CN108396381B - Light-driven deformation material and preparation method and application thereof - Google Patents

Light-driven deformation material and preparation method and application thereof Download PDF

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CN108396381B
CN108396381B CN201710064088.7A CN201710064088A CN108396381B CN 108396381 B CN108396381 B CN 108396381B CN 201710064088 A CN201710064088 A CN 201710064088A CN 108396381 B CN108396381 B CN 108396381B
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semiconductor oxide
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CN108396381A (en
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李琦
杨炜沂
冯凡
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Institute of Metal Research of CAS
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Abstract

The invention discloses a light-driven deformation material and a preparation method and application thereof, and belongs to the technical field of inorganic non-metal nano material preparation, detectors and exciters. The element with photoproduction charge storage and release capacity is uniformly doped into the semiconductor oxide crystal by utilizing a technical means of bulk metal element doping, and then the crystal structure of the semiconductor oxide is adjusted by selectively storing and releasing photoproduction charges through the doping element, so that the reversible expansion of an oxide lattice is realized, an optical signal is converted into a mechanical signal, and the material can be directly used in the fields of a light wave detector, an exciter and a variable optical window, and simultaneously the defect that the traditional optical detector material only can convert the optical signal into an electrical signal is overcome.

Description

Light-driven deformation material and preparation method and application thereof
Technical Field
The invention relates to the technical field of inorganic non-metal nano material preparation, optical detection and excitation and variable optical windows, in particular to an optical drive deformation material and a preparation method and application thereof.
Background
The light detector can detect the light power incident on its surface and convert the change of the light power into corresponding current. The performance requirements of optical detectors are high due to the loss and distortion of the optical signal in the optical fiber. Existing photodetectors are based on the conversion of optical signals into electrical signals to detect incident optical radiation. The conventional optical detection technology needs the semiconductor detection material to be realized by combining a thermoelectric detector and a photomultiplier, which puts high requirements on the design of the semiconductor material and the photoelectric circuit. The development of the technology in the field of optical detectors would be greatly facilitated if semiconductor materials of this type could be designed to convert optical signals into other forms of signals that could be easily detected or collected.
Mechanical signals, such as strain, are one of the more easily observed signals, and the existing research shows that under the action of an external electric field, the nano-metal material can convert the external excitation signal into the mechanical signal, and thus can be used as a detector or an actuator material [ J.Weissmusmuller et al, Science 300,312(2003) ]. However, the structure of some organic materials is changed under the action of light field [ d.poli et al, Nature 467,440(2010) ], but there is no report that the oxide crystal structure is reversibly deformed under the action of light field (photochromic materials are out of the category because new phases are generated). Under the excitation of proper incident light, a semiconductor material generates electron-hole pairs, and electrons and holes are finally lost in a form of being recombined or migrating to the surface to participate in a redox reaction, and the prior research reports show that the material can capture and store photogenerated electrons through material design [ k.ariga et al, adv.mater.24,158 (2012); q.li et, adv.mater.20,3717 (2008); q.li et al, j.mater.chem.20,1068(2010) ], to make full use of the light energy. If the technology is further applied to the field of optical detectors or exciters, the change of ionic radius and coordination caused by the change of the valence state of metal ions in semiconductor oxide after photo-generated electrons are captured can change the physical and chemical properties of the material, even the crystal structure of the material, and then optical signals can be converted into other signals (such as mechanical signals) convenient to measure through the novel material, so that the novel optical detection technology can be obtained.
Disclosure of Invention
The invention aims to provide a light-driven deformation material and a preparation method and application thereof, which utilize the technical means of bulk metal element doping to uniformly dope elements with photoproduction charge storage and release capacity into a semiconductor oxide crystal, further adjust the crystal structure of the semiconductor oxide in a mode of selectively storing and releasing the photoproduction charge by doping elements, realize the reversible expansion of the oxide crystal lattice, and convert optical signals into mechanical signals, thereby being directly used in the fields of detectors, exciters and variable optical windows of light waves, and simultaneously solving the defect that the traditional optical detector material can only convert the optical signals into electrical signals.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the light-driven deformation material is a semiconductor oxide nano material doped with a metal element bulk phase and having photo-generated charge storage and release capacity; the light-driven deformation material adjusts the crystal structure of the semiconductor oxide nano material in a mode of selectively storing and releasing photo-generated charges by doping elements, so that reversible expansion of crystal lattices of the semiconductor oxide nano material is realized, and optical signals are converted into mechanical signals.
The metal element with the capacity of storing and releasing photo-generated charges is one or more of tungsten, molybdenum and vanadium; the semiconductor oxide nano material is a semiconductor nano material with sunlight partial spectrum or full spectrum response.
In the light-driven deformation material, a metal element with photo-generated charge storage and release capacity is uniformly doped in a semiconductor oxide crystal lattice, and the atomic percentage content of the metal element with photo-generated charge storage and release capacity is 0.1-20%.
The preparation method of the light-driven deformable material is characterized in that a metal element with photo-generated charge storage and release capacity is uniformly doped into a semiconductor oxide crystal by utilizing a bulk phase doping technical means, so that the light-driven deformable material is obtained. The method adopts a technical route of metal alloying, oxidation treatment and crystallization treatment to realize the acquisition of the optically-driven deformable material, and specifically comprises the following steps:
(1) alloying the metal:
mixing the metal with the capacity of storing and releasing photo-generated charges with other metals, and repeatedly smelting for more than three times to uniformly mix the metals to obtain an alloy ingot; carrying out homogenizing annealing on the alloy ingot, and directly quenching to room temperature to obtain single-phase alloy;
(2) oxidation treatment:
carrying out oxidation treatment on the single-phase alloy obtained in the step (1) to obtain an amorphous semiconductor oxide nano material; the oxidation treatment is electrochemical anodic oxidation treatment, chemical corrosion oxidation treatment or gas phase oxidation treatment;
(3) crystallization treatment:
crystallizing the amorphous semiconductor oxide nano material obtained in the step (2), wherein in the crystallization treatment process: the heating rate is 1-3 ℃/min, the crystallization temperature is 450-.
In the step (1), the other metal is a metal element without photogenerated charge storage and release capability, that is, the element cannot be oxidized or reduced by the photogenerated charge and then exists in the crystal lattice in a metastable valence state.
In the step (1), the atomic percentage content of the metal with the photo-generated charge storage and release capacity in the alloy ingot is 0.1-20%; when the alloy ingot is subjected to homogenizing annealing, the alloy ingot is heated up to 1000-1500 ℃ for homogenizing annealing at the heating rate of 5-10 ℃/min, and the heat preservation time is 3-10 h.
In the step (2), the electrochemical anodic oxidation method specifically comprises the steps of putting the single-phase alloy obtained in the step (1) into a fluorine-containing electrolyte, oxidizing for 5min to 12h under the condition that the working voltage is 5 to 60V, and oxidizing and growing an amorphous semiconductor oxide nano film on the surface of the alloy; the chemical oxidation method specifically comprises the steps of putting the single-phase alloy obtained in the step (1) in a fluorine-containing corrosion oxidation solution, reacting for 1-12h at the temperature of 110-180 ℃, and oxidizing and growing a semiconductor oxide nano material on the surface of the alloy; the gas phase oxidation method specifically comprises the steps of suspending the single-phase alloy obtained in the step (1) in a closed reaction kettle, and utilizing HNO in the reaction kettle3Or the thermal steam oxidation of HF water solution, reacting for 1-12h at the temperature of 150-180 ℃, and oxidizing and growing the semiconductor oxide nano material on the surface of the alloy.
The fluorine-containing electrolyte is a solution obtained by dissolving hydrofluoric acid or ammonium fluoride in a mixed solvent, wherein: the mixed solvent is formed by mixing ethylene glycol and water according to the weight ratio of 0:100-99:1, and the content of hydrofluoric acid or ammonium fluoride in the fluorine-containing electrolyte is 0.1-2 wt.%.
The optical drive deformation material can be directly used in the fields of detection of light waves and optical exciters; in the process of storing and releasing photo-generated charges, the light absorption characteristic of the material is reversibly changed at the same time, and the material can be directly used in the field of variable optical windows.
The invention has the advantages that:
1. the invention adopts the technical means of bulk phase doping, metal elements with photo-generated charge storage and release capacity are uniformly doped into crystal lattices of semiconductor oxides, and because the doping elements occupy lattice positions, the change of crystal volume is realized by the change of ion radius after the doping elements acquire charges, so that optical signals are converted into mechanical signals, and the reversible change of physical and chemical properties of materials is promoted.
2. The invention adopts the process of alloying and oxidation treatment, so that the doping of metal ions is more uniform, and the doping process is easier to operate.
3. The invention successfully converts the optical signal into the mechanical signal and more conveniently detects the incident light wave.
4. The optical drive deformation material has the advantages of long retention time of mechanical change, wide application range, reversible change of physical and chemical properties, and applicability to the field of variable optical windows.
Description of the drawings:
fig. 1 is a microscopic topography of the 5 at.% tungsten doped titanium dioxide nanotube array of example 1.
FIG. 2 is the X-ray diffraction results of 5 at.% tungsten doped titanium dioxide nanotube material (Ti-5W-O) before and after Ultraviolet (UV) irradiation in example 1; wherein: (b) and (c) are partial enlargements of the 25 ° and 48 ° main peaks in (a), respectively.
Fig. 3 is a graph of the light absorption of the 5 at.% tungsten doped titania nanotube material of example 1 after different periods of UV pre-irradiation.
FIG. 4 shows the pure titanium dioxide nanotubes of comparative example 1Material (TiO)2) X-ray diffraction results before and after Ultraviolet (UV) irradiation.
The specific implementation mode is as follows:
the invention is further described with reference to the following figures and examples:
example 1
The light-driven deformable material prepared by the embodiment is a titanium dioxide nanotube material doped with a tungsten element bulk phase, and the specific process is as follows:
1. alloying the metal: the titanium sponge and the tungsten powder are uniformly mixed according to the atomic ratio of 95:5, and are repeatedly smelted in a non-consumable vacuum arc furnace for more than three times to be uniformly mixed, so that the Ti-5W alloy is obtained. Carrying out homogenizing annealing on the Ti-5W alloy ingot in a tubular heat treatment furnace, wherein the heating rate is 10 ℃/min, the annealing temperature is 1400 ℃, the heat preservation time is 5h, and then directly quenching the Ti-5W alloy ingot in 15 wt.% of NaCl aqueous solution to room temperature to obtain the single-phase Ti-5W alloy.
2. Electrochemical anodic oxidation: and oxidizing and growing the tungsten-doped titanium dioxide nanotube array film on the surface of the Ti-5W alloy by using an ethylene glycol solution with 0.3 wt.% of ammonium fluoride and 3 vol.% of water as an electrolyte under the conditions of 60V of working voltage and 3h of oxidation time.
3. High-temperature crystallization: and (3) crystallizing the amorphous tungsten-doped titanium dioxide nanotube array film obtained by anodic oxidation at high temperature in a tubular heat treatment furnace, wherein the heating rate is 3 ℃/min, the crystallization temperature is 550 ℃, the heat preservation time is 2 hours, and the cooling mode is furnace cooling, so that the tungsten element bulk phase-doped titanium dioxide nanotube material with good crystallization is obtained. Fig. 1 is a microscopic topography of the 5 at.% tungsten-doped titanium dioxide nanotube array prepared in this example, as shown in the figure, the titanium dioxide material after the tungsten bulk phase doping still maintains the morphology of the nanotubes.
Example 2
The light-driven deformation material prepared by the embodiment is a titanium dioxide nanotube material doped with a molybdenum element bulk phase, and the specific process is as follows:
1. alloying the metal: the titanium sponge and the molybdenum powder are uniformly mixed according to the atomic ratio of 90:10, and are repeatedly smelted in a non-consumable vacuum arc furnace for more than three times to be uniformly mixed, so that the Ti-10Mo alloy is obtained. Carrying out homogenizing annealing on the Ti-10Mo alloy ingot in a tubular heat treatment furnace at the heating rate of 5 ℃/min and the annealing temperature of 1000 ℃ for 4h, and then directly quenching the Ti-10Mo alloy ingot in 15 wt.% NaCl aqueous solution to room temperature to obtain the single-phase Ti-10Mo alloy.
2. Electrochemical anodic oxidation: an ethylene glycol solution with the ammonium fluoride content of 0.5 wt.% and the water content of 3 vol.% is used as an electrolyte, and a molybdenum-doped titanium dioxide nanotube array film is oxidized and grown on the surface of the Ti-10Mo alloy under the conditions of a working voltage of 30V and an oxidation time of 2 h.
3. High-temperature crystallization: and (3) crystallizing the amorphous molybdenum-doped titanium dioxide nanotube array film obtained by anodic oxidation at high temperature in a tubular heat treatment furnace, wherein the heating rate is 2 ℃/min, the crystallization temperature is 500 ℃, the heat preservation time is 2 hours, and the cooling mode is furnace cooling, so that the titanium dioxide nanotube material doped with 10 at.% of molybdenum element phase with good crystallization is obtained.
Example 3
1. The wavelength is 254nm, and the light intensity is 6mW/cm2The ultraviolet lamp tube is used as a light source, and the Ti-5W-O nanotube material prepared in the example 1 is irradiated for 8 hours in advance under the conditions that the temperature is 20 ℃ and the relative humidity is 50%.
2. After the illumination is finished, the Ti-5W-O nanotube material is quickly placed into an X-ray diffractometer to test an XRD (X-ray diffraction) pattern, and the XRD pattern is compared with that of an original sample which is not irradiated by UV (ultraviolet) in advance. As can be seen from FIG. 2, after UV irradiation, the XRD diffraction peak of Ti-5W-O shifts to a small angle, the lattice expands, and the optical signal is successfully converted into the mechanical signal. Fig. 3 is a graph of the light absorption of 5 at.% tungsten doped titania nanotube material after different periods of UV pre-irradiation. It can be seen that after the material is irradiated in advance by the UV, the optical characteristics of the material are changed due to the fact that the doping elements in the material capture photo-generated electrons, the light absorption intensity of the Ti-5W-O in the visible light and near infrared light ranges is obviously enhanced, and the light absorption intensity is gradually enhanced along with the extension of the UV irradiation time, so that the material can be used in the field of variable optical windows.
Example 4
The difference from the embodiment 1 is that: in the metal alloying preparation link, metals without photo-generated charge storage and release capacity such as Zr, Nb and Ta and W, Mo or V with photo-generated charge storage and release capacity are selected to be smelted to form an alloy ingot, and meanwhile, in the metal element bulk phase doping process, technological parameters are properly adjusted according to the selected material system, so that the prepared light-driven deformation material has the technical effect which is closer to that in the embodiment 3.
Comparative example 1
1. The same electrochemical anodic oxidation and high temperature crystallization process as in example 1 was used to grow and crystallize a titanium dioxide nanotube array film on the surface of a pure titanium sheet with a purity of 99.99%.
2. The pure titanium dioxide nanotube material was pre-irradiated using exactly the same UV irradiation conditions as in example 3.
3. After the illumination is finished, the XRD pattern and the light absorption curve are tested and compared with the original sample which is not irradiated by UV in advance. As shown in fig. 4, when the titanium dioxide nanotube material doped with no metal element with photo-generated electron storage capacity is irradiated in advance by UV, the XRD diffraction peak is not shifted, the crystal structure is not changed, and the optical signal cannot be converted into the mechanical signal.
The above examples are given by way of reference only and any materials having a shape similar to or extending from the teachings of this patent, methods of making the same, and uses thereof are within the scope of the patent.

Claims (8)

1. The application of the light-driven deformation material is characterized in that: the optical drive deformation material can be directly used in the fields of detection of light waves and optical exciters; in the process of storing and releasing photo-generated charges, the light absorption characteristic of the material is reversibly changed at the same time, and the material can be directly used in the field of variable optical windows;
the light-driven deformation material is a semiconductor oxide nano material doped with a metal element body phase with photo-generated charge storage and release capacity; the optical drive deformation material adjusts the crystal structure of the semiconductor oxide nano material in a mode of selectively storing and releasing photo-generated charges by doping elements, so that reversible expansion of crystal lattices of the semiconductor oxide nano material is realized, and optical signals are converted into mechanical signals; the bulk phase doping refers to uniformly doping metal elements with photogenerated charge storage and release capacity into crystal lattices of the semiconductor oxide nano material;
the metal element with the capacity of storing and releasing photo-generated charges is one or more of tungsten, molybdenum and vanadium; the semiconductor oxide nano material is a titanium dioxide nano tube material.
2. Use of an optically driven deformable material according to claim 1, characterized in that: in the light-driven deformation material, a metal element with photo-generated charge storage and release capacity is uniformly doped in a semiconductor oxide crystal lattice, and the atomic percentage content of the metal element with photo-generated charge storage and release capacity is 0.1-20%.
3. Use of an optically driven deformable material according to claim 1 or 2, characterized in that: the preparation method of the light-driven deformable material is characterized in that a metal element with photo-generated charge storage and release capacity is uniformly doped into a semiconductor oxide crystal by utilizing a bulk phase doping technical means, so that the light-driven deformable material is obtained.
4. Use of an optically actuated deformable material as claimed in claim 3, characterized in that: the method adopts a technical route of metal alloying, oxidation treatment and crystallization treatment to realize the acquisition of the optically-driven deformable material, and specifically comprises the following steps:
(1) alloying the metal:
mixing the metal with the capacity of storing and releasing photo-generated charges with other metals, and repeatedly smelting for more than three times to uniformly mix the metals to obtain an alloy ingot; carrying out homogenizing annealing on the alloy ingot, and directly quenching to room temperature to obtain single-phase alloy;
(2) oxidation treatment:
carrying out oxidation treatment on the single-phase alloy obtained in the step (1) to obtain an amorphous semiconductor oxide nano material; the oxidation treatment is electrochemical anodic oxidation treatment, chemical corrosion oxidation treatment or gas phase oxidation treatment;
(3) crystallization treatment:
crystallizing the amorphous semiconductor oxide nano material obtained in the step (2), wherein in the crystallization treatment process: the heating rate is 1-3 ℃/min, the crystallization temperature is 450-.
5. Use of an optically driven deformable material according to claim 4, characterized in that: in the step (1), the other metal is a metal element without photogenerated charge storage and release capacity, that is, the element cannot be oxidized or reduced by the photogenerated charge and then exists in the crystal lattice in a metastable valence state.
6. Use of an optically driven deformable material according to claim 4, characterized in that: in the step (1), the atomic percentage content of the metal with the photo-generated charge storage and release capacity in the alloy ingot is 0.1-20%; when the alloy ingot is subjected to homogenizing annealing, the alloy ingot is heated up to 1000-1500 ℃ for homogenizing annealing at the heating rate of 5-10 ℃/min, and the heat preservation time is 3-10 h.
7. Use of an optically driven deformable material according to claim 4, characterized in that: in the step (2), the electrochemical anodic oxidation method specifically comprises the steps of putting the single-phase alloy obtained in the step (1) into fluorine-containing electrolyte, oxidizing for 5min-12h under the condition that the working voltage is 5-60V, and oxidizing and growing an amorphous semiconductor oxide nano film on the surface of the alloy; the chemical oxidation method specifically comprises the steps of putting the single-phase alloy obtained in the step (1) in a fluorine-containing corrosion oxidation solution, reacting for 1-12h at the temperature of 110-180 ℃, and oxidizing and growing a semiconductor oxide nano material on the surface of the alloy; the gas phase oxidation method specifically refers to the step of subjecting the single-phase alloy obtained in the step (1) toSuspending in the air and placing in a closed reaction kettle, and utilizing HNO in the reaction kettle3Or the thermal steam oxidation of HF water solution, reacting for 1-12h at the temperature of 150-180 ℃, and oxidizing and growing the semiconductor oxide nano material on the surface of the alloy.
8. Use of an optically driven deformable material according to claim 7, characterized in that: the fluorine-containing electrolyte is a solution obtained by dissolving hydrofluoric acid or ammonium fluoride in a mixed solvent, wherein: the mixed solvent is formed by mixing ethylene glycol and water according to the weight ratio of 0:100-99:1, and the content of hydrofluoric acid or ammonium fluoride in the fluorine-containing electrolyte is 0.1-2 wt.%.
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Citations (3)

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Publication number Priority date Publication date Assignee Title
CN101204649A (en) * 2006-12-20 2008-06-25 中国科学院金属研究所 Process for preparing cationic nanotube array intermingling titanium oxide
CN103011346A (en) * 2011-09-20 2013-04-03 同济大学 Titanium-tungsten alloy oxide nano-tube electrode with characteristic of in-situ vertical growth, preparation method and applications thereof
CN103924280A (en) * 2014-04-29 2014-07-16 张家港格林台科环保设备有限公司 Molybdenum and carbon-codoped titanium oxide nanotube array thin film material and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110127167A1 (en) * 2005-12-13 2011-06-02 University Of Nevada, Reno Preparation of nano-tubular titania substrates having gold and carbon particles deposited thereon and their use in photo-electrolysis of water

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101204649A (en) * 2006-12-20 2008-06-25 中国科学院金属研究所 Process for preparing cationic nanotube array intermingling titanium oxide
CN103011346A (en) * 2011-09-20 2013-04-03 同济大学 Titanium-tungsten alloy oxide nano-tube electrode with characteristic of in-situ vertical growth, preparation method and applications thereof
CN103924280A (en) * 2014-04-29 2014-07-16 张家港格林台科环保设备有限公司 Molybdenum and carbon-codoped titanium oxide nanotube array thin film material and preparation method thereof

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