CN114540875B - Photoelectrode material based on InGaN/organic heterostructure and preparation method and application thereof - Google Patents

Photoelectrode material based on InGaN/organic heterostructure and preparation method and application thereof Download PDF

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CN114540875B
CN114540875B CN202210105589.6A CN202210105589A CN114540875B CN 114540875 B CN114540875 B CN 114540875B CN 202210105589 A CN202210105589 A CN 202210105589A CN 114540875 B CN114540875 B CN 114540875B
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CN114540875A (en
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李国强
谢少华
刘乾湖
梁杰辉
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South China University of Technology SCUT
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Abstract

The invention discloses a photoelectrode material based on an InGaN/organic heterostructure, and a preparation method and application thereof. The photoelectrode material comprises a Si substrate, inGaN nano-pillars arranged on the Si substrate, and an organic material layer arranged on the upper surfaces of the InGaN nano-pillars; the organic material layer is a non-fullerene material layer. The organic material IT-4F is used, so that the absorption spectrum range of the photoelectrode material is widened, surface charge recombination is effectively passivated, and meanwhile, the dissociation and transmission of charge carriers and reduction reaction of the charge carriers at an electrode/electrolyte interface are promoted by the heterostructure of the photoelectrode material and the InGaN nanorod, so that the photoelectric conversion efficiency is greatly improved, the realization of photoelectrochemical water electrolysis hydrogen production under no bias is facilitated, and an effective strategy is provided for efficiently utilizing solar energy to convert hydrogen energy.

Description

Photoelectrode material based on InGaN/organic heterostructure and preparation method and application thereof
Technical Field
The invention relates to the field of InGaN nano-pillars, in particular to an InGaN/organic heterostructure-based photoelectrode material, and a preparation method and application thereof.
Background
Photoelectrochemical water splitting hydrogen production without bias has great potential in solving global energy crisis and environmental problems. InGaN nanopillar band gap is adjustable (E) g 0.65 eV-3.4 eV), the light absorption can be regulated by regulating and controlling the indium component, thereby becoming an ideal candidate of the photoelectrode. Moreover, inGaN nanopillars have energy band sites suitable for water redox reactions, longer charge diffusion distances, higher electron mobility, high specific surface area and outstanding theoretical solar energy to hydrogen (STH) efficiency (-27%), making InGaN nanopillars advantageous for photoelectrochemical total water decomposition. But bulk phase sum of InGaN nanopillarsSurface charge rapid recombination and slow oxidation kinetics, external bias is required to facilitate charge transport. Therefore, the development of the photoelectrochemical hydrogen production system based on the InGaN nano-pillars under no bias has important research significance.
Common organic materials are mainly conductive polymers, fullerenes and non-fullerenes, and are a big research hot spot in the field of photoelectric material devices because of low preparation cost, light weight, abundant sources, excellent solution processability and capability of being processed into flexible large-area devices. In recent years, with the rapid development of non-fullerene materials, various photoelectric devices based on non-fullerene are excellent in performance. Therefore, constructing photoelectrochemical cells based on non-fullerene materials is also another novel approach to further improve the photoelectric conversion performance. In addition, because the InGaN nano-pillar has the problem of rapid surface charge recombination, the InGaN nano-pillar/organic heterostructure photoelectrode structure is constructed, which is favorable for widening the absorption spectrum and promoting the transmission of charge carriers, thereby providing a novel approach for constructing a bias-free photoelectrochemical hydrogen production system. In addition, the organic material can be attached to the surface of the InGaN nanopillar, so that the surface state of the InGaN nanopillar is eliminated, electrons are transferred from the InGaN nanopillar to the organic material, and the reduction reaction at the interface of the organic material and the electrolyte is realized. In addition, the InGaN nanopillar is complementary with the absorption spectrum of the organic material, and the energy level is matched, so that a better electron transmission channel is formed, and the photoelectrochemistry hydrogen production process under no bias is realized. Therefore, the construction of the InGaN/organic heterostructure-based photoelectrode material provides an effective strategy for efficiently utilizing solar energy to convert it into hydrogen energy.
Disclosure of Invention
The invention aims to provide an InGaN/organic heterostructure-based photoelectrode material and a preparation method and application thereof, aiming at the defect of rapid recombination of surface charges of an InGaN nano column. The invention uses the organic heterojunction to widen the absorption spectrum range, is beneficial to the dissociation and transmission of photogenerated carriers, and greatly improves the photoelectric property of the nano-column, thereby realizing unbiased photoelectrochemical water-splitting hydrogen production.
The aim of the invention is achieved by the following technical scheme.
An InGaN/organic heterostructure-based photoelectrode material comprises a Si substrate, inGaN nano-pillars arranged on the Si substrate, and an organic material layer arranged on the upper surface of the InGaN nano-pillars; the organic material layer is a non-fullerene material layer.
Preferably, the organic material is IT-4F, and the structural formula is as follows:
preferably, the proportion of In atoms In the InGaN nano-pillars is 5-30% of metal atoms, the height of the nano-pillars is 100-600 nm, the diameter is 50-100 nm, and the density is 100-300 μm -2 The method comprises the steps of carrying out a first treatment on the surface of the The metal atoms include In and Ga.
Preferably, the Si substrate is ultra-low resistance silicon, and the resistivity is less than 1 Ω & cm.
A method for preparing an InGaN/organic heterostructure-based photoelectrode material according to any of the preceding claims, comprising the steps of:
(1) Growing InGaN nano-pillars on the Si substrate by adopting a molecular beam epitaxial growth process;
(2) Depositing an organic material layer on the InGaN nano-pillars by spin coating; wherein, spin coating conditions are: the concentration of the organic material solution is 8-12 mg/mL, the rotating speed is 3500-4500 r/min, the time is 30-45 s, the annealing temperature is 90-100 ℃, and the annealing time is 10-15 min.
Preferably, the spin coating conditions are: the concentration of the organic material solution is 10mg/mL, the rotating speed is 4000r/min, the time is 30s, the annealing temperature is 100 ℃, and the annealing time is 10min.
Preferably, the growing InGaN nanopillars on the Si substrate comprises the steps of:
the molecular beam epitaxial growth process is adopted, the temperature of the Si substrate is controlled to be 450-980 ℃, the rotating speed of the Si substrate is 5-10 r/min, and the equivalent pressure of Ga beam is 1.0x10 -8 ～1.5×10 -7 Torr, in beam equivalent pressure of 1.0X10 -8 ～5×10 -7 And the Torr, the nitrogen flow is 1-5 sccm, the power of the plasma source is 200-400W, the growth time is 1-5 h, and InGaN nano-pillars are grown on the Si substrate.
Preferably, the Si substrate selects a Si (111) crystal face (conductivity <0.005 omega), and needs to be subjected to cleaning treatment and annealing treatment; the cleaning treatment is that firstly organic solvent is used for removing organic pollutants on the surface of Si substrate, then HF solution is used for treating the Si substrate to treat the surface oxide layer, and finally high-purity dry nitrogen is used for drying; the annealing treatment is to put the Si substrate obtained after the cleaning treatment into a reaction chamber, and anneal the Si substrate for 10-30 min at 900-980 ℃ to obtain the reconstructed surface.
Preferably, the organic pollutants on the surface of the Si substrate are removed by using an organic solvent, and the Si substrate is sequentially cleaned in acetone and absolute ethyl alcohol, and then rinsed with water; the solubility of the HF solution is 5-20%.
The application of the photoelectrode material based on InGaN/organic heterostructure in preparing a photoelectrode, wherein the photoelectrode is a photoanode and is a heterostructure electrode.
Preferably, the photoelectrode is formed by connecting a wire with the back surface of the Si substrate based on the InGaN/organic heterostructure photoelectrode material by using Ti-Au alloy.
The photoelectrode is applied to a photoelectrochemical hydrogen production system under no bias, and the system comprises a photoanode, a photocathode, electrolyte, a light source and an electrolytic cell; the photo-anode and the photo-cathode are connected through a lead and are placed in electrolyte, and the photo-electrode is irradiated by sunlight to prepare hydrogen.
Preferably, the pH of the electrolyte is 0-14; the sunlight irradiation photoelectrode mode is parallel light irradiation or full irradiation.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The invention uses the heterostructure of the organic material and the InGaN nano column, and the complementary absorption spectrum and better energy level matching are beneficial to promoting the generation and transmission of photo-generated carriers, thereby greatly improving the photoelectric conversion efficiency of the photoelectrochemical water decomposition of the InGaN nano column.
(2) According to the invention, the organic material and the InGaN nano column are used for heterostructure, a good Schottky barrier can be formed between the organic material and the InGaN nano column, and electrons in the InGaN nano column are effectively transferred into the organic material, so that the reduction reaction of an organic material/electrolyte interface is promoted.
(3) The organic material and the InGaN nano column are used for heterostructure, so that the surface state of the InGaN nano column can be passivated, the charge recombination center is reduced, and the separation and transport performances of charge carriers are promoted, thereby improving the photoelectric performance of the device.
(4) When the photoelectrochemical hydrogen production system based on InGaN nano-column/organic heterostructure is applied under no bias voltage, the spectral absorption can be greatly widened, the photovoltage required by water decomposition is improved, the unbiased photoelectrochemical water decomposition hydrogen production is realized, and the large-scale solar hydrogen production is facilitated.
Drawings
Fig. 1 is a schematic diagram of a structure of an InGaN/organic heterostructure-based photoelectrode according to embodiment 1.
Fig. 2 is a schematic structural diagram of a parallel photoelectrochemical cell in a photoelectrochemical hydrogen production system based on InGaN/organic heterostructure photoelectrode material in example 2 under no bias.
Fig. 3 is a schematic diagram of a full-irradiation photoelectrochemical cell structure in a photoelectrochemical hydrogen production system based on InGaN/organic heterostructure photoelectrode material in example 3 under no bias.
Fig. 4 is a schematic structural diagram of InGaN nanopillar photoelectrode material in comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto.
Example 1
The photoelectrochemical hydrogen production system construction and application based on InGaN/organic heterostructure photoelectrode material under no bias voltage comprise the following steps:
(1) Selecting a substrate: n-type Si was used as the substrate (conductivity <0.005 Ω).
(2) Preparing a photo anode: then, adopting a molecular beam epitaxial growth process, controlling the substrate temperature to 900 ℃, the substrate rotating speed to 10r/min and the Ga beam equivalent pressure to 1 multiplied by 10 -7 Torr, equivalent pressure of In beam is 2.0X10 -7 The Torr, the nitrogen flow is 2sccm, the power of a plasma source is 400W, the growth time is 3h, and InGaN nano-pillars are grown on the Si substrate; wherein, the InGaN nano-pillar has an In atom ratio of 20%, the height of the nano-pillar is 100-400 nm, the diameter is 60-90 nm, and the density is 100-300 μm -2 . Depositing an organic material IT-4F on the InGaN nanopillars, wherein spin coating conditions are: the mass concentration of the IT-4F chlorobenzene solution is 10mg/mL, the rotating speed is 4000r/min, the time is 30s, the annealing temperature is 100 ℃, and the annealing time is 10min. Finally, connecting the lead with the back of the Si substrate by using Ti-Au alloy to prepare the photo-anode.
(3) Construction of photoelectrochemical cell: the prepared photo-anode is connected with the Pt electrode in series, the light source adopts parallel light irradiation, and the electrolyte adopts 0.5M H 2 SO 4 Electrolyte (ph=0).
As shown in fig. 1, a photo-anode structure of the photoelectrochemical hydrogen production system based on InGaN/organic heterostructure photoelectrode material in this embodiment is shown in the schematic diagram.
The photoelectrochemical hydrogen production system based on the InGaN/organic heterostructure photoelectrode material in the embodiment is used for producing hydrogen by solar energy, and the conversion efficiency of the obtained solar energy to the hydrogen energy is 1.6%.
Example 2
The photoelectrochemical hydrogen production system construction and application based on InGaN/organic heterostructure photoelectrode material under no bias voltage comprise the following steps:
(1) Selecting a substrate: n-type Si was used as the substrate (conductivity <0.005 Ω).
(2) Preparing a photo anode: then, adopting a molecular beam epitaxial growth process, controlling the substrate temperature to 900 ℃, the substrate rotating speed to 10r/min and the Ga beam equivalent pressure to 1 multiplied by 10 -7 Torr, equivalent pressure of In beam is 2.0X10 -7 Torr, nitrogen flow rate of 2sccm, plasma source power of 400W, rawGrowing InGaN nano-pillars on the Si substrate for 3 hours; wherein, the In atom ratio In InGaN nano-column is 20%, the height of the nano-column is 100-400 nm, the diameter is 60-90 nm, and the density is 100-300 m -2 . Depositing an organic material IT-4F on the InGaN nanopillars, wherein spin coating conditions are: the mass concentration of the IT-4F chlorobenzene solution is 10mg/mL, the rotating speed is 4000r/min, the time is 30s, the annealing temperature is 100 ℃, and the annealing time is 10min. Finally, connecting the lead with the back of the Si substrate by using Ti-Au alloy to prepare the photo-anode.
(3) Construction of photoelectrochemical cell: the prepared photo-anode was connected in series with a Pt electrode, the light source was irradiated with parallel light, and the electrolyte was 1M NaOH electrolyte (ph=14).
Fig. 2 is a schematic structural diagram of a parallel photoelectrochemical cell in a photoelectrochemical hydrogen production system based on InGaN/organic heterostructure photoelectrode materials according to the present embodiment.
The photoelectrochemical hydrogen production system based on the InGaN/organic heterostructure photoelectrode material in the embodiment is used for producing hydrogen by solar energy, and the conversion efficiency of the obtained light to hydrogen energy is 2.5%.
Example 3
The photoelectrochemical hydrogen production system construction and application based on InGaN/organic heterostructure photoelectrode material under no bias voltage comprise the following steps:
(1) Selecting a substrate: n-type Si was used as the substrate (conductivity <0.005 Ω).
(2) Preparing a photo anode: then, adopting a molecular beam epitaxial growth process, controlling the substrate temperature to 900 ℃, the substrate rotating speed to 10r/min and the Ga beam equivalent pressure to 1 multiplied by 10 -7 Torr, equivalent pressure of In beam is 2.0X10 -7 The Torr, the nitrogen flow is 2sccm, the power of a plasma source is 400W, the growth time is 3h, and InGaN nano-pillars are grown on the Si substrate; wherein, the In atom ratio In InGaN nano-column is 20%, the height of the nano-column is 100-400 nm, the diameter is 60-90 nm, and the density is 100-300 m -2 . Depositing an organic material IT-4F on the InGaN nanopillars, wherein spin coating conditions are: the mass concentration of the chlorobenzene solution of IT-4F is 10mg/mL, the rotating speed is 4000r/min, the time is 30s,the annealing temperature is 100 ℃ and the annealing time is 10min. Finally, connecting the lead with the back of the Si substrate by using Ti-Au alloy to prepare the photo-anode.
(3) Construction of photoelectrochemical cell: the prepared photo-anode is connected with the Pt electrode in series, the light source adopts parallel light irradiation, and the electrolyte adopts 1M Na 2 SO 4 Electrolyte (ph=7).
Fig. 3 is a schematic structural diagram of a full-irradiation photoelectrochemical cell in a photoelectrochemical hydrogen production system based on InGaN/organic heterostructure photoelectrode materials under no bias.
The photoelectrochemical hydrogen production system based on the InGaN/organic heterostructure photoelectrode material in the embodiment is used for producing hydrogen by solar energy, and the conversion efficiency of the obtained light to hydrogen energy is 3.2%.
Comparative example 1
The photoelectrochemical hydrogen production system construction and application of the InGaN nano-pillar photoelectrode material comprise the following steps:
(1) Selecting a substrate: n-type Si was used as the substrate (conductivity <0.005 Ω).
(2) Preparing a photo anode: then, adopting a molecular beam epitaxial growth process, controlling the substrate temperature to 900 ℃, the substrate rotating speed to 10r/min and the Ga beam equivalent pressure to 1 multiplied by 10 -7 Torr, equivalent pressure of In beam is 2.0X10 -7 The Torr, the nitrogen flow is 2sccm, the power of a plasma source is 400W, the growth time is 3h, and InGaN nano-pillars are grown on the Si substrate; wherein, the In atom ratio In InGaN nano-column is 20%, the height of the nano-column is 100-400 nm, the diameter is 60-90 nm, and the density is 100-300 m -2 . Finally, connecting the lead with the back of the Si substrate by using Ti-Au alloy to prepare the photo-anode.
(3) Construction of photoelectrochemical cell: the prepared photo-anode is connected with the Pt electrode in series, the light source adopts parallel light irradiation, and the electrolyte adopts 1M Na 2 SO 4 Electrolyte (ph=7).
Fig. 4 is a schematic structural diagram of InGaN nanopillar photoelectrode materials in the present comparative example.
The photoelectrochemical hydrogen production system of the InGaN nanopillar photoelectrode material in the comparative example under no bias is used for producing hydrogen by solar energy, and the conversion efficiency of the obtained light to hydrogen energy is 0.06%.
The embodiments described above are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the embodiments described above, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principles of the present invention should be made in the equivalent manner, and are included in the scope of the present invention.

Claims (8)

1. The light anode material based on the InGaN/organic heterostructure is characterized by comprising a Si substrate, inGaN nano-pillars arranged on the Si substrate, and an organic material layer arranged on the upper surface of the InGaN nano-pillars; the organic material layer is a non-fullerene material layer; the non-fullerene material is IT-4F;
the IT-4F is deposited on the InGaN nano-pillars by spin coating under the following conditions: the concentration of the organic material solution is 8-12 mg/mL, the rotating speed is 3500-4500 r/min, the time is 30-45 s, the annealing temperature is 90-100 ℃, and the annealing time is 10-15 min;
the proportion of In atoms In the InGaN nano-pillars In metal atoms is 20-30%, the height of the nano-pillars is 100-600 nm, the diameter is 50-100 nm, and the density is 100-300 μm -2 。
2. The InGaN/organic heterostructure-based photoanode material of claim 1, wherein the Si substrate is ultra low resistance silicon with a resistivity of less than 1 Ω -cm.
3. A method of preparing an InGaN/organic heterostructure-based photoanode material according to any of claims 1 to 2, comprising the steps of:
(1) Growing InGaN nano-pillars on the Si substrate by adopting a molecular beam epitaxial growth process;
(2) Depositing an organic material layer on the InGaN nano-pillars by spin coating; wherein, spin coating conditions are: the concentration of the organic material solution is 8-12 mg/mL, the rotating speed is 3500-4500 r/min, the time is 30-45 s, the annealing temperature is 90-100 ℃, and the annealing time is 10-15 min.
4. A method of preparing an InGaN/organic heterostructure-based photoanode material according to claim 3, characterized in that the spin-coating conditions are: the concentration of the organic material solution is 10mg/mL, the rotating speed is 4000r/min, the time is 30s, the annealing temperature is 100 ℃, and the annealing time is 10min.
5. A method of preparing InGaN/organic heterostructure based photoanode material as claimed in claim 3, wherein the growing InGaN nanopillars on the Si substrate comprises the steps of:
the molecular beam epitaxial growth process is adopted, the temperature of the Si substrate is controlled to be 450-980 ℃, the rotating speed of the Si substrate is 5-10 r/min, and the equivalent pressure of Ga beam is 1.0x10 -8 ～1.5×10 -7 Torr, in beam equivalent pressure of 1.0X10 -8 ～5×10 - 7 And the Torr, the nitrogen flow is 1-5 sccm, the power of the plasma source is 200-400W, the growth time is 1-5 h, and InGaN nano-pillars are grown on the Si substrate.
6. Use of an InGaN/organic heterostructure based photoanode material according to any of claims 1 to 2 in a photoelectrochemical hydrogen production system without bias, characterized in that the system comprises: taking a photo-anode material based on InGaN/organic heterostructure as a photo-anode, a platinum cathode, electrolyte, a light source and an electrolytic cell; the photo-anode is connected with the platinum cathode through a lead and is placed in electrolyte, and the photo-anode is irradiated by sunlight to prepare hydrogen.
7. The use of InGaN/organic heterostructure based photoanode material according to claim 6 in a photoelectrochemical hydrogen production system without bias, characterized in that the pH of the electrolyte is 0-14; the sunlight irradiates the photo-anode in a parallel light irradiation or full irradiation mode.
8. The application of the photo-anode material based on the InGaN/organic heterostructure in the photoelectrochemical hydrogen production system without bias according to claim 6, wherein the photo-anode is formed by connecting a wire with the back surface of the Si substrate based on the InGaN/organic heterostructure photo-anode material by using Ti-Au alloy.
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