氧化钒基纳米材料及器件研究
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摘要
氧化钒是重要的半导体材料，有着良好的光学、电学性能,有着巨大的潜在价值，可以应用在温度传感器、光电调节器、可充电锂离子电池、智能窗、非制冷红外探测器、气体传感器、掩模、快速光电开关、光存储器等方面。由于对于氧化钒体材料的研究已近较为成熟，对其纳米材料特性逐渐成为目前研究的热点。
本文分别采用新的方法制备了氧化钒基的一维和二维纳米材料，并进行了详细的分析和理论解释，开发它们的自身特性制作了几种简单的纳米器件传感器。
利用改进的化学气相沉积方法(MCVD)在硅基底上合成了超长单晶五氧化二钒纳米带，宽度为20-500nm，长度为厘米量级，长径比大于5个数量级。并对其生长条件、形貌、结晶性和生长机理等进行了研究。五氧化二钒纳米带的最优生长方向为[010]晶向。
利用五氧化二钒纳米带制作了超快的光电开关。在一维金属氧化物纳米结构中，其具有对可见光超快的响应速度（最快响应时间约为100μs）和非常良好的可重复性与稳定性（包括长时间照射和温度稳定性）。证明了五氧化二钒纳米带光电开关具有超快响应速度是因为其导电机制为小极化子导电。对五氧化二钒纳米带光电开关器件进行的功能演示，表明了其器件的实用性。
还探讨了其制作应力传感器和气敏传感器的可能性。五氧化二钒纳米带压阻效应明显，对外力较为敏感，重复性、稳定性较好，非常适合制作纳米应变传感器。证明其压阻的机理并不是因为相变导致。五氧化二钒纳米带对氨气和二氧化氮均有气敏特性，但是单根纳米带灵敏度较低。有待制作成阵列集成进行研究和采用其他气体试验研究。
利用磁控溅射制备金属钒膜，并用激光直写进行氧化。得到了激光在金属钒膜上的氧化阈值是7mW cm~(-2)。用XPS分析了氧化钒薄膜的化学组分，初步建立了激光功率密度与氧化钒薄膜主要价态之间的关系，10mW cm~(-2)功率密度对应的以VO_2为主，20mW cm~(-2)功率密度对应的以V_2O_5为主。此外，不同的功率密度可以直写出不同颜色梯度和高度的氧化钒薄膜。
As important semiconductor material, Vanadium oxide (VOx) has a greatpotential value due to its good optical, electrical properties. It can be applied in thetemperature sensor, photoelectric regulator, rechargeable lithium-ion batteries, smartwindows, uncooled infrared detectors, gas sensors, mask, fast photoelectric switchesand optical memory. Over the past few year, Vanadium oxide bulk materials havebeen studied in depth. Vanadium oxide nanomaterials have gradually become a hottopic of current research.
In this paper, new approaches were developed in the preparation of VOx-based,one-dimensional and two-dimensional materials. Detailed analysis and theoreticalinterpretation were then proposed. A few sample of nanosensors were made by theirown characteristics.
Ultralong single crystalline vanadium pentoxide (V_2O_5) nanobelts weresynthesized on silicon substrates using the modified chemical vapor deposition(MCVD),which have width in20-500nm, length in centimeter magnitude, and theaspect ratio in more than five orders of magnitude. The growth conditions,morphology, crystallization and growth mechanism were studied. Vanadiumpentoxide nanobelts have optimal growth direction in [010] crystallization.
A photoelectric switch with ultrafast response to visible light (<100μs), suitablephotosensitivity and excellent repeatability is proposed based on the ultralong singlecrystalline V_2O_5nanobelt. Its photoconductive mechanism can well be explained bysmall polaron hopping theory. Moreover, a switching test circuit, including a LEDlight, displays the practicality of the switch.
The possibility of usage in strain sensors and gas sensors were also discussed.V_2O_5nanobelt has obvious piezoresistive effect. Due to its sensitiveness to externalforces, good repeatability and good stability, V_2O_5nanobelt is very suitable formaking nanostrain sensors. Phase transition is not the mechanism of its piezoresistiveeffect.
A single V_2O_5nanobelt has a low sensitivity to ammonia and nitrogen dioxide asgas sensor. Array integration and other gas test need to be done for further research.
Vanadium film was deposited by Magnetron sputtering. After that, it wasoxidized by laser direct writing (LDW). The oxidation threshold of the laser in the metal vanadium film is7mW cm~(-2). X-ray photoelectron spectroscopy (XPS) was usedto analyse the chemical composition of VOxthin films. The relationship between thelaser power density and the valence state of VOxthin films was established initially,where10mW cm~(-2)and20mW cm~(-2)power density correspond to main VO_2and V_2O_5,respectively. In addition, the power density has relationship with the gray-scale andheight of VOxthin films.
本文分别采用新的方法制备了氧化钒基的一维和二维纳米材料，并进行了详细的分析和理论解释，开发它们的自身特性制作了几种简单的纳米器件传感器。
利用改进的化学气相沉积方法(MCVD)在硅基底上合成了超长单晶五氧化二钒纳米带，宽度为20-500nm，长度为厘米量级，长径比大于5个数量级。并对其生长条件、形貌、结晶性和生长机理等进行了研究。五氧化二钒纳米带的最优生长方向为[010]晶向。
利用五氧化二钒纳米带制作了超快的光电开关。在一维金属氧化物纳米结构中，其具有对可见光超快的响应速度（最快响应时间约为100μs）和非常良好的可重复性与稳定性（包括长时间照射和温度稳定性）。证明了五氧化二钒纳米带光电开关具有超快响应速度是因为其导电机制为小极化子导电。对五氧化二钒纳米带光电开关器件进行的功能演示，表明了其器件的实用性。
还探讨了其制作应力传感器和气敏传感器的可能性。五氧化二钒纳米带压阻效应明显，对外力较为敏感，重复性、稳定性较好，非常适合制作纳米应变传感器。证明其压阻的机理并不是因为相变导致。五氧化二钒纳米带对氨气和二氧化氮均有气敏特性，但是单根纳米带灵敏度较低。有待制作成阵列集成进行研究和采用其他气体试验研究。
利用磁控溅射制备金属钒膜，并用激光直写进行氧化。得到了激光在金属钒膜上的氧化阈值是7mW cm~(-2)。用XPS分析了氧化钒薄膜的化学组分，初步建立了激光功率密度与氧化钒薄膜主要价态之间的关系，10mW cm~(-2)功率密度对应的以VO_2为主，20mW cm~(-2)功率密度对应的以V_2O_5为主。此外，不同的功率密度可以直写出不同颜色梯度和高度的氧化钒薄膜。
As important semiconductor material, Vanadium oxide (VOx) has a greatpotential value due to its good optical, electrical properties. It can be applied in thetemperature sensor, photoelectric regulator, rechargeable lithium-ion batteries, smartwindows, uncooled infrared detectors, gas sensors, mask, fast photoelectric switchesand optical memory. Over the past few year, Vanadium oxide bulk materials havebeen studied in depth. Vanadium oxide nanomaterials have gradually become a hottopic of current research.
In this paper, new approaches were developed in the preparation of VOx-based,one-dimensional and two-dimensional materials. Detailed analysis and theoreticalinterpretation were then proposed. A few sample of nanosensors were made by theirown characteristics.
Ultralong single crystalline vanadium pentoxide (V_2O_5) nanobelts weresynthesized on silicon substrates using the modified chemical vapor deposition(MCVD),which have width in20-500nm, length in centimeter magnitude, and theaspect ratio in more than five orders of magnitude. The growth conditions,morphology, crystallization and growth mechanism were studied. Vanadiumpentoxide nanobelts have optimal growth direction in [010] crystallization.
A photoelectric switch with ultrafast response to visible light (<100μs), suitablephotosensitivity and excellent repeatability is proposed based on the ultralong singlecrystalline V_2O_5nanobelt. Its photoconductive mechanism can well be explained bysmall polaron hopping theory. Moreover, a switching test circuit, including a LEDlight, displays the practicality of the switch.
The possibility of usage in strain sensors and gas sensors were also discussed.V_2O_5nanobelt has obvious piezoresistive effect. Due to its sensitiveness to externalforces, good repeatability and good stability, V_2O_5nanobelt is very suitable formaking nanostrain sensors. Phase transition is not the mechanism of its piezoresistiveeffect.
A single V_2O_5nanobelt has a low sensitivity to ammonia and nitrogen dioxide asgas sensor. Array integration and other gas test need to be done for further research.
Vanadium film was deposited by Magnetron sputtering. After that, it wasoxidized by laser direct writing (LDW). The oxidation threshold of the laser in the metal vanadium film is7mW cm~(-2). X-ray photoelectron spectroscopy (XPS) was usedto analyse the chemical composition of VOxthin films. The relationship between thelaser power density and the valence state of VOxthin films was established initially,where10mW cm~(-2)and20mW cm~(-2)power density correspond to main VO_2and V_2O_5,respectively. In addition, the power density has relationship with the gray-scale andheight of VOxthin films.
引文
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