阅读说明：本技术 一种柔性日盲紫外光电探测器及其制备方法 (Flexible solar blind ultraviolet photoelectric detector and preparation method thereof ) 是由 王顺利 郭道友 孙翰林 于 2019-11-17 设计创作，主要内容包括：本发明涉及一种柔性日盲紫外光电探测器及其制备方法，所述探测器包括柔性衬底、位于柔性衬底上的β?Ga<Sub>2</Sub>O<Sub>3</Sub>纳米线和位于所述β?Ga<Sub>2</Sub>O<Sub>3</Sub>纳米线上的银电极。本发明制备的光电探测器具有良好的日盲紫外光响应。同时，光电探测器具有良好的稳定性和重复性，在不影响其性能的情况下实现不同程度的弯曲。本发明方法工艺简单，产品性能优异，可以实现工业化生产，在未来柔性光电探测器原材料生产中具有巨大的应用前景。(The invention relates to a flexible solar blind ultraviolet photoelectric detector and a preparation method thereof, wherein the detector comprises a flexible substrate and β -Ga arranged on the flexible substrate 2 O 3 Nanowires and nanoparticles located in β -Ga 2 O 3 Silver electrodes on the nanowires. The photoelectric detector prepared by the invention has good solar blind ultraviolet response. Meanwhile, the photoelectric detector has good stability and repeatability, and can be bent to different degrees under the condition of not influencing the performance of the photoelectric detector. The method has simple process and excellent product performance, can realize industrial production, and is flexible in the futureThe photoelectric detector has great application prospect in the production of raw materials.)

1. A flexible solar blind ultraviolet photoelectric detector is characterized by comprising a flexible substrate, β -Ga on the flexible substrate₂O₃Nanowires and nanoparticles located in β -Ga₂O₃Silver electrodes on the nanowires.

2. The flexible of claim 1Solar blind ultraviolet photodetector, characterized in that said β -Ga₂O₃Nanowire crossbars are deposited on the flexible substrate.

3. The flexible solar-blind ultraviolet photodetector of claim 2, wherein the β -Ga is₂O₃And the nano wire is synthesized in situ on the flexible substrate by a plasma enhanced chemical vapor deposition method.

4. The flexible solar-blind ultraviolet photodetector of any one of claims 1 to 3, characterized in that β -Ga₂O₃The diameter of the nano-wire is 40 nm-120 nm, and the length is 1 micron-100 microns.

5. The flexible solar blind ultraviolet photodetector of claim 1, wherein the flexible substrate comprises flexible fiberglass cloth.

6. A method for preparing the flexible solar blind ultraviolet photoelectric detector as claimed in any one of claims 1 to 5, which comprises sequentially depositing a layer of gold on a flexible substrate, and synthesizing a layer β -Ga on the gold layer by using a gallium source as a precursor₂O₃Nanowire layer, at β -Ga₂O₃And arranging two drops of Ag mixed slurry on the nanowire layer, and drying to form two silver electrodes.

7. The method of claim 6, wherein the synthesizing of the layer β -Ga on the Au layer from the Ga source as the precursor₂O₃The nanowire layer includes:

placing a flexible substrate/gold layer sample in a horizontal tube furnace, evacuating the tube by a mechanical rotary pump, purging with argon of 500sccm, heating to 500-₂O₃And a nanowire layer.

8. The method as claimed in claim 7, wherein the temperature raising rate for raising the temperature to 500-600 ℃ is 30 ℃/min; the deposition time for depositing the gallium oxide material on the gold layer is 5 h.

9. The method of claim 7, wherein the pressure in the evacuated tube is 1 Pa; the ratio of the mixed gas of the high-purity argon and the oxygen is 10: 1; the pressure of the cavity is 3 multiplied by 10 after the mixed gas is introduced¹Pa; the radio frequency power is 50-300W.

10. The method of claim 7, wherein the gold layer has a thickness of 10nm, and is deposited on the flexible substrate by radio frequency magnetron sputtering; the flexible substrate is flexible glass fiber cloth.

Technical Field

The invention relates to the field of solar blind ultraviolet photoelectric detectors, in particular to a flexible solar blind ultraviolet photoelectric detector and a manufacturing method thereof.

Background

Due to the absorption of the ozone layer, deep ultraviolet light with the wavelength of 200-280nm hardly exists on the earth surface, the light in the wave band is called solar blind ultraviolet light, and a photoelectric detector working in the region, namely a so-called solar blind photoelectric detector. Because the solar blind ultraviolet detection device is not influenced by sunlight background, the solar blind ultraviolet detection device can work all weather, has the characteristics of high sensitivity and low false alarm rate, and has wide application in the fields of missile early warning and tracking, rocket tail flame detection, forest fire alarm, ozone layer detection, medical diagnosis, near-earth secret communication, biochemical analysis and the like.

The solid solar blind ultraviolet detector requires that the forbidden band width of a semiconductor material is more than 4.4eV, and GaN, ZnO, SiC, diamond and Ga are used at present₂O₃A wide bandgap semiconductor material as a representative has been rapidly developed in recent years. Especially Ga₂O₃The band gap of the crystal is about 4.9eV, the crystal is a natural solar blind material, is a direct band gap III-VI wide band gap semiconductor and is easy to be combined with Al₂O₃And In₂O₃The method has the characteristics of forming a continuous solid solution to realize complete coverage in the solar blind area, having good chemical stability and thermal stability and the like, is an oxide semiconductor candidate material very suitable for preparing a solar blind ultraviolet photoelectric detector, and has attracted attention of scientific researchers in recent years.

β -Ga based on single crystal, thin film, nano wire and nano belt₂O₃Solar blind photodetectors have been fabricated on rigid substrates and have been extensively studied. However, these photodetectors often require thicker materials to achieve larger photoelectric response, and have many disadvantages such as fragility, high price, and harsh preparation process and working environment, which limit the application development.

With the rapid development of the modern electronic technology industry, people continuously pursue portable, entertaining and healthful wearable electronic devices, and the corresponding flexible electronic devices are promoted to develop towards the directions of high efficiency, low cost, large-area manufacturing and the like. Taking a photoelectric detector as an example, the photoelectric detector has the advantages of easy carrying, excellent portability, large-area compatibility, higher expandability, low preparation cost and the like, so that the photoelectric detector has potential application in portable and wearable optoelectronic devices, deformable displays, artificial bionic tissues, intelligent skins and the like.

However, most of themGa₂O₃The thin film is amorphous in low temperature growth on the flexible substrate, and the device shows instability due to contact problems caused by physical instability between the thin film and the flexible substrate.

Disclosure of Invention

The invention aims to solve the technical problems and provides a flexible solar blind ultraviolet photoelectric detector and a manufacturing method thereof.

The invention achieves the aim, and provides a flexible solar blind ultraviolet photoelectric detector which comprises a flexible substrate and β -Ga arranged on the flexible substrate₂O₃Nanowires and nanoparticles located in β -Ga₂O₃Silver electrodes on the nanowires.

Wherein, the β -Ga₂O₃Nanowire crossbars are deposited on the flexible substrate.

Wherein, the β -Ga₂O₃And the nano wire is synthesized in situ on the flexible substrate by a plasma enhanced chemical vapor deposition method.

Wherein, the β -Ga₂O₃The diameter of the nano-wire is 40 nm-120 nm, and the length is 1 micron-100 microns.

Wherein the flexible substrate comprises a flexible fiberglass cloth substrate.

The invention also comprises a second technical scheme, and provides a method for preparing the flexible solar blind ultraviolet photoelectric detector, which comprises the steps of sequentially depositing a layer of gold on a flexible substrate, and synthesizing a layer of β -Ga on the gold layer by taking a gallium source as a precursor₂O₃Nanowire layer, at β -Ga₂O₃And arranging two drops of Ag mixed slurry on the nanowire layer, and drying to form two silver electrodes.

Wherein, the layer β -Ga is synthesized on the gold layer by taking a gallium source as a precursor₂O₃The nanowire layer includes: placing the flexible substrate/gold layer sample in a horizontal tube furnace, evacuating the tube by a mechanical rotary pump, and purging with 500sccm argon; heating to 500 ℃ and 600 ℃, and simultaneously introducing a mixed gas of high-purity argon and oxygen and gallium trichloride gas into the tube; turning on the radio frequency power supply and setting the radio frequency powerDepositing a gallium oxide material on the gold layer to form β -Ga₂O₃And a nanowire layer.

Wherein, the purities of the high-purity argon, the oxygen and the gallium trichloride are all 99.999 percent.

Wherein the temperature rise speed of raising the temperature to 500-600 ℃ is 30 ℃/min; the deposition time for depositing the gallium oxide material on the gold layer is 5 h.

Wherein the pressure in the vacuum-pumped tube is 1 Pa; the ratio of the mixed gas of high purity argon and oxygen was about 10: 1.

Wherein, the pressure of the cavity is 3 multiplied by 10 after the mixed gas is introduced¹Pa; the radio frequency power is 50-300W.

The thickness of the gold layer is 10nm, and the gold layer is deposited on the flexible substrate through radio frequency magnetron sputtering.

Wherein the flexible substrate is flexible glass fiber cloth.

Further, the flexible glass fiber cloth substrate is treated before a layer of gold is deposited on the flexible glass fiber cloth substrate, the flexible glass fiber cloth substrate is subjected to ultrasonic cleaning for 10min by acetone, absolute ethyl alcohol and deionized water respectively, and then is dried for 12 hours in an oven at 60 ℃.

Wherein each Ag electrode area is about 0.25mm²The gap between the two electrodes is about 5 mm.

The invention has the beneficial effects that:

1. the flexible solar blind ultraviolet photoelectric detector of the invention is β -Ga formed on a flexible substrate₂O₃Nanowires, β -Ga₂O₃The nano-wire is a crystalline phase material, and is firmly combined with the flexible substrate, so that the detector displays stably,

2. the flexible glass fiber substrate used in the flexible solar blind ultraviolet photoelectric detector is a novel inorganic non-metallic material, has excellent performances of high temperature resistance, nonflammability, high strength, chemical corrosion resistance and the like compared with other flexible substrates, and meets the basic requirements of devices working under high temperature conditions.

3. The flexible solar blind ultraviolet photoelectric detector of the invention, β -Ga₂O₃The nano-wire is synthesized in situ on a flexible substrate, and the prepared nano-wire is based on β -Ga₂O₃The flexible solar-blind nanowire photoelectric detector has excellent solar-blind photoelectric performance, for example, the light-dark ratio of the flexible solar-blind nanowire photoelectric detector is about 260 under 254nm illumination, the response time is only 0.19s, and meanwhile, the performance of the device is not influenced by bending conditions and has high working temperature and high stability.

4. The flexible solar blind ultraviolet photoelectric detector provided by the invention adopts a plasma enhanced chemical vapor deposition method, improves the activity of gallium trichloride gas and a substrate by means of glow discharge plasma, obviously reduces the reaction temperature, improves the deposition efficiency and quality of a gallium oxide material, has simple process flow, low cost, short period and good repeatability, and creates good conditions for large-scale production of the gallium oxide nano base material.

5. The flexible solar blind ultraviolet photoelectric detector has good stability and repeatability, and can be bent to different degrees without affecting the performance of the flexible solar blind ultraviolet photoelectric detector. The method has simple process and excellent product performance, can realize industrial production, and has huge application prospect in the production of raw materials of flexible photoelectric detectors in the future.

Drawings

Fig. 1 is a schematic structural diagram of a flexible solar blind ultraviolet photodetector of the present invention.

FIG. 2 is a schematic structural diagram of a PECVD system used in the method of the present invention.

FIG. 3 shows β -Ga prepared by the process of the present invention₂O₃X-ray diffraction pattern of nanowires.

FIG. 4 shows β -Ga prepared by the process of the present invention₂O₃The ultraviolet and visible light absorption spectrum of the nano-wire is calculated β -Ga₂O₃The band gap of the nanowires.

FIG. 5 shows β -Ga prepared by the process of the present invention₂O₃Scanning electron microscopy of nanowires.

FIG. 6 shows β -Ga prepared by the process of the present invention₂O₃Transmission electron microscopy of nanowires.

FIG. 7 is a method of the present inventionObtained β -Ga base₂O₃The linear and exponential curve diagrams of the current-voltage characteristics of the nanowire flexible solar blind ultraviolet photoelectric detector under dark and light.

FIGS. 8 and 9 respectively show β -Ga-based materials prepared by the method of the present invention₂O₃And (3) a graph of the change of photocurrent with the change of incident ultraviolet power of the nanowire flexible solar blind ultraviolet photodetector under the irradiation of 254nm under the bias voltage of 20V, wherein each line corresponds to the change of the incident light power rule.

FIG. 10 shows β -Ga-based alloy prepared by the process of the present invention₂O₃The nanowire flexible solar blind ultraviolet photoelectric detector measures a current-voltage characteristic diagram under the bias of 20V and different bending radiuses, and the inset diagram is a schematic diagram of the device under flat and bending conditions.

Detailed Description

The invention is further explained below with reference to examples and figures.