CN111500986A - Optical device and method for efficiently preparing nano tungsten and nano tungsten oxide - Google Patents

Optical device and method for efficiently preparing nano tungsten and nano tungsten oxide Download PDF

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CN111500986A
CN111500986A CN201910271450.7A CN201910271450A CN111500986A CN 111500986 A CN111500986 A CN 111500986A CN 201910271450 A CN201910271450 A CN 201910271450A CN 111500986 A CN111500986 A CN 111500986A
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nano
nano tungsten
tungsten
tungsten oxide
metal
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赵波
郑昕
杨建军
郭春雷
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Changchun Institute of Optics Fine Mechanics and Physics of CAS
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Changchun Institute of Optics Fine Mechanics and Physics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/083—Oxides of refractory metals or yttrium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon

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Abstract

The optical device and the processing method for efficiently preparing the nano tungsten and the nano tungsten oxide have the advantages that a laser beam emitted by a femtosecond laser light source sequentially passes through the beam adjusting device, the energy adjusting device and the optical focusing device and then is focused on the surface of the metal tungsten on the three-dimensional moving platform, so that the nano tungsten and the nano tungsten oxide generated by laser ablation on the metal surface are deposited on the transparent substrate material to form a nano tungsten and nano tungsten oxide material film, and the nano tungsten oxide material film are subjected to high-temperature treatment to obtain a nano tungsten trioxide film material Is suitable for industrial production.

Description

Optical device and method for efficiently preparing nano tungsten and nano tungsten oxide
Technical Field
The invention relates to the technical field of optical processing, in particular to an optical device and method for efficiently preparing nano tungsten and nano tungsten oxide.
Background
Tungsten (W) is a transition metal, and its oxide belongs to a semiconductor material. The outermost electrons of the tungsten atom have equivalent valence states of +2, +3, +4, +5, and + 6. Thus, tungsten oxide has WO2、WO2.75、WO3、W18O49、W20O58And the like in a variety of stoichiometric forms. Tungsten oxide crystals exist in various lattice structures such as monoclinic, triclinic, orthorhombic, tetragonal and cubic structures. Tungsten oxide has the advantages of stable chemical properties, strong corrosion resistance, no toxicity and the like, is an important functional material, has excellent characteristics of electrochromism, photochromism, gasochromism, field emission and the like, and is widely applied to the fields of solar cells, intelligent display devices, photocatalytic materials, gas-sensitive chemical sensors and the like.
The nano tungsten oxide material has the excellent performances of large surface, strong surface activity, quantum localization effect and the like. As a premise that the nano tungsten oxide material can be widely applied in various fields, the preparation process of the nano tungsten oxide material becomes one of the research hotspots in the field of nano materials. The current preparation process of the nano tungsten oxide mainly comprises a sol-gel method, a water solution/solution method, a template method, a vapor deposition method, a sputtering method, a pulse laser deposition method and the like. The sol-gel method is to hydrolyze or alcoholyze inorganic salt or metal alkoxide to generate active monomer, polymerize the active monomer into sol, perform polycondensation and aging to polymerize colloidal particles into gel, and finally dry and bake the gel to obtain the final nano material. The nano tungsten oxide prepared by the method has small size, good uniformity and high purity. However, the method has the defects of difficult control of sol-gel conversion, easy agglomeration of dried gel, complicated operation process, long period, chemical pollution and the like. The water-soluble/solution method utilizes the principle of dissolving and re-crystallizing substances under high-temperature and high-pressure environment to prepare the nano material. The nanometer tungsten oxide prepared by the method has few defects, high crystallinity and good uniformity, but also has the defects of complicated operation process, harsh conditions, easy chemical pollution and the like. The template method is a method for regulating and synthesizing a material with specific size, shape and arrangement by utilizing the limiting effect of a template material. The template method is used for preparing the nano tungsten oxide material, the post-treatment is complicated, and residual template impurity pollution exists. The vapor deposition method converts the raw material from solid to gas by using a thermal evaporation mode, performs biological change or chemical reaction in the gas, and then is cooled and condensed into nano powder. The nano tungsten oxide sample prepared by the method has the advantages of high purity, good dispersion, narrow particle size distribution and the like. The sputtering method bombards the target material with high-energy inert gas particles, and the bombarded atoms are deposited on the substrate to form a film. The nano tungsten oxide film material prepared by the method has high density, uniform thickness and firm combination with the substrate. The pulsed laser deposition method uses high-energy pulsed laser to instantaneously gasify the target material to generate plasma plume consisting of atoms, particles and atom clusters, the plasma plume is sprayed to the substrate along the direction vertical to the target material to deposit and nucleate on the substrate to form nano particles, and the high-quality nano tungsten oxide film can be prepared by the method. However, the three methods have the disadvantages of expensive equipment and high preparation cost; the preparation conditions are harsh, and the preparation needs to be carried out in a vacuum environment and a high-temperature system.
Disclosure of Invention
Therefore, there is a need to provide an optical device and method for preparing nano tungsten and nano tungsten oxide efficiently, which is simple, easy to control and free of pollution.
In order to achieve the purpose, the invention adopts the following technical scheme:
an optical device for efficiently preparing nano tungsten and nano tungsten oxide, comprising: the laser device comprises a femtosecond laser light source, a light beam adjusting device, an energy adjusting device, an optical focusing device, a three-dimensional moving platform and a computer, wherein the light beam adjusting device is used for changing the spot size of a laser beam emitted by the femtosecond laser light source, the energy adjusting device is used for changing the pulse energy of the laser beam, metal tungsten is fixed on the three-dimensional moving platform, the surface of the metal tungsten is covered with a transparent substrate material, and the three-dimensional moving platform is electrically connected with the computer; wherein:
and laser beams emitted by the femtosecond laser light source sequentially pass through the light beam adjusting device, the energy adjusting device and the optical focusing device and then are focused on the surface of the metal tungsten on the three-dimensional moving platform, so that the nano tungsten and the nano tungsten oxide generated on the surface of the metal tungsten through laser ablation are deposited on the transparent substrate material.
In some preferred embodiments, the femtosecond laser source uses chirped amplified pulses generated by a titanium sapphire laser as a light source.
In some preferred embodiments, the beam conditioning device is an aperture.
In some preferred embodiments, the energy conditioning device comprises a half wave plate and a corresponding set of half wave plates of a grazing-taylor prism.
In some preferred embodiments, the optical focusing device is a plano-convex cylindrical lens.
In some preferred embodiments, the plano-convex cylindrical lens has a focusing function on the incident femtosecond beam in only one direction to obtain an elliptical focusing spot with an elongated shape, and the elliptical major axis of the elliptical focusing spot is the diameter of the incident spot.
In some preferred embodiments, the position of the surface of the metal tungsten, which is 100 to 300 μm away from the focal point of the light beam, is before the focal point, and the computer controls the scanning speed of the laser beam emitted from the femtosecond laser light source to be 0.01 to 0.1mm/s on the surface of the metal tungsten.
In addition, the invention also provides a preparation method of the optical device for efficiently preparing the nano tungsten and the nano tungsten oxide, which comprises the following steps:
cleaning and drying the metal surface, and fixing the metal surface on the three-dimensional moving platform, wherein the metal tungsten surface is covered with a transparent substrate material;
adjusting the light beam adjusting device and the energy adjusting device to enable the laser beam emitted by the femtosecond laser light source to sequentially pass through the light beam adjusting device, the energy adjusting device and the optical focusing device and then be focused on the metal surface on the three-dimensional moving platform, and enabling the nano tungsten and the nano tungsten oxide generated by laser ablation on the metal tungsten surface to be deposited on the transparent substrate material to form a nano tungsten and nano tungsten oxide material film;
and (3) carrying out high-temperature treatment on the nano tungsten and nano tungsten oxide material film layer to obtain the nano tungsten trioxide film layer material.
In some preferred embodiments, the width of the nano tungsten and nano tungsten oxide material film is about 3 to 10mm, and the thickness is about 50 to 500 μm.
In some preferred embodiments, the particle size of the nano tungsten and the nano tungsten oxide is 10 to 40 nm.
In some preferred embodiments, the prepared nano tungsten and nano tungsten oxide material can be converted into a nano tungsten trioxide material after being subjected to high-temperature heat treatment at 400 ℃ for 1 hour.
The invention adopts the technical scheme that the method has the advantages that:
the optical device and the processing method for efficiently preparing the nano tungsten and the nano tungsten oxide provided by the invention have the advantages that a laser beam emitted by a femtosecond laser light source sequentially passes through the beam adjusting device, the energy adjusting device and the optical focusing device and then is focused on the surface of the metal tungsten on the three-dimensional moving platform, so that the nano tungsten and the nano tungsten oxide generated on the surface of the metal tungsten through laser ablation are deposited on the transparent substrate material to form a nano tungsten and nano tungsten oxide material film layer, and the nano tungsten oxide material film layer are subjected to high-temperature treatment to obtain a nano tungsten trioxide film layer material Is suitable for industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic structural diagram of an optical device for efficiently preparing nano tungsten and nano tungsten oxide according to an embodiment of the present invention.
Fig. 2 is a flowchart illustrating steps of a method for efficiently manufacturing an optical device containing nano-tungsten and nano-tungsten oxide according to an embodiment of the present invention.
FIG. 3 is a Scanning Electron Microscope (SEM) image of nano tungsten and nano tungsten oxide efficiently prepared by femtosecond laser before and after heat treatment in the embodiment of the invention;
FIG. 4 is a Transmission Electron Microscope (TEM) image of nano tungsten and nano tungsten oxide before and after heat treatment provided by the embodiment of the invention;
fig. 5 is an electron diffraction pattern of nano tungsten and nano tungsten oxide before and after heat treatment according to an embodiment of the present invention;
FIG. 6 shows X-ray diffraction spectra (XRD) of nano-tungsten and nano-tungsten oxide before and after heat treatment according to embodiments of the present invention;
FIG. 7 is X-ray photoelectron diffraction Spectroscopy (XPS) charts of nano tungsten and nano tungsten oxide provided in the examples of the present invention before and after heat treatment;
fig. 8 shows raman spectra of nano tungsten and nano tungsten oxide before and after heat treatment according to an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Referring to fig. 1, a schematic structural diagram of an optical device for efficiently preparing nano tungsten and nano tungsten oxide according to an embodiment of the present invention includes: a femtosecond laser source 110, a beam adjusting device 120, an energy adjusting device 130, an optical focusing device 140, a three-dimensional moving platform 150 and a computer 160.
The beam adjusting device 120 is used for changing the spot size of the laser beam emitted by the femtosecond laser source 110, the energy adjusting device 130 is used for changing the pulse energy of the laser beam, the three-dimensional moving platform 150 is fixed with metal tungsten 170, the surface of the metal tungsten 170 is covered with a transparent substrate material 180, and the three-dimensional moving platform 150 is electrically connected with the computer 160.
The optical device for efficiently preparing the nano tungsten and the nano tungsten oxide provided by the invention has the following implementation mode:
the laser beam emitted from the femtosecond laser source 110 sequentially passes through the beam adjusting device 120, the energy adjusting device 130, and the optical focusing device 140 and then is focused on the surface of the metal tungsten on the three-dimensional moving platform 150, so that the nano tungsten and the nano metal tungsten oxide generated by laser ablation on the surface of the metal tungsten are deposited on the transparent substrate material 180 to form a nano tungsten and nano tungsten oxide material film.
In some preferred embodiments, the femtosecond laser source 110 employs amplified chirped pulses of a titanium sapphire laser as a light source, the center wavelength of the light source is 800nm, the repetition frequency is 1kHz, the pulse width is 40fs, the maximum single pulse energy is 7mJ, and the polarization direction is along the horizontal direction.
In some preferred embodiments, the beam conditioning device 120 is an aperture.
In some preferred embodiments, the energy adjusting device 130 includes a half wave plate 131 and a corresponding Glan-Taylor prism 132 disposed on the half wave plate 131.
In some preferred embodiments, the optical focusing device 140 is a plano-convex cylindrical lens.
Further, the focal length f of the plano-convex cylindrical lens is 50 mm.
Specifically, the plano-convex cylindrical lens 140 has a focusing function on the incident femtosecond beam only in one direction to obtain an elliptical focusing spot with a long and thin shape, and the elliptical long axis of the elliptical focusing spot is the diameter of the incident spot, so that high-efficiency preparation of large-area nano tungsten and tungsten oxide film layer materials can be realized.
In some preferred embodiments, the distance between the surface of the metal tungsten and the focal point of the light beam is 100 to 300 μm before the focal point, and the computer 160 controls the scanning speed of the laser beam emitted from the femtosecond laser light source on the surface of the metal to be 0.01 to 0.1 mm/s.
It can be understood that the computer 160 can precisely control the moving speed of the metal tungsten sample and the transparent substrate material fixed on the three-dimensional moving platform 150, and can realize the adjustment of the thickness of the prepared nanometer tungsten and nanometer tungsten oxide material film.
It can be understood that the metal material provided by the present invention is tungsten, and in practice, the metal material is not limited to tungsten, and may be molybdenum, titanium, nickel, copper, etc., the nano metal is not limited to nano tungsten, and may be nano molybdenum, nano titanium, nano nickel, nano copper, etc., and the nano metal oxide is not limited to nano tungsten oxide, and may be nano molybdenum oxide, nano titanium oxide, nano nickel oxide, nano copper oxide, etc.
The optical device for efficiently preparing the nano tungsten and the nano tungsten oxide, provided by the invention, has the advantages of no need of precise mechanical parts, no chemical corrosive, loose processing environment, simple process, easiness in operation, high efficiency, environmental friendliness, low cost and suitability for industrial production.
Example 2
Referring to fig. 2, a method for efficiently manufacturing an optical device of nano tungsten and nano tungsten oxide according to an embodiment of the present invention includes the following steps:
step S110: cleaning and drying the surface of metal tungsten, and fixing the metal tungsten on the three-dimensional moving platform 150, wherein the surface of the metal tungsten is covered with a transparent substrate material;
in some preferred embodiments, the transparent substrate material is glass.
In some preferred embodiments, the distance between the surface of the metal tungsten sample and the focus of the light beam is 100 to 300 μm before the focus, and the scanning speed of the femtosecond laser on the surface of the metal tungsten sample is controlled to be 0.01 to 0.1 mm/s.
Step S120: adjusting the beam adjusting device 120 and the energy adjusting device 130 to enable the laser beam emitted by the femtosecond laser light source to sequentially pass through the beam adjusting device 120, the energy adjusting device 130 and the optical focusing device 140 and then to be focused on the surface of the metal tungsten on the three-dimensional moving platform 150, and enabling the nano tungsten and the nano tungsten oxide generated by laser ablation on the surface of the metal tungsten 170 to be deposited on the transparent substrate material 180 to form a nano tungsten and nano metal tungsten oxide material film;
furthermore, the diameter of a light spot of a laser beam emitted by the femtosecond laser light source is 3-10 mm, and the pulse energy is 0.2-2 mJ.
In some preferred embodiments, the particle size of the prepared nano tungsten and nano tungsten oxide is 10-40 nm, and the nano tungsten and nano tungsten oxide are polycrystalline structures.
In some preferred embodiments, the time required for preparing the film material of nano tungsten and nano tungsten oxide with the area of 1cm × 1cm is 1.7-16.7 minutes.
Step S130: and (3) carrying out high-temperature treatment on the nano tungsten and nano tungsten oxide material film layer to obtain the nano tungsten trioxide film layer material.
In some preferred embodiments, the width of the nano tungsten and nano tungsten oxide material film is 3 to 10mm, and the thickness is 50 to 500 μm.
Further, the prepared nano tungsten and nano tungsten oxide material can be converted into a nano tungsten trioxide material after being subjected to high-temperature heat treatment at 400 ℃ for 1 hour.
It can be understood that the metal material provided by the present invention is tungsten, and in practice, the metal material is not limited to tungsten, and may be molybdenum, titanium, nickel, copper, etc., the nano metal is not limited to nano tungsten, and may be nano molybdenum, nano titanium, nano nickel, nano copper, etc., and the nano metal oxide is not limited to nano tungsten oxide, and may be nano molybdenum oxide, nano titanium oxide, nano nickel oxide, nano copper oxide, etc.
The optical processing method for efficiently preparing the nano tungsten and the nano tungsten oxide, provided by the invention, has the advantages of no need of precise mechanical parts, no chemical corrosive, loose processing environment, simple and easy process, high efficiency, environmental friendliness, low cost and suitability for industrial production.
The above technical means of the present invention will be described below with reference to detailed examples.
Examples
In this embodiment, a metal sample is a circular sheet of metal tungsten with a purity of 99.95%, the surface of the circular sheet is cleaned, dried and then fixed on the three-dimensional moving platform, and the surface of the metal tungsten is covered with a transparent substrate material;
adjusting the light beam adjusting device and the energy adjusting device to enable the laser beam emitted by the femtosecond laser light source to sequentially pass through the light beam adjusting device, the energy adjusting device and the optical focusing device and then be focused on the surface of the metal tungsten on the three-dimensional moving platform, and enabling the nano tungsten and the nano tungsten oxide generated by laser ablation on the surface of the metal to be deposited on the transparent substrate material to form a nano tungsten and nano tungsten oxide material film; the nano tungsten and the nano tungsten oxide are in polycrystalline structures. Wherein:
the femtosecond laser source 110 adopts amplified chirped pulses of a titanium sapphire laser as a light source, the central wavelength of the light source is 800nm, the repetition frequency is 1kHz, the pulse width is 40fs, the maximum single pulse energy is 7mJ, and the polarization direction is along the horizontal direction; the parameters of the laser beam emitted by the femtosecond laser light source are as follows: the wavelength is 800nm, the pulse width is 40fs, the energy is 0.5mJ, the diameter of a light spot is 8mm, the position of the tungsten away from the focus of the light beam is 100 mu m before the focus, and the scanning speed of the femtosecond laser on the surface of the tungsten is controlled to be 0.02 mm/s.
It can be understood that the width of the prepared nano tungsten and nano tungsten oxide film layer can be controlled by adjusting the diameter of the spot of the incident femtosecond laser through the light beam adjusting device 120, and the particle size of the nano tungsten and nano tungsten oxide film layer material prepared by the embodiment is 10-40 nm.
It can be understood that the thickness of the prepared nano tungsten and nano tungsten oxide material film can be controlled by adjusting the incident femtosecond laser energy through the energy adjusting device 130, and the width of the prepared nano tungsten and nano tungsten oxide material film is about 8mm, the thickness of the prepared nano tungsten and nano tungsten oxide material film is about 150 μm, and the length of the prepared nano tungsten and nano tungsten oxide material film is the sample moving length.
It can be understood that the optical focusing device (plano-convex cylindrical lens) is adjusted to have a focusing function on light in only one direction, a focusing light spot is in a slender ellipse shape, the length of the light spot in the direction of the major axis of the ellipse is about the diameter (8mm) of an incident light spot, and the efficient preparation of large-area nano tungsten and nano tungsten oxide film layer materials can be realized.
It can be understood that the thickness of the prepared nano tungsten and nano tungsten oxide material film can be controlled by the moving speed of the computer 160 precisely moving the metal tungsten sample and the transparent substrate fixed on the three-dimensional translation stage 150.
And (3) carrying out high-temperature treatment on the nano tungsten and nano tungsten oxide material film layer to obtain the nano tungsten trioxide film layer material.
Specifically, the prepared nano tungsten and nano tungsten oxide material can be converted into a nano tungsten trioxide material after being subjected to high-temperature heat treatment at 400 ℃ for 1 hour.
As shown in fig. 3, optical micrographs (inset) and Scanning Electron Microscope (SEM) images of nano-tungsten and nano-tungsten oxide prepared on a transparent glass substrate in this example before and after heat treatment. As can be seen from the optical microscopic image, the color of the deposited film layer in the femtosecond laser-prepared area appears black, and the color changes to light yellow after the deposited film layer is placed in a muffle furnace and is subjected to high-temperature heat treatment at 400 ℃ for 1 hour. As can be seen from the scanning electron micrograph, the particle size of the deposited film layer in the femtosecond laser prepared region was not uniform, but the particle size became large and uniform after it was heat-treated at a high temperature of 400 ℃ for 1 hour in a muffle furnace.
As shown in fig. 4, Transmission Electron Microscope (TEM) images of nano tungsten and nano tungsten oxide prepared on a transparent glass substrate in this example before and after heat treatment are shown. As can be seen, the particle size of the deposited film layer in the femtosecond laser preparation area is 10-20 nm. When the particles are placed in a muffle furnace for heat treatment at a high temperature of 400 ℃ for 1 hour, the particle size is increased to about 30-40 nm.
As shown in fig. 5, a selected area electron diffraction image of the nano tungsten and the nano tungsten oxide prepared on the transparent glass substrate in the present example before and after the heat treatment is shown. From the irregular electron diffraction pattern, the deposited film layer in the femtosecond laser region is in a polycrystalline structure before and after heat treatment.
As shown in fig. 6, the X-ray diffraction energy spectrum (XRD) patterns before and after the heat treatment of the nano tungsten and the nano tungsten oxide prepared on the transparent glass substrate in this example are shown. The main diffraction peaks (200), (210), (211), (222), (320), (321) and (400) of the deposition film layer in the femtosecond laser preparation area before heat treatment are matched with the standard calorific value of the cubic system (JCPDS 47-1319) of tungsten, and the main diffraction peaks (002), (020), (200) and (022) are matched with the standard calorific values of the monoclinic system (JCPDS 04-0806) and the triclinic system (JCPDS 04-0806) of tungsten trioxide, so that the deposition film layer in the femtosecond laser preparation area is a mixture of nano tungsten and nano tungsten oxide. After heat treatment for 1 hour at 400 ℃ in an air environment, the main diffraction peaks (100), (110), (210) and (211) of the deposited film layer are matched with the standard calorie value of the cubic system (JCPDS 41-0905) of tungsten trioxide; the main diffraction peaks (002), (020), (200), (-112), (202) and (140) are consistent with the standard calorific value of monoclinic system (JCPDS 43-1035) of tungsten trioxide; the main diffraction peaks (002), (020), (200) and (222) are consistent with the standard calorific value of the triclinic system (JCPDS 46-1096) of the tungsten trioxide, which indicates that the nano tungsten and the nano tungsten oxide film layer material prepared by the femtosecond laser are placed in a muffle furnace for heat treatment at the high temperature of 400 ℃ for 1 hour and then are converted into the nano tungsten trioxide material, and the nano tungsten trioxide material is in a polycrystalline structure.
As shown in fig. 7, it is an X-ray photoelectron diffraction spectroscopy (XPS) graph of the nano tungsten and the nano tungsten oxide prepared on the transparent glass substrate by the femtosecond laser of the present embodiment before and after the heat treatment. As can be seen from the figure, the energy spectrum of the deposition film layer in the femtosecond laser preparation area before the heat treatment mainly has four peaks at the positions of 31.25eV, 33.4eV, 36eV and 38.1 eV. Wherein 33.4eV and 31.25eV correspond to 4f for metallic tungsten, respectively5/2And 4f7/2Electron binding energy of the rail; 38.1eV and 36eV respectively correspond to W in tungsten trioxide 6+4f of5/2And 4f7/2The electron binding energy of the orbitals indicates that the deposited film layer in the femtosecond laser preparation area is a mixture of tungsten and tungsten oxide. When the tungsten trioxide is placed in a muffle furnace for heat treatment at a high temperature of 400 ℃ for 1 hour, the energy spectrum only has two peaks with electron binding energies of 38.1eV and 36eV which respectively correspond to W in tungsten trioxide 6+4f of5/2And 4f7/2A track. Illustrating the film layer at this timeThe material is converted into a nano tungsten trioxide material.
As shown in fig. 8, the raman spectra before and after the heat treatment of the nano tungsten and the nano tungsten oxide prepared on the transparent glass substrate in this example are shown. As can be seen from the figure, the Raman spectrum of the nano tungsten and nano tungsten oxide film layer material of the femtosecond laser before heat treatment is 808cm-1、715cm-1、135cm-1And 71cm-1Distinct signal peaks appear at four positions. Wherein, 808cm-1And 715cm-1The signal peak at the position is related to the O-W-O stretching vibration in the crystal; 135cm-1And 71cm-1The signal peak of (a) is associated with the W-W vibration bond. After the sample is placed in a muffle furnace and subjected to high-temperature heat treatment at 400 ℃ for 1 hour, signal peaks at four positions still exist, but 808cm-1And 715cm-1The intensity of the signal peak at the location is significantly enhanced compared to before the heat treatment. In addition, at 272cm-1A new signal peak appears at the position, which is related to the O-W-O bending vibration in the crystal, and shows that the nano tungsten and the nano tungsten oxide film layer material are subjected to oxidation reaction after heat treatment.
The nano tungsten trioxide material obtained by the optical device for efficiently preparing nano metal and nano tungsten oxide provided by the invention can be widely applied to the fields of photocatalysis, solar cells, intelligent display, gas-sensitive sensing and the like.
Of course, the optical device for efficiently preparing nano tungsten and nano tungsten oxide of the present invention may have various changes and modifications, and is not limited to the specific structure of the above embodiments. In conclusion, the scope of the present invention should include those changes or substitutions and modifications which are obvious to those of ordinary skill in the art.

Claims (11)

1. An optical device for efficiently preparing nano tungsten and nano metal tungsten oxide, which is characterized by comprising: the laser device comprises a femtosecond laser light source, a light beam adjusting device, an energy adjusting device, an optical focusing device, a three-dimensional moving platform and a computer, wherein the light beam adjusting device is used for changing the spot size of a laser beam emitted by the femtosecond laser light source, the energy adjusting device is used for changing the pulse energy of the laser beam, metal tungsten is fixed on the three-dimensional moving platform, the surface of the metal tungsten is covered with a transparent substrate material, and the three-dimensional moving platform is electrically connected with the computer; wherein:
and laser beams emitted by the femtosecond laser light source sequentially pass through the light beam adjusting device, the energy adjusting device and the optical focusing device and then are focused on the metal surface on the three-dimensional moving platform, so that nano tungsten and nano metal tungsten oxide generated by laser ablation on the metal tungsten surface are deposited on the transparent substrate material to form a nano tungsten and nano metal tungsten oxide material film.
2. The optical device for efficiently manufacturing nano tungsten and nano tungsten oxide according to claim 1, wherein the femtosecond laser source uses chirped amplified pulses generated by a titanium sapphire laser as a light source.
3. The optical device for efficiently manufacturing nano tungsten and nano tungsten oxide according to claim 1, wherein the light beam adjusting device is an aperture.
4. The optical device for efficiently manufacturing nano tungsten and nano tungsten oxide according to claim 1, wherein the energy adjusting means comprises a half wave plate and a Glan-Taylor prism arranged corresponding to the half wave plate.
5. The optical device for efficiently manufacturing nano tungsten and nano tungsten oxide according to claim 1, wherein the optical focusing device is a plano-convex cylindrical lens.
6. The optical device for efficiently manufacturing nano tungsten and nano tungsten oxide according to claim 5, wherein the plano-convex cylindrical lens has a focusing function on the incident femtosecond beam only in one direction to obtain an elliptical focusing spot with a slender shape, and the elliptical major axis of the elliptical focusing spot is the diameter of the incident spot.
7. The optical device for efficiently preparing nano tungsten and nano tungsten oxide according to claim 6, wherein the position of the surface of the metal tungsten, which is away from the focus of the light beam, is 100 to 300 μm before the focus, and the computer controls the scanning speed of the laser beam emitted by the femtosecond laser light source on the surface of the metal tungsten to be 0.01 to 0.1 mm/s.
8. The method for preparing the optical device of nano tungsten and nano tungsten oxide with high efficiency as claimed in claim 1, which comprises the following steps:
cleaning and drying the surface of metal tungsten, and fixing the metal tungsten on the three-dimensional moving platform, wherein the surface of the metal tungsten is covered with a transparent substrate material;
adjusting the light beam adjusting device and the energy adjusting device to enable the laser beam emitted by the femtosecond laser light source to sequentially pass through the light beam adjusting device, the energy adjusting device and the optical focusing device and then be focused on the surface of the metal tungsten on the three-dimensional moving platform, and enabling the nano tungsten and the nano tungsten oxide generated by laser ablation on the surface of the metal tungsten to be deposited on the transparent substrate material to form a nano tungsten and nano tungsten oxide material film;
and (3) carrying out high-temperature treatment on the nano tungsten and nano metal tungsten oxide material film to obtain the nano tungsten trioxide film material.
9. The method for preparing the optical device of nano tungsten and nano tungsten oxide in high efficiency according to claim 8, wherein the width of the nano tungsten and nano tungsten oxide material film is 3-10 mm, and the thickness is 50-500 μm.
10. The method for efficiently manufacturing an optical device of nano tungsten and nano tungsten oxide according to claim 8, wherein the nano tungsten and the nano tungsten oxide have a particle size of 10 to 40 nm.
11. The method for efficiently manufacturing an optical device of nano tungsten and nano tungsten oxide according to claim 8, wherein the manufactured nano tungsten and nano tungsten oxide material can be converted into a nano tungsten trioxide material after being heat-treated at a high temperature of 400 ℃ for 1 hour.
CN201910271450.7A 2019-04-04 2019-04-04 Optical device and method for efficiently preparing nano tungsten and nano tungsten oxide Pending CN111500986A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015062022A1 (en) * 2013-10-31 2015-05-07 East China University Of Science And Technology Methods and apparatuses for producing patterned graphene
CN108648890A (en) * 2018-05-10 2018-10-12 广州大学 The preparation method of nano particle linear array resistance
CN111375897A (en) * 2018-12-29 2020-07-07 中国科学院长春光学精密机械与物理研究所 Optical device for polishing metal surface

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015062022A1 (en) * 2013-10-31 2015-05-07 East China University Of Science And Technology Methods and apparatuses for producing patterned graphene
CN108648890A (en) * 2018-05-10 2018-10-12 广州大学 The preparation method of nano particle linear array resistance
CN111375897A (en) * 2018-12-29 2020-07-07 中国科学院长春光学精密机械与物理研究所 Optical device for polishing metal surface

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