CN107195707B - Quantum dot/graphene film light detection material based on photoresponse and preparation and application thereof - Google Patents
Quantum dot/graphene film light detection material based on photoresponse and preparation and application thereof Download PDFInfo
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- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
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- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
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Abstract
The invention relates to a quantum dot/graphene film light detection material based on photoresponse and preparation and application thereof. Adding graphite oxide GO into deionized water at room temperature, stirring, performing ultrasonic dispersion to obtain GO dispersion liquid, and then performing centrifugal separation to obtain supernatant; placing the flexible material into a sand core funnel, placing the sand core funnel on a microporous filter membrane, pouring the supernatant into the sand core funnel, carrying out vacuum filtration, and then carrying out chemical reduction to obtain a graphene film taking the flexible material as a substrate; and loading a quantum dot material with photoresponse on the surface of the graphene film taking the flexible material as the substrate to obtain the graphene film. The preparation method is simple, and the prepared optical detector has high sensitivity, broadband response, flexibility and high strength, and is suitable for the field of intelligent wearability.
Description
Technical Field
The invention belongs to the field of optical detection materials and preparation and application thereof, and particularly relates to a quantum dot/graphene film optical detection material based on photoresponse and preparation and application thereof.
Background
With the advent of intelligent wearable electronics, sensor devices have the potential to play a key role in the detection of humans and their surroundings. The flexible sensing device has the advantages of being easy to process, low in cost, light in weight and excellent in impact resistance and durability, and new possibilities are provided for creating a smart wearable system. Particularly for Ultraviolet (UV), visible and Infrared (IR) light, have a variety of uses, such as missile detection, biosensing, optical communications, astronomy research, and the like.
Currently, different semiconductor materials cover these spectral ranges. Narrow bandgap inorganic semiconductor materials such as PbS, PbSe, HgTe, etc. can detect the infrared region, but their toxicity and chemical instability limit their application. Whereas wide bandgap semiconductor materials such as ZnO and GaN have only uv and deep uv optical properties. Therefore, there is an urgent need to develop a new functional material that can simultaneously cover the range of uv, visible and ir light and satisfy the requirements of flexibility and wearability.
Graphene is a new carbonaceous material with a two-dimensional honeycomb lattice structure formed by tightly stacking single-layer carbon atoms, and has the advantages of excellent mechanical strength, high carrier mobility, capability of covering the light absorption range from ultraviolet to far infrared and the like, so that the graphene is always recognized as a promising optoelectronic material for a flexible broadband photodetector. However, the photoresponse of graphene photodetectors has been limited to a few milliamps per watt due to the zero bandgap structure of graphene, and the light absorption rate of single-layer graphene is very low (2.3%), which have all seriously hindered the application of graphene in optoelectronic devices. Therefore, by combining graphene with a material having excellent light absorption, it is currently most urgently required to strive for designing a new photodetector.
Disclosure of Invention
The invention aims to solve the technical problem of providing a quantum dot/graphene film optical detection material based on optical response and preparation and application thereof.
The invention relates to a quantum dot/graphene film optical detection material based on photoresponse, which sequentially comprises the following components from bottom to top: the device comprises a substrate layer, a response transmission double-function layer and an enhanced response layer; wherein the base layer is made of flexible material; the response transmission double-function layer is made of a material with electric conduction and light response; the enhanced response layer material is a photoresponse quantum dot material.
The flexible material is a PET film or cotton cloth; the material with electric conduction and photoresponse is graphene; the light-responsive quantum dot material is one or more of ZnO, CdSe, undoped graphene quantum dots and sulfur-nitrogen co-doped graphene quantum dots.
Preferably, the flexible material is cotton cloth; according to the invention, cotton cloth is preferably selected as a substrate, so that the strength is higher, and the cotton cloth is less corroded by HI reduction;
materials with electrical conductivity and photoresponse can be selected from, but are not limited to, conductive polymers, preferably rGO, which is chosen as a response-transporting bifunctional layer because rGO can not only be electrically conductive but also have a broad light absorption range.
The preferred photo-responsive quantum dot material is a sulfur and nitrogen co-doped graphene quantum dot, preferably a sulfur and nitrogen co-doped graphene quantum dot (S, N-GQDs), which has a wider light absorption range compared to undoped graphene quantum dots, and
the preparation method has the advantages of no toxicity, good biocompatibility and the like, and meets the requirements of the wearable field.
The invention discloses a preparation method of a quantum dot/graphene film light detection material based on photoresponse, which comprises the following steps:
(1) preparing a graphene film with a flexible material as a substrate:
adding graphite oxide GO into deionized water at room temperature, stirring, performing ultrasonic dispersion to obtain GO dispersion liquid, and then performing centrifugal separation to obtain supernatant; placing the flexible material into a sand core funnel, placing the sand core funnel on a microporous filter membrane, pouring the supernatant into the sand core funnel, carrying out vacuum filtration, and then carrying out chemical reduction to obtain a graphene film taking the flexible material as a substrate;
(2) preparation of the enhanced response layer:
and loading a quantum dot material with photoresponse on the surface of the graphene film taking the flexible material as the substrate to obtain the quantum dot/graphene film photodetection material based on photoresponse.
The concentration of the GO dispersion liquid in the step (1) is 0.5-3 mg/mL, and the centrifugal separation speed is 2000-5000 r/min.
The flexible material in the step (1) is a pretreated flexible material, and specifically comprises the following steps: alternately cleaning with ethanol and deionized water, cleaning with hydrochloric acid, performing ultrasonic treatment, alternately cleaning with ethanol and deionized water, and vacuum drying.
The cleaning is carried out by using hydrochloric acid with the concentration of 1-6 mol/L, and the ultrasonic time is 1-8 h; the vacuum drying temperature is 40-70 ℃, and the drying time is 4-8 h.
The chemical reduction in the step (1) is as follows: and chemically reducing by using hydroiodic acid for 1-3 h.
The load in the step (2) is as follows: the loading was carried out by spraying, doctor blading, spin coating, vapour deposition.
The invention discloses application of a quantum dot/graphene film optical detection material based on photoresponse, and the quantum dot/graphene film optical detection material based on photoresponse is used for intelligent wearable equipment.
The preparation method of the sulfur and nitrogen co-doped graphene quantum dots (S, N-GQDs) is preferably selected, and specifically comprises the following steps: weighing citric acid and thiourea, dissolving in a solvent (dimethyl formamide DMF), transferring the solution to a polytetrafluoroethylene lining, putting the polytetrafluoroethylene lining into a stainless steel autoclave for hydrothermal reaction at the temperature of 150-200 ℃ for 6-10 hours, cooling to room temperature after the hydrothermal reaction is finished, and centrifuging to obtain sulfur-nitrogen co-doped graphene quantum dots S, N-GQDs; wherein the molar ratio of the citric acid to the thiourea is 1: 3; the centrifugation speed is 5000-12000 r/min, and the centrifugation time is 5-30 min.
Advantageous effects
(1) The preparation method is simple, and has low requirements on production equipment;
(2) the prepared sulfur-nitrogen co-doped graphene quantum dot/graphene film optical detection material has good flexibility, high responsivity and detection range, and can be used in the field of intelligent wearability.
Drawings
FIG. 1 is a TEM image of S, N-GQDs prepared in example 1;
FIG. 2 is an SEM image of a cotton-based graphene film prepared in example 1;
fig. 3 is a schematic diagram of the sulfur-nitrogen co-doped graphene quantum dot/graphene thin film light detection material prepared in example 1;
fig. 4 is a time-current curve of the sulfur-nitrogen co-doped graphene quantum dot/graphene film photodetection material prepared in example 1; fig. 5 is a wavelength-responsivity curve of the sulfur-nitrogen co-doped graphene quantum dot/graphene thin film photodetection material prepared in example 1.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The drawings are merely schematic representations of idealized embodiments of the present invention wherein the thicknesses of selected layers and regions are exaggerated as appropriate for the purpose of clearly illustrating the structure of the devices to which the present invention relates, and which, as a schematic representation, should not be considered to reflect strictly the geometric relationships of scale. In addition, the illustrated embodiments of the invention should not be considered limited to the particular shapes of regions illustrated in the drawings. The drawings described herein are for illustration in general and should not be construed to limit the scope of the present invention.
Example 1
Preparation of S, N-GQDs: 1.26g (6mmol) of citric acid and 1.36g (18mmol) of thiourea were weighed into 30mL of DMF at room temperature, stirred until completely dissolved, and then the solution was transferred to a 50mL inner polytetrafluoroethylene liner, put into a stainless steel autoclave, and subjected to hydrothermal reaction in an oven at 180 ℃ for 8h, after completion of the reaction, cooled to room temperature, and centrifuged at 12000 rpm for 15 minutes to obtain S, N-GQDs. FIG. 1 is a TEM photograph of S, N-GQDs synthesized in this example, and it can be seen that: the S, N-GQDs are dispersed uniformly without agglomeration, and the size is about 5 nm.
Preparing a graphene film with cotton cloth as a substrate: weighing 30mg of GO to dissolve in 30mL of deionized water, and ultrasonically dispersing for 2h by using an ultrasonic cleaner to obtain a uniform 1mg/mL GO dispersion liquid. The resulting brown GO dispersion was then centrifuged at 3000 rpm to remove the non-exfoliated large GO, and the centrifuged supernatant was taken. And (3) placing the pretreated cotton cloth into a sand core funnel, placing the cotton cloth on a microporous filter membrane, pouring supernatant of GO dispersion liquid obtained after centrifugal separation into the sand core funnel, and performing vacuum filtration to obtain the graphite oxide film loaded on the cotton cloth substrate. And reducing by using hydroiodic acid for 12 hours to prepare the graphene film with the cotton cloth as the substrate. Fig. 2 is an SEM image of the cotton-based graphene film synthesized in this example, and it can be seen that: graphene forms a dense film on the surface of cotton cloth.
The spraying process comprises the following steps: 10mg of S, N-GQDs was weighed and dissolved in 5mL of deionized water, and ultrasonically dispersed for 30min using an ultrasonic cleaner to obtain a uniform 2mg/mL dispersion of S, N-GQDs. The graphene film is placed on a 70 ℃ hot table, a spray pen with a nozzle diameter of 0.2mm is used, and the vertical height of the nozzle from the graphene film is 5 cm. And after the spraying process is finished, the sulfur-nitrogen co-doped graphene quantum dot/graphene film light detection material taking cotton cloth as a substrate is obtained. Fig. 3 is a time-current curve of the sulfur-nitrogen co-doped graphene quantum dot/graphene film photodetection material synthesized in this embodiment, and it can be seen that when light is irradiated to the material, the current is significantly increased, and after the light is removed, the current immediately returns to the initial value. It can also be seen that the material has a fast photoresponse time and excellent cycling stability. FIG. 4 reflects the trend of responsivity change of the material under different wavelengths, and it can be seen that the optical detection material has good response in the wavelength range of 300-800nm, and the maximum response is about 400 nm.
Example 2
Preparation of S, N-GQDs: 1.26g (6mmol) of citric acid and 1.36g (18mmol) of thiourea were weighed into 30mL of DMF at room temperature, stirred until completely dissolved, and then the solution was transferred to a 50mL inner polytetrafluoroethylene liner, put into a stainless steel autoclave, and subjected to hydrothermal reaction in an oven at 180 ℃ for 8h, after completion of the reaction, cooled to room temperature, and centrifuged at 12000 rpm for 15 minutes to obtain S, N-GQDs.
Preparing a graphene film with cotton cloth as a substrate: 60mg of GO is weighed and dissolved in 30mL of deionized water, and an ultrasonic cleaner is used for ultrasonic dispersion for 2 hours to obtain a uniform GO dispersion liquid with the concentration of 2 mg/mL. The resulting brown GO dispersion was then centrifuged at 3000 rpm to remove the non-exfoliated large GO, and the centrifuged supernatant was taken. And (3) placing the pretreated cotton cloth into a sand core funnel, placing the cotton cloth on a microporous filter membrane, pouring supernatant of GO dispersion liquid obtained after centrifugal separation into the sand core funnel, and performing vacuum filtration to obtain the graphite oxide film loaded on the cotton cloth substrate. And reducing by using hydroiodic acid for 12 hours to prepare the graphene film with the cotton cloth as the substrate.
The spraying process comprises the following steps: 10mg of S, N-GQDs was weighed and dissolved in 5mL of deionized water, and ultrasonically dispersed for 30min using an ultrasonic cleaner to obtain a uniform 2mg/mL dispersion of S, N-GQDs. The graphene film is placed on a 70 ℃ hot table, a spray pen with a nozzle diameter of 0.2mm is used, and the vertical height of the nozzle from the graphene film is 5 cm. And after the spraying process is finished, the sulfur-nitrogen co-doped graphene quantum dot/graphene film light detection material taking cotton cloth as a substrate is obtained.
Example 3
Preparation of S, N-GQDs: 1.26g (6mmol) of citric acid and 1.36g (18mmol) of thiourea were weighed into 30mL of DMF at room temperature, stirred until completely dissolved, and then the solution was transferred to a 50mL inner polytetrafluoroethylene liner, put into a stainless steel autoclave, and subjected to hydrothermal reaction in an oven at 180 ℃ for 8h, after completion of the reaction, cooled to room temperature, and centrifuged at 12000 rpm for 15 minutes to obtain S, N-GQDs.
Preparing a graphene film with cotton cloth as a substrate: weighing 30mg of GO to dissolve in 30mL of deionized water, and ultrasonically dispersing for 2h by using an ultrasonic cleaner to obtain a uniform 1mg/mL GO dispersion liquid. The resulting brown GO dispersion was then centrifuged at 3000 rpm to remove the non-exfoliated large GO, and the centrifuged supernatant was taken. And (3) placing the pretreated cotton cloth into a sand core funnel, placing the cotton cloth on a microporous filter membrane, pouring supernatant of GO dispersion liquid obtained after centrifugal separation into the sand core funnel, and performing vacuum filtration to obtain the graphite oxide film loaded on the cotton cloth substrate. And reducing by using hydroiodic acid for 12 hours to prepare the graphene film with the cotton cloth as the substrate.
The spraying process comprises the following steps: 20mg of S, N-GQDs was weighed and dissolved in 5mL of deionized water, and ultrasonically dispersed for 30min using an ultrasonic cleaner to obtain a uniform 4mg/mL dispersion of S, N-GQDs. The graphene film is placed on a 70 ℃ hot table, a spray pen with a nozzle diameter of 0.2mm is used, and the vertical height of the nozzle from the graphene film is 5 cm. And after the spraying process is finished, the sulfur-nitrogen co-doped graphene quantum dot/graphene film light detection material taking cotton cloth as a substrate is obtained.
Claims (8)
1. A quantum dot/graphene film light detection material based on photoresponse is characterized in that: the probe material includes: the device comprises a substrate layer, a response transmission double-function layer and an enhanced response layer; wherein the base layer is made of flexible material; the response transmission double-function layer is made of a material with electric conduction and light response; the enhanced response layer material is a photo-response quantum dot material; wherein the flexible material is a PET film or cotton cloth; the material with electric conduction and photoresponse is graphene; the photoresponse quantum dot material is sulfur and nitrogen co-doped with the graphene quantum dot.
2. The preparation method of the photoresponse-based quantum dot/graphene thin film light detection material according to claim 1, comprising the following steps of:
adding graphite oxide GO into deionized water at room temperature, stirring, performing ultrasonic dispersion to obtain GO dispersion liquid, and then performing centrifugal separation to obtain supernatant; placing the flexible material into a sand core funnel, placing the sand core funnel on a microporous filter membrane, pouring the supernatant into the sand core funnel, carrying out vacuum filtration, and then carrying out chemical reduction to obtain a graphene film taking the flexible material as a substrate;
and (2) loading a quantum dot material with photoresponse on the surface of the graphene film taking the flexible material as the substrate to obtain the quantum dot/graphene film photodetection material based on photoresponse.
3. The preparation method of the quantum dot/graphene film light detection material based on the photoresponse as claimed in claim 2, characterized in that: the concentration of the GO dispersion liquid in the step (1) is 0.5-3 mg/mL, and the centrifugal separation speed is 2000-5000 r/min.
4. The preparation method of the quantum dot/graphene film light detection material based on the photoresponse as claimed in claim 2, characterized in that: the flexible material in the step (1) is a pretreated flexible material, and specifically comprises the following steps: alternately cleaning with ethanol and deionized water, cleaning with hydrochloric acid, performing ultrasonic treatment, alternately cleaning with ethanol and deionized water, and vacuum drying.
5. The preparation method of the quantum dot/graphene film light detection material based on the photoresponse, according to claim 4, is characterized in that: the cleaning with hydrochloric acid is performed with hydrochloric acid with the concentration of 1-6 mol/L, and the ultrasonic time is 1-8 h; the vacuum drying temperature is 40-70 ℃, and the drying time is 4-8 h.
6. The preparation method of the quantum dot/graphene film light detection material based on the photoresponse as claimed in claim 2, characterized in that: the chemical reduction in the step (1) is as follows: and chemically reducing by using hydroiodic acid for 1-3 h.
7. The preparation method of the quantum dot/graphene film light detection material based on the photoresponse as claimed in claim 2, characterized in that: the load in the step (2) is as follows: the loading was carried out by spraying, doctor blading, spin coating, vapour deposition.
8. The application of the photoresponse-based quantum dot/graphene film light detection material as claimed in claim 1, wherein: the quantum dot/graphene film optical detection material based on the photoresponse is used for intelligent wearable equipment.
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| CN108767051B (en) * | 2018-06-21 | 2020-11-06 | 湖北大学 | Visible light-sensitive transistor and preparation method thereof |
| CN109802043A (en) * | 2019-01-15 | 2019-05-24 | 新疆交通建设集团股份有限公司 | Nitrogen sulphur codope graphene quantum dot perovskite light-absorption layer and preparation method thereof |
| CN110148643B (en) * | 2019-06-06 | 2021-05-04 | 上海纳米技术及应用国家工程研究中心有限公司 | Construction method of semiconductor quantum dot/graphene van der waals junction flexible device |
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