CN110655035A - Two-dimensional MXene functionalized InxGa1-xN nano column and preparation method and application thereof - Google Patents
Two-dimensional MXene functionalized InxGa1-xN nano column and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses two-dimensional MXene functionalized InxGa1‑xN nano-column and its preparation method and application. The two-dimensional MXene functionalized InxGa1‑xThe N nano column comprises a substrate, an MXene layer on the substrate, and In grown on the MXene layerxGa1‑xN nano-pillars; wherein x is more than or equal to 0 and less than or equal to 1. The invention adopts two-dimensional MXene as a substrate and InxGa1‑xThe functional layer between the N nano-columns not only widens the selection range of the substrate, but also reduces the cost; also effectively reduces the substrate and the nanometerThe interface impedance between the columns is beneficial to enhancing the carrier transport performance and greatly improving the photoelectric performance of the nano-columns; meanwhile, the defect that the nano-column is easy to etch on the substrate is avoided, and the photoelectric stability of the nano-column is improved. In summary, two-dimensional MXene functionalized InxGa1‑xThe N nano-column has important application prospect in hydrogen production by photoelectrolysis, photoelectric detectors and solar cells.
Description
Technical Field
The present invention relates to InxGa1-xN nano-column, energy and catalysis field, In particular to two-dimensional MXene functionalized InxGa1-xN nano-column and its preparation method and application.
Background
The hydrogen production by water splitting through Photoelectrochemistry (PEC) can effectively convert and store solar energy into clean and renewable hydrogen energy, and is one of the most promising means for solving the current energy crisis.
In recent years, ternary compound semiconductor InxGa1-xN nano-columns have important application prospects In PEC decomposition water, mainly due to InxGa1-xThe N band gap is adjustable from 0.68 eV to 3.4 eV, and the photoelectrolysis water in a wide spectral range can be realized; in addition InxGa1-xThe N electron mobility is high, the conductivity is strong, and the cost of photolysis of water can be effectively reduced; second, InxGa1-xThe N nano column has large specific surface area, can enhance light absorption and can provide more reactive sites. However, InxGa1-xN-nanorod growth is mainly based on sapphire, single crystal Si substrates. While they tend to have a relatively high resistivity (sapphire 10)14Ω · cm, doped Si ~ 10 Ω · cm), high cost, and the like, and In grown when single crystal Si is used as a substrate, for examplexGa1-xSiN is formed between the N nano-pillars and the Si substratexAn insulating layer. The insulating layer can increase the carrier transport resistance; while In is being formedxGa1-xThe N nano-pillar electrode is used for photo-electrolyzing water In the electrolyte, and the insulating layer is easily etched away, so that InxGa1-xThe N nano-column can be seriously corroded by light, so that the photoelectric performance is obviously reduced. At present, mainly adoptThe metal layer with larger work function reduces the interface impedance, however, the metal layer will bring surface state to cause the recombination of carriers [ Ebaid M, Min J W, ZHao C, et al. Water splitting to hydrogen overhead InGaN nano windows titanium/silicon template: reduced interface transfer reactivity and improved stability to hydrogen [ J W]. Journal of Materials Chemistry A, 2018, 6(16): 6922-6930.]. Therefore, a method for reducing the substrate interface resistance and increasing In is soughtxGa1-xPhotoelectric property stability of N nano-pillar photoelectrode to InxGa1-xThe N nano-column photoelectrolysis water hydrogen production has great significance.
MXene (Ti) was first discovered since 20113C2) MXene, a novel transition metal carbide or nitride, is widely applied to multiple fields of energy storage, conversion and the like. MXene has the chemical formula of Mn+1XnT, (n =1, 2, 3, M is transition metal element, X is carbon or nitrogen element, T is active functional group such as-OH, -F, -O, etc.). The material is mainly obtained by acid etching of a layered ceramic material MAX phase, and has excellent electrochemical and chemical reactivity. Meanwhile, the material is of a two-dimensional crystal structure, the surface of the material is rich in active functional groups, and the material is an excellent carrier for realizing a new-structure and high-performance nano catalyst.
Disclosure of Invention
The invention aims to provide MXene functionalized In aiming at the defects of the prior artxGa1-xN nano-column and its preparation method and application. The two-dimensional MXene effectively reduces the larger impedance between the nano-column and the surface of the substrate, and can remarkably improve InxGa1-xThe photoelectric conversion efficiency of the N nano-column is improved, and the use stability is enhanced; in addition, the preparation method overcomes the single selectivity of the substrate, reduces the cost, has simple process, low energy consumption, and is time-saving and efficient.
The purpose of the invention is realized by the following technical scheme.
Two-dimensional MXene functionalized InxGa1-xThe N nano-column comprises a substrate, an MXene layer on the substrate, and In grown on the MXene layerxGa1-xN nano column(ii) a Wherein x is more than or equal to 0 and less than or equal to 1.
Further, the substrate is a Si or FTO substrate.
Further, MXene is Ti3C2、V2C、Ta4C3、MoC3、Ti3CN and one or two of two-dimensional transition metal carbide, nitride and carbonitride.
Further, the thickness of the MXene layer on the substrate was 3nm ~ 200 nm.
Further, In grown on MXene layerxGa1-xThe N nano-column comprises one or more of a GaN nano-column, an InGaN nano-column, an InN nano-column, an InGaN/GaN core/shell structure nano-column and an InN/InGaN core/shell structure nano-column.
Further, In grown on MXene layerxGa1-xThe height of the N nano-column is 50 ~ 2000 nm, and the diameter is 15 ~ 500 nm.
The two-dimensional MXene functionalized InxGa1-xThe preparation method of the N nano-column comprises the following steps:
(1) preparing an MXene layer on a substrate, namely plating an MXene film on the substrate by adopting a dip coating method, a spin coating method or a spraying method, drying, putting the substrate into a Molecular Beam Epitaxy (MBE) reaction chamber, and annealing the MXene film at 700 ~ 900 ℃ to obtain a clean surface to obtain the substrate/MXene;
(2) in on MXene layerxGa1-xAnd (3) growing the N nano column by adopting a molecular beam epitaxial growth process, controlling the temperature of the substrate/MXene obtained in the step (2) to be 450-450 ~ 980 ℃, controlling the rotating speed of the substrate/MXene to be 5 ~ 10 r/min, and controlling the equivalent pressure of the Ga beam to be 1.0 multiplied by 10-8~1.5×10-7 Torr, equivalent pressure of In beam is 1.0X 10-8~5×10-7 Torr, nitrogen flow rate of 1 ~ 5sccm, plasma source power of 200 ~ 400W, growth time of 1 ~ 5h, In growth on the substrate/MXene layer obtained In step (2)xGa1- xAnd (4) N nano columns.
Further, the surface treatment is carried out on the substrate before the MXene film is plated in the step (1), the surface treatment comprises plasma treatment or acid-base solution etching, then ultra-pure water is used for carrying out ultrasonic cleaning, and then high-purity nitrogen is used for blow-drying, the plasma treatment time is 10 ~ 30min, the acid-base solution is BOE solution or Piranha solution, and the etching time is 1 ~ 5 min.
Further, the drying in the step (1) is vacuum drying, the drying temperature is 50 ~ 65 ℃, the drying time is 10 ~ 30min, and the annealing time is 10 ~ 30 min.
The two-dimensional MXene functionalized InxGa1-xThe N nano column is applied to the photoelectrolysis hydrogen production, a photoelectric detector and a solar cell.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the present invention uses MXene as InxGa1-xThe dielectric layer grown by the N nano-column can enlarge the selection of the substrate and avoid the selection of InxGa1-xThe quality of the grown nano-column crystal is poor due to the substrate material with high N lattice mismatch degree, good conductivity and low price, and the preparation cost is reduced.
(2) The present invention uses MXene as InxGa1-xThe quality of the nano-column crystal grown from the dielectric layer grown from the N nano-column is greatly improved, the specific surface area is large, the probability of non-radiative recombination of current carriers is greatly reduced, the light absorption range is increased, and the interface reaction area of a semiconductor/electrolyte is increased, so that In is enabledxGa1-xThe photoelectric conversion efficiency of the N nano-column is greatly improved.
(3) The present invention uses MXene as InxGa1-xThe medium layer grown by the N nano-pillars increases the conductivity of the photoelectrode and enhances the carrier transport mechanism.
(4) The invention uses MXene as substrate and InxGa1-xThe electron transmission layer between the N nano-pillars greatly reduces the impedance between the substrate and the nano-pillars, accelerates the electron transfer rate between the substrate and the nano-pillars, and greatly improves InxGa1-xThe photoelectric conversion efficiency of the N nano-column photoelectrolysis water.
(5) The inventionTwo-dimensional MXene functionalized InxGa1-xN nano-pillars due to SiN between the substrate and the nano-pillarsxThe elimination of the insulating layer and the excellent chemical stability of the catalyst greatly improve the photoelectric stability.
（6）InxGa1-xThe band gap of the N nano column is adjustable In the range of 0.67-3.4 eV by adjusting the In component, so that the hydrogen production by photoelectrolysis water In the visible light spectrum range can be realized, and the utilization rate of sunlight is improved.
(7) Two-dimensional MXene functionalized InxGa1-xIn of N nano column In application of photoelectrolysis water hydrogen productionxGa1-xThe nano-column structure of the N nano-column reduces the migration distance from a photon-generated carrier to a semiconductor/electrolyte interface, reduces the recombination probability of the photon-generated carrier, and is more beneficial to allowing photon-generated electrons and holes to participate in hydrogen evolution and oxygen evolution reactions respectively.
(8) The invention uses two-dimensional MXene as a functional layer between the nano column and the Si substrate, is beneficial to the transport of current carriers in a system, and is not only suitable for photoelectrocatalysis, but also suitable for the fields of solar cells and photoelectric detectors.
Drawings
FIG. 1 shows two-dimensional MXene functionalized In example 1xGa1-xA schematic cross-sectional view of an N nanorod.
FIG. 2 shows two-dimensional MXene functionalized In example 1xGa1-xSEM top view of N nanopillars.
FIG. 3 shows two-dimensional MXene functionalized In example 1xGa1-xAnd (3) a graph of the photocurrent and the voltage of the N nano-pillar photo-anode.
Fig. 4 is a graph of photocurrent and voltage of the two-dimensional MXene functionalized InGaN nanorod photoelectrode in example 2.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
Two-dimensional MXene functionalized InxGa1-xPreparation of N nano-columnThe method comprises the following steps:
(1) selection of the substrate: a Si substrate is used.
(2) Substrate surface treatment: and (3) etching the substrate in the step (1) for 1min by using a Piranha solution. Then, ultra-pure water is used for ultrasonic cleaning, and high-purity nitrogen is used for blow drying.
(3) Preparation of an MXene layer on a substrate: MXene (Ti) was spin-coated3C2) And (3) coating the solution on the substrate in the step (2), and then drying for 30min at the temperature of 50 ℃ in vacuum to obtain a film with the thickness of 3 nm. Finally, the obtained product is placed into a Molecular Beam Epitaxy (MBE) reaction chamber, and MXene is subjected to annealing treatment at 700 ℃ for 30min to obtain a clean surface.
(4) In on MXene layerxGa1-xAnd (3) growing the N nano-pillars: a molecular beam epitaxial growth process is adopted, the temperature of the substrate is controlled to 880 ℃, the rotating speed of the substrate is 10 r/min, and the equivalent pressure of Ga beam is 3.5 multiplied by 10-8 Torr, equivalent pressure of In beam is 9.0X 10-8 Torr, nitrogen flow rate of 2.0 sccm, plasma source power of 400W, growth time of 3 h, InGaN nanopillars having a height of 300 nm, a diameter of 75 nm, and an In/Ga ratio of 25/75 were grown on the substrate/MXene layer In step (3).
As shown in fig. 1, a schematic cross-sectional view of a two-dimensional MXene functionalized InGaN nanorod in the present embodiment includes a Si substrate 1, an MXene layer 2 on the Si substrate 1, and an InGaN nanorod 3 grown on the MXene layer 2.
As shown in fig. 2, this embodiment is a top view of a scanning electron microscope of a two-dimensional MXene functionalized InGaN nano-column.
The two-dimensional MXene functionalized InGaN nano column of the embodiment is subjected to photoelectrolysis to produce hydrogen: the preparation method of the InGaN nanorod into the photoelectrode comprises the following specific steps: and forming ohmic contact between the metal layer and the Si back surface by electron beam evaporation deposition, connecting the metal layer by a metal wire, and protecting the whole metal back surface by insulating epoxy resin. Finally, an electrochemical workstation was used for the photoelectrochemical tests, as follows: use 0.5 mol/L H2SO4The solution is used as electrolyte, the prepared photoelectrode is used as an anode,saturated Calomel Electrode (SCE) as reference electrode, Pt wire as cathode, and 300W Xe lamp (light intensity ~ 100 mW/cm)2) As a light source, a photocurrent density-bias curve was obtained by testing. The InGaN nanorod-based photoelectrode based on two-dimensional MXene prepared by the process has the photocurrent density of 1 mA/cm under the bias of 1.0V vs. SCE2The bias photoelectric conversion efficiency (ABPE) was 1.2%.
As shown in fig. 3, a graph of photocurrent and voltage of a two-dimensional MXene functionalized InGaN nanorod photoelectrode is shown in this embodiment.
Example 2
A preparation method of a two-dimensional MXene functionalized GaN nanorod comprises the following steps:
(1) selection of the substrate: a Si substrate is used.
(2) Substrate surface treatment: and (3) etching the substrate in the step (1) by using a Piranha solution for 5 min. Then, ultra-pure water is used for ultrasonic cleaning, and high-purity nitrogen is used for blow drying.
(3) Preparation of an MXene layer on a substrate: MXene (Ti) was spin-coated3C2) And (3) coating the solution on the substrate in the step (2), and then drying for 30min at the vacuum temperature of 65 ℃ to obtain a film with the thickness of 80 nm. Finally, the obtained product is placed into a Molecular Beam Epitaxy (MBE) reaction chamber, and MXene is subjected to annealing treatment at 800 ℃ for 20 min to obtain a clean surface.
(4) Growth of GaN nanopillars on MXene layer: a molecular beam epitaxial growth process is adopted, the substrate temperature is controlled to be 980 ℃, the substrate rotating speed is 5 r/min, and the equivalent pressure of Ga beam is 1.5 multiplied by 10-7Torr, equivalent pressure of In beam is 1.0X 10-8 And (3) Torr, the nitrogen flow is 1.0 sccm, the plasma source power is 200W, the growth time is 5h, and GaN nano columns are grown on the substrate/MXene layer in the step (3), the height of each nano column is 150 nm, and the diameter of each nano column is 50 nm.
The two-dimensional MXene functionalized GaN nanorod is used for photoelectrolysis and hydrogen production: the GaN nanorod prepared in this embodiment is fabricated into a photoelectrode, and the specific steps are as follows: using electron beam to evaporate and deposit metal layer to form ohmic contact with Si back surface, and then using metal wire to connect with metal layerThen, the entire metal back is protected with an insulating epoxy. Finally, an electrochemical workstation was used for the photoelectrochemical tests, as follows: use 0.5 mol/L H2SO4The solution was used as an electrolyte, a photoelectrode was prepared as an anode, a Saturated Calomel Electrode (SCE) as a reference electrode, a Pt wire as a cathode, and a 300W Xe lamp (light intensity ~ 100 mW/cm)2) As a light source, a photocurrent density-bias curve was obtained by testing. The GaN nanorod-based photoelectrode based on two-dimensional MXene prepared by the process has the photocurrent density of 2.9 mA/cm under the bias of 1.0V/s and SCE2The bias photoelectric conversion efficiency (ABPE) was 0.8%.
Fig. 4 is a graph showing photocurrent and voltage curves of a two-dimensional MXene functionalized InGaN nanorod photoelectrode in this embodiment.
Example 3
A preparation method of a two-dimensional MXene functionalized InN nano-column comprises the following steps:
(1) selection of the substrate: si is used.
(2) Substrate surface treatment: and (3) etching the substrate in the step (1) for 2 min by using a Piranha solution. Then, ultra-pure water is used for ultrasonic cleaning, and high-purity nitrogen is used for blow drying.
(3) Preparation of an MXene layer on a substrate: MXene (Ti) was spin-coated3C2) And (3) coating the solution on the substrate in the step (2), and then drying for 10 min at the vacuum temperature of 65 ℃ to obtain a film with the thickness of 120 nm. And finally, placing the nano-column into a Molecular Beam Epitaxy (MBE) reaction chamber, and annealing MXene at 900 ℃ for 10 min to obtain a clean surface, wherein the height of the nano-column is 1200nm, and the diameter of the nano-column is 80 nm.
(4) Growth of InN nano-pillars on MXene layer: a molecular beam epitaxial growth process is adopted, the temperature of the substrate is controlled to be 450 ℃, the rotating speed of the substrate is 10 r/min, and the equivalent pressure of Ga beam is 1.0 multiplied by 10-8 Torr, equivalent pressure of In beam is 5.0X 10-7And (4) growing the InN nano column on the substrate/MXene layer in the step (3) by the aid of the Torr, the nitrogen flow rate of 5.0 sccm, the plasma source power of 400W and the growth time of 1 h.
Example 4
A preparation method of a two-dimensional MXene functionalized GN nanometer column comprises the following steps:
(1) selection of the substrate: an FTO substrate is used.
(2) Substrate surface treatment: and (3) etching the substrate in the step (1) for 2 min by using a Piranha solution. Then, ultra-pure water is used for ultrasonic cleaning, and high-purity nitrogen is used for blow drying.
(3) Preparation of an MXene layer on a substrate: MXene (Ti) was spin-coated3C2) And (3) coating the solution on the substrate in the step (2), and then drying for 30min at the vacuum temperature of 65 ℃ to obtain a film with the thickness of 80 nm. Finally, the obtained product is placed into a Molecular Beam Epitaxy (MBE) reaction chamber, and MXene is subjected to annealing treatment at 800 ℃ for 20 min to obtain a clean surface.
(4) Growth of GaN nanopillars on MXene layer: a molecular beam epitaxial growth process is adopted, the substrate temperature is controlled to be 980 ℃, the substrate rotating speed is 5 r/min, and the equivalent pressure of Ga beam is 1.5 multiplied by 10-7Torr, equivalent pressure of In beam is 1.0X 10-8 And (3) Torr, the nitrogen flow is 1.0 sccm, the plasma source power is 200W, the growth time is 5h, and GaN nano columns are grown on the substrate/MXene layer in the step (3), the height of the nano columns is 250 nm, and the diameter of the nano columns is 65 nm.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. Two-dimensional MXene functionalized InxGa1-xThe N nano column is characterized by comprising a substrate (1), an MXene layer (2) on the substrate (1) and In grown on the MXene layer (2)xGa1-xAn N nanopillar (3); wherein x is more than or equal to 0 and less than or equal to 1.
2. The two-dimensional MXene functionalized In of claim 1xGa1-xN nano columnAnd the substrate is a Si or FTO substrate.
3. The two-dimensional MXene functionalized In of claim 1xGa1-xThe N nano column is characterized in that MXene is Ti3C2、V2C、Ta4C3、MoC3、Ti3One or two of CN.
4. The two-dimensional MXene functionalized In of claim 1xGa1-xThe N nano column is characterized in that the thickness of the MXene layer on the substrate is 3nm ~ 200 nm.
5. The two-dimensional MXene functionalized In of claim 1xGa1-xN nano-pillars characterized In that In grown on MXene layerxGa1-xThe N nano-column comprises one or more of a GaN nano-column, an InGaN nano-column, an InN nano-column, an InGaN/GaN core/shell structure nano-column and an InN/InGaN core/shell structure nano-column.
6. The two-dimensional MXene functionalized In of claim 1xGa1-xN nano-pillars characterized In that In grown on MXene layerxGa1-xThe height of the N nano-column is 50 ~ 2000 nm, and the diameter is 15 ~ 500 nm.
7. Preparation of a two-dimensional MXene functionalized In according to any one of claims 1-6xGa1-xThe method for preparing the N nano column is characterized by comprising the following steps of:
(1) preparing an MXene layer on a substrate, namely plating an MXene film on the substrate by adopting a dip coating method, a spin coating method or a spraying method, drying, then placing the substrate into a molecular beam epitaxy reaction chamber, and annealing the MXene film at 700 ~ 900 ℃ to obtain the substrate/MXene;
(2) in on MXene layerxGa1-xAnd (3) growing the N nano-pillars: adopting molecular beam epitaxial growth process to controlThe temperature of the substrate/MXene obtained in the step (2) is 450 ~ 980 ℃ and 980 ℃, the rotating speed of the substrate/MXene is 5 ~ 10 r/min, and the equivalent pressure of the Ga beam is 1.0 multiplied by 10-8~1.5×10-7 Torr, equivalent pressure of In beam is 1.0X 10-8~5×10-7 Torr, nitrogen flow rate of 1 ~ 5sccm, plasma source power of 200 ~ 400W, growth time of 1 ~ 5h, In growth on the substrate/MXene layer obtained In step (2)xGa1- xAnd (4) N nano columns.
8. The preparation method according to claim 7, wherein the surface treatment of the substrate in the step (1) before MXene film plating comprises plasma treatment or acid-base solution etching, ultrasonic cleaning with ultrapure water, and drying with high-purity nitrogen gas, wherein the plasma treatment time is 10 ~ 30min, the acid-base solution is BOE solution or Piranha solution, and the etching time is 1 ~ 5 min.
9. The preparation method of claim 7, wherein the drying in the step (1) is vacuum drying, the drying temperature is 50 ~ 65 ℃, the drying time is 10 ~ 30min, and the annealing time is 10 ~ 30 min.
10. A two-dimensional MXene functionalized In of any one of claims 1-6xGa1-xThe N nano column is applied to the photoelectrolysis hydrogen production, a photoelectric detector and a solar cell.
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