CN111986928A - Silicon-based semiconductor PN junction structure, preparation method thereof, photoelectric cathode and application - Google Patents
Silicon-based semiconductor PN junction structure, preparation method thereof, photoelectric cathode and application Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 57
- 239000010703 silicon Substances 0.000 title claims abstract description 57
- 239000004065 semiconductor Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 80
- 230000009467 reduction Effects 0.000 claims abstract description 73
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000001257 hydrogen Substances 0.000 claims abstract description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002052 molecular layer Substances 0.000 claims abstract description 32
- 239000000758 substrate Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 238000006303 photolysis reaction Methods 0.000 claims abstract description 3
- 230000015843 photosynthesis, light reaction Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 45
- 238000000151 deposition Methods 0.000 claims description 34
- 230000008021 deposition Effects 0.000 claims description 29
- 238000000231 atomic layer deposition Methods 0.000 claims description 20
- 238000005286 illumination Methods 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 230000002441 reversible effect Effects 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000006701 autoxidation reaction Methods 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 238000005538 encapsulation Methods 0.000 claims 1
- 239000000969 carrier Substances 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 35
- 238000006243 chemical reaction Methods 0.000 description 31
- 238000004806 packaging method and process Methods 0.000 description 12
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000001354 calcination Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000004502 linear sweep voltammetry Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
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- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
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- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000002120 nanofilm Substances 0.000 description 2
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- 229910052697 platinum Inorganic materials 0.000 description 2
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- 238000001228 spectrum Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
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- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
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- 238000001341 grazing-angle X-ray diffraction Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention belongs to the technical field of semiconductor electrodes and discloses a silicon-based semiconductor PN junction structure, a preparation method thereof, a photocathode and application2Nanocrystalline layer, TiO2The nanocrystalline layer is subjected to reduction treatment and then forms Schottky contact with the p-type silicon substrate to obtain a p-type silicon-titanium dioxide heterojunction structure; crystalline TiO thereof2The Pt auxiliary agent is loaded on the nano layer to form a silicon-based semiconductor PN junction photocathode, and the photocathode is applied to hydrogen production by water photolysis of a photoelectrochemical cell. The silicon-based semiconductor PN junction structure can generate higher photoproduction voltage, has higher stability, is simple and easy to implement, has strong controllability and can realize large-scale production; the silicon-based semiconductor PN junction photocathode utilizes n-type TiO2NanocrystalThe layer successfully promotes the separation of photon-generated carriers, promotes the initial potential of the silicon-based photocathode and simultaneously plays a role in protecting the p-type silicon substrate.
Description
Technical Field
The invention belongs to the technical field of semiconductor electrodes, and particularly relates to a silicon-based semiconductor PN junction structure and a preparation method and application thereof.
Background
Solar energy is one of the most abundant and inexhaustible energy sources and is a promising solution for energy crisis. At present, the solar cell is utilized to generate electricity, or the photoelectrocatalysis water decomposition hydrogen production based on solar energy is an ideal way for obtaining energy in the future, and the solar cell has wide development and application prospects. In the design of photoelectrode, a semiconductor material with excellent light absorption capability, electron transport capability, high self-stability and less defects is required as a substrate to obtain a larger photoelectric conversion efficiency. The monocrystalline silicon material has excellent light absorption (wavelength less than 930nm) and charge transfer (electron and hole of 1600 and 400cm, respectively)2s-1V-1) And higher theoretical photoelectric conversion efficiency (29%) have received much attention from the industry. In recent decades, monocrystalline silicon has made a series of breakthroughs in the application of photovoltaic cells and the field of hydrogen production by photoelectrolysis of water. However, as a narrow bandgap semiconductor, the photovoltaic voltage generated by single crystal silicon is small and the corrosion resistance of single crystal silicon itself is poor, which is a problem to be solved in the application of the semiconductor in the photovoltaic cell field and the photo-electrolyzed water field.
In the fields of photovoltaic cells and photoelectrolysis of water, the most common method for improving the photoproduction voltage of a monocrystalline silicon electrode is to carry out surface heavy doping. For a photocathode, the p-type silicon energy band position cannot form an effective solid-liquid junction with the hydrogen production potential, so that the p-type silicon surface needs to be heavily doped to form pn+The structure accelerates the separation and transmission of carriers and generates higher photogenerated voltage, thereby improving the conversion efficiency of the silicon electrode. However, heavy surface doping also has some inherent drawbacks: 1. in order to form a better heavy doping effect, the preparation temperature is often higher, and the service life of the body-oriented current carrier is reduced; 2. in the preparation process, besides the high-temperature annealing is used for realizing the phosphorus diffusion doping, an additional surface passivation process is needed, the whole preparation process is complex, and the preparation cost is high; 3. the method has no universality, and a plurality of semiconductor materials, such as Copper Indium Gallium Selenide (CIGS), InP and other semiconductor materials, are not suitable for improving the self photogenerated voltage by adopting a heavily doped method.
Disclosure of Invention
The invention provides a high-efficiency and stable silicon-based semiconductor PN junction structure and a preparation method thereof, and provides a silicon-based semiconductor PN junction photocathode and application thereof on the basis of the high-efficiency and stable silicon-based semiconductor PN junction structure, aiming at solving the technical problems that the cost of forming PN junctions by heavy doping on the surface of the existing monocrystalline silicon electrode is high and the preparation process is complex. The silicon-based semiconductor PN junction structure can generate higher photoelectric voltage and has higher stability, and meanwhile, the preparation method of the silicon-based semiconductor PN junction structure is simple and easy to implement, has strong controllability and can realize large-scale production.
In order to solve the technical problems, the invention is realized by the following technical scheme:
according to one aspect of the invention, a silicon-based semiconductor PN junction structure is provided, and is characterized in that TiO is deposited on the surface of a p-type silicon substrate2Nanocrystalline layer of said TiO2The nanocrystalline layer forms Schottky contact with the p-type silicon substrate after reduction treatment, and a p-type silicon-titanium dioxide heterojunction structure is constructed.
Further, the TiO2The crystal form of the nanocrystalline layer is anatase.
Further, the TiO2The thickness of the nano-crystalline layer is 10-200 nm.
According to another aspect of the present invention, there is provided a method for preparing a silicon-based semiconductor PN junction structure, the method comprising the steps of:
(1) removing SiO generated by autoxidation on the surface of p-type silicon wafer body2；
(2) Taking the p-type silicon wafer body obtained in the step (1) as a substrate, and depositing TiO on the surface of the p-type silicon substrate2A nanocrystalline layer;
(3) the p-type silicon-TiO prepared in the step (2) is used2And carrying out reduction treatment on the nanocrystalline layer to obtain the p-type silicon-titanium dioxide heterojunction structure.
Further, the deposition method in the step (2) is atomic layer deposition, and the precursors are tetraisopropyl titanate and water.
Furthermore, the deposition temperature of the atomic layer deposition is 130-350 ℃;
wherein the deposition temperature is 130-210 ℃ to prepareTiO of definite structure2A nano-layer of said amorphous structure TiO2The nano-layer is crystallized and converted into TiO by roasting2A nanocrystalline layer; the temperature of 130-210 ℃ does not comprise 210 ℃;
wherein the deposition temperature is 210-350 ℃ to directly prepare TiO2A nanocrystalline layer.
Further, the reduction treatment in the step (3) is photoelectrochemical reduction, electrochemical reduction, hydrogen reduction or two-step reduction; the second step of the two-step reduction is photoelectrochemical reduction, and the first step of the two-step reduction is nitrogen reduction, hydrogen reduction or vacuum reduction.
Further, the photoelectrochemical reduction is to encapsulate the p-Si/TiO2Placing in strong acid solution, and scanning for 3-5 times in the range of 0.2V-1.5V compared with reversible hydrogen electrode under illumination.
According to another aspect of the invention, a silicon-based semiconductor PN junction photocathode is provided, which comprises the silicon-based semiconductor PN junction structure, and the crystalline TiO of the silicon-based semiconductor PN junction structure2The nano-layer is loaded with a Pt cocatalyst.
According to another aspect of the invention, the application of the silicon-based semiconductor PN junction photocathode in hydrogen production by water photolysis in a photoelectrochemical cell is provided.
The invention has the beneficial effects that:
the silicon-based semiconductor PN junction structure successfully combines n-type TiO with strong stability2The nanocrystalline layer is combined with the p-type silicon substrate to construct a high-efficiency stable heterojunction structure. Firstly, high-quality p-Si/TiO is constructed by a deposition method2And the interface improves the separation efficiency of photon-generated carriers, so that the initial potential of the silicon-based photocathode is effectively improved. Secondly, by means of reduction treatment on the TiO2Oxygen vacancies with proper distribution are introduced into the nanocrystalline layer, so that the transmission of photon-generated carriers is effectively promoted, and the carrier collection capability of the surface of the electrode is improved.
The preparation method of the silicon-based semiconductor PN junction structure is simple and feasible, and each step is accurate and adjustable. By adjusting the deposition temperature and deposition time, the method canControlling TiO2The thickness and crystallinity of the nanolayer; TiO can be regulated and controlled by regulating and controlling the reduced voltage scanning times and voltage2The degree of reduction of the nanocrystalline layer; therefore, the whole process is simple, the controllability is strong, and the method is suitable for large-scale production.
The silicon-based semiconductor PN junction photocathode utilizes n-type TiO2The nanocrystalline layer successfully promotes the separation of photon-generated carriers, promotes the initial potential of the silicon-based photocathode and simultaneously plays a role in protecting the p-type silicon substrate. Compared with pn formed by pure surface heavy doping+Si and ZnO, Fe2O3Iso-n-type semiconductor material, TiO2The nano layer shows extremely high stability in harsh solution environments such as strong acid, strong alkali and the like, can be more suitable for the test environment of strong acid, and obtains more excellent stability.
Drawings
FIG. 1 shows p-Si/TiO prepared in example 12Scanning electron microscope top view of the heterojunction electrode.
FIG. 2 shows p-Si/TiO compound prepared in example 12Scanning electron microscope top view of/Pt heterojunction electrode.
FIG. 3 shows p-Si/TiO prepared in example 12A Pt heterojunction electrode performance graph; wherein, (a) is a photocurrent-potential curve diagram; (b) the photoelectric efficiency is converted.
FIG. 4 shows p-Si/TiO compound prepared in example 12Current-time stability plots for the/Pt heterojunction electrodes.
FIG. 5 illustrates TiO preparation at different ALD deposition temperatures2Grazing incidence XRD patterns of nanolayers.
FIG. 6 is TiO2The deposition temperature of the nano layer is below 200 ℃ (including 200 ℃), and the p-Si/TiO is crystallized2Current-time stability plots for the/Pt heterojunction electrodes.
FIG. 7 is TiO2Anatase nano-layer p-Si/TiO under different reduction methods (one-step reduction including photoelectric reduction, electric reduction and hydrogen reduction)2Current-time stability plots for the/Pt heterojunction electrodes.
FIG. 8 shows various TiO2Nano-layer reduction method (two-step reduction) with p-Si/TiO2Current-time stability plots for the/Pt heterojunction electrodes.
Detailed Description
The present invention is further described in detail below by way of specific examples, which will enable one skilled in the art to more fully understand the present invention, but which are not intended to limit the invention in any way.
Example 1
(1) Silicon wafer cleaning
Placing a p-Si single crystal (100) silicon wafer in an HF solution with the volume concentration of 1% for soaking for 15s, and washing the p-Si single crystal with deionized water to be clean, wherein N is2Drying; this step can remove SiO generated by autoxidation on the surface of a p-Si single crystal (100) silicon wafer2；
(2)TiO2Preparation of anatase type nano-layer
Will N2Blow-dried p-Si single crystal (100) silicon wafer is placed in a cavity of an atomic layer deposition system for deposition, precursors are tetraisopropyl titanate and water, and TiO deposition on the surface of a p-type silicon substrate is realized2A nanocrystalline layer; the deposition temperature of the atomic layer deposition is 270 ℃, the atomic layer deposition period number is 850, and TiO2The nanocrystalline layer was deposited to a thickness of 26 nm.
(3)TiO2Anatase nanolayer reduction
Packaging the p-Si/TiO2The heterojunction structure as a working electrode is placed in 1M perchloric acid solution under illumination (the illumination intensity is 100 mW/cm)2AM 1.5G) using linear sweep voltammetry to scan 3-5 times within the interval of 0.2V-1.5V (compared to a reversible hydrogen electrode) (photoelectrochemical reduction, standard three-electrode device, silicon electrode as working electrode, platinum sheet as counter electrode, silver/silver chloride electrode as reference electrode).
(4) Deposition of Pt promoter
0.0082g of chloroplatinic acid was dissolved in 20mL of an aqueous solution to prepare a solution of 0.1mol/L chloroplatinic acid. And then placing the reduced p-type silicon-titanium dioxide heterojunction electrode in the chloroplatinic acid solution. Adopts a standard three-electrode device and a p-type silicon-titanium dioxide heterojunction electrode as a workThe electrode, Pt sheet electrode as the counter electrode, silver/silver chloride electrode as the reference electrode, deposit the whole course and adopt the constant voltage mode, deposit the voltage and carry on the load of Pt promoter at-0.2V (relative to silver/silver chloride electrode); the deposition amount of Pt of the catalyst is 200mC cm-2。
(5) Photoelectrolysis of water applications test
Carrying out Pt auxiliary agent loading on the p-Si/TiO2the/Pt heterojunction electrode was placed in a 1M perchloric acid solution under illumination (AM1.5G, illumination intensity 100 mW/cm)2) And testing the photoelectric property of the electrode. The test uses a standard three-electrode device, p-Si/TiO2the/Pt heterojunction electrode is a working electrode, the platinum sheet is a counter electrode, and the silver/silver chloride electrode is a reference electrode.
FIG. 1 is a surface deposition of TiO on the p-Si substrate prepared in example 12And (3) a top view of a scanning electron microscope of the nanocrystalline layer. The prepared TiO is shown by a scanning electron microscope2The nanocrystalline layer can be grown uniformly on the p-Si surface. Meanwhile, the TiO prepared in example 1 was measured by spectroscopic ellipsometry2The thickness of the nanocrystalline layer was 26 nm. FIG. 2 shows p-Si/TiO compound prepared in example 12And (3) a top view of a scanning electron microscope of the/Pt heterojunction electrode. As shown by a scanning electron microscope, Pt particles are uniformly grown on p-Si/TiO2The particle size on the surface of the film is about 40-45 nm. FIG. 3 shows p-Si/TiO prepared in example 12A photocurrent-potential curve diagram and a photoelectric efficiency conversion diagram of the/Pt heterojunction electrode. As shown in FIG. 3, the p-Si/TiO prepared in example 12The initial potential of the/Pt heterojunction electrode can reach 485mV, and the photoelectric conversion efficiency can reach 5.9% through calculation. p-Si/TiO electrodes compared to pure p-Si electrodes2The initial potential of the electrode is improved by 480mV, proving that p-Si and TiO2Forming a schottky contact therebetween. FIG. 4 shows p-Si/TiO compound prepared in example 12Graph of photocurrent-time stability of/Pt heterojunction electrode. As can be seen from fig. 4, the electrode can maintain an operation stability of 90h or more under the operation voltage.
Example 2:
the preparation and reaction were carried out by the method of example 1, differing only in the deposition of the original layer in step (2)Period number 350, TiO2The thickness of the nanocrystalline layer was 10 nm.
Example 3:
the preparation and reaction were carried out by the method of example 1, except that in step (2), the number of deposition cycles of the atomic layer was 1200, and TiO was used2The thickness of the nanocrystalline layer was 36 nm.
Example 4:
the preparation and the reaction were carried out by the method of example 1, differing only in the number of deposition cycles 2400 of the primary layer in step (2), TiO2The thickness of the nanocrystalline layer was 73 nm.
Example 5:
the preparation and reaction were carried out by the method of example 1, differing only in the number of cycles of deposition of the atomic layer of 4800, TiO, in step (2)2The thickness of the nanocrystalline layer was 150 nm.
Example 6:
the preparation and reaction were carried out by the method of example 1, differing only in the number of deposition cycles of the atomic layer of 6000, TiO in step (2)2The thickness of the nanocrystalline layer was 200 nm.
Example 7:
the preparation and reaction were carried out by the method of example 1, except that the deposition temperature of the seed layer in step (2) was 130 ℃ and the sample was placed in a tube furnace for crystallization before the start of step (3). The calcination was carried out under hydrogen (a mixture of hydrogen and argon with a hydrogen volume fraction of 10%), at a calcination temperature of 400 ℃ for 1h, at a gas flow rate of 40 sccm.
Example 8:
the preparation and reaction were carried out by the method of example 1, except that the deposition temperature of the seed layer in step (2) was 170 ℃ and the sample was placed in a tube furnace for crystallization before the start of step (3). The calcination was carried out under hydrogen (a mixture of hydrogen and argon with a hydrogen volume fraction of 10%), at a calcination temperature of 400 ℃ for 1h, at a gas flow rate of 40 sccm.
Example 9:
the preparation and reaction were carried out by the method of example 1, except that the deposition temperature of the seed layer in step (2) was 200 ℃ and the sample was placed in a tube furnace for crystallization before the start of step (3). The calcination was carried out under hydrogen (a mixture of hydrogen and argon with a hydrogen volume fraction of 10%), at a calcination temperature of 400 ℃ for 1h, at a gas flow rate of 40 sccm.
Example 10:
the preparation and reaction were carried out by the method of example 1, except that the deposition temperature of the seed layer in step (2) was 210 ℃.
Example 11:
the preparation and reaction were carried out by the method of example 1, except that the deposition temperature of the original layer in step (2) was 350 ℃.
Example 12:
preparation and reaction were carried out by the method of example 1, differing only in TiO in step (3)2The nano-layer reduction mode is electrochemical reduction. The specific operation steps are as follows: adding p-Si/TiO2After the electrode is packaged, a scanning process is carried out for 3-5 times in a range of 0.2V-1.5V (compared with a reversible hydrogen electrode) by utilizing a linear scanning voltammetry method in 1M perchloric acid solution.
Example 13:
preparation and reaction were carried out by the method of example 1, differing only in TiO in step (3)2The nanolayer reduction mode is hydrogen reduction. The specific operation steps are as follows: at the electrode p-Si/TiO2Before packaging, p-Si/TiO2The sheet is placed in a tubular furnace for hydrogen roasting (hydrogen-argon mixed gas with 10% hydrogen volume fraction), the roasting temperature is 400 ℃, the roasting time is 1h, the gas flow rate is 40sccm, and after the roasting and sintering, p-Si/TiO is carried out2And (5) packaging the electrodes.
Example 14:
preparation and reaction were carried out by the method of example 1, differing only in TiO in step (3)2The nano-layer reduction mode is hydrogen reduction and photoelectrochemical reduction. The specific operation steps are as follows:
(1) at the electrode p-Si/TiO2Before packaging, p-Si/TiO2The sheet is placed in a tubular furnace for hydrogen roasting (hydrogen-argon mixed gas with 10% hydrogen volume fraction), the roasting temperature is 400 ℃, the roasting time is 1h, the gas flow rate is 40sccm, and after the roasting and sintering, p-Si/TiO is carried out2Electrode for electrochemical cellAnd (4) packaging.
(2) And then carrying out photoelectrochemical reduction according to the step (3) in the embodiment 1, wherein the specific operation steps are as follows: packaging the p-Si/TiO2The heterojunction structure as a working electrode is placed in 1M perchloric acid solution under illumination (the illumination intensity is 100 mW/cm)2AM 1.5G) was scanned 3-5 times in the interval of 0.2V to 1.5V (compared to reversible hydrogen electrodes) using linear sweep voltammetry.
Example 15:
preparation and reaction were carried out by the method of example 1, differing only in TiO in step (3)2The nano-layer reduction mode is nitrogen reduction and photoelectrochemical reduction. The specific operation steps are as follows:
(1) at the electrode p-Si/TiO2Before packaging, p-Si/TiO2The sheet is placed in a tubular furnace for nitrogen roasting at 400 ℃ for 1h at a gas flow rate of 40sccm, and p-Si/TiO is carried out after roasting and sintering2And (5) packaging the electrodes.
(2) And then carrying out photoelectrochemical reduction according to the step (3) in the embodiment 1, wherein the specific operation steps are as follows: packaging the p-Si/TiO2The heterojunction structure as a working electrode is placed in 1M perchloric acid solution under illumination (the illumination intensity is 100 mW/cm)2AM 1.5G) was scanned 3-5 times in the interval of 0.2V to 1.5V (compared to reversible hydrogen electrodes) using linear sweep voltammetry.
Example 16:
preparation and reaction were carried out by the method of example 1, differing only in TiO in step (3)2The nano-layer reduction mode is vacuum reduction and photoelectrochemical reduction. The specific operation steps are as follows:
(1) at the electrode p-Si/TiO2Before packaging, p-Si/TiO2The sheet is placed in a tubular furnace to be roasted under low vacuum degree, the apparent pressure is 0Pa, the roasting temperature is 400 ℃, the roasting time is 1h, the gas flow rate is 40sccm, and the p-Si/TiO is carried out after the roasting and sintering are finished2And (5) packaging the electrodes.
(2) And then carrying out photoelectrochemical reduction according to the step (3) in the embodiment 1, wherein the specific operation steps are as follows: packaging the p-Si/TiO2Heterojunction structureUsed as a working electrode and placed in a 1M perchloric acid solution under illumination (the illumination intensity is 100 mW/cm)2AM 1.5G) was scanned 3-5 times in the interval of 0.2V to 1.5V (compared to reversible hydrogen electrodes) using linear sweep voltammetry.
For the results of the above examples, the stabilized photocurrent-potential curves were compared, and the test conditions and methods were the same as in step (5) of example 1 to examine the p-Si/TiO ratio of different parameters2Influence of Pt photocathode reaction performance.
(mono) TiO2Thickness of nano layer to p-Si/TiO2The effect of/Pt photocathode reactivity is shown in Table 1. The reaction conditions were the same as in examples 1 to 6.
TABLE 1 different TiO2Thickness of nano layer to p-Si/TiO2Effect of Pt photocathode reactivity
| Thickness (nm) | 0 | 10 | 26 | 36 | 73 | 150 | 200 |
| Initial potential (V) | 0 | 0.4 | 0.48 | 0.42 | 0.39 | 0.35 | 0.3 |
As can be seen from Table 1, when TiO2When the thickness of the nano layer is 10-200nm, the initial potential is improved to a certain degree compared with a pure p-Si electrode, and the initial potential improvement degree is higher than 0.3V; the increase in the initial potential demonstrates that p-Si and TiO2Forming a schottky contact therebetween. Wherein when TiO2When the thickness of the nano layer is 26nm, p-Si/TiO2The Pt/heterojunction electrode has the best performance, and the initial potential can reach 0.48V.
(di) TiO2Nano layer atomic layer deposition temperature vs. p-Si/TiO2Effect of reaction Performance of/Pt heterojunction electrode referring to FIG. 5, FIG. 6, Table 2, the reaction conditions were the same as in examples 1, 7-11.
FIG. 5 shows TiO prepared at different atomic layer deposition temperatures2XRD spectrum of the film. As shown in FIG. 5, when the atomic layer deposition temperature is less than 200 ℃, the XRD spectrum does not show anatase crystalline TiO2Characteristic peak of (D), indicating deposited TiO2The film is an amorphous layer. When the atomic layer deposition temperature was increased to 200 ℃, anatase crystalline TiO began to appear2But the peak intensities are relatively weak, indicating that it is less crystalline. With the further increase of the atomic layer deposition temperature, anatase crystalline TiO in the XRD spectrogram2The characteristic peak intensity of the anatase titanium dioxide is improved and tends to be stable, which indicates that more stable anatase crystalline TiO is formed2A film.
Based on this, amorphous TiO deposited with atomic layer deposition temperature below 200 ℃ (including 200 ℃), and the method comprises2P-Si/TiO treated by crystalline calcination of nano-layer2the/Pt heterojunction electrode was subjected to photoelectric performance testing, see FIG. 6. As shown in FIG. 6, when the deposition temperature for atomic layer is 200 ℃ or lower (bag)Containing 200 ℃) deposited amorphous TiO2After the nano layer is subjected to crystallization treatment, the initial potential of the electrode is improved to a certain degree compared with that of a p-Si electrode. Experiments prove that in the electrode structure, when TiO is used2After the nano film is crystallized, Schottky contact can be formed between the nano film and p-Si to form a high-quality PN junction, so that the photoelectrochemical property of the electrode is improved.
On the basis, the electrode after further crystallization treatment and the TiO directly obtained at the atomic layer deposition temperature of more than 200 DEG C2P-Si/TiO prepared from nano crystalline film2The Pt heterojunction electrode is used for testing the reaction performance of the heterojunction electrode to probe TiO2Atomic layer deposition temperature vs. p-Si/TiO in the preparation of anatase nanolayers2Influence of reaction performance of the/Pt heterojunction electrode. See table 2 for specific properties.
TABLE 2 different TiO2Nano layer atomic layer deposition temperature p-Si/TiO2Effect of/Pt heterojunction electrode reaction Performance
| Deposition temperature (. degree.C.) | 130 | 170 | 200 | 210 | 270 | 350 |
| Initial potential (V) | 0.42 | 0.42 | 0.45 | 0.42 | 0.48 | 0.40 |
As can be seen from Table 2, when TiO is deposited2Nano-layer processing into anatase type TiO2In nanolayers, direct preparation of anatase TiO, whether by calcination crystallization or by increasing the temperature of atomic layer deposition2The initial potentials of the nano-layer and the finally prepared electrode are improved to a certain degree, and the results prove that the p-Si and the TiO are2Forming a schottky contact therebetween. Wherein the electrode prepared by ALD deposition directly at 270 ℃ shows the optimal electrode performance, which shows that the atomic layer deposition temperature is helpful for obtaining higher-quality p-Si/TiO2Interface, thereby increasing p-Si/TiO2Quality of the PN junction.
(III) TiO2Reduction method of anatase nano-layer (one-step reduction including photoelectric reduction, electric reduction and hydrogen reduction) on p-Si/TiO2Influence of reaction Performance of the/Pt heterojunction electrode referring to FIG. 7, the reaction conditions were the same as in examples 1, 12 and 13.
As shown in FIG. 7, for TiO2The nano layer is reduced, which is beneficial to improving the p-Si/TiO2Reaction performance of Pt heterojunction electrode. Meanwhile, compared with two methods of hydrogen reduction and electro-reduction, the method of photo-electro-reduction described in example 1 can obtain higher electrode performance.
(IV) TiO2Anatase nano-layer reduction method (two-step reduction) on p-Si/TiO2Effect of reaction Performance of/Pt heterojunction electrode referring to FIG. 8, the reaction conditions were the same as in examples 14 to 16.
As shown in fig. 8, hydrogen reduction plus photoelectric reduction exhibited the highest electrode performance in the three examples using the two-step reduction method. However, the performance of the electrode obtained by the two reduction methods of nitrogen reduction and photoelectric reduction and vacuum reduction and photoelectric reduction is the same as that obtained by the first-step photoelectric reduction method. The operation complexity and the performance improvement degree are comprehensively considered, the cost performance of the one-step photoelectric reduction method is considered to be the highest, and the highest electrode performance can be obtained by the simplest controllable method.
Although the preferred embodiments of the present invention have been described above with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, which are merely illustrative and not restrictive, and those skilled in the art can make various changes and modifications within the spirit and scope of the present invention without departing from the spirit and scope of the appended claims.
Claims (10)
1. A silicon-based semiconductor PN junction structure is characterized in that TiO is deposited on the surface of a p-type silicon substrate2Nanocrystalline layer of said TiO2The nanocrystalline layer forms Schottky contact with the p-type silicon substrate after reduction treatment, and a p-type silicon-titanium dioxide heterojunction structure is constructed.
2. The silicon-based semiconductor PN junction structure of claim 1, wherein the TiO is doped with a nitrogen-containing compound2The crystal form of the nanocrystalline layer is anatase.
3. The silicon-based semiconductor PN junction structure of claim 1, wherein the TiO is doped with a nitrogen-containing compound2The thickness of the nano-crystalline layer is 10-200 nm.
4. A method for the preparation of a silicon-based semiconductor PN junction structure according to any of claims 1-3, wherein the method is performed according to the following steps:
(1) removing SiO generated by autoxidation on the surface of p-type silicon wafer body2；
(2) Taking the p-type silicon wafer body obtained in the step (1) as a substrate, and depositing TiO on the surface of the p-type silicon substrate2A nanocrystalline layer;
(3) the p type prepared in the step (2) issilicon-TiO2And carrying out reduction treatment on the nanocrystalline layer to obtain the p-type silicon-titanium dioxide heterojunction structure.
5. The method for preparing a silicon-based semiconductor PN junction structure according to claim 4, wherein the deposition method in the step (2) is atomic layer deposition, and the precursors are tetraisopropyl titanate and water.
6. The method as claimed in claim 5, wherein the deposition temperature of the atomic layer deposition is 130-350 ℃;
wherein the deposition temperature is 130-210 ℃ to prepare amorphous TiO2A nano-layer of said amorphous structure TiO2The nano-layer is crystallized and converted into TiO by roasting2A nanocrystalline layer; the temperature of 130-210 ℃ does not comprise 210 ℃;
wherein the deposition temperature is 210-350 ℃ to directly prepare TiO2A nanocrystalline layer.
7. The method for preparing a silicon-based semiconductor PN junction structure according to claim 4, wherein the reduction treatment in the step (3) is photoelectrochemical reduction, electrochemical reduction, hydrogen reduction or two-step reduction; the second step of the two-step reduction is photoelectrochemical reduction, and the first step of the two-step reduction is nitrogen reduction, hydrogen reduction or vacuum reduction.
8. The method of claim 7, wherein the photoelectrochemical reduction is performed on the p-Si/TiO after encapsulation2Placing in strong acid solution, and scanning for 3-5 times in the range of 0.2V-1.5V compared with reversible hydrogen electrode under illumination.
9. A silicon-based semiconductor PN junction photocathode, comprising the silicon-based semiconductor PN junction structure according to any one of claims 1 to 5, wherein the crystalline TiO of the silicon-based semiconductor PN junction structure2On the nano-layer is loaded withA Pt promoter.
10. The use of the silicon-based semiconductor PN junction photocathode of claim 9 in hydrogen production by photolysis of water in a photoelectrochemical cell.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060220092A1 (en) * | 2005-04-04 | 2006-10-05 | National Yunlin University Of Science And Technology | Titanium oxide extended gate field effect transistor |
| US20100019335A1 (en) * | 2008-04-18 | 2010-01-28 | Igor Constantin Ivanov | Materials, Fabrication Equipment, and Methods for Stable, Sensitive Photodetectors and Image Sensors Made Therefrom |
| CN105609580A (en) * | 2015-12-28 | 2016-05-25 | 江南大学 | Positive/negative (P/N) heterojunction based silicon/titanium dioxide three-dimensional composite material with synergic anti-reflection performance and application thereof |
| CN106449845A (en) * | 2016-09-14 | 2017-02-22 | 南昌大学 | Si/TiOx heterojunction-based double-sided crystalline silicon solar cell |
| KR101724692B1 (en) * | 2015-12-16 | 2017-04-10 | 서울대학교 산학협력단 | Manufacturing method of titanium dioxide nanorod using hydrothermal method and photoelectrode comprising titanium dioxide nanorod prepared therefrom |
| CN108950518A (en) * | 2018-07-07 | 2018-12-07 | 云南师范大学 | A kind of sub- thin film of titanium oxide preparation method based on technique for atomic layer deposition |
| CN110923817A (en) * | 2019-11-21 | 2020-03-27 | 天津大学 | Pyramid silicon-based photocathode with uniform pn homojunction layer and preparation method thereof |
| CN111354806A (en) * | 2020-03-13 | 2020-06-30 | 中国石油大学(华东) | TiO 22film/SiO2P-Si heterojunction photosensitive material and preparation method and application thereof |
-
2020
- 2020-07-29 CN CN202010744485.0A patent/CN111986928B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060220092A1 (en) * | 2005-04-04 | 2006-10-05 | National Yunlin University Of Science And Technology | Titanium oxide extended gate field effect transistor |
| US20100019335A1 (en) * | 2008-04-18 | 2010-01-28 | Igor Constantin Ivanov | Materials, Fabrication Equipment, and Methods for Stable, Sensitive Photodetectors and Image Sensors Made Therefrom |
| KR101724692B1 (en) * | 2015-12-16 | 2017-04-10 | 서울대학교 산학협력단 | Manufacturing method of titanium dioxide nanorod using hydrothermal method and photoelectrode comprising titanium dioxide nanorod prepared therefrom |
| CN105609580A (en) * | 2015-12-28 | 2016-05-25 | 江南大学 | Positive/negative (P/N) heterojunction based silicon/titanium dioxide three-dimensional composite material with synergic anti-reflection performance and application thereof |
| CN106449845A (en) * | 2016-09-14 | 2017-02-22 | 南昌大学 | Si/TiOx heterojunction-based double-sided crystalline silicon solar cell |
| CN108950518A (en) * | 2018-07-07 | 2018-12-07 | 云南师范大学 | A kind of sub- thin film of titanium oxide preparation method based on technique for atomic layer deposition |
| CN110923817A (en) * | 2019-11-21 | 2020-03-27 | 天津大学 | Pyramid silicon-based photocathode with uniform pn homojunction layer and preparation method thereof |
| CN111354806A (en) * | 2020-03-13 | 2020-06-30 | 中国石油大学(华东) | TiO 22film/SiO2P-Si heterojunction photosensitive material and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| LIU, SHANSHAN; LUO, ZHIBIN; LI, LULU; ET AL.: ""Multifunctional TiO2 overlayer for p-Si/n-CdS heterojunction photocathode with improved efficiency and stability"", 《NANO ENERGY 》 * |
| MAKSYM M. PLAKHOTNYUK, NADINE SCHÜLER, EVGENIY SHKODIN,ET AL.: ""Surface passivation and carrier selectivity of the thermal-atomic-layer-deposited TiO2 on crystalline silicon"", 《JAPANESE JOURNAL OF APPLIED PHYSICS》 * |
| 刘珊珊: ""单晶硅光电阴极表面改性及机理研究"", 《中国优秀博硕士学位论文全文数据库(硕士) 工程科技Ⅰ辑》 * |
| 邢卓: ""硅基半导体复合结构的制备及其光电催化性能研究"", 《中国优秀博硕士学位论文全文数据库(博士) 工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114108037A (en) * | 2021-11-22 | 2022-03-01 | 湖南大学 | Photoelectric cathode and preparation method thereof, and metal lithium extraction method and extraction device |
| CN114108037B (en) * | 2021-11-22 | 2023-03-03 | 湖南大学 | Photoelectric cathode and preparation method thereof, and metal lithium extraction method and extraction device |
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