing a counter electrode and a reference electrode, injecting electrolyte into the electrolytic cell, and assembling the electrolytic cell into a three-electrode system electrolytic cell to obtain the optical detector. At an incident light intensity of 1W/m 2 Under the irradiation of incident light, a voltage of 1.0V vs. Ag/AgCl is applied to the working electrode, and the light responsivity can reach 1883mA/WThe response speed is high, and can reach the order of ms.
Example 4
Acid etching of silicon wafers: treating the silicon wafer with 25% hydrofluoric acid diluted water solution for 1min;
preparing a high molecular layer on the surface of a silicon wafer: preparing polymethyl methacrylate solution with the mass fraction of 3% by taking chlorobenzene as a solvent, spin-coating on a silicon substrate at the rotating speed of 2000 rpm for 40s, and performing heat treatment at 80 ℃ for 1min to finish curing, wherein the thickness of the polymethyl methacrylate is 200nm;
deposition of SiO 2 Layer (c): deposition of SiO on polymer layer by chemical vapor deposition technique 2 A layer having a thickness of 20nm;
preparing a phase separation structural film: spin-coating PS and PPSQ polymer blend and solution on the substrate, wherein the mass ratio of PS to PPSQ is 1:1, the total solution concentration is 2%, the solvent is toluene, the spin-coating rate of the polymer blend solution is 3000 rpm, and the spin-coating time is 60s;
and (3) selective etching: by O 2 Plasma (10 sccm, 35W) etching for 250s, removing the polystyrene continuous phase, then using O 2 /CHF 3 Etching with mixed gas (20 sccm/20sccm, 40W) for 50s, removing the polyphenyl silsesquioxane adhered together at the bottom of the nanometer column, forming a film with nanometer holes on the silicon wafer substrate, and continuing using CF with the film as mask 4 /CHF 3 Etching the mixed gas downwards for 105s to remove SiO in the holes 2 Layer, reuse of O 2 Etching downwards by plasma (10 sccm, 35W) for 100s to remove the polymethyl methacrylate polymer layer below the hole, so as to obtain a nano-pore phase separation template;
acid etching of silicon wafers: treating the sample with 25% hydrofluoric acid diluted water solution for 1min;
coating: plating a 2nm metal nickel film on the substrate by utilizing an electron beam evaporation technology, wherein the plating rate is thatVacuum degree is 2 x 10 when coating film -3 Pa；
Lifting: removing a phase separation hole template on a silicon wafer substrate by ultrasonic lifting of acetone, wherein the ultrasonic time is 5min, and the discontinuous distribution of metallic nickel is obtained, and the duty ratio is 83.1%;
packaging the small electrode: and encapsulating the sample by silica gel to prepare a small electrode serving as a working electrode for standby. Providing a counter electrode and a reference electrode, injecting electrolyte into the electrolytic cell, and assembling the electrolytic cell into a three-electrode system electrolytic cell to obtain the optical detector. At an incident light intensity of 1W/m 2 Under the irradiation of incident light, a voltage of 1.0V vs. Ag/AgCl is applied to the working electrode, the photoresponsivity can reach the order of 1867mA/W, the response speed is high, and the response speed can reach the order of ms.
Example 5
Acid etching of silicon wafers: treating the silicon wafer with 25% hydrofluoric acid diluted water solution for 1min;
preparing a high molecular layer on the surface of a silicon wafer: preparing a SU-8 photoresist solution with the mass fraction of 3% by taking cyclohexanone as a solvent, spin-coating on a silicon substrate at the rotating speed of 2000 rpm for 40s, performing ultraviolet irradiation for 7min, and performing heat treatment at 130 ℃ for 10min to complete curing, wherein the thickness of the SU-8 photoresist is 200nm.
Deposition of SiO 2 Layer (c): deposition of SiO on polymer layer by chemical vapor deposition technique 2 A layer having a thickness of 20nm;
preparing a phase separation structural film: spin-coating PS and PPSQ polymer blend and solution on the substrate, wherein the mass ratio of PS to PPSQ is 5:1, the concentration of the total solution is 2%, the solvent is chlorobenzene, the spin-coating rate of the polymer blend solution is 4000 rpm, and the spin-coating time is 40s;
and (3) selective etching: by O 2 Plasma (10 sccm, 35W) etching for 350s to remove the polystyrene continuous phase, then using O 2 /CHF 3 Etching with mixed gas (20 sccm/20sccm, 40W) for 100s, removing the polyphenyl silsesquioxane adhered together at the bottom of the nanometer column, forming a film with nanometer holes on the silicon wafer substrate, and continuing using CF with the film as mask 4 /CHF 3 Etching the mixed gas downwards for 105s to remove SiO in the holes 2 Layer, reuse of O 2 Etching downwards by plasma (30 sccm, 35W) for 150s to remove the polymethyl methacrylate polymer layer below the holes, so as to obtain a nano-pore phase separation template;
acid etching of silicon wafers: treating the sample with 25% hydrofluoric acid diluted water solution for 1min;
coating: plating a 2nm metal nickel film on the substrate by utilizing an electron beam evaporation technology, wherein the plating rate is thatVacuum degree is 3 x 10 when coating film -3 Pa；
Lifting: removing a phase separation hole template on a silicon wafer substrate by ultrasonic lifting of acetone, wherein the ultrasonic time is 30min, and the discontinuous distribution of metallic nickel is obtained, and the duty ratio is 90.1%;
packaging the small electrode: and encapsulating the sample by silica gel to prepare a small electrode serving as a working electrode for standby. Providing a counter electrode and a reference electrode, injecting electrolyte into the electrolytic cell, and assembling the electrolytic cell into a three-electrode system electrolytic cell to obtain the optical detector. At an incident light intensity of 1W/m 2 Under the irradiation of incident light, a voltage of 1.0V vs. Ag/AgCl is applied to the working electrode, the photoresponsivity can reach the magnitude of 287mA/W, the response speed is high, and the magnitude of ms can be reached.
Claims (10)
1. A preparation method of a photoelectrochemistry type weak light detection film comprises the following specific steps:
a) Etching the surface of the silicon wafer by acid;
b) Preparing an organic solution containing no silicon polymer;
c) Spin-coating an organic solution without a silicon polymer on the surface of a silicon wafer substrate, and curing to obtain a polymer layer without silicon;
d) Depositing a layer of SiO on the polymer layer without silicon 2 A film;
e) Dissolving polystyrene and polyphenyl silsesquioxane in an organic solvent, and performing ultrasonic treatment to form a blending phase separation solution;
f) Spin-coating the solution on the substrate to obtain a phase separation blend film;
g) Selectively etching the separated blend film by utilizing a reactive ion etching technology to form a discontinuous film structure template on the surface of the silicon wafer substrate;
h) Etching the surface of the template by acid;
i) Evaporating a layer of metal nickel catalyst film on the surface of the template by utilizing an electron beam evaporation technology;
j) After the ultrasonic lift-off treatment by using an organic solvent, a discontinuous photoelectrochemical weak light detection film is obtained.
2. The method according to claim 1, wherein the acid in step a) is hydrofluoric acid or an aqueous solution of hydrochloric acid; the mass concentration of the solution is 20-40%; the treatment time is 1-3min.
3. The method according to claim 1, wherein the organic solution containing no silicon polymer in step b) is a cyclohexanone solution of SU-8 photoresist or a chlorobenzene solution of polymethyl methacrylate; the mass concentration of the organic solution without the silicon polymer is 3-10%; the rotating speed of the spin coating in the step c) is 1000-4000 rpm, and the spin coating time is 40-60s; the curing process in step c) is: when the cyclohexanone solution of the SU-8 photoresist is spin-coated, the ultraviolet irradiation is carried out for 5-7min, and the heat treatment is carried out for 5-10min at 120-130 ℃ to finish the solidification; after spin-coating the chlorobenzene solution of polymethyl methacrylate, drying and curing at 80-90 ℃ for 1-3min; the thickness of the obtained polymer layer without silicon is 100-500nm.
4. The method of claim 1, wherein the SiO deposition in step d) is performed by 2 The method of the layer is plasma enhanced chemical vapor deposition technology, deposited SiO 2 The layer thickness is 15-40nm.
5. The process according to claim 1, wherein the organic solvent in step e) is toluene or chlorobenzene; the mass ratio of the polystyrene to the polyphenyl silsesquioxane is (1-5): 1, a step of; the mass concentration of the solution is 2-6%.
6. The method according to claim 1, wherein the spin-coating speed in step f) is 2000 to 4000 rpm and the spin-coating time is 40 to 60s.
7. The method of claim 1, wherein the reactive ion etching apparatus in step g) is a ULVAC ICPRIE etcher; the selective etching process comprises the following steps: firstly using O 2 Removing part of the continuous phase of the polystyrene by plasma etching to form a polyphenyl silsesquioxane dispersed phase of the nano column, wherein the etching time is 250-350s; then O is used 2 /CHF 3 Partially removing the polyphenyl silsesquioxane adhered together at the bottom of the nano column by mixed gas etching, wherein the etching time is 45-100s; then using this as mask, using CF continuously 4 /CHF 3 Etching SiO downward by mixed gas 2 Etching the layer for 90-210s, and then using O 2 Etching the silicon-free polymer layer downwards by using plasma for 100-400s; the flow rate of the plasmas is 10-30sccm, and the power is 35-40W.
8. The preparation method according to claim 1, wherein the acid in the step h) is hydrofluoric acid or dilute aqueous solution of hydrochloric acid, and the mass concentration is 20-40%; the treatment time is 1-3min.
9. The method according to claim 1, wherein the electron beam evaporation process in step i) is as follows: deflating the film plating instrument to break the vacuum state, clamping the template on the sample stage, adding metal nickel steaming material into the lower tungsten crucible, vacuumizing until the vacuum degree is 1-5 x 10 -3 Pa, turning on high voltage electron beam, evaporating 1-5nm metal nickel layer, and coating at the rate of
10. The method according to claim 1, wherein the organic solvent in step j) is acetone or toluene, and the ultrasonic time is 5-30min; the duty ratio of the discontinuous photoelectrochemical type weak light detection film obtained in the step j) is 4.9-90.1%.
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