CN114284372B - Three-layer nanorod array heterojunction structure and preparation method thereof - Google Patents
Three-layer nanorod array heterojunction structure and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 95
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 20
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
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- 238000002156 mixing Methods 0.000 claims description 12
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 10
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 9
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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 discloses a three-layer nanorod array heterojunction structure and a preparation method thereof, and relates to the technical field. The three-layer nano rod array heterojunction structure comprises a SnO 2 nano rod array layer, a TiO 2 nano rod array layer and a ZnO nano rod array layer which are sequentially stacked. According to the invention, through constructing a three-layer nano rod array and reasonably selecting materials in each layer of nano rod array, on one hand, the heterojunction structure has a gradient energy band structure, so that the separation of photo-generated electrons and holes can be accelerated, and on the other hand, through designing each layer into a one-dimensional nano rod array structure, a high-speed channel is provided for the transmission of photo-generated carriers, the two layers cooperate with each other, the charge transmission efficiency is improved together, and the photoelectrochemical property of the three-layer nano rod array heterojunction structure is excellent; in addition, the three-layer nano rod array heterojunction structure also has the characteristic of large specific surface area, so that the light utilization rate is high.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a three-layer nanorod array heterojunction structure and a preparation method thereof.
Background
A heterojunction is an interfacial region formed by two different semiconductor materials in contact. Heterojunctions can be classified into homoheterojunctions (P-junctions or N-junctions) and heteroheterojunctions (P-N or P-N) according to the conductivity types of the two materials, and multilayer heterojunctions are called heterostructures.
Titanium dioxide (TiO 2) and zinc oxide (ZnO) are important N-type wide-bandgap semiconductor materials, have good physical and chemical properties, are low in material cost and nontoxic, are regarded as ideal materials for solving environmental problems and energy crisis, and have wide application in the fields of solar cells, photocatalytic pyrolysis water or photocatalytic degradation of organic pollutants, electrochemical energy storage, sensors and the like.
Along with development of nano technology, a plurality of nano materials of TiO 2 and ZnO are developed, and mainly comprise nanorods, nanowires, nanoparticles, nano films and the like, wherein the nanorod array layer structure can provide a directional transmission channel for electrons, so that the transmission rate of the electrons is improved, and the loss in the electron transmission process is reduced. The single-component TiO 2 and ZnO nano-rod array layer material has lower photoelectrochemical property due to the problem that internal carriers are easy to be compounded.
Compared with a single-layer nano-structure material formed by single titanium dioxide or zinc oxide, the heterojunction material with the zinc oxide and titanium dioxide nano-structure with the multi-layer composite structure has larger specific surface area, better light scattering and absorption capacity and better photoelectrochemical property, and therefore becomes a hot spot for researching the field of nano-materials. However, the heterojunction composite structure of the one-dimensional zinc oxide nano rod array and the two-dimensional titanium dioxide film is generally prepared at present, and the photoelectrochemical property of the composite structure is still low, so that the application of the composite structure is limited.
Disclosure of Invention
The invention mainly aims to provide a three-layer nano rod array heterojunction structure and a preparation method thereof, and aims to provide the three-layer nano rod array heterojunction structure with excellent photoelectrochemical properties.
In order to achieve the above purpose, the invention provides a three-layer nanorod array heterojunction structure, which comprises a SnO 2 nanorod array layer, a titanium dioxide nanorod array layer and a ZnO nanorod array layer which are sequentially stacked.
Optionally, the thickness of the SnO 2 nano rod array layer is 350-400 nm, and the rod diameter of each SnO 2 nano rod in the SnO 2 nano rod array layer is 50-120 nm; and/or the number of the groups of groups,
The thickness of the TiO 2 nano rod array layer is 1-2 mu m, and the rod diameter of each TiO 2 nano rod in the TiO 2 nano rod array layer is 50-120 nm; and/or the number of the groups of groups,
The thickness of the ZnO nano rod array layer is 0.5-1 mu m, and the rod diameter of each ZnO nano rod in the ZnO nano rod array layer is 50-100 nm.
Furthermore, the invention also provides a preparation method of the three-layer nanorod array heterojunction structure, which comprises the following steps:
S10, providing a substrate, coating a SnO 2 solution on the substrate, and then carrying out high-temperature annealing to obtain a SnO 2 seed layer;
s20, placing the substrate containing the SnO 2 seed layer into a SnO 2 precursor solution, and performing hydrothermal reaction at 180-220 ℃ to grow on the SnO 2 seed layer to obtain a SnO 2 nanorod array layer;
S30, depositing TiO 2 nano particles on the SnO 2 nano rod array layer to obtain a TiO 2 seed layer;
S40, placing the substrate containing the TiO 2 seed layer in a TiO 2 precursor solution, and performing hydrothermal reaction at 150-170 ℃ to grow on the TiO 2 seed layer to obtain a TiO 2 nanorod array layer;
S50, depositing ZnO nano particles on the TiO 2 nano rod array layer to obtain a ZnO seed layer;
S60, placing the substrate containing the ZnO seed layer into a ZnO precursor solution, performing hydrothermal reaction at 110-130 ℃, taking out, cleaning and drying to obtain the three-layer nanorod array heterojunction structure arranged on the substrate.
Optionally, in step S10, the molar concentration of the SnO 2 solution is 0.12 to 0.13mol/L.
Optionally, in step S10, the annealing temperature in the high-temperature annealing step is 480-520 ℃ and the annealing time is 30-45 min.
Optionally, in step S20, the SnO 2 precursor solution is prepared by the steps of:
Uniformly mixing deionized water and ethanol in equal volume to obtain a mixed solution A, and then dissolving SnCl 4 crystals in the mixed solution A to obtain a SnO 2 precursor solution;
wherein the ratio of the volume of deionized water to the mass of SnCl 4 crystal is 9.375mL: 16-17.5 mg.
Optionally, in step S30, a radio frequency magnetron sputtering process is used to deposit TiO 2 nanoparticles; and/or the number of the groups of groups,
In step S50, znO nanoparticles are deposited using a radio frequency magnetron sputtering process.
Optionally, in step S30, tiO 2 nano particles are deposited by adopting a radio frequency magnetron sputtering process, wherein the sputtering air pressure is 10-15 mTorr, the sputtering power is 100-150W, the rotation speed of the grade sheet is 0-10 r/min, and the sputtering time is 10-20 min; and/or the number of the groups of groups,
In the step S50, znO nano particles are deposited by adopting a radio frequency magnetron sputtering process, wherein the sputtering air pressure is 10-15 mTorr, the sputtering power is 100-150W, the rotation speed of the grade sheet is 0-10 r/min, and the sputtering time is 30-40 min.
Optionally, in step S40, the TiO 2 precursor solution is prepared by the steps of:
uniformly mixing deionized water and concentrated hydrochloric acid in equal volume to obtain a mixed solution B, and dissolving tetrabutyl titanate in the mixed solution B to obtain a TiO 2 precursor solution;
wherein the volume ratio of deionized water to tetrabutyl titanate is 9-13: 1 to 1.5.
Optionally, in step S60, the ZnO precursor solution is prepared by:
Zinc nitrate and urotropine are dissolved in deionized water to obtain ZnO precursor solution;
Wherein, the addition amount of zinc nitrate and urotropine is 1.5-2 g and 0.7g in every 100mL deionized water.
According to the technical scheme provided by the invention, through constructing the three layers of nano rod arrays and reasonably selecting materials in each layer of nano rod array, on one hand, the heterojunction structure is provided with a gradient energy band structure, so that the separation of photo-generated electrons and holes can be accelerated, and on the other hand, through designing each layer into a one-dimensional nano rod array structure, a high-speed channel is provided for the transmission of photo-generated carriers, and the two nano rod arrays cooperate with each other, so that the charge transmission efficiency is improved together, and the photoelectrochemical property of the heterojunction structure of the three layers of nano rod arrays is excellent; in addition, the three-layer nano rod array heterojunction structure also has the characteristic of large specific surface area, so that the light utilization rate is high.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other related drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a cross-sectional SEM image of a three-layer nanorod array heterojunction structure fabricated in example 1 of the present invention;
FIG. 2 is a surface SEM image of a three-layer nanorod array heterojunction structure prepared in example 1 of the present invention;
FIG. 3 is a schematic diagram of the energy bands and the structure of a heterojunction structure of a three-layer nanorod array provided by the invention;
FIG. 4 is an XRD pattern of the three-layer nanorod array heterojunction structure of FIG. 1;
FIG. 5 is a graph showing the linear sweep voltammogram of the nanorod array structures produced in example 1 and comparative examples 1 and 2 of the present invention;
FIG. 6 is an electrochemical impedance spectrum of the nanorod array structures prepared in example 1 and comparative examples 1 and 2 according to the present invention.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In addition, the meaning of "and/or" as it appears throughout includes three parallel schemes, for example "A and/or B", including the A scheme, or the B scheme, or the scheme where A and B are satisfied simultaneously. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be regarded as not exist and not within the protection scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Compared with a single-layer nano-structure material formed by single titanium dioxide or zinc oxide, the heterojunction material with the zinc oxide and titanium dioxide nano-structure with the multi-layer composite structure has larger specific surface area, better light scattering and absorption capacity and better photoelectrochemical property, and therefore becomes a hot spot for researching the field of nano-materials. However, the heterojunction composite structure of the one-dimensional zinc oxide nano rod array and the two-dimensional titanium dioxide film is generally prepared at present, and the photoelectrochemical property of the composite structure is still low, so that the application of the composite structure is limited.
In view of the above, the present invention provides a three-layer nanorod array heterojunction structure, and aims to provide a three-layer nanorod array heterojunction structure with excellent photoelectrochemical properties. Referring to fig. 1 and fig. 2 in combination, in an embodiment, the three-layer nanorod array heterojunction structure includes a SnO 2 nanorod array layer, a TiO 2 nanorod array layer, and a ZnO nanorod array layer, which are sequentially stacked.
Referring to fig. 3 in combination, the energy band structures of SnO 2、TiO2 and ZnO in the three-layer nanorod array heterojunction structure are matched to form a gradient energy band, so that the heterojunction structure with the gradient energy band structure can inhibit the recombination of electron hole pairs by using a built-in electric field, and accelerate the separation of carrier ions, thereby improving the charge transmission efficiency.
Furthermore, the three-layer nano rod array heterojunction structure is formed by compounding a one-dimensional SnO 2 nano rod array, a one-dimensional TiO 2 nano rod array and a one-dimensional ZnO nano rod array, and each layer is designed into a one-dimensional nano rod array structure, so that a high-speed channel is provided for the transmission of photogenerated carriers, and the charge transmission efficiency is further improved. Compared with a composite structure formed by one dimension and two dimensions, the one dimension and one dimension composite pair electron transmission has better and more direct driving force and higher light utilization rate.
It should be noted that, compared with the composite structure formed by the one-dimensional TiO 2 nanorod array and the one-dimensional ZnO nanorod array, the three-layer nanorod heterojunction structure forms a gradient energy band by arranging the SnO 2 nanorod array at the bottom of the one-dimensional TiO 2 nanorod array, which is equivalent to applying a driving force at the bottom of the TiO 2 nanorod array, so that electrons driving the TiO 2 are more smoothly transferred to the SnO 2, and further the charge transmission efficiency is increased. In addition, the three-layer nano rod array heterojunction structure has the advantages that the number of layers is large, so that the specific surface area of the whole array is larger, the capturing effect of light is better, and the light utilization rate is higher. It is understood that FTO in fig. 1 and 2 refers to fluorine doped SnO 2 conductive glass, i.e., a substrate.
According to the technical scheme provided by the invention, through constructing the three layers of nano rod arrays and reasonably selecting materials in each layer of nano rod array, on one hand, the heterojunction structure is provided with a gradient energy band structure, so that the separation of photo-generated electrons and holes can be accelerated, and on the other hand, through designing each layer into a one-dimensional nano rod array structure, a high-speed channel is provided for the transmission of photo-generated carriers, and the two nano rod arrays cooperate with each other, so that the charge transmission efficiency is improved together, and the photoelectrochemical property of the heterojunction structure of the three layers of nano rod arrays is excellent; in addition, the three-layer nano rod array heterojunction structure also has the characteristic of large specific surface area, so that the light utilization rate is high.
In one embodiment, the thickness of the SnO 2 nanorod array layer (i.e., the rod length of the nanorods) is 350-400 nm, and the rod diameter of each SnO 2 nanorod in the SnO 2 nanorod array layer is 50-120 nm. In another embodiment, the thickness of the TiO 2 nanorod array layer (i.e., the rod length of the nanorods) is 1-2 μm, and the rod diameter of each TiO 2 nanorod in the TiO 2 nanorod array layer is 50-120 nm. In another embodiment, the thickness of the ZnO nano-rod array layer (i.e., the rod length of the nano-rods) is 0.5-1 μm, and the rod diameter of each ZnO nano-rod in the ZnO nano-rod array layer is 50-100 nm. Preferably, the three-layer nanorod array heterojunction structure is a combination of the three embodiments, so that the photoelectrochemical performance of the three-layer nanorod array heterojunction structure is better and the three-layer nanorod array heterojunction structure is easy to prepare through the adjustment and control of the size of each layer of nanorod array layer.
Based on the above objective, the present invention also provides a method for preparing the three-layer nanorod array heterojunction structure, which in one embodiment comprises the following steps:
Step S10, providing a substrate, coating a SnO 2 solution on the substrate, and then annealing at a high temperature to obtain a SnO 2 seed layer.
The substrate is FTO conductive glass. Wherein the molar concentration of the SnO 2 solution is 0.12-0.13 mol/L. In addition, the annealing temperature in the high-temperature annealing step is 480-520 ℃ and the annealing time is 30-45 min. Further, the annealing temperature is preferably 500 ℃.
In specific implementation, step S10 includes: cleaning FTO conductive glass to be used as a substrate, maintaining the substrate at the rotating speed of 1000r/min for 10s by adopting a spin coater, maintaining the substrate at 4000r/min for 30s to spin-coat SnO 2 aqueous solution (the molar concentration is 0.12-0.13 mol/L) on the substrate, and then placing the substrate on a heat table at 480-520 ℃ for high-temperature annealing for 30-45 min to obtain the SnO 2 seed layer.
And step S20, placing the substrate containing the SnO 2 seed layer into a SnO 2 precursor solution, and performing hydrothermal reaction at 180-220 ℃ to grow on the SnO 2 seed layer to obtain the SnO 2 nanorod array layer.
In this embodiment, the SnO 2 precursor solution is prepared by the steps of: uniformly mixing deionized water and ethanol in equal volume to obtain a mixed solution A, and then dissolving SnCl 4 crystals in the mixed solution A to obtain a SnO 2 precursor solution; wherein the ratio of the volume of deionized water to the mass of SnCl 4 crystal is 9.375mL: 16-17.5 mg; in this way, the rod length and the rod diameter of the nanorods in the SnO 2 nanorod array are controlled by designing the concentration of the SnO 2 precursor solution and the temperature of the hydrothermal reaction.
And step S30, depositing TiO 2 nano particles on the SnO 2 nano rod array layer to obtain a TiO 2 seed layer.
If the hydrothermal reaction is directly performed to prepare the nanorod array, a disordered structure is easy to generate, in the embodiment, the TiO 2 seed layer is formed first, and then the hydrothermal reaction is performed to grow on the TiO 2 seed layer to obtain the TiO 2 nanorod array, so that the subsequently grown heterogeneous TiO 2 nanorods can continue to grow along the growth direction of the underlying SnO 2 nanorods, a one-dimensional connected one-dimensional morphology is obtained, and a high-speed channel is provided for the transmission of photo-generated carriers.
The specific arrangement mode for forming the TiO 2 seed layer is not limited, a sol-gel method can be adopted, a magnetron sputtering method can also be adopted, and in the embodiment, the radio frequency magnetron sputtering technology is adopted to deposit TiO 2 nano particles so as to obtain the TiO 2 seed layer. By adopting the magnetron sputtering method, the nano-particle deposition is more uniform, the efficiency is higher, and the large-scale deposition is more facilitated.
Further, the sputtering air pressure of the radio frequency magnetron sputtering process is 10-15 mTorr, the sputtering power is 100-150W, the rotation speed of the grade sheet is 0-10 r/min, and the sputtering time is 10-20 min.
Step S40, placing the substrate containing the TiO 2 seed layer in a TiO 2 precursor solution, and performing hydrothermal reaction at 150-170 ℃ to grow on the TiO 2 seed layer to obtain a TiO 2 nanorod array layer;
In this embodiment, the TiO 2 precursor solution is prepared by the following steps: uniformly mixing deionized water and concentrated hydrochloric acid in equal volume to obtain a mixed solution B, and dissolving tetrabutyl titanate in the mixed solution B to obtain a TiO 2 precursor solution; wherein the volume ratio of deionized water to tetrabutyl titanate is 9-13: 1 to 1.5.
And S50, depositing ZnO nano particles on the TiO 2 nano rod array layer to obtain a ZnO seed layer.
The principle of depositing ZnO nano particles by adopting a radio frequency magnetron sputtering process to obtain a ZnO seed layer is similar to that of preparing a TiO 2 seed layer, and the description is omitted here. Further, the sputtering air pressure of the radio frequency magnetron sputtering process is 10-15 mTorr, the sputtering power is 100-150W, the rotation speed of the grade sheet is 0-10 r/min, and the sputtering time is 30-40 min.
And step S60, placing the substrate containing the ZnO seed layer in a ZnO precursor solution, performing hydrothermal reaction at 110-130 ℃, taking out, cleaning and drying to obtain the three-layer nanorod array heterojunction structure arranged on the substrate.
In this example, the ZnO precursor solution was prepared by the following steps: zinc nitrate and urotropine are dissolved in deionized water to obtain ZnO precursor solution; wherein, the addition amount of zinc nitrate and urotropine is 1.5-2 g and 0.7g in every 100mL deionized water.
According to the preparation method of the three-layer nano rod array heterojunction structure, the seed layer is formed firstly, so that the growth direction of the corresponding nano rod array formed subsequently is highly ordered, and the three-layer nano rod array heterojunction structure is of a one-dimensional and one-dimensional structure, and the charge transmission efficiency is high; the nano rod array is prepared by adopting a hydrothermal method with mature technology, low cost and good process controllability, so that the preparation method is easy to popularize in large-scale industrial production; by designing the concentration of the precursor solution and the hydrothermal reaction temperature, the shape, the size and the like of each layer of nano rod array are well controlled, so that the electrochemical performance of the three-layer SnO 2/TiO2/ZnO nano rod heterojunction structure is further improved.
The following technical solutions of the present invention will be described in further detail with reference to specific examples and drawings, and it should be understood that the following examples are only for explaining the present invention and are not intended to limit the present invention.
Example 1
(1) And cleaning the FTO conductive glass to serve as a substrate, maintaining the substrate at the rotating speed of 1000r/min for 10s by adopting a spin coater, maintaining the substrate at 4000r/min for 30s to spin-coat an SnO 2 aqueous solution (the molar concentration is 0.126 mol/L) on the substrate, and then placing the substrate on a 500 ℃ hot table for high-temperature annealing for 40min to obtain the SnO 2 seed layer.
(2) Uniformly mixing 9.375mL of deionized water and 9.375mL of ethanol to obtain a mixed solution A, and then dissolving 17mg of SnCl 4 crystals in the mixed solution A to obtain a SnO 2 precursor solution; and placing the FTO containing the SnO 2 seed layer into the SnO 2 precursor solution, performing hydrothermal reaction at 200 ℃, cooling to room temperature, taking out, cleaning and drying to obtain the SnO 2 nanorod array layer.
(3) And depositing TiO 2 nano particles on the SnO 2 nano rod array layer by adopting a radio frequency magnetron sputtering method to obtain a TiO 2 seed layer, wherein the sputtering air pressure of the radio frequency magnetron sputtering process is 12mTorr, the sputtering power is 120W, the rotation speed of the grade sheet is 5r/min, and the sputtering time is 10min.
(4) Uniformly mixing 10mL of deionized water and 10mL of concentrated hydrochloric acid to obtain a mixed solution B, and dissolving 1mL of tetrabutyl titanate in the mixed solution B to obtain a TiO 2 precursor solution; and placing the FTO containing the TiO 2 seed layer in the TiO 2 precursor solution, performing hydrothermal reaction at 160 ℃, cooling to room temperature, taking out, cleaning and drying to obtain the TiO 2 nanorod array layer.
(5) And depositing ZnO nano particles on the TiO 2 nano rod array layer by adopting a radio frequency magnetron sputtering method to obtain a ZnO seed layer, wherein the sputtering air pressure of the radio frequency magnetron sputtering process is 12mTorr, the sputtering power is 120W, the rotation speed of the grade sheet is 5r/min, and the sputtering time is 35min.
(6) 1.8G of zinc nitrate and 0.7g of urotropine are dissolved in 100mL of deionized water to obtain ZnO precursor solution; and placing the FTO containing the ZnO seed layer in the ZnO precursor solution, carrying out hydrothermal reaction at 120 ℃, taking out, cleaning and drying to obtain the three-layer SnO 2/TiO2/ZnO nano-rod array heterojunction structure arranged on the FTO.
Example 2
(1) And cleaning the FTO conductive glass to serve as a substrate, maintaining the substrate at the rotating speed of 1000r/min for 10s by adopting a spin coater, maintaining the substrate at 4000r/min for 30s to spin-coat an SnO 2 aqueous solution (the molar concentration is 0.12 mol/L) on the substrate, and then placing the substrate on a 480 ℃ hot table for high-temperature annealing for 45min to obtain the SnO 2 seed layer.
(2) Uniformly mixing 9.375mL of deionized water and 9.375mL of ethanol to obtain a mixed solution A, and then dissolving 17.5mg of SnCl 4 crystals in the mixed solution A to obtain a SnO 2 precursor solution; and placing the FTO containing the SnO 2 seed layer into the SnO 2 precursor solution, performing hydrothermal reaction at 220 ℃, cooling to room temperature, taking out, cleaning and drying to obtain the SnO 2 nanorod array layer.
(3) And depositing TiO 2 nano particles on the SnO 2 nano rod array layer by adopting a radio frequency magnetron sputtering method to obtain a TiO 2 seed layer, wherein the sputtering air pressure of the radio frequency magnetron sputtering process is 15mTorr, the sputtering power is 150W, the rotation speed of the grade sheet is 10r/min, and the sputtering time is 15min.
(4) Uniformly mixing 13mL of deionized water and 13mL of concentrated hydrochloric acid to obtain a mixed solution B, and dissolving 1.5mL of tetrabutyl titanate in the mixed solution B to obtain a TiO 2 precursor solution; and placing the FTO containing the TiO 2 seed layer in the TiO 2 precursor solution, performing hydrothermal reaction at 150 ℃, cooling to room temperature, taking out, cleaning and drying to obtain the TiO 2 nanorod array layer.
(5) And depositing ZnO nano particles on the TiO2 nano rod array layer by adopting a radio frequency magnetron sputtering method to obtain a ZnO seed layer, wherein the sputtering air pressure of the radio frequency magnetron sputtering process is 15mTorr, the sputtering power is 150W, the rotation speed of the grade sheet is 10r/min, and the sputtering time is 30min.
(6) 2G of zinc nitrate and 0.7g of urotropine are dissolved in 100mL of deionized water to obtain ZnO precursor solution; and placing the FTO containing the ZnO seed layer in the ZnO precursor solution, carrying out hydrothermal reaction at 110 ℃, taking out, cleaning and drying to obtain the three-layer SnO 2/TiO2/ZnO nano-rod array heterojunction structure arranged on the FTO.
Example 3
(1) And cleaning the FTO conductive glass to serve as a substrate, maintaining the substrate at the rotating speed of 1000r/min for 10s by adopting a spin coater, maintaining the substrate at 4000r/min for 30s to spin-coat an SnO 2 aqueous solution (the molar concentration is 0.13 mol/L) on the substrate, and then placing the substrate on a 520 ℃ hot table for high-temperature annealing for 30min to obtain the SnO 2 seed layer.
(2) Uniformly mixing 9.375mL of deionized water and 9.375mL of ethanol to obtain a mixed solution A, and then dissolving 16mg of SnCl 4 crystals in the mixed solution A to obtain a SnO 2 precursor solution; and placing the FTO containing the SnO 2 seed layer into the SnO 2 precursor solution, performing hydrothermal reaction at 180 ℃, cooling to room temperature, taking out, cleaning and drying to obtain the SnO 2 nanorod array layer.
(3) And depositing TiO 2 nano particles on the SnO 2 nano rod array layer by adopting a radio frequency magnetron sputtering method to obtain a TiO 2 seed layer, wherein the sputtering air pressure of the radio frequency magnetron sputtering process is 10mTorr, the sputtering power is 100W, the rotation speed of the grade sheet is 1r/min, and the sputtering time is 20min.
(4) Uniformly mixing 9mL of deionized water and 9mL of concentrated hydrochloric acid to obtain a mixed solution B, and dissolving 1.2mL of tetrabutyl titanate in the mixed solution B to obtain a TiO 2 precursor solution; and placing the FTO containing the TiO 2 seed layer in the TiO 2 precursor solution, performing hydrothermal reaction at 170 ℃, cooling to room temperature, taking out, cleaning and drying to obtain the TiO 2 nanorod array layer.
(5) And depositing ZnO nano particles on the TiO2 nano rod array layer by adopting a radio frequency magnetron sputtering method to obtain a ZnO seed layer, wherein the sputtering air pressure of the radio frequency magnetron sputtering process is 15mTorr, the sputtering power is 150W, the rotation speed of the grade sheet is 10r/min, and the sputtering time is 40min.
(6) 1.5G of zinc nitrate and 0.7g of urotropine are dissolved in 100mL of deionized water to obtain ZnO precursor solution; and placing the FTO containing the ZnO seed layer in the ZnO precursor solution, carrying out hydrothermal reaction at 130 ℃, taking out, cleaning and drying to obtain the three-layer SnO 2/TiO2/ZnO nano-rod array heterojunction structure arranged on the FTO.
Comparative example 1
The preparation method of the TiO 2 precursor solution is the same as that in the embodiment 1, the FTO conductive glass is cleaned to be used as a substrate, the TiO 2 nano particles are deposited on the substrate by adopting a radio frequency magnetron sputtering method to obtain a TiO 2 seed layer, the FTO containing the TiO 2 seed layer is placed in the TiO 2 precursor solution, the hydrothermal reaction is carried out at 160 ℃, and then the FTO is taken out after being cooled to room temperature, cleaned and dried, so that the single-layer TiO 2 nano rod array structure is obtained.
Comparative example 2
(1) The preparation method of the TiO 2 precursor solution is the same as that in the embodiment 1, the FTO conductive glass is cleaned to be used as a substrate, the TiO 2 nano particles are deposited on the substrate by adopting a radio frequency magnetron sputtering method to obtain a TiO 2 seed layer, the FTO containing the TiO 2 seed layer is placed in the TiO 2 precursor solution, the hydrothermal reaction is carried out at 160 ℃, and then the TiO 2 nano rod array layer is obtained after cooling to room temperature, cleaning and drying.
(2) And depositing ZnO nano particles on the TiO 2 nano rod array layer by adopting a radio frequency magnetron sputtering method to obtain a ZnO seed layer, wherein the sputtering air pressure of the radio frequency magnetron sputtering process is 12mTorr, the sputtering power is 120W, the rotation speed of the grade sheet is 5r/min, and the sputtering time is 35min.
(3) 1.8G of zinc nitrate and 0.7g of urotropine are dissolved in 100mL of deionized water to obtain ZnO precursor solution; and placing the FTO containing the ZnO seed layer in the ZnO precursor solution, carrying out hydrothermal reaction at 120 ℃, taking out, cleaning and drying to obtain the double-layer TiO 2/ZnO nano-rod array structure arranged on the FTO.
The three-layer SnO 2/TiO2/ZnO nanorod array heterojunction structure prepared in example 1 was characterized under a Scanning Electron Microscope (SEM), and FIGS. 1 and 2 are a cross-section and a surface diagram of the three-layer SnO 2/TiO2/ZnO nanorod array heterojunction structure, respectively.
As can be seen from fig. 1, the three-layer nanorod array structure is successfully manufactured, wherein the bottom layer is a SnO 2 nanorod array, the middle layer is a TiO 2 nanorod array, and the uppermost layer is a ZnO nanorod array. As can be seen from fig. 2, the surface layer of the three-layer nanorod array heterojunction structure is a ZnO nanorod array with a distinct regular hexagonal structure.
X-ray diffraction is carried out on the three-layer SnO 2/TiO2/ZnO nano-rod array heterojunction structure prepared in the embodiment 1, and an XRD diffraction pattern shown in figure 4 is obtained. Wherein 2θ= 26.534 °, 30.21 °, 31.8 °, 37.9 °, 62.7 °, 64.7 °, 65.4 °, 69.0 ° are diffraction peaks of the hexagonal wurtzite ZnO nanorod array (JCPDS No. 36-1451), corresponding to (100), (002) (101), (102), (103), (200), (112), (201) crystal planes, respectively; 2θ=36.2 °, 61.7 °, 47.5 °, 51.5 °, 56.6 ° are diffraction peaks of the rutile titanium dioxide nanorod array (JCPDS No. 88-1175), corresponding to (101), (002), (200), (211), (220) crystal planes, respectively. 2θ=33.5°, 57.8 ° are diffraction peaks (JCPDS 41-1445) of the rutile SnO 2 nanorod array, corresponding to (301) (002) crystal planes, respectively. Namely, the preparation method provided by the invention successfully prepares the three-layer SnO 2/TiO2/ZnO nano rod array heterojunction structure.
Fig. 5 is a linear sweep voltammogram of a three-layer SnO 2/TiO2/ZnO nanorod array heterojunction made in example 1, a two-layer TiO 2/ZnO nanorod array made in comparative example 1, and a single-layer TiO 2 nanorod array made in comparative example 2, and as can be seen from fig. 5, the three-layer SnO 2/TiO2/ZnO nanorod array heterojunction structure has a higher photocurrent response at the same bias voltage as the two-layer TiO 2/ZnO nanorod array and the single-layer TiO 2 nanorod array.
Fig. 6 shows electrochemical impedance spectra of the three-layer SnO 2/TiO2/ZnO nanorod array heterojunction prepared in example 1, the two-layer TiO 2/ZnO nanorod array prepared in comparative example 1, and the single-layer TiO 2 nanorod array prepared in comparative example 2, and as can be seen from fig. 6, the three-layer SnO 2/TiO2/ZnO nanorod array heterojunction has the smallest composite resistance, mainly because the gradient band structure accelerates carrier transport, and effectively reduces the recombination of electron hole pairs.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the scope of the present invention, but various modifications and variations will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The three-layer nano rod array heterojunction structure is characterized by comprising a SnO 2 nano rod array layer, a TiO 2 nano rod array layer and a ZnO nano rod array layer which are sequentially stacked.
2. The three-layer nanorod array heterojunction structure of claim 1, wherein the thickness of the SnO 2 nanorod array layer is 350-400 nm, and the rod diameter of each SnO 2 nanorod in the SnO 2 nanorod array layer is 50-120 nm; and/or the number of the groups of groups,
The thickness of the TiO 2 nano rod array layer is 1-2 mu m, and the rod diameter of each TiO 2 nano rod in the TiO 2 nano rod array layer is 50-120 nm; and/or the number of the groups of groups,
The thickness of the ZnO nano rod array layer is 0.5-1 mu m, and the rod diameter of each ZnO nano rod in the ZnO nano rod array layer is 50-100 nm.
3. A method for preparing the three-layer nanorod array heterojunction structure according to claim 1 or 2, comprising the following steps:
S10, providing a substrate, coating a SnO 2 solution on the substrate, and then carrying out high-temperature annealing to obtain a SnO 2 seed layer;
s20, placing the substrate containing the SnO 2 seed layer into a SnO 2 precursor solution, and performing hydrothermal reaction at 180-220 ℃ to grow on the SnO 2 seed layer to obtain a SnO 2 nanorod array layer;
S30, depositing TiO 2 nano particles on the SnO 2 nano rod array layer to obtain a TiO 2 seed layer;
S40, placing the substrate containing the TiO 2 seed layer in a TiO 2 precursor solution, and performing hydrothermal reaction at 150-170 ℃ to grow on the TiO 2 seed layer to obtain a TiO 2 nanorod array layer;
S50, depositing ZnO nano particles on the TiO 2 nano rod array layer to obtain a ZnO seed layer;
S60, placing the substrate containing the ZnO seed layer into a ZnO precursor solution, performing hydrothermal reaction at 110-130 ℃, taking out, cleaning and drying to obtain the three-layer nanorod array heterojunction structure arranged on the substrate.
4. The method of fabricating a three-layer nanorod array heterojunction structure according to claim 3, wherein in the step S10, the molar concentration of the SnO 2 solution is 0.12-0.13 mol/L.
5. The method of fabricating a three-layer nanorod array heterojunction structure according to claim 3, wherein in the step S10, the annealing temperature in the high-temperature annealing step is 480-520 ℃ and the annealing time is 30-45 min.
6. The method of fabricating a three-layer nanorod array heterojunction structure according to claim 3, wherein in step S20, the SnO 2 precursor solution is prepared by:
Uniformly mixing deionized water and ethanol in equal volume to obtain a mixed solution A, and then dissolving SnCl 4 crystals in the mixed solution A to obtain a SnO 2 precursor solution;
wherein the ratio of the volume of deionized water to the mass of SnCl 4 crystal is 9.375mL: 16-17.5 mg.
7. The method for fabricating a three-layer nanorod array heterojunction structure according to claim 3, wherein in step S30, tiO 2 nanoparticles are deposited by using a radio frequency magnetron sputtering process; and/or, in step S50, the ZnO nanoparticles are deposited using a radio frequency magnetron sputtering process.
8. The method for preparing the three-layer nanorod array heterojunction structure according to claim 3, wherein in the step S30, tiO 2 nano particles are deposited by adopting a radio frequency magnetron sputtering process, wherein the sputtering air pressure is 10-15 mTorr, the sputtering power is 100-150W, the rotation speed of the grade sheet is 0-10 r/min, and the sputtering time is 10-20 min; and/or the number of the groups of groups,
In the step S50, znO nano particles are deposited by adopting a radio frequency magnetron sputtering process, wherein the sputtering air pressure is 10-15 mTorr, the sputtering power is 100-150W, the rotation speed of the grade sheet is 0-10 r/min, and the sputtering time is 30-40 min.
9. The method of fabricating a three-layer nanorod array heterojunction structure according to claim 3, wherein in step S40, the TiO 2 precursor solution is prepared by:
uniformly mixing deionized water and concentrated hydrochloric acid in equal volume to obtain a mixed solution B, and dissolving tetrabutyl titanate in the mixed solution B to obtain a TiO 2 precursor solution;
wherein the volume ratio of deionized water to tetrabutyl titanate is 9-13: 1 to 1.5.
10. The method of fabricating a three-layer nanorod array heterojunction structure according to claim 3, wherein in step S60, the ZnO precursor solution is prepared by:
Zinc nitrate and urotropine are dissolved in deionized water to obtain ZnO precursor solution;
Wherein, the addition amount of zinc nitrate and urotropine is 1.5-2 g and 0.7g in every 100mL deionized water.
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