CN114015990B - Preparation method and application of nickel oxide-gold-zinc oxide coaxial nano-array - Google Patents

Preparation method and application of nickel oxide-gold-zinc oxide coaxial nano-array Download PDF

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CN114015990B
CN114015990B CN202111190422.6A CN202111190422A CN114015990B CN 114015990 B CN114015990 B CN 114015990B CN 202111190422 A CN202111190422 A CN 202111190422A CN 114015990 B CN114015990 B CN 114015990B
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zinc oxide
gold
nanowire array
sputtering
nickel oxide
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CN114015990A (en
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徐春祥
董秀秀
王茹
石增良
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Southeast University
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    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/305—Electrodes, e.g. test electrodes; Half-cells optically transparent or photoresponsive electrodes

Abstract

The invention discloses a preparation method and application of a nickel oxide-gold-zinc oxide coaxial nano-array. Belongs to the field of nano photoelectric functional materials, and comprises the following specific steps: 1. placing the pretreated conductive substrate in a magnetron sputtering instrument, and sputtering a zinc oxide target in a mixed gas of high-purity oxygen and high-purity argon to obtain a zinc oxide seed layer; 2. then adding the nano-wires into an aqueous solution of zinc acetate and hexamethylenetetramine, and performing hydrothermal synthesis to prepare a zinc oxide nanowire array; 3. then washing and drying the obtained product, and then sputtering the plasma nano gold; obtaining a gold-zinc oxide nanowire array; 4. and finally, placing the gold-coated zinc oxide nanowire array (gold-zinc oxide nanowire array) in a magnetron sputtering instrument for nickel oxide modification, and finally obtaining the nickel oxide-gold-zinc oxide coaxial nanowire array. The nickel oxide-gold-zinc oxide coaxial nanowire array has the characteristics of controllable morphology, photoelectric synergy, good repeatability and the like.

Description

Preparation method and application of nickel oxide-gold-zinc oxide coaxial nano-array
Technical Field
The invention belongs to the field of nano photoelectric functional materials, and relates to a preparation method of a nickel oxide-gold-zinc oxide coaxial nanowire array for photoelectric sensing and application thereof in photoelectric sensing.
Background
The nano photoelectric material, especially the semiconductor material, has wide application prospect in the fields of photoelectric detection, luminescent devices, catalytic degradation, gas sensing and the like. The composition, morphology and size of the nano photoelectric material can influence the application performance of the nano photoelectric material. Thus, obtaining nano heterojunction with different compositions, morphologies and sizes has attracted research interest. As transition metal oxides, zinc oxide and nickel oxide exhibit excellent properties in the fields of photoelectric detection, light emitting devices, catalytic degradation, gas sensing, and the like. Compared with a single component, the p-n heterojunction constructed by compounding zinc oxide and nickel oxide can greatly improve the photoelectric property of the material. Meanwhile, the surface plasmon resonance effect of the nano metal particles (such as nano gold) can further improve the photoelectric conversion of the semiconductor. Therefore, the composite material based on zinc oxide, nickel oxide and nano gold is expected to achieve the synergistic enhancement of photoelectric signals.
The current preparation method for synthesizing the nickel oxide-gold-zinc oxide composite material generally comprises the following steps: surface reaction, self-assembly, solution, hydrothermal, electrodeposition, etc. For nickel oxide-gold-zinc oxide composite materials, a solution method is generally adopted to achieve a uniform and compact wrapping effect of a shell layer material, but the solution preparation environment is complex, the process stability is poor, large-area growth is difficult to carry out, and a zinc oxide substrate is soaked in an aqueous solution for multiple times or for a long time, so that the surface defect state of zinc oxide can be changed in the process.
Disclosure of Invention
The invention aims to: the invention aims to provide a coaxial heterojunction composite material based on nickel oxide-gold-zinc oxide nanowires, another aim of the invention is to controllably construct a coaxial heterojunction of a ternary system by a physical deposition method, and still another aim of the invention is to realize photoelectric detection of the composite material in a liquid environment.
The technical scheme is as follows: the invention relates to a preparation method of a nickel oxide-gold-zinc oxide coaxial nanowire array; the specific preparation steps are as follows:
(1) Placing the pretreated conductive substrate into a magnetron sputtering instrument, and vacuumizing by a mechanical pump and a molecular pump to ensure that the vacuum degree in the cavity is less than or equal to 7.0x10 -4 Pa, adjusting a radio frequency system to enable the zinc oxide target to start, pre-sputtering to enable the surface of the target to be clean, and then introducing high-purity oxygen and high-purity argon to obtain a substrate sputtered with a zinc oxide seed layer;
(2) Preparing equimolar zinc acetate and hexamethylenetetramine aqueous solution, adding the substrate, the zinc acetate and the hexamethylenetetramine aqueous solution obtained in the step (1) into a hydrothermal reaction kettle, then placing into a baking oven at 90-120 ℃ for reaction for 4-10h, flushing with ultrapure water, and airing or drying to obtain a zinc oxide nanowire array;
(3) Placing the obtained zinc oxide nanowire array in a plasma sputtering instrument and sputtering under a gold target, thereby obtaining a gold-zinc oxide nanowire array;
(4) Finally, placing the obtained gold-zinc oxide nanowire array in a magnetron sputtering instrument to perform in-situ compounding of a nickel oxide layer, thereby finally obtaining the nickel oxide-gold-zinc oxide coaxial nanowire array;
in the step (1), the conductive substrate is FTO conductive glass;
the pretreated conductive substrate refers to: sequentially carrying out ultrasonic treatment on the untreated conductive substrate in ultrapure water, acetone, absolute ethyl alcohol and ultrapure water, and then washing and airing the conductive substrate by using the ultrapure water so as to obtain a pretreated conductive substrate;
the radio frequency power of the magnetron sputtering instrument is 50-200W;
the gas flow of the high-purity oxygen is 5-15sccm, the gas flow of the high-purity argon is 40-100sccm, and the working pressure of the high-purity oxygen and the high-purity argon is 1-3Pa;
the thickness of the substrate of the obtained sputtering zinc oxide seed layer is 10-30nm;
in the step (2), the concentration of the zinc acetate and the hexamethylenetetramine is 0.005-0.05mol/L;
in the step (3), the sputtering time of the plasma sputtering instrument is 45-120s;
in the step (4), the magnetron sputtering time of the magnetron sputtering instrument is 1-20min.
Further, a nano photoelectric functional material with a coaxial structure is prepared by the method; it has synergistically enhanced photo-sensing properties; the application is as follows: taking a conductive substrate of the modified composite material as a working electrode, and taking a platinum net and a silver/silver chloride electrode as a counter electrode and a reference electrode respectively to complete photoelectric sensing in a liquid environment; the photoelectric superiority of the prepared nickel oxide-gold-zinc oxide nanowire array is verified by comparing the current responses of different modification materials; the nano photoelectric functional material has excellent photoelectric sensing performance.
The beneficial effects are that: compared with the prior art, when the zinc oxide nanowire array is prepared, the zinc oxide seed layer is prepared by adopting magnetron sputtering, and the obtained zinc oxide nanowire preferentially grows along one crystal face; the coaxial heterojunction of the nickel oxide-gold-zinc oxide nanowire array is obtained by a physical deposition method (such as plasma sputtering and magnetron sputtering); the zinc oxide is an n-type semiconductor, has a wide direct band gap (3.37 eV) and high exciton binding energy (60 meV), and the zinc oxide array is more beneficial to light absorption, carrier separation and transportation; the nano hardware fitting has good surface plasma resonance effect; and nickel oxide serving as a p-type semiconductor can form a p-n heterojunction with zinc oxide to promote carrier transport, so that the nanocomposite prepared by combining the nickel oxide, the nano gold and the zinc oxide has excellent photoelectric performance.
Drawings
FIG. 1 is an X-ray diffraction diagram of a fourth embodiment of the present invention;
FIG. 2 is a scanning electron microscope image and a transmission electron microscope image according to a fourth embodiment of the present invention;
FIG. 3 is a graph showing the diffuse reflection spectrum of ultraviolet-visible light according to a fifth embodiment of the present invention;
FIG. 4 is a fluorescence spectrum of a sixth embodiment of the present invention;
FIG. 5 is a graph showing the photocurrent results of the composite modified electrode according to the fourth embodiment of the present invention in a liquid environment;
fig. 6 is a flow chart of the operation of the present invention.
Detailed Description
The invention will be further described with reference to the drawings and the specific embodiments.
As shown in fig. 6, the invention relates to a preparation method of a nickel oxide-gold-zinc oxide coaxial nanowire array; the specific preparation steps are as follows:
(1) Placing the pretreated conductive substrate into a magnetron sputtering instrument, and vacuumizing by a mechanical pump and a molecular pump to ensure that the vacuum degree in the cavity is less than or equal to 7.0x10 -4 Pa, adjusting a radio frequency system to enable the zinc oxide target to be started, pre-sputtering for a period of time to enable the surface of the target to be clean, stabilizing the system, and then introducing high-purity oxygen and high-purity argon to obtain a substrate sputtered with a zinc oxide seed layer;
(2) Preparing equimolar zinc acetate [ Zn (CH) 3 COO) 2 ·2H 2 O]And hexamethylenetetramine [ (CH) 2 ) 6 N 4 ]Adding the substrate obtained in the step (1), zinc acetate and hexamethylenetetramine aqueous solution into a hydrothermal reaction kettle, then placing the hydrothermal reaction kettle into a baking oven at 90-120 ℃ for reaction for 4-10 hours, flushing the aqueous solution with ultrapure water, and airing or drying the aqueous solution to obtain a zinc oxide nanowire array;
(3) Placing the zinc oxide nanowire array obtained in the step (2) in a plasma sputtering instrument and sputtering under a gold target, thereby obtaining a gold-zinc oxide nanowire array;
(4) Finally, placing the gold-zinc oxide nanowire array obtained in the step (3) in a magnetron sputtering instrument to perform in-situ compounding of a nickel oxide layer, thereby finally obtaining a nickel oxide-gold-zinc oxide coaxial nanowire array;
in the step (1), the conductive substrate is FTO conductive glass;
the pretreated conductive substrate refers to: sequentially carrying out ultrasonic treatment on the untreated conductive substrate in ultrapure water, acetone, absolute ethyl alcohol and ultrapure water, and then washing and airing the conductive substrate by using the ultrapure water so as to obtain a pretreated conductive substrate;
the radio frequency power of the magnetron sputtering instrument is 50-200W;
the gas flow of the high-purity oxygen is 5-15sccm, the gas flow of the high-purity argon is 40-100sccm, and the working pressure of the high-purity oxygen and the high-purity argon is 1-3Pa;
the thickness of the substrate of the obtained sputtering zinc oxide seed layer is 10-30nm;
in the step (2), the concentration of the zinc acetate and the hexamethylenetetramine is 0.005-0.05mol/L;
in the step (3), the sputtering time of the plasma sputtering instrument is 45-120s;
in the step (4), the magnetron sputtering time of the magnetron sputtering instrument is 1-20min.
Further, a nano photoelectric functional material with a coaxial structure is prepared by the method; it has synergistically enhanced photo-sensing properties; the application is as follows: taking a conductive substrate of the modified composite material as a working electrode, and taking a platinum net and a silver/silver chloride electrode as a counter electrode and a reference electrode respectively to complete photoelectric sensing in a liquid environment; the photoelectric superiority of the prepared nickel oxide-gold-zinc oxide nanowire array is verified by comparing the current responses of different modification materials; the nano photoelectric functional material has excellent photoelectric sensing performance.
Working principle: the physical deposition method is an in-situ synthesis method, and can adjust the morphology of the material to controllably synthesize the multi-element nanocomposite. The composition, morphology, energy level structure and the like of the photoelectric material can influence the photoelectric characteristics of the photoelectric material.
Embodiment 1,
(1) Cutting FTO conductive glass into pieces of 0.5X1.0 cm 2 Sequentially ultrasonic treating the small pieces in ultrapure water, acetone, absolute ethyl alcohol and ultrapure water for 10min, cleaning with ultrapure water, airing, and soaking in absolute ethyl alcohol for standby;
(2) Firstly, fixing clean FTO conductive glass with high temperature resistant adhesive tape to 0.5 multiplied by 0.5cm 2 Is arranged in a magnetic control cavity, and then the vacuum degree in the cavity reaches 5.0x10 by a mechanical pump and a molecular pump for vacuum pumping -4 Pa, adjusting the radio frequency system to start the zinc oxide target, sputtering for a period of time to clean the surface of the target, and the same asThe system is stabilized when in use; after the temperature in the cavity is stable, 5sccm high-purity oxygen and 50sccm high-purity argon are simultaneously introduced, the air pressure is 2Pa when the sputtering device works, the radio frequency power is 50W, the sputtering time is 40min, and a sputtered zinc oxide seed layer with the thickness of 12nm is obtained;
(3) Dissolving 0.219g of zinc acetate in 100mL of ultrapure water, magnetically stirring for 10min to completely dissolve the zinc acetate, adding 0.140g of hexamethylenetetramine, continuously stirring for 10min, and uniformly mixing to obtain a precursor solution; adding the solution into a hydrothermal reaction kettle, soaking the FTO conductive substrate modified in the step (2) in a precursor solution with a conductive surface facing downwards at a certain angle relative to the wall of the hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an oven, carrying out hydrothermal treatment for 4 hours at 90 ℃, flushing with ultrapure water, and drying at 40 ℃ to obtain a zinc oxide nanowire array;
(4) Placing the zinc oxide nano rod array obtained in the step (3) into a plasma sputtering instrument to sputter 50s of nano gold to obtain a gold-zinc oxide nano wire array;
(5) And (3) placing the gold-zinc oxide nanowire array obtained in the step (4) in a magnetron sputtering instrument to sputter nickel oxide for 3min for in-situ compounding, so as to obtain the nickel oxide-gold-zinc oxide nanowire array.
Example two
(1) Cutting FTO conductive glass into pieces of 0.5X1.0 cm 2 Sequentially ultrasonic treating the small pieces in ultrapure water, acetone, absolute ethyl alcohol and ultrapure water for 10min, cleaning with ultrapure water, airing, and soaking in absolute ethyl alcohol for standby;
(2) Firstly, fixing clean FTO conductive glass with high temperature resistant adhesive tape to 0.5 multiplied by 0.5cm 2 Is arranged in a magnetic control cavity, and then the vacuum degree in the cavity reaches 6.0x10 by a mechanical pump and a molecular pump for vacuum pumping -4 Pa, adjusting a radio frequency system to enable the zinc oxide target to start, pre-sputtering for a period of time to enable the surface of the target to be clean, and stabilizing the system; when the temperature in the cavity is stable, 10sccm of high-purity oxygen and 100sccm of high-purity argon are simultaneously introduced, the air pressure is 3Pa when the sputtering device works, the radio frequency power is 200W, the sputtering time is 40min, and the sputtered zinc oxide seed layer with the thickness of 36nm is obtained;
(3) Dissolving 2.190g of zinc acetate in 100mL of ultrapure water, magnetically stirring for 10min to completely dissolve the zinc acetate, adding 1.400g of hexamethylenetetramine, continuously stirring for 10min, and uniformly mixing to obtain a precursor solution; adding the solution into a hydrothermal reaction kettle, soaking the FTO conductive substrate modified in the step (2) in a precursor solution with a conductive surface facing downwards at a certain angle relative to the wall of the hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an oven, carrying out hydrothermal treatment at 120 ℃ for 10 hours, flushing with ultrapure water, and drying in the sun to obtain a zinc oxide nanowire array;
(4) Placing the zinc oxide nanowire array obtained in the step (3) into a plasma sputtering instrument to sputter the gold nanoparticles for 110 seconds to obtain a gold-zinc oxide nanowire array;
(5) And (3) placing the gold-zinc oxide nanowire array obtained in the step (4) in a magnetron sputtering instrument to sputter nickel oxide for 8min for in-situ compounding, so as to obtain the nickel oxide-gold-zinc oxide nanowire array.
Example III
(1) Cutting FTO conductive glass into pieces of 0.5X1.0 cm 2 Sequentially ultrasonic treating the small pieces in ultrapure water, acetone, absolute ethyl alcohol and ultrapure water for 10min, cleaning with ultrapure water, airing, and soaking in absolute ethyl alcohol for standby;
(2) Firstly, fixing clean FTO conductive glass with high temperature resistant adhesive tape to 0.5 multiplied by 0.5cm 2 Is arranged in a magnetic control cavity, and then the vacuum degree in the cavity reaches 4.0x10 by a mechanical pump and a molecular pump for vacuum pumping -4 Pa, adjusting a radio frequency system to enable the zinc oxide target to start, pre-sputtering for a period of time to enable the surface of the target to be clean, and stabilizing the system; after the temperature in the cavity is stable, introducing 8sccm high-purity oxygen and 80sccm high-purity argon, wherein the air pressure is 2Pa, the radio frequency power is 125W, and the sputtering time is 40min, so as to obtain a sputtered zinc oxide seed layer with the thickness of 24 nm;
(3) Dissolving 1.095g of zinc acetate in 100mL of ultrapure water, magnetically stirring for 10min to completely dissolve the zinc acetate, adding 0.700g of hexamethylenetetramine, continuously stirring for 10min, and uniformly mixing to obtain a precursor solution; adding the solution into a hydrothermal reaction kettle, soaking the FTO conductive substrate modified in the step (2) in a precursor solution with a conductive surface facing downwards at a certain angle relative to the wall of the hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an oven, carrying out hydrothermal reaction for 7 hours at 105 ℃, flushing with ultrapure water, and drying at 50 ℃ to obtain a zinc oxide nanowire array;
(4) Placing the zinc oxide nanowire array obtained in the step (3) into a plasma sputtering instrument to sputter the gold nanoparticles for 90 seconds to obtain a gold-zinc oxide nanowire array;
(5) And (3) placing the gold-zinc oxide nanowire array obtained in the step (4) in a magnetron sputtering instrument to sputter nickel oxide for 12min for in-situ compounding, so as to obtain the nickel oxide-gold-zinc oxide nanowire array.
Example IV
(1) Cutting FTO conductive glass into pieces of 0.5X1.0 cm 2 Sequentially ultrasonic treating the small pieces in ultrapure water, acetone, absolute ethyl alcohol and ultrapure water for 10min, cleaning with ultrapure water, airing, and soaking in absolute ethyl alcohol for standby;
(2) Firstly, fixing clean FTO conductive glass with high temperature resistant adhesive tape to 0.5 multiplied by 0.5cm 2 Is arranged in a magnetic control cavity, and then the vacuum degree in the cavity reaches 7.0x10 by a mechanical pump and a molecular pump for vacuum pumping -4 Pa, adjusting a radio frequency system to enable the zinc oxide target to start, pre-sputtering for a period of time to enable the surface of the target to be clean, and stabilizing the system; when the temperature in the cavity is stable, 5sccm high-purity oxygen and 55sccm high-purity argon are simultaneously introduced, the air pressure is 2Pa when the sputtering device works, the radio frequency power is 100W, the sputtering time is 40min, and a sputtered zinc oxide seed layer with the thickness of 15nm is obtained;
(3) Dissolving 0.549g of zinc acetate in 100mL of ultrapure water, magnetically stirring for 10min to completely dissolve the zinc acetate, adding 0.351g of hexamethylenetetramine, continuously stirring for 10min, and uniformly mixing to obtain a precursor solution; adding the solution into a hydrothermal reaction kettle, soaking the FTO conductive substrate modified in the step (2) in a precursor solution with a conductive surface facing downwards at a certain angle relative to the wall of the hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an oven, carrying out hydrothermal treatment for 4 hours at 90 ℃, flushing with ultrapure water, and drying at 60 ℃ to obtain a zinc oxide nanowire array;
(4) Placing the zinc oxide nanowire array obtained in the step (3) into a plasma sputtering instrument to sputter 70 seconds of nano gold to obtain a gold-zinc oxide nanowire array;
(5) And (3) placing the gold-zinc oxide nanowire array obtained in the step (4) in a magnetron sputtering instrument to sputter nickel oxide for 10min for in-situ compounding, so as to obtain the nickel oxide-gold-zinc oxide nanowire array.
Example five
(1) Cutting FTO conductive glass into pieces of 0.5X1.0 cm 2 Sequentially ultrasonic treating the small pieces in ultrapure water, acetone, absolute ethyl alcohol and ultrapure water for 10min, cleaning with ultrapure water, airing, and soaking in absolute ethyl alcohol for standby;
(2) Firstly, fixing clean FTO conductive glass with high temperature resistant adhesive tape to 0.5 multiplied by 0.5cm 2 Is arranged in a magnetic control cavity, and then the vacuum degree in the cavity reaches 7.0x10 by a mechanical pump and a molecular pump for vacuum pumping -4 Pa, adjusting a radio frequency system to enable the zinc oxide target to start, pre-sputtering for a period of time to enable the surface of the target to be clean, and stabilizing the system; when the temperature in the cavity is stable, 5sccm high-purity oxygen and 55sccm high-purity argon are simultaneously introduced, the air pressure is 2Pa when the sputtering device works, the radio frequency power is 100W, the sputtering time is 30min, and a sputtered zinc oxide seed layer with the thickness of 24nm is obtained;
(3) Dissolving 0.549g of zinc acetate in 100mL of ultrapure water, magnetically stirring for 10min to completely dissolve the zinc acetate, adding 0.351g of hexamethylenetetramine, continuously stirring for 10min, and uniformly mixing to obtain a precursor solution; adding the solution into a hydrothermal reaction kettle, soaking the FTO conductive substrate modified in the step (2) in a precursor solution with a conductive surface facing downwards at a certain angle relative to the wall of the hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an oven, carrying out hydrothermal reaction for 4 hours at 90 ℃, flushing with ultrapure water, and drying at 60 ℃ to obtain a zinc oxide nanowire array;
(4) Placing the zinc oxide nanowire array obtained in the step (3) into a plasma sputtering instrument to respectively sputter 10s, 30s, 50s, 70s, 90s and 110s of nano gold to obtain a gold-zinc oxide nanowire array;
(5) And (3) placing the gold-zinc oxide nanowire array obtained in the step (4) in a magnetron sputtering instrument to sputter nickel oxide for 15min for in-situ compounding, so as to obtain the nickel oxide-gold-zinc oxide nanowire array.
Example six
(1) Cutting FTO conductive glass into pieces of 0.5X1.0 cm 2 Sequentially ultrasonic treating the small pieces in ultrapure water, acetone, absolute ethyl alcohol and ultrapure water for 10min, cleaning with ultrapure water, airing, and soaking in absolute ethyl alcohol for standby;
(2) Firstly, fixing clean FTO conductive glass with high temperature resistant adhesive tape to 0.5 multiplied by 0.5cm 2 Is arranged in a magnetic control cavity, and then the vacuum degree in the cavity reaches 7.0x10 by a mechanical pump and a molecular pump for vacuum pumping -4 Pa, adjusting a radio frequency system to enable the zinc oxide target to start, pre-sputtering for a period of time to enable the surface of the target to be clean, and stabilizing the system; when the temperature in the cavity is stable, 5sccm high-purity oxygen and 55sccm high-purity argon are simultaneously introduced, the air pressure is 2Pa when the sputtering device works, the radio frequency power is 100W, the sputtering time is 30min, and a sputtered zinc oxide seed layer with the thickness of 24nm is obtained;
(3) Dissolving 0.549g of zinc acetate in 100mL of ultrapure water, magnetically stirring for 10min to completely dissolve the zinc acetate, adding 0.351g of hexamethylenetetramine, continuously stirring for 10min, and uniformly mixing to obtain a precursor solution; adding the solution into a hydrothermal reaction kettle, soaking the FTO conductive substrate modified in the step (2) in a precursor solution with a conductive surface facing downwards at a certain angle relative to the wall of the hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an oven, carrying out hydrothermal reaction for 4 hours at 90 ℃, flushing with ultrapure water, and drying at 60 ℃ to obtain a zinc oxide nanowire array;
(4) And (3) placing the zinc oxide nanowire array obtained in the step (3) into a plasma sputtering instrument to respectively sputter 70 seconds of nano gold to obtain the gold-zinc oxide nanowire array.
(5) And (3) placing the gold-zinc oxide nanowire array obtained in the step (4) into a magnetron sputtering instrument to sputter for 5,8, 10 and 15 minutes to perform in-situ recombination on nickel oxide, so as to obtain the nickel oxide-gold-zinc oxide nanowire array.
The X-ray diffraction pattern, scanning electron microscope pattern and transmission electron microscope pattern of the nickel oxide-gold-zinc oxide modified electrode (NiO-Au NPs-ZnO NWs/FTO) obtained in the fourth embodiment are shown in figures 1 and 2 respectively; as can be seen from FIG. 1, the diffraction peaks of NiO-Au NPs-ZnO NRs/FTO are consistent with those of standard cards (NiO: 47-1049, au:04-0784, znO:36-1451, FTO: 41-1445); as shown in fig. 2 (a), the ternary composite material based on nickel oxide-gold-zinc oxide is in the shape of a nano array; further, as shown in fig. 2 (b), nickel oxide and nano gold are uniformly distributed on the surface of the zinc oxide nanowire, so that a ternary coaxial heterojunction is formed.
The absorption spectrum of the nano gold-zinc oxide composite material obtained by sputtering the nano gold in different time in the fifth embodiment is shown in figure 3, and the sputtering time of the corresponding nano gold is 10, 30, 50, 70, 90 and 110s; as can be seen from fig. 3 (a), the nano gold particles are distributed on the surface of the zinc oxide nanowire so that the ultraviolet absorption of zinc oxide is weakened; as shown in fig. 3 (b), as the nano-gold sputtering time increases, the absorption spectrum of the visible region of the composite structure is significantly red-shifted and the intensity becomes greater; the red shift of the absorption spectrum is related to the size of the surface nano gold particles, and the energy transfer between zinc oxide and nano gold is realized when the spectrum intensity is increased; comprehensively considering the ultraviolet absorption and visible absorption intensity of the composite structure, sputtering 70s of nano gold on the surface of the zinc oxide nanowire as the basis of subsequent experiments.
In the sixth embodiment, a layer of NiO is continuously modified on the surface of the Au NPs/ZnO NWs, and a P-N heterojunction is constructed to further improve the photoelectric conversion efficiency; the sputtering time of nickel oxide is 5,8, 10 and 15min respectively, and as can be seen from a fluorescence spectrum chart (figure 4), the luminescence of the composite structure is gradually weakened along with the extension of the sputtering time, and the luminescence is weakest when the sputtering time is 10 min; then sputtering for 15min, the luminous intensity is increased; therefore, sputtering of NiO was chosen for 10 min.
The photoelectric composite material obtained by the invention is applied to a liquid environment, and shows excellent photoelectric sensing performance:
in addition, niO-Au NPs-ZnO NWs/FTO in the fourth example was placed in an electrolyte with a concentration of 0.01mol/L phosphate buffer (PBS, pH 7.0) and platinum mesh and silver/silver chloride electrode electrodes were used as a counter electrode and a reference electrode, respectively; under simulated sunlight, 10s of illumination and 10s of darkness are carried out, and the photocurrent of the composite material is measured; as can be seen from fig. 5, after the surface modification of nickel oxide and nano gold and zinc oxide, the photocurrent response is enhanced, and the photocurrent response is strongest when the ternary composite material is formed.
The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above examples, and all technical solutions belonging to the concept of the present invention belong to the protection scope of the present invention. It should be noted that modifications and adaptations to the invention without departing from the principles thereof are intended to be within the scope of the invention as set forth in the following claims.

Claims (2)

1. A preparation method of a nickel oxide-gold-zinc oxide coaxial nanowire array, which is characterized by comprising the steps of; the specific preparation steps are as follows:
(1) Placing the pretreated conductive substrate into a magnetron sputtering instrument, and vacuumizing by a mechanical pump and a molecular pump to ensure that the vacuum degree in the cavity is less than or equal to 7.0x10 -4 Pa, adjusting a radio frequency system to enable the zinc oxide target to start, pre-sputtering to enable the surface of the target to be clean, and then introducing high-purity oxygen and high-purity argon to obtain a substrate sputtered with a zinc oxide seed layer;
the conductive substrate is FTO conductive glass;
the pretreated conductive substrate refers to: sequentially carrying out ultrasonic treatment on the untreated conductive substrate in ultrapure water, acetone, absolute ethyl alcohol and ultrapure water, and then washing and airing the conductive substrate by using the ultrapure water so as to obtain a pretreated conductive substrate;
the radio frequency power of the magnetron sputtering instrument is 50-200W;
the gas flow of the high-purity oxygen is 5-15sccm, the gas flow of the high-purity argon is 40-100sccm, and the working pressure of the high-purity oxygen and the high-purity argon is 1-3Pa;
the thickness of the obtained sputtering zinc oxide seed layer is 10-30nm;
(2) Preparing equimolar zinc acetate and hexamethylenetetramine aqueous solution, adding the substrate, the zinc acetate and the hexamethylenetetramine aqueous solution obtained in the step (1) into a hydrothermal reaction kettle, then placing the hydrothermal reaction kettle into a 90-120 ℃ oven for reaction of 4-10h, flushing with ultrapure water, and airing or drying to obtain a zinc oxide nanowire array;
the concentration of the zinc acetate and the hexamethylenetetramine is 0.005-0.05mol/L;
(3) Placing the obtained zinc oxide nanowire array in a plasma sputtering instrument and sputtering under a gold target, thereby obtaining a gold-zinc oxide nanowire array;
the sputtering time of the plasma sputtering instrument is 45-120s;
(4) Finally, placing the obtained gold-zinc oxide nanowire array in a magnetron sputtering instrument to perform in-situ compounding of a nickel oxide layer, thereby finally obtaining the nickel oxide-gold-zinc oxide coaxial nanowire array;
the magnetron sputtering time of the magnetron sputtering instrument is 1-20min.
2. The application of the nickel oxide-gold-zinc oxide coaxial nanowire array prepared by the preparation method of claim 1 in photoelectric sensing is characterized in that:
the application is as follows: the prepared nickel oxide-gold-zinc oxide coaxial nanowire array conductive substrate is used as a working electrode, and platinum mesh and silver/silver chloride electrodes are respectively used as a counter electrode and a reference electrode, so that photoelectric sensing in a liquid environment is completed.
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