阅读说明：本技术 一种基于硼烯的光热电转换薄膜器件及其制备方法 (Boron alkene-based photo-thermal-electric conversion thin film device and preparation method thereof ) 是由 鲍桥梁 吴�琳 于 2021-02-05 设计创作，主要内容包括：本发明公开了一种光热电转换薄膜器件及其制备方法,涉及基于硼烯的光热电转换薄膜器件及其制备方法领域,包括温差发电层、位于温差发电层一侧的光吸收层,和位于所述温差发电层另一侧的散热层,所述光吸收层由具有周期性纳米结构的硼烯薄膜构成,所述温差发电层为Bi_2Te_3或Sb_2Te_3；所述温差发电层在厚度方向形成温度梯度,产生电势差。硼烯作为本征宽带吸收的等离激元材料,其二维结构易于组装和加工,是理想的光热转换材料。解决宽谱光热转换器件加工难度大、成本高的问题。(The invention discloses a photothermal-electric conversion thin film device and a preparation method thereof, and relates to the field of a boron-alkene-based photothermal-electric conversion thin film device and a preparation method thereof 2 Te 3 Or Sb 2 Te 3 (ii) a The thermoelectric generation layer forms a temperature gradient in the thickness direction to generate a potential difference. The boron alkene is taken as a plasmon material for intrinsic broadband absorption, the two-dimensional structure of the boron alkene is easy to assemble and process, and the boron alkene is an ideal photo-thermal conversion material. To solve the problem of widthThe problems of high processing difficulty and high cost of the spectrum photothermal conversion device.)

1. A borolene-based photothermal-to-electrical conversion thin film device, comprising:

thermoelectric generation layer, be located the light absorption layer of thermoelectric generation layer one side, and be located the heat dissipation layer of thermoelectric generation layer opposite side, the light absorption layer comprises boron alkene film, thermoelectric generation layer is Bi₂Te₃Or Sb₂Te₃(ii) a The thermoelectric generation layer forms a temperature gradient in the thickness direction, and generates a potential difference through a thermoelectric effect.

2. The borolene-based photothermal conversion thin film device according to claim 1, wherein a heat conductive layer is provided between the light absorbing layer and the thermoelectric generation layer.

3. The thin film device of claim 2, wherein the thermally conductive layer is a thin film material of gold, silver, copper, silicon, boron nitride, graphene, Polyimide (PI), or polyethylene terephthalate (PET).

4. The borefine-based photothermal conversion thin film device according to claim 1, wherein said heat dissipation layer is a thin film structure having heat dissipation channels or a heat dissipation coating having a function of enhancing heat dissipation.

5. The bornene-based photothermal conversion thin film device according to any of claims 1-4, wherein the light absorbing layer has periodic nanostructures with increased surface area and light absorption, and the periodic nanostructures are wave-shaped, square-shaped, or triangular-shaped.

6. A preparation method of a boron alkene-based photo-thermal-electric conversion thin film device is characterized in that,

step 1) selecting the area of 0.25cm²To 25cm²Bi of 1 to 200 μm thickness₂Te₃Or Sb₂Te₃The thin film material is used as a thermoelectric generation layer; constructing a heat conduction layer on the surface of one side, wherein the thickness of the heat conduction layer is 50nm to 10 mu m; the other side of the thermoelectric generation layer is compounded with the heat dissipation layer;

step 2) proportioning a boron alkene nano material dispersion liquid with the concentration of 0.1mg/mL to 10.0mg/mL, and then uniformly coating the boron alkene nano material dispersion liquid on the surface of the film with the heat conduction layer;

and 3) writing the periodic nanostructure of the boron-containing alkene film by femtosecond laser etching or ultraviolet exposure to form a light absorption layer.

Technical Field

The invention designs a photothermal-electric conversion thin film device and a preparation method thereof, in particular to a boron-alkene-based photothermal-electric conversion thin film device and a preparation method thereof.

Background

A photothermal detector is a detector based on two fundamental energy conversion processes of photothermal conversion and thermoelectric conversion. When light is irradiated on one end of the thermoelectric material, light energy is first converted into heat energy through photo-thermal conversion, thereby establishing a temperature difference (Δ T) across the thermoelectric material. Driven by the temperature difference, the carriers can diffuse to the cold end (i.e. the Seebeck effect in thermoelectric conversion), and an electric potential difference is established between the two ends of the material. The photothermal detector has the advantages of self power supply, no refrigeration, wide response wavelength range and the like, and has important application prospect in military and civil fields such as optical detection, infrared thermal imaging, temperature monitoring and the like. The responsivity of the photo-thermal detector is proportional to the Seebeck coefficient (S) of the material and the Δ T across the material. In the photothermographic detector that has been commercialized at present, p-type and n-type thermoelectric films constitute a thermoelectric pair, and a plurality of thermoelectric units constitute a thermoelectric stack around an absorption layer. The absorption layer absorbs light and generates heat, and a temperature difference is generated on two sides of the thermopile, so that voltage response is generated.

The multilayer composite material formed by the material with high photothermal conversion capability and the traditional thermoelectric material realizes high-efficiency photothermal conversion, and is one of the main targets of the current research on high-performance photothermal devices. In recent years, photothermal conversion thin films based on metamaterials, which are artificial structural materials composed of sub-wavelength unit arrays and have excellent electromagnetic properties, have been widely researched and developed in many fields. The metamaterial wave-absorbing material can be generally divided into a narrow-band light-absorbing material and a wide-band light-absorbing material. The narrow-band metamaterial mainly depends on a resonance structure interacted with light with a specific frequency, and the broadband metamaterial depends on a structure with the electromagnetic response independent of the frequency, so that the light absorption characteristic of a wide band is realized.

At present, a wide-spectrum photothermal conversion device is mainly of a metal micro-nano structure, and the inherent defect of narrow-band absorption of the wide-spectrum photothermal conversion device is overcome through the optical coupling effect between plasmon micro-nano structures. However, the complex metal nanostructure has great processing difficulty and high cost, so that the practical application thereof is greatly limited. Compared with the traditional metal material, the two-dimensional material surface plasmon represented by graphene and black phosphorus has excellent performances of high optical field compression, easy tuning and the like, but the resonance frequency of the two-dimensional material surface plasmon is low due to limited carrier concentration, and the two-dimensional material surface plasmon can only occur in the middle infrared to terahertz wave bands. In recent years, a new two-dimensional material, borolene, has received much attention from researchers. Boron is a neighboring element of carbon and has chemical similarity with carbon, but the special electronic structure (valence electron number is 3, and valence electron layer cannot be filled in bonding time) enables boron to have shorter covalent bond radius and rich valence state, and diversified structure and unique property. Bulk boron is non-metallic, but theory predicts that boronenes are metallic, with the arrangement of vacancies in their triangular lattice leading to anisotropic and diverse electronic properties. More importantly, theoretical calculation results show that the boron alkene has higher intrinsic carrier concentration and plasmon resonance frequency than the graphene, and can excite surface plasmons in a visible near-infrared band. The boron alkene is taken as a plasmon material for intrinsic broadband absorption, the two-dimensional structure of the boron alkene is easy to assemble and process, and the boron alkene is an ideal photo-thermal conversion material.

Disclosure of Invention

The invention provides a boron alkene-based photo-thermal-electric conversion thin-film device and a preparation method thereof, and solves the problems of high processing difficulty and high cost of a wide-spectrum photo-thermal conversion device.

The invention adopts the following technical scheme that the photothermal-electric conversion thin film device based on the boron alkene and the preparation method thereof comprise the following steps:

the thermoelectric generation layer, be located the light absorption layer of thermoelectric generation layer one side, and be located the heat dissipation layer of thermoelectric generation layer opposite side, the light absorption layer comprises boron alkene film, and the thermoelectric generation layer is Bi₂Te₃Or Sb₂Te₃(ii) a The thermoelectric generation layer forms a temperature gradient in the thickness direction, and generates a potential difference by a thermoelectric effect.

Further, the light absorbing layer and the thermoelectric generation layer have a heat conductive layer therebetween.

Further, the heat conductive layer is a thin film material of gold, silver, copper, silicon, boron nitride, graphite, Polyimide (PI), or polyethylene terephthalate (PET).

Further, the heat dissipation layer is a thin film structure with heat dissipation channels or a heat dissipation coating with enhanced heat dissipation function, and is made of a material such as copper, graphene or boron nitride.

Further, the light absorbing layer has periodic nanostructures increasing surface area and light absorption rate, the periodic nanostructures being wave-shaped, square-shaped, or triangular-shaped.

A method for preparing a boron alkene-based photo-thermal-electric conversion thin-film device,

step 1) selecting the area of 0.25cm²To 25cm²Bi of 1 to 200 μm thickness₂Te₃Or Sb₂Te₃The thin film material is used as a thermoelectric generation layer. Gold, silver, copper, silicon or boron nitride, graphene, Polyimide (PI), polyethylene terephthalate (PET) is evaporated on the surface of one side to form a heat conductive layer having a thickness of 50nm to 10 μm. The other side of the thermoelectric generation layer is compounded with the heat dissipation layer;

step 2) proportioning a boron alkene nano material dispersion liquid with the concentration of 0.1mg/mL to 10.0mg/mL, and then uniformly coating the boron alkene nano material dispersion liquid on the surface of the film with the heat conduction layer;

and 3) writing the periodic nanostructure of the boron-containing alkene film by femtosecond laser etching or ultraviolet exposure to form a light absorption layer.

Compared with the prior art, the photothermal-electric conversion thin film device based on the boron alkene and the preparation method thereof have the beneficial effects that:

(1) the processing is simple, and the two-dimensional structure is easy to assemble.

(2) Can realize the manufacture of ultrathin photothermal-electric conversion thin-film devices of micron or even submicron level.

Drawings

FIG. 1 is a schematic diagram of a square wave-shaped structure of a boron-ene based photothermal-electric conversion thin film device of the present invention;

FIG. 2 is a high resolution transmission electron microscope image of a borolene material in a square waveform structure of a borolene-based photothermal-electrical conversion thin film device of the present invention;

FIG. 3 is a transmission electron microscopy energy spectrum of a borolene material with a square waveform structure of a borolene-based photothermal-electrical conversion thin-film device according to the present invention;

FIG. 4 is a schematic diagram of a full-solar spectrum test of a borolene based photothermal-to-electrical conversion thin film device of the present invention;

FIG. 5 is a graph showing the test of the photothermal conversion performance of the boron-ene based photothermal-electric conversion thin film device of the present invention in a square waveform configuration;

FIG. 6 is a schematic illustration of the waved structure of a borolene based photothermal-to-electrical conversion thin film device of the present invention;

FIG. 7 is a high resolution transmission electron microscope image of the waved structure of a boron-ene based photothermal-electric conversion thin film device of the present invention;

FIG. 8 is a diagram showing a test of photothermal conversion performance of a waved structure of a boron-ene-based photothermal-electric conversion thin film device according to the present invention;

FIG. 9 is a schematic representation of a delta-waveform structure for a boron-ene based photothermal-to-electrical conversion thin film device of the present invention;

FIG. 10 is a high resolution transmission electron microscope image of a triangular waveform configuration of a boracene-based photothermal-to-electrical conversion thin film device of the present invention;

FIG. 11 is a diagram illustrating the photo-thermal conversion performance of a triangular waveform structure of a boron-ene-based photo-thermal-electric conversion thin-film device according to the present invention;

wherein: 1: light absorbing layer, 2: thermoelectric generation layer, 3: heat dissipation layer, 4: a thermally conductive layer.

Detailed Description

The following detailed description of the specific implementation steps is provided in conjunction with the accompanying drawings:

example one

As shown in fig. 1, the present invention is an embodiment of a boron-alkene-based photothermal-to-electrical conversion thin film device and a method for manufacturing the same, and the device is manufactured by the following method:

step 1) selecting the area of 0.25cm²Bi of 1 μm thickness₂Te₃The material was used as a thermoelectric generation layer (purchased from Sigma-Aldrich, cat # and Specification: 733482-5G). And gold is evaporated on the surface of one side to form a heat conduction layer, and the thickness of the heat conduction layer is 50 nm. The other side of the thermoelectric generation layer is bonded with a heat dissipation layer by adopting heat-conducting silica gel, and the heat dissipation layer is made of 50 mu m copper;

step 2) proportioning a boron alkene nano material dispersion liquid with the concentration of 0.1mg/mL, and then uniformly coating the boron alkene nano material dispersion liquid on the surface of the film with the heat conduction layer; as shown in fig. 2, the transmission electron microscopy image shows an ultrathin nanosheet structure and clear lattice fringes, reflecting the good crystalline properties of the borolene nanomaterial. As shown in FIG. 3, it can be seen that the boron element is uniformly distributed throughout the entire flake, and the shell layer is observed to be composed of C and O elements. The presence of small amounts of C and O may be due to surface contamination by exposure to air and carbon films;

and 3) writing the periodic nanostructure of the boron-containing alkene film by femtosecond laser etching or ultraviolet exposure to form a light absorption layer.

As shown in fig. 1, the resulting photothermal-to-electrical conversion thin film device includes: the temperature difference power generation layer, the light absorption layer positioned on one side of the temperature difference power generation layer and the heat dissipation layer positioned on the other side of the temperature difference power generation layer are arranged, and the light absorption layer is formed by a boron-olefin film with a periodic nano structure and is in a square waveform, so that the surface area and the light absorption rate are increased; the thermoelectric generation layer forms a temperature gradient in the thickness direction to generate a potential difference.

The thermally conductive layer in some embodiments may also be coated with silver, copper, silicon, or a thin film material of boron nitride, graphite, Polyimide (PI), or polyethylene terephthalate (PET), with the same or similar effect.

The conversion performance test of the photothermal-electric conversion thin film device was performed according to the test method shown in fig. 4. The photothermal conversion capability of the device is monitored by using an infrared thermometer (professional 890, de Testo corporation), under the infrared illumination condition with the wavelength of 980 nm, when the illumination power reaches 100 mW, the temperature of the device can reach 165 ℃ (as shown in FIG. 5), and the current value which can be output by the device at this time is 0.12 mA.

Example two

As shown in fig. 6, the present invention is an embodiment of a boron alkene-based photothermal-electric conversion thin film device and a method for manufacturing the same, and the device is manufactured by the following method:

step 1) selecting a 25cm area²Sb having a thickness of 15 μm₂Te₃The thin film material was used as a thermoelectric layer (purchased from Sigma-Aldrich, cat # and Specification: 733490-1G). Silver is evaporated on the surface of one side to form a heat conducting layer, the thickness of which is 10 μm. The other side of the thermoelectric generation layer is bonded with a heat dissipation layer by adopting heat-conducting silica gel, and the heat dissipation layer is graphene with the thickness of 1 mu m;

step 2) proportioning a boron alkene nano material dispersion liquid with the concentration of 1.0mg/mL, and then uniformly coating the boron alkene nano material dispersion liquid on the surface of the film with the heat conduction layer; as shown in fig. 7, it can be seen that boron alkene nanoplatelets form a small amount of aggregates, but still have good crystalline properties;

and 3) writing the periodic nano array structure of the boron-alkene film by femtosecond laser etching or ultraviolet exposure to form a light absorption layer.

As shown in fig. 6, the resulting photothermal-to-electrical conversion thin film device includes: the solar cell comprises a temperature difference power generation layer, a light absorption layer and a heat dissipation layer, wherein the light absorption layer is positioned on one side of the temperature difference power generation layer, the heat dissipation layer is positioned on the other side of the temperature difference power generation layer, and the light absorption layer is formed by a boron-olefin film with a periodic nano structure, is wavy and increases the surface area and the light absorption rate; the thermoelectric generation layer forms a temperature gradient in the thickness direction to generate a potential difference.

The conversion performance test of the photothermal-electric conversion thin film device was performed according to the test method shown in fig. 4. The photothermal conversion capability of the device is monitored by using an infrared thermometer (professional 890, de tegos), under the infrared illumination condition with the wavelength of 980 nm, when the illumination power reaches 100 mW, the temperature of the device can reach 161 ℃ (as shown in FIG. 8), and the current value which can be output by the device at this time is 0.11 mA.

EXAMPLE III

As shown in fig. 9, the present invention is an embodiment of a boron alkene-based photothermal-electric conversion thin film device and a method for manufacturing the same, and the device is manufactured by the following method:

step 1) selecting a 25cm area²Sb of 200 μm thickness₂Te₃The thin film material was used as a thermoelectric layer (purchased from Sigma-Aldrich, cat # and Specification: 733490-1G). One side of the thermoelectric generation layer is bonded with a heat dissipation layer by adopting heat-conducting silica gel, and the heat dissipation layer is 16 mu m of boron nitride;

step 2), proportioning a boron-alkene nano material dispersion liquid with the concentration of 10.0mg/mL, and then uniformly coating the boron-alkene nano material dispersion liquid on the other side of the thermoelectric generation layer; as shown in fig. 10, it can be seen that the lateral size distribution of the dispersed boron-containing alkene nanomaterial sheet is uniform, approximately between 8 and 30 nm;

and 3) writing the periodic nano array structure of the boron-alkene film by femtosecond laser etching or ultraviolet exposure to form a light absorption layer.

As shown in fig. 9, the resulting photothermal-to-electrical conversion thin film device includes: the solar cell comprises a temperature difference power generation layer, a light absorption layer and a heat dissipation layer, wherein the light absorption layer is positioned on one side of the temperature difference power generation layer, the heat dissipation layer is positioned on the other side of the temperature difference power generation layer, and the light absorption layer is formed by a boron-olefin film with a periodic nano structure and is in a triangular waveform, so that the surface area and the light absorption rate are increased; the thermoelectric generation layer forms a temperature gradient in the thickness direction to generate a potential difference.

The conversion performance test of the photothermal-electric conversion thin film device was performed according to the test method shown in fig. 4. The photothermal conversion capability of the device is monitored by using an infrared thermometer (professional 890, de tegos), under the infrared illumination condition with the wavelength of 980 nm, when the illumination power reaches 100 mW, the temperature of the device can reach 150 ℃ (as shown in FIG. 11), and the current value which can be output by the device at this time is 0.08 mA.