CN113675283B - Antimony-based photocathode Sb2S3/Sb2O3Heterojunction structure and preparation method thereof - Google Patents
Antimony-based photocathode Sb2S3/Sb2O3Heterojunction structure and preparation method thereof Download PDFInfo
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- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 40
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052959 stibnite Inorganic materials 0.000 title description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 81
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 34
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000001301 oxygen Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 238000004544 sputter deposition Methods 0.000 claims abstract description 12
- 238000004073 vulcanization Methods 0.000 claims abstract description 5
- 239000010408 film Substances 0.000 claims description 72
- 238000000034 method Methods 0.000 claims description 43
- 239000007789 gas Substances 0.000 claims description 23
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 17
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- 238000005229 chemical vapour deposition Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 239000010409 thin film Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 5
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 claims description 4
- 238000007740 vapor deposition Methods 0.000 claims description 4
- 229910052951 chalcopyrite Inorganic materials 0.000 claims description 2
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000224 chemical solution deposition Methods 0.000 claims description 2
- 238000004070 electrodeposition Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 229910052683 pyrite Inorganic materials 0.000 claims description 2
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 2
- 239000011028 pyrite Substances 0.000 claims description 2
- 238000005118 spray pyrolysis Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 9
- 239000000969 carrier Substances 0.000 abstract description 8
- 230000005540 biological transmission Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 description 22
- 239000002184 metal Substances 0.000 description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- 238000001228 spectrum Methods 0.000 description 15
- 229910052786 argon Inorganic materials 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 239000012535 impurity Substances 0.000 description 6
- 230000031700 light absorption Effects 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000001755 magnetron sputter deposition Methods 0.000 description 4
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229940026189 antimony potassium tartrate Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- WBTCZEPSIIFINA-MSFWTACDSA-J dipotassium;antimony(3+);(2r,3r)-2,3-dioxidobutanedioate;trihydrate Chemical compound O.O.O.[K+].[K+].[Sb+3].[Sb+3].[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O.[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O WBTCZEPSIIFINA-MSFWTACDSA-J 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
The invention relates to an antimony-based photocathode Sb 2S3/Sb2O3 heterojunction structure and a preparation method thereof, and belongs to the technical field of photoelectric materials. The antimony-based photocathode Sb 2S3/Sb2O3 heterojunction structure consists of a p-type Sb 2S3 film bottom layer, an Sb 2S3/Sb2O3 buffer layer and an n-type Sb 2O3 film top layer; sputtering Sb on a substrate to obtain a Sb film, performing vulcanization reaction on the Sb film to obtain a Sb 2S3 film, and reacting the Sb 2S3 film with oxygen to generate a Sb 2S3/Sb2O3 buffer layer and an n-type Sb 2O3 conduction band bottom to obtain the Sb 2S3/Sb2O3 heterojunction structure of the antimony-based photocathode. The narrow-bandgap p-type Sb 2S3 film absorbs light energy, the wide-bandgap Sb 2O3 film is used as a transmission channel, a catalytic layer and a corrosion-resistant layer of photo-generated electrons, photo-generated carriers are separated by means of extremely poor energy among Sb 2S3/Sb2O3 heterojunctions, and the Sb 2S3/Sb2O3 buffer layer improves charge transmission efficiency and stability and enhances conductivity of an electrode and corrosion resistance of a material.
Description
Technical Field
The invention relates to a preparation method of an antimony-based photocathode Sb 2S3/Sb2O3 heterojunction structure, and belongs to the technical field of photoelectric materials.
Background
The crystal structure of the antimony sulfide (Sb 2S3) belongs to an orthorhombic stibium structure, and is a material which is green, nontoxic, rich in reserves (the abundance of Sb crust is 0.2 ppm) and low in cost. Sb 2S3 is a direct band gap P-type semiconductor, the band gap width of which is related to the crystalline state of the material, the band gap width is 1.72Ev, ec=0.22V (vs.nhe), ev=1.94V (vs.nhe), and the short wave absorption coefficient for visible light reaches 1.8x 5cm-1. Therefore, sunlight on the radiation surface can be fully absorbed only by the thickness of about 600nm, so that the material consumption is reduced, the migration/diffusion distance of carriers is shortened, and the carrier collection efficiency is improved. However, sb 2S3 has a narrow band gap width and good solar light absorption characteristics, but is sensitive to light, is easy to corrode and is very unstable, so that photoelectrochemical reduction is required to be completed efficiently, and photoelectrochemical corrosion is also required to be solved.
Antimony oxide (Sb 2O3) is an n-type semiconductor having a face-centered cubic structure with a bandgap width of 3.0Ev, ec=0.32V (vs.nhe), ev=3.32V (vs.nhe), lattice constant(222) The band gap value is 2.75-2.85 eV for preferential growth crystal face. The electron conductivity increases with increasing thickness and the optical bandgap increases with decreasing thickness; sb 2O3 can be converted from cubic to orthorhombic antimonide phase with increasing temperature. Sb 2O3 has strong ultraviolet light absorption capability, strong optical refractive index and good catalytic effect. However, the band gap width of Sb 2O3 is 3.0eV, and only about 5% of the total solar energy is absorbed and utilized, which limits the improvement of energy conversion efficiency, and the semiconductor with large band gap width has lower conductivity, which results in limited separation and transmission speed of photon-generated carriers, thus reducing carrier separation efficiency and further limiting the improvement of energy conversion efficiency.
Disclosure of Invention
Aiming at the problems of the antimony-based photocathode in the prior art, the invention provides an antimony-based photocathode Sb 2S3/Sb2O3 heterojunction structure and a preparation method thereof, namely the structure bottom layer of the antimony-based photocathode Sb 2S3/Sb2O3 heterojunction structure is a light absorption layer p-type Sb 2S3 film with good crystallization quality and few defects, the middle buffer layer is Sb 2S3/Sb2O3, and the upper layer is an n-type Sb 2O3 film with small particles and high specific surface area; the narrow-bandgap p-type Sb 2S3 film absorbs light energy, the wide-bandgap Sb 2O3 film is used as a transmission channel, a catalytic layer and a corrosion-resistant layer of photo-generated electrons, photo-generated carriers are separated by means of extremely poor energy among Sb 2S3/Sb2O3 heterojunctions, and the conductivity of the electrode and the corrosion resistance of the material are enhanced.
An antimony-based photocathode Sb 2S3/Sb2O3 heterojunction structure consists of a p-type Sb 2S3 film bottom layer, an Sb 2S3/Sb2O3 buffer layer and an n-type Sb 2O3 film top layer.
The preparation method of the antimony-based photocathode Sb 2S3/Sb2O3 heterojunction structure comprises the following specific steps:
(1) Sputtering Sb on a substrate to obtain an Sb film;
(2) The Sb film is subjected to vulcanization reaction to obtain a Sb 2S3 film;
(3) The Sb 2S3 film reacts with oxygen to generate an Sb 2S3/Sb2O3 buffer layer and an n-type Sb 2O3 film top layer to obtain an antimony-based photocathode Sb 2S3/Sb2O3 heterojunction structure;
The substrate of the step (1) comprises, but is not limited to, ITO, FTO and common glass;
the sputtering method in the step (1) comprises a vapor deposition method, a spray pyrolysis method, a chemical bath deposition method, an electrodeposition method, an evaporation coating method, a plasma coating method and a PECVD coating method;
The Sb source comprises, but is not limited to, a high-purity metal Sb target, high-purity metal Sb powder, sbCl 3 solution and antimony potassium tartrate;
The sulfur source of the vulcanization reaction in the step (2) is a solid sulfur source or a gas sulfur source, wherein the solid sulfur source is elemental sulfur, chalcopyrite or pyrite, and the gas sulfur source is H 2 S or SO 2; the atomic mole ratio of the sulfur atom of the sulfur source to the antimony atom in the metal antimony film is (1.5-20): 1; the preparation method of the Sb 2S3 film comprises, but is not limited to, a chemical vapor deposition method, a plasma method, a heating method, a spin coating method and PECVD;
The purity of the oxygen in the step (3) is not lower than 99.99 percent; methods for preparing the Sb 2S3/Sb2O3 buffer layer and the n-type Sb 2O3 thin film top layer include, but are not limited to, chemical vapor deposition, plasma, heating, PECVD;
the oxidation reaction temperature of the heating method is 100-300 ℃, the oxidation time is 30S-20 min, and the partial pressure of oxygen in the mixed gas of oxygen and inert gas is 50-100%;
The oxidation temperature of the chemical vapor deposition method is 200-600 ℃, the oxidation time is 10-120 min, and the partial pressure of oxygen in the mixed gas of oxygen and inert gas is 50-100%;
The radio frequency power of the plasma method is 150-500W, the plasma radio frequency time is 10-60 min, and the oxygen partial pressure in the mixed gas of oxygen and inert gas is 50-100%;
The PECVD plasma radio frequency power is 100-300W, the oxidation heating temperature is 150-500 ℃, the oxidation time is 5-30 min, and the oxygen partial pressure in the mixed gas of oxygen and inert gas is 50-100%.
The beneficial effects of the invention are as follows:
(1) The invention utilizes a substrate/Sb 2S3/Sb2O3 heterojunction film constructed by homoantimonide Sb 2S3、Sb2O3, has similar lattice structures, is respectively an orthorhombic system and a cubic system, has better lattice matching property, has better co-dissolution characteristic, realizes optimization among heterojunction interfaces, has wider band gap Sb 2O3 in the conductivity of Sb 2S3, is favorable for charge transmission between an electrode substrate and an electrode material, can obtain larger photocathode current by taking a semiconductor Sb 2S3 with a high light absorption coefficient and a wide spectral response range as a main light absorption layer, has good electron conductivity by taking electrons as majority carriers by an n-type semiconductor Sb 2O3, can effectively extract photo-generated electrons from Sb 2S3 when being used as a photocathode, reduces the accumulation of carriers in the material, is favorable for improving the stability of the electrode material, has good energy level difference of Sb 2S3/Sb2O3 heterojunction energy band matching, is favorable for effectively separating the photo-generated carriers, and can be used for photocathode hydrogen production by applying smaller negative potential (negative-0.32V);
(2) The invention uses the narrow-band gap p-type Sb 2S3 film to absorb light energy, the wide-band gap Sb 2O3 film is used as a transmission channel, a catalytic layer and a corrosion-resistant layer of photo-generated electrons, photo-generated carriers are separated by means of extremely poor energy among Sb 2S3/Sb2O3 heterojunctions, and the Sb 2S3/Sb2O3 buffer layer improves the charge transmission efficiency and stability, and enhances the conductivity of the electrode and the corrosion resistance of the material.
Drawings
FIG. 1 is an EDS energy spectrum of the product Sb 2S3/Sb2O3 heterojunction of example 1;
FIG. 2 is an XRD spectrum of the heterojunction of the product Sb 2S3/Sb2O3 of example 1;
FIG. 3 is an EDS energy spectrum of the product Sb 2S3/Sb2O3 heterojunction of example 2;
FIG. 4 is an XRD spectrum of the heterojunction of the product Sb 2S3/Sb2O3 of example 2;
FIG. 5 is an EDS energy spectrum of the product Sb 2S3/Sb2O3 heterojunction of example 3;
FIG. 6 is an XRD spectrum of the heterojunction of the product Sb 2S3/Sb2O3 of example 3;
FIG. 7 is a graph of photocurrent response of the intermediate Sb 2S3 film of example 3;
fig. 8 is a graph of photocurrent response of the heterojunction of the product Sb 2S3/Sb2O3 of example 3.
Detailed Description
The invention will be described in further detail with reference to specific embodiments, but the scope of the invention is not limited to the description.
Example 1: an antimony-based photocathode Sb 2S3/Sb2O3 heterojunction structure consists of a p-type Sb 2S3 film bottom layer, an Sb 2S3/Sb2O3 buffer layer and an n-type Sb 2O3 film top layer;
The preparation method of the antimony-based photocathode Sb 2S3/Sb2O3 heterojunction structure comprises the steps of preparing a metal Sb film by adopting a vapor deposition method, selecting high-purity metal Sb powder as a Sb source, and selecting ITO as a substrate; the preparation of Sb 2S3 adopts a heating method, and the S source adopts solid sublimed sulfur; the Sb 2S3/Sb2O3 heterojunction is prepared by adopting a heating method; the method comprises the following specific steps:
(1) Sputtering Sb on a substrate to obtain an Sb film: 5g of high-purity metal antimony powder is arranged in a crucible, the crucible is placed in a tube furnace, a cleaned ITO substrate is placed above the antimony powder crucible in a quartz tube, high-purity argon (more than or equal to 99.99%) is introduced into the crucible for three times to purge the reaction system of impurity gases, the reaction system is filled with the high-purity argon to 101Kpa to reach a normal pressure state, the tube furnace is controlled to be heated to 600 ℃ from room temperature within 30min, and the heat preservation time is 1h, so that a uniform and compact metal Sb film is deposited on the ITO substrate;
(2) The Sb film is vulcanized to obtain a Sb 2S3 film: taking out a metal Sb film, placing the metal Sb film in a tubular furnace, loading 3g of sublimed sulfur powder in a crucible, introducing high-purity argon (more than or equal to 99.99%) for three times to purge the impurity gas in a reaction system, introducing the high-purity argon to 101Kpa into the reaction system to enable the reaction system to reach a normal pressure state, controlling the tubular furnace to heat from room temperature to 300 ℃ within 20min, and keeping the temperature for 30min, so that the metal Sb film is vulcanized into a Sb 2S3 film;
(3) The Sb 2S3 film reacts with oxygen to generate an Sb 2S3/Sb2O3 buffer layer and an n-type Sb 2O3 film top layer to obtain an Sb-based photocathode Sb 2S3/Sb2O3 heterojunction structure: the temperature of the reaction system is reduced to 200 ℃, the pressure of the system is pumped to be lower than 30Pa, high-purity O 2 (more than or equal to 99.99%) is filled into the reaction system to reach 101Kpa so as to enable the reaction system to reach a normal pressure state, the reaction system is kept at 200 ℃ for 30min to generate an Sb 2S3/Sb2O3 buffer layer and an n-type Sb 2O3 film top layer, and an antimony-based photocathode Sb 2S3/Sb2O3 heterojunction structure is obtained;
The EDS energy spectrum of the Sb 2S3/Sb2O3 heterojunction is shown in figure 1, and the XRD energy spectrum of the product Sb 2S3/Sb2O3 heterojunction is shown in figure 2; obvious Sb, O, S peaks can be observed in the EDS spectrum of fig. 1, and the combination of corresponding Sb 2S3 and Sb 2O3 phase peaks in the XRD spectrum of fig. 2 can prove that this example completes the preparation of Sb 2S3/Sb2O3 heterojunction.
Example 2: an antimony-based photocathode Sb 2S3/Sb2O3 heterojunction structure consists of a p-type Sb 2S3 film bottom layer, an Sb 2S3/Sb2O3 buffer layer and an n-type Sb 2O3 film top layer;
The preparation method of the antimony-based photocathode Sb 2S3/Sb2O3 heterojunction structure comprises the steps of preparing a metal Sb film by adopting a magnetron sputtering method, selecting high-purity metal Sb powder as a Sb source, and selecting ITO as a substrate; the preparation of Sb 2S3 adopts a PECVD method, and the preparation of an S source adopts an H 2S;Sb2S3/Sb2O3 heterojunction and adopts a PECVD method; the method comprises the following specific steps:
(1) Sputtering Sb on a substrate to obtain an Sb film: placing a high-purity metal antimony target (more than or equal to 99.99%) on a metal target seat in a magnetron sputtering furnace chamber; reversely buckling the cleaned ITO on a sample stage in a magnetron sputtering furnace chamber, introducing high-purity argon (more than or equal to 99.99%) to perform three times of gas washing to remove impurity gas in a reaction system, adjusting the sputtering power to 20W, adjusting the rotating speed of the sample stage to 5r/min, adjusting the working pressure of the magnetron sputtering system to 0.4Pa, setting the sputtering time to 50min, and sputtering to obtain a metal Sb film with uniform and compact surface;
(2) The Sb film is vulcanized to obtain a Sb 2S3 film: placing the Sb film in an induction coil of a PECVD device, introducing high-purity argon (more than or equal to 99.99%) for three times to purge the impurity gas in a reaction system, introducing high-purity H 2 S (more than or equal to 99.99%) gas, adjusting the flow rate to 800ml/min, adjusting the PECVD radio frequency power to 150W and the radio frequency time to 30min, and vulcanizing the Sb film into the Sb 2S3 film;
(3) The Sb 2S3 film reacts with oxygen to generate an Sb 2S3/Sb2O3 buffer layer and an n-type Sb 2O3 film top layer to obtain an Sb-based photocathode Sb 2S3/Sb2O3 heterojunction structure: introducing high-purity O 2 (more than or equal to 99.99%), adjusting the flow rate to 500ml/min, adjusting the PECVD radio frequency power to 180W, and adjusting the radio frequency time to 40min to generate an Sb 2S3/Sb2O3 buffer layer and an n-type Sb 2O3 film top layer to obtain an Sb-based photocathode Sb 2S3/Sb2O3 heterojunction structure;
The EDS spectrum of the Sb 2S3/Sb2O3 heterojunction is shown in fig. 3, the XRD spectrum of the product Sb 2S3/Sb2O3 heterojunction is shown in fig. 4, obvious Sb, O, S peaks can be observed in the EDS spectrum of fig. 3, and the preparation of the Sb 2S3/Sb2O3 heterojunction can be proved to be completed by combining the corresponding Sb 2S3 and Sb 2O3 phase peaks in the XRD spectrum of fig. 4.
Example 3: an antimony-based photocathode Sb 2S3/Sb2O3 heterojunction structure consists of a p-type Sb 2S3 film bottom layer, an Sb 2S3/Sb2O3 buffer layer and an n-type Sb 2O3 film top layer;
the preparation method of the antimony-based photocathode Sb 2S3/Sb2O3 heterojunction structure comprises the steps of preparing a metal Sb film by adopting a vapor deposition method, selecting high-purity metal Sb powder as a Sb source, and selecting FTO as a substrate; the preparation of Sb 2S3 adopts a plasma method, and the S source adopts solid sublimed sulfur; the preparation of the Sb 2S3/Sb2O3 heterojunction adopts a PECVD method; the method comprises the following specific steps:
(1) Sputtering Sb on a substrate to obtain an Sb film: 5g of high-purity metal antimony powder is arranged in a crucible, the crucible is placed in a tube furnace, a cleaned ITO substrate is placed above the antimony powder crucible in a quartz tube, high-purity argon (more than or equal to 99.99%) is introduced into the crucible for three times to purge the reaction system of impurity gases, the reaction system is filled with the high-purity argon to 101Kpa to reach a normal pressure state, the tube furnace is controlled to be heated to 600 ℃ from room temperature within 30min, and the heat preservation time is 1h, so that a uniform and compact metal Sb film is deposited on the ITO substrate;
(2) The Sb film is vulcanized to obtain a Sb 2S3 film: placing a metal Sb film in a plasma induction coil, placing 5g of sublimed sulfur in a crucible and placing the crucible on the left side of the metal Sb film, introducing high-purity argon (more than or equal to 99.99%) for three times to purge the reaction system of impurity gas, introducing the high-purity argon into the reaction system to 101Kpa so as to enable the reaction system to reach a normal pressure state, adjusting the plasma power to be 220W, and vulcanizing the metal Sb film into a Sb 2S3 film for 20 min;
(3) The Sb 2S3 film reacts with oxygen to generate an Sb 2S3/Sb2O3 buffer layer and an n-type Sb 2O3 film top layer to obtain an Sb-based photocathode Sb 2S3/Sb2O3 heterojunction structure: placing the Sb 2S3 film into a PECVD reaction furnace, introducing high-purity O 2 (more than or equal to 99.99%), adjusting the flow speed to 600ml/min, adjusting the radio frequency power to 250W, and adjusting the radio frequency time to 30min to generate an Sb 2S3/Sb2O3 buffer layer and an n-type Sb 2O3 film top layer to obtain an antimony-based photocathode Sb 2S3/Sb2O3 heterojunction structure;
The EDS energy spectrum of the Sb 2S3/Sb2O3 heterojunction is shown in fig. 5, the XRD energy spectrum of the product Sb 2S3/Sb2O3 heterojunction is shown in fig. 6, obvious Sb, O, S peaks can be observed in the EDS energy spectrum of fig. 5, and the preparation of the Sb 2S3/Sb2O3 heterojunction can be proved to be completed by combining the corresponding Sb 2S3 and Sb 2O3 phase peaks in the XRD energy spectrum of fig. 6;
The photo-current response graph of the intermediate Sb 2S3 thin film is shown in fig. 7, the photo-current response graph of the product Sb 2S3/Sb2O3 heterojunction is shown in fig. 8, fig. 7 is a photo-current response graph of the Sb 2S3 thin film, wherein the dark current is about 3nA, the photo-current is about 10nA, the ratio of the photo-current to the dark current is about 3 times, and fig. 8 is a photo-current response graph of the Sb 2S3/Sb2O3 heterojunction, wherein the dark current is about 5nA, the photo-current is about 30nA, and the ratio of the photo-current to the dark current is about 6 times; the Sb 2S3/Sb2O3 heterojunction can be obtained from the photocurrent data, whether the light/dark current value or the ratio of the photocurrent to the dark current is obviously improved compared with the common Sb 2S3 film, and the Sb 2S3/Sb2O3 heterojunction is more suitable for being applied to the field of photoelectricity.
While the present invention has been described in detail with reference to the drawings, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (7)
1. An antimony-based photocathode Sb 2S3/Sb2O3 heterojunction structure, characterized in that: the structure consists of a p-type Sb 2S3 film bottom layer, an Sb 2S3/Sb2O3 buffer layer and an n-type Sb 2O3 film top layer;
The preparation method of the antimony-based photocathode Sb 2S3/Sb2O3 heterojunction structure comprises the following specific steps:
(1) Sputtering Sb on a substrate to obtain an Sb film;
(2) The Sb film is subjected to vulcanization reaction to obtain a Sb 2S3 film;
(3) The Sb 2S3 film reacts with oxygen to generate an Sb 2S3/Sb2O3 buffer layer and an n-type Sb 2O3 film top layer to obtain an antimony-based photocathode Sb 2S3/Sb2O3 heterojunction structure;
The preparation methods of the Sb 2S3/Sb2O3 buffer layer and the n-type Sb 2O3 thin film top layer are a chemical vapor deposition method, a plasma method or a heating method;
The oxidation reaction temperature of the heating method is 100-300 ℃, the oxidation time is 30S-20 min, and the partial pressure of oxygen in the mixed gas of oxygen and inert gas is 50-100%;
The oxidation temperature of the chemical vapor deposition method is 200-600 ℃, the oxidation time is 10-120 min, and the partial pressure of oxygen in the mixed gas of oxygen and inert gas is 50-100%;
the radio frequency power of the plasma method is 150-500W, the plasma radio frequency time is 10-60 min, and the oxygen partial pressure in the mixed gas of oxygen and inert gas is 50-100%.
2. The antimony-based photocathode Sb 2S3/Sb2O3 heterojunction structure according to claim 1, characterized in that: the preparation methods of the Sb 2S3/Sb2O3 buffer layer and the n-type Sb 2O3 thin film top layer are PECVD; the PECVD plasma radio frequency power is 100-300W, the oxidation heating temperature is 150-500 ℃, the oxidation time is 5-30 min, and the oxygen partial pressure in the mixed gas of oxygen and inert gas is 50-100%.
3. The method for preparing the heterojunction structure of the antimony-based photocathode Sb 2S3/Sb2O3, as set forth in claim 1, is characterized by comprising the following specific steps:
(1) Sputtering Sb on a substrate to obtain an Sb film;
(2) The Sb film is subjected to vulcanization reaction to obtain a Sb 2S3 film;
(3) The Sb 2S3 film reacts with oxygen to generate an Sb 2S3/Sb2O3 buffer layer and an n-type Sb 2O3 film top layer to obtain an antimony-based photocathode Sb 2S3/Sb2O3 heterojunction structure;
The preparation methods of the Sb 2S3/Sb2O3 buffer layer and the n-type Sb 2O3 thin film top layer are a chemical vapor deposition method, a plasma method or a heating method;
The oxidation reaction temperature of the heating method is 100-300 ℃, the oxidation time is 30S-20 min, and the partial pressure of oxygen in the mixed gas of oxygen and inert gas is 50-100%;
The oxidation temperature of the chemical vapor deposition method is 200-600 ℃, the oxidation time is 10-120 min, and the partial pressure of oxygen in the mixed gas of oxygen and inert gas is 50-100%;
the radio frequency power of the plasma method is 150-500W, the plasma radio frequency time is 10-60 min, and the oxygen partial pressure in the mixed gas of oxygen and inert gas is 50-100%.
4. The method for preparing the heterojunction structure of the antimony-based photocathode Sb 2S3/Sb2O3 according to claim 3, characterized in that: the substrate in the step (1) is ITO, FTO or common glass.
5. The method for preparing the heterojunction structure of the antimony-based photocathode Sb 2S3/Sb2O3 according to claim 3, characterized in that: the sputtering method in the step (1) is a vapor deposition method, a spray pyrolysis method, a chemical bath deposition method, an electrodeposition method, an evaporation coating method or a plasma coating method.
6. The method for preparing the heterojunction structure of the antimony-based photocathode Sb 2S3/Sb2O3 according to claim 3, characterized in that: the sulfur source of the vulcanizing reaction in the step (2) is a solid sulfur source or a gas sulfur source, wherein the solid sulfur source is elemental sulfur, chalcopyrite or pyrite, and the gas sulfur source is H 2 S or SO 2.
7. The method for preparing the heterojunction structure of the antimony-based photocathode Sb 2S3/Sb2O3 according to claim 3, characterized in that: the purity of the oxygen in the step (3) is not lower than 99.99 percent.
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