阅读说明：本技术 一种硫化铜/氧化锌异质结柔性透明自驱动紫外光电探测器 (Copper sulfide/zinc oxide heterojunction flexible transparent self-driven ultraviolet photoelectric detector ) 是由 李谊 王跃 张�杰 杨秋月 韦晓静 马延文 于 2021-06-21 设计创作，主要内容包括：本发明涉及一种硫化铜/氧化锌异质结柔性透明自驱动紫外光电探测器,包括柔性透明衬底、硫化铜/氧化锌异质结活性层和电极层。将铜纳米线进行硫化处理,得到p型硫化铜层包裹的铜纳米线；在p型硫化铜层表面生长n型氧化锌纳米线层后制得硫化铜/氧化锌p-n异质结纳米线；将硫化铜/氧化锌p-n异质结纳米线喷涂于柔性透明衬底上,制得硫化铜/氧化锌p-n异质结薄膜活性层；在硫化铜/氧化锌p-n异质结薄膜活性层上沉积叉指结构透明电极,获得柔性透明自驱动紫外光电探测器。该紫外光电探测器的响应时间小于20 ms,透光度在80%以上,在不施加额外电压条件下显示出良好的紫外传感性能。(The invention relates to a copper sulfide/zinc oxide heterojunction flexible transparent self-driven ultraviolet photoelectric detector which comprises a flexible transparent substrate, a copper sulfide/zinc oxide heterojunction active layer and an electrode layer. Carrying out vulcanization treatment on the copper nanowire to obtain a copper nanowire wrapped by a p-type copper sulfide layer; growing an n-type zinc oxide nanowire layer on the surface of the p-type copper sulfide layer to prepare a copper sulfide/zinc oxide p-n heterojunction nanowire; spraying copper sulfide/zinc oxide p-n heterojunction nanowires on a flexible transparent substrate to obtain a copper sulfide/zinc oxide p-n heterojunction film active layer; and depositing an interdigital structure transparent electrode on the copper sulfide/zinc oxide p-n heterojunction film active layer to obtain the flexible transparent self-driven ultraviolet photoelectric detector. The response time of the ultraviolet photoelectric detector is less than 20 ms, the transmittance is more than 80%, and the ultraviolet photoelectric detector shows good ultraviolet sensing performance under the condition of not applying additional voltage.)

1. The utility model provides a flexible transparent self-driven ultraviolet photoelectric detector of copper sulfide/zinc oxide heterojunction which characterized in that: the copper-zinc-sulfide heterojunction solar cell comprises a substrate, a copper sulfide/zinc oxide p-n heterojunction active layer and an electrode layer from inside to outside in sequence;

the substrate is sprayed with a copper sulfide/zinc oxide p-n heterojunction active layer with a grid structure,

and forming an electrode layer on the copper sulfide/zinc oxide p-n heterojunction active layer through an interdigital structure formed by mask plate patterning spraying deposition, and finally obtaining the self-driven flexible ultraviolet photoelectric detector.

2. The flexible transparent ultraviolet photodetector of copper sulfide/zinc oxide nanostructure of claim 1, characterized in that: the substrate is made of transparent flexible materials, and the transparent flexible materials comprise PET, PDMS, PI and TPU.

3. The flexible transparent self-driven ultraviolet photodetector of copper sulfide/zinc oxide heterojunction as claimed in claim 1, wherein: the copper sulfide/zinc oxide p-n heterojunction active layer is a grid structure formed by spraying copper sulfide/zinc oxide p-n heterojunction nanowires on the surface of a flexible transparent substrate.

4. The flexible transparent ultraviolet photodetector of copper sulfide/zinc oxide nanostructure of claim 3, characterized in that: the copper sulfide/zinc oxide p-n heterojunction nanowire is obtained by performing vulcanization treatment on a copper nanowire to prepare a p-type copper sulfide layer and growing an n-type branched zinc oxide layer nanowire array on the surface of the p-type copper sulfide layer.

5. The flexible transparent ultraviolet photodetector of copper sulfide/zinc oxide nanostructure according to claim 4, characterized in that: the p-type copper sulfide layer is of a thin film or nanowire structure.

6. The flexible transparent ultraviolet photodetector of copper sulfide/zinc oxide nanostructure according to claim 4, characterized in that: the thickness of the p-type copper sulfide layer is 0.3-1 mu m; the n-type zinc oxide layer is a branched nanowire array structure, is prepared by growing on the surface of the copper sulfide layer by a hydrothermal method, and has the thickness of 0.2-0.6 mu m.

7. The flexible transparent ultraviolet photodetector of copper sulfide/zinc oxide nanostructure of claim 1, characterized in that: the copper sulfide/zinc oxide p-n heterojunction active layer is of a nanowire grid structure, is deposited on the surface of the flexible transparent substrate through a spraying technology, and has the thickness of 1-2 mu m and the transmittance of more than 85 percent.

8. The flexible transparent ultraviolet photodetector of copper sulfide/zinc oxide nanostructure of claim 1, characterized in that: the electrode layer is an interdigital flexible transparent conductive film, and the sheet resistance of the electrode layer is 2-25 omega^–1。

9. The flexible transparent ultraviolet photodetector of copper sulfide/zinc oxide nanostructure of claim 8, characterized in that: the interdigital structure flexible transparent conductive film is prepared by patterning, spraying and depositing on the surface of a copper sulfide/zinc oxide p-n heterojunction active layer through a mask plate; the conductive material in the flexible transparent conductive film is gold nano-wire, silver nano-wire, copper nano-wire or carbon nano-tube.

Technical Field

The invention relates to a copper sulfide/zinc oxide heterojunction self-driven flexible transparent ultraviolet photoelectric detector, and belongs to the technical field of nano material preparation and ultraviolet photoelectric detectors.

Background

The ultraviolet photoelectric detector is a key device of a photoelectric device system, and can be widely applied to the fields of flame sensing, optical communication, environmental monitoring and the like. Portable and wearable ultraviolet photodetectors are an important development direction. The wearable ultraviolet photoelectric detector has the characteristics of flexibility, transparency, small size, light weight and the like. In addition, the self-driving function is also an important requirement of the wearable ultraviolet photoelectric detector. Therefore, the self-driven flexible transparent ultraviolet photoelectric detector attracts people's extensive attention.

The zinc oxide material has the characteristics of low cost, wide band gap (3.37 eV), large binding energy (60 meV) and the like, and is considered as an active material of an ultraviolet light detector with great prospect. Ultraviolet photodetectors based on zinc oxide materials, particularly self-driven devices, have been extensively studied. The ultraviolet photoelectric detector based on the pure zinc oxide material limits the charge transfer process in the device due to a large number of defect states in the zinc oxide material, and generally shows poor photoresponse performance. The p-n heterojunction material and the device based on the zinc oxide material have the advantages of low response time, high on-off ratio and the like, and are ideal choices of self-driven ultraviolet photodetectors. Researchers compound zinc oxide with different p-type materials such as Si, GaN, CuO, NiO and the like to prepare a plurality of p-n heterojunction materials, and construct a self-driven ultraviolet photoelectric detector. However, most of these devices are based on thin film p-n heterojunctions and electrodes, resulting in limited response speed, low transparency and poor flexibility.

Disclosure of Invention

The invention aims to provide a flexible transparent self-driven ultraviolet photoelectric detector with high response speed, high stability and high transparency, which is used for wearable electronic equipment with bending resistance, stretching resistance and transparency requirements.

The invention provides a copper sulfide/zinc oxide heterojunction flexible transparent self-driven ultraviolet photoelectric detector which sequentially comprises a substrate, a copper sulfide/zinc oxide p-n heterojunction active layer and an electrode layer from inside to outside. And a grid-structured copper sulfide/zinc oxide p-n heterojunction active layer is sprayed on the substrate, an electrode layer is formed on the copper sulfide/zinc oxide p-n heterojunction active layer through an interdigital structure formed by mask plate patterning spraying deposition, and finally the self-driven flexible transparent ultraviolet photoelectric detector device is obtained.

Further, the substrate is made of a transparent flexible material, and the transparent flexible material comprises PET, PDMS, PI and TPU.

Further, the copper sulfide/zinc oxide p-n heterojunction active layer is a grid structure formed by spraying copper sulfide/zinc oxide p-n heterojunction nano wires on the surface of the flexible transparent substrate.

Further, the copper sulfide/zinc oxide p-n heterojunction nanowire is obtained by performing vulcanization treatment on the copper nanowire to prepare a p-type copper sulfide layer, and growing an n-type branched zinc oxide layer nanowire array on the surface of the p-type copper sulfide layer.

Further, the p-type copper sulfide layer is of a thin film or nanowire structure.

Further, the thickness of the p-type copper sulfide layer is 0.3-1 μm; the n-type zinc oxide layer is a branched nanowire array structure, is prepared by growing on the surface of the copper sulfide layer by a hydrothermal method, and has the thickness of 0.2-0.6 mu m.

Furthermore, the copper sulfide/zinc oxide p-n heterojunction active layer is of a nanowire grid structure, is deposited on the surface of the flexible transparent substrate through a spraying technology, and has the thickness of 1-2 mu m and the light transmittance of more than 85 percent.

Furthermore, the electrode layer is an interdigital structure flexible transparent conductive film,the sheet resistance is 2-25 omega, sq^–1。

Furthermore, the interdigital structure flexible transparent conductive thin film is prepared by patterning, spraying and depositing on the surface of the copper sulfide/zinc oxide p-n heterojunction active layer through a mask plate; the conductive material in the flexible transparent conductive film is gold nano-wire, silver nano-wire, copper nano-wire or carbon nano-tube

Compared with the prior art, the invention adopting the technical scheme has the following technical effects: the self-driven flexible transparent ultraviolet photoelectric detector adopts copper nanowires as active materials, and copper sulfide/zinc oxide p-n heterojunction nanowires continuously growing on a substrate have the advantages of high active specific surface area, high ultraviolet absorptivity and the like. The self-driven flexible transparent ultraviolet photoelectric detector adopts the flexible transparent electrode of the one-dimensional nano material nano grid as the electrode layer, and has the advantages of high ultraviolet transmittance, good flexibility and the like. The self-driven flexible transparent ultraviolet photoelectric detector has the characteristics of short response time, high transparency and high flexibility, the response time is less than 20 ms, the transparency is more than 80%, and the performance is not obviously attenuated after being bent for 10000 times. The self-driven flexible transparent ultraviolet photoelectric detector is constructed by adopting a low-cost full-solution process, has a simple preparation process and low cost, and has good large-scale popularization and application prospects.

Drawings

Figure 1 is an SEM image of copper sulfide/zinc oxide p-n heterojunction material.

Fig. 2 is the ultraviolet light detection performance of a flexible transparent self-driven ultraviolet light detector.

Detailed Description

The invention is further described below

Example 1

(1) Growing p-type copper sulfide layer on copper nanowire

Adding 0.1 g of copper nanowire into a sulfur saturated solution of ethanol, and reacting for 8-10 h at 60 ℃ to obtain the material with the surface of the copper nanowire covered with the p-type copper sulfide film.

(2) Preparing copper sulfide/zinc oxide p-n heterojunction nanowires:

1) preparing zinc oxide seed crystal: 0.055 g of zinc acetate dihydrate was dissolved in 50 ml of ethanol to obtain a 5 mM seed solution. And dripping the crystal seed solution on the copper sulfide/copper nanowire, and heating the copper sulfide/copper nanowire in a water bath at 80 ℃ for 40 min to obtain a sample with the zinc oxide crystal seed attached on the copper sulfide/copper nanowire.

2) Preparing a zinc oxide growth solution: 1.4 g of hexamethylenetetramine and 2.98 g of zinc nitrate hexahydrate are respectively dissolved in 100 mL of deionized water; the two solutions after complete dissolution were mixed, 0.2 ml of polyethyleneimine was added, and stirring was carried out for five minutes to obtain 50 mM zinc oxide growth solution.

3) Growth of zinc oxide nanowires: adding 0.05 g of copper sulfide/copper nanowire attached with zinc oxide seed crystals into a reaction kettle filled with 200 mL of zinc oxide growth solution, and growing for 1-3 h under the water bath heating condition of 95 ℃ to obtain the copper sulfide/zinc oxide p-n heterojunction material.

(3) Construction of flexible transparent self-driven ultraviolet detector

Firstly, carrying out plasma surface treatment on a PET substrate; and then, uniformly depositing the ethanol dispersion liquid of the copper sulfide/zinc oxide p-n heterojunction nanowire on the treated PET substrate in a spraying mode to obtain the copper sulfide/zinc oxide heterojunction film with the nanowire grid structure. And finally, depositing a silver nanowire transparent electrode layer with an interdigital structure on the surface of the copper sulfide/zinc oxide heterojunction nanowire film through mask patterning to obtain the flexible transparent self-driven ultraviolet detector.

Example 2

(1) Growing a p-type copper sulfide layer on the copper nanowire: adding 0.1 g of copper nanowire into a sulfur saturated solution of ethanol, and reacting at 80 ℃ for 12-16 h to obtain the material with the surface of the copper nanowire covered with the p-type copper sulfide nanowire.

(2) Preparing copper sulfide/zinc oxide p-n heterojunction nanowires:

1) preparing zinc oxide seed crystal: 0.055 g of zinc acetate dihydrate was dissolved in 50 ml of ethanol to obtain a 5 mM seed solution. And dripping the crystal seed solution on the copper sulfide/copper nanowire, and heating the copper sulfide/copper nanowire in a water bath at 80 ℃ for 40 min to obtain a sample with the zinc oxide crystal seed attached on the copper sulfide/copper nanowire.

2) Preparing a zinc oxide growth solution: 1.4 g of hexamethylenetetramine and 2.98 g of zinc nitrate hexahydrate are respectively dissolved in 100 mL of deionized water; the two solutions after complete dissolution were mixed, 0.2 ml of polyethyleneimine was added, and stirring was carried out for five minutes to obtain 50 mM zinc oxide growth solution.

3) Growth of zinc oxide nanowires: adding 0.05 g of copper sulfide/copper nanowire attached with zinc oxide seed crystals into a reaction kettle filled with 200 mL of zinc oxide growth solution, and growing for 1-3 h under the water bath heating condition of 95 ℃ to obtain the copper sulfide/zinc oxide p-n heterojunction nanowire material.

(3) Constructing a flexible transparent self-driven ultraviolet detector: firstly, carrying out plasma surface treatment on a PET substrate; and then, uniformly depositing the ethanol dispersion liquid of the copper sulfide/zinc oxide p-n heterojunction nanowire material on the treated PET substrate in a spraying mode to obtain the copper sulfide/zinc oxide heterojunction film with the nanowire grid structure. And finally, depositing a silver nanowire transparent electrode layer with an interdigital structure on the surface of the copper sulfide/zinc oxide heterojunction nanowire film through mask patterning to obtain the flexible transparent self-driven ultraviolet detector.

In the preparation process, the transparent flexible material comprises PET, PDMS, PI and TPU. The conductive material in the flexible transparent conductive film can be gold nanowires, silver nanowires, copper nanowires or carbon nanotubes.

The invention has various embodiments, and all technical solutions formed by adopting equivalent transformation or equivalent transformation are within the protection scope of the invention.