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CN-122028523-A - CuI, alpha-Ga 2O3 pn junction bipolar photoresponsive device and preparation method thereof

CN122028523ACN 122028523 ACN122028523 ACN 122028523ACN-122028523-A

Abstract

The application relates to the field of photoelectric detection devices, and discloses a CuI, alpha-Ga 2O3 pn junction bipolar photoelectric response device and a preparation method thereof, wherein the preparation method comprises the steps of firstly growing an alpha-Ga 2O3 nano column array with good crystallinity on an FTO substrate through hydrothermal reaction and a high-temperature annealing process; then dispersing CuI powder in a mixed solvent of dipropyl sulfide and chlorobenzene in a specific proportion, adopting a drop-by-drop dipping and heating volatilizing method to construct a CuI microsphere coating layer on the surface of the nano column in situ, and finally combining electrolyte and an electrode system to assemble the device. The application utilizes CuI with high hole mobility and wide band gap alpha-Ga 2O3 to construct II-type energy band heterojunction, and the generated built-in electric field realizes the rapid separation and zero bias self-powered detection of photo-generated carriers. The device has excellent bipolar light response characteristic, high sensitivity and good chemical stability, and has wide application prospect in the fields of underwater solar blind ultraviolet secret communication, photoelectric logic gates, intelligent imaging identification and the like.

Inventors

  • XU KAI
  • XU HANGJIE
  • GUO DAOYOU
  • CHEN KAI
  • Hu Haizheng
  • QI SONG
  • TANG WEIHUA

Assignees

  • 苏州镓和半导体有限公司
  • 浙江理工大学

Dates

Publication Date
20260512
Application Date
20260211

Claims (10)

  1. The CuI and alpha-Ga 2O3 pn junction bipolar photoresponsive device is characterized by comprising a tin-doped indium oxide Fluoride (FTO) conductive glass substrate (1), an alpha-Ga 2O3 nano-pillar array growing on the surface of the substrate and a p-type CuI layer modified on the surface of the nano-pillar array.
  2. 2. The CuI, α -Ga2O3 pn junction bipolar photoresponsive device of claim 1, wherein a heterojunction interface is formed between the α -Ga2O3 nanopillar array and a p-type CuI layer, the p-type CuI layer being composed of a plurality of CuI microspheres and coated on the α -Ga2O3 nanopillar surface.
  3. 3. The CuI, α -Ga2O3 pn junction bipolar photoresponsive device of claim 1, further comprising a working electrode, a platinum counter electrode, a calomel reference electrode, and an electrolyte, wherein said tin-doped indium oxide Fluoride (FTO) conductive glass substrate, said α -Ga2O3 nanopillar array, and said p-type CuI layer together comprise said working electrode and are co-immersed in said electrolyte with said platinum counter electrode, said calomel reference electrode.
  4. 4. A method for manufacturing a CuI, a-Ga 2O3 pn junction bipolar light-responsive device according to any one of claims 1-3, comprising the steps of: S1, cleaning and drying a tin-doped indium oxide Fluoride (FTO) conductive glass substrate; s2, using gallium nitrate nonahydrate as a precursor, growing a gallium hydroxide nano-pillar array intermediate on the surface of the substrate through a hydrothermal reaction, and then converting the gallium hydroxide nano-pillar array intermediate into an alpha-Ga 2O3 nano-pillar array through annealing treatment; S3, dispersing gamma-CuI powder in a mixed solvent to prepare CuI suspension, loading the CuI suspension on the alpha-Ga 2O3 nano column array, and performing heat treatment to form the p-type CuI layer; S4, configuring electrolyte and an electrode system, and assembling to obtain the CuI and alpha-Ga 2O3 pn junction bipolar photoresponsive device.
  5. 5. The method for fabricating a CuI, α -Ga2O3 pn junction bipolar photoresponsive device according to claim 4, wherein said cleaning in step S1 comprises sequentially performing ultrasonic cleaning on said tin-doped indium oxide Fluoride (FTO) conductive glass substrate with acetone, absolute ethanol, and deionized water for 10-20 minutes, respectively, followed by drying.
  6. 6. The method for preparing the CuI and alpha-Ga 2O3 pn junction bipolar photoresponsive device according to claim 4, wherein in the step S2, gallium nitrate nonahydrate is prepared into precursor liquid with the concentration of 3-6 g/L, the injection amount is 3-6 mL, the hydrothermal reaction temperature is 150-180 ℃, the reaction time is 12-14 hours, the annealing treatment temperature is 450-550 ℃, and the heat preservation time is 4 hours.
  7. 7. The method for preparing the CuI and alpha-Ga 2O3 pn junction bipolar photoresponsive device according to claim 4, wherein in the step S3, the preparation of the CuI suspension is carried out by grinding gamma-CuI powder for 8-20 minutes, dispersing in a mixed solvent, and carrying out ultrasonic auxiliary stirring for 15-40 minutes, wherein the mixed solvent consists of dipropyl sulfide and chlorobenzene, and the volume ratio of the dipropyl sulfide to the chlorobenzene is 1:19.
  8. 8. The method for preparing a bipolar photoresponsive device with a CuI and alpha-Ga 2O3 pn junction according to claim 4, wherein in the step S3, the loading and heating treatment is specifically that a substrate with an alpha-Ga 2O3 nano-pillar array grown is placed on a heat table at 80-110 ℃, the CuI suspension is dripped by adopting a drop-by-drop dipping method, and the substrate is kept stand and heated for 10-15 minutes.
  9. 9. The method for manufacturing a CuI, α -Ga2O3 pn junction bipolar photoresponsive device according to claim 4, wherein in step S4, said electrolyte is a Na2SO4 solution having a concentration of 0.5 to 0.8 mol/L.
  10. 10. An underwater solar blind ultraviolet communication system is characterized by comprising a signal transmitting module and a signal receiving module, wherein the signal receiving module adopts the CuI and alpha-Ga 2O3 pn junction bipolar light response device as claimed in any one of claims 1 to 3 as a photoelectric detection core element and is used for receiving ultraviolet light signals of 200-280 nm wave bands and converting the ultraviolet light signals into electric signals.

Description

CuI, alpha-Ga 2O3 pn junction bipolar photoresponsive device and preparation method thereof Technical Field The invention relates to the technical field of photoelectric detection devices, in particular to a CuI and alpha-Ga 2O3 pn junction bipolar light response device and a preparation method thereof. Background Currently, with the deep implementation of ocean national strategies and the iterative upgrade of ocean informatization technologies, the construction of all-weather and full-depth underwater stereoscopic observation and communication networks has become the focus of global technology competition, and the demands of human beings on underwater operation technologies are increasing. This trend drives the innovation of related technology and the application of multi-scene fusion, and simultaneously, places more stringent demands on high-reliability communication and imaging technologies in underwater complex environments. In these application scenarios, how to realize information transmission and target identification with concealment, interference resistance and low energy consumption becomes a hot spot of current research. Conventional underwater optical communication and detection systems rely primarily on the visible or near infrared band. However, these bands are easily interfered by ambient background light such as sunlight, resulting in a reduced signal-to-noise ratio, and generally do not have self-powered characteristics, so that the system maintenance cost is high, and the application development of the system in the fields of deep sea detection, long-endurance underwater imaging and the like is greatly limited. In contrast, due to the unique 'solar blind' characteristic, the deep ultraviolet light with the wave band of 200-280 nm can effectively avoid natural light background noise during the transmission under the atmosphere and the water, has extremely high signal to noise ratio and confidentiality, and is considered as an ideal information carrier for underwater covert communication and high-sensitivity detection. Among the numerous solar blind ultraviolet detection materials, ultra-wide band gap semiconductor gallium oxide (α -Ga2O3, band gap of about 4.9 eV) has been attracting attention due to its extremely high breakdown field strength and excellent solar blind light response characteristics. However, intrinsic gallium oxide materials face a number of technical bottlenecks in practical applications, firstly, the carrier mobility is low, more oxygen vacancy defects exist in the intrinsic gallium oxide materials, the response speed of the device is limited, secondly, efficient p-type doping of gallium oxide is difficult to achieve, high-quality homogeneous p-n junctions are difficult to construct, and most importantly, devices based on pure gallium oxide generally only have unipolar photoresponse and cannot realize bipolar polarity of photocurrent (namely, change of current direction according to wavelength or light intensity), so that the intrinsic gallium oxide materials are difficult to apply to photoelectric logic gates and complex signal processing systems requiring multispectral distinction and processing. To solve the above problems, the construction of heterojunction is an effective strategy. Finding a suitable p-type semiconductor material to match with n-type Ga2O3 is of paramount importance. Traditional p-type materials such as doped zinc oxide, cuprous thiocyanate and the like often contain rare metals or have toxicity, and the preparation process is complex. And cuprous iodide (gamma-CuI) is used as a natural p-type direct band gap semiconductor, and by virtue of the copper vacancy defect in the crystal structure, the semiconductor can provide a high-concentration hole acceptor level, has hole mobility of more than 40 cm < 2 >/(V.s), and can obviously improve the conductivity of the device. In addition, the CuI has rich reserves, no toxicity and low cost, has high transmittance (> 80%) in a visible light region, and is an ideal candidate material for constructing a transparent conductive film and a high-performance photoelectric device. Although CuI and Ga2O3 theoretically have the potential to build high performance photovoltaic devices, research on the application of cui@α -Ga 2O3 heterojunctions in underwater environments is still in the beginning. How to construct heterojunction with built-in electric field through energy band engineering to realize rapid separation and self-powered detection of carriers, how to break through a single light response mode to realize bipolar regulation and control of photocurrent to meet the requirements of optical communication and logic operation, and how to combine such advanced materials with artificial intelligent algorithms (such as neural networks) to realize accurate identification of underwater targets are key technical problems to be solved in the current development of high-sensitivity solar blind ultraviolet detectors and un