硅纳米线/氧化钒纳米棒复合材料的制备与气敏性能研究

采用纳米球光刻和金属辅助刻蚀法以p型单晶硅片制备了硅纳米线阵列, 并以此作为基底, 通过溅射不同时长的金属钒薄膜并进行热退火氧化处理, 制备出硅纳米线/氧化钒纳米棒复合材料. 采用扫描电子显微镜和X射线衍射仪表征了该复合材料的微观特性, 结果表明该结构增大了材料的比表面积, 有利于气体传感, 并且镀膜时间对后续生长的氧化钒纳米棒形貌有明显影响. 采用静态配气法在室温下测试了该复合材料对NO₂的气敏性能, 气敏测试结果表明沉积钒膜的时间对复合材料的气敏性能影响较大. 当选择合适的镀膜时间时, 适量氧化钒纳米棒增加了材料表面积并形成大量pn结结构, 相比纯硅纳米线对NO₂气体的灵敏度有明显提升, 且在室温下表现出优良的选择性. 同时, 对气敏机理做了定性解释, 认为硅纳米线与氧化钒纳米棒之间形成的pn结及能带结构在接触NO₂ 时的动态变化是其气敏响应提升的主要机制.     

Room temperature NO_2 gas sensing of Au-loaded tungsten oxide nanowires/porous silicon hybrid structure

In this work, we report an enhanced nitrogen dioxide(NO_2) gas sensor based on tungsten oxide(WO_3)nanowires/porous silicon(PS) decorated with gold(Au) nanoparticles. Au-loaded WO_3 nanowires with diameters of 10 nm–25 nm and lengths of 300 nm–500 nm are fabricated by the sputtering method on a porous silicon substrate. The high-resolution transmission electron microscopy(HRTEM) micrographs show that Au nanoparticles are uniformly distributed on the surfaces of WO_3 nanowires. The effect of the Au nanoparticles on the NO_2-sensing performance of WO_3 nanowires/porous silicon is investigated over a low concentration range of 0.2 ppm–5 ppm of NO_2 at room temperature(25℃). It is found that the 10-? Au-loaded WO_3 nanowires/porous silicon-based sensor possesses the highest gas response characteristic. The underlying mechanism of the enhanced sensing properties of the Au-loaded WO_3 nanowires/porous silicon is also discussed.     

Room temperature NO_2-sensing properties of hexagonal tungsten oxide nanorods

Hexagonal WO_3 nanorods were synthesized through a facile hydrothermal method. The nanorods properties were investigated by scanning electron microscope(SEM), transmission electron microscope(TEM), energy dispersive spectroscopy(EDS), and x-ray diffraction(XRD). The NO_2-sensing performances in terms of sensor response, response/recovery times and repeatability at room temperature were optimized by varying the heat treatment temperature of WO_3 nanorods. The optimized NO_2sensor(400-℃-annealed WO_3 nanorods) showed an ultra-high sensor response of 3.2 and short response time of 1 s to 5-ppm NO_2. In addition, the 400-℃-annealed sample exhibited more stable repeatability.Furthermore, dynamic responses measurements of annealed samples showed that all the annealed WO_3 nanorods sensors presented p-type behaviors. We suppose the p-type behavior of the WO_3 nanorods sensor to be that an inversion layer is formed in the space charge layer when the sensor is exposed to NO_2 at room temperature.Therefore, the 400-℃-annealed WO_3 nanorods sensor is one of the most energy conservation candidates to detect NO_2 at room temperature.     

Lithium ion batteries cathode material: V2O5

Among all the known electrode materials, vanadium pentoxide (V₂O₅) has high reversible capacity. It is a very valuable material for research of the complexity, rich structure and morphology. However, it also has some disadvantages, such as poor cycle stability, low discharge voltage, low conductivity and Li⁺ diffusion coefficient. In this regard, researchers have carried out a lot of research, such as using various methods to improve the nanostructures, introducing heterostructures, introducing point defects or cation doping in the crystal structure, etc. The electrochemical performance of V₂O₅ has been significantly improved in reversible capacity, high-rate capacity and long-term cycle stability. In this paper, V₂O₅ based nanostructure with different chemical composition are briefly introduced, and it covers V₂O₅ nanomaterials with different morphology, including 1D nanorods, nanobelts, nanotubes, 2D leaf like nanosheets and other nanosheets, and 3D hollow structures, porous nanostructures, porous eggshell microsphere structures. The composite nanomaterials of V₂O₅ and different carbonaceous supports are also introduced. Finally, the V₂O₅ composite materials doped with cations are discussed. The electrochemical performance of V₂O₅ based electrode can be improved effectively by obtaining appropriate nanostructure and optimized chemical composition.     

Controllable synthesis of ultrathin vanadium oxide nanobelts via an EDTA-mediated hydrothermal process

Ultrathin VO_2 nanobelts with rough alignment features are prepared on the induction layer-coated substrates by an ethylenediaminetetraacetic acid(EDTA)-mediated hydrothermal process. EDTA acts as a chelating reagent and capping agent to facilitate the one-dimensional(1D) preferential growth of ultrathin VO_2 nanobelts with high crystallinities and good uniformities. The annealed induction layer and concentration of EDTA are found to play crucial roles in the formation of aligned and ultrathin nanobelts. Variation in EDTA concentration can change the VO_2 morphology of ultrathin nanobelts into that of thick nanoplates. Mild annealing of ultrathin VO_2 nanobelts at 350℃ in air results in the formation of V_2O_5 nanobelts with a nearly unchanged ultrathin structure. The nucleation and growth mechanism involved in the formations of nanobelts and nanoplates are proposed. The ethanol gas sensing properties of the V_2O_5 nanobelt networks-based sensor are investigated in a temperature range from 100℃ to 300℃ over ethanol concentrations ranging from 3 ppm to 500 ppm.The results indicate that the V_2O_5 nanobelt network sensor exhibits high sensitivity, good reversibility, and fast responserecovery characteristics with an optimal working temperature of 250℃.     

氧化钨纳米线气敏传感器的制备及其室温NO_2敏感特性

纳米结构的氧化钨有高比表面积和气体吸附能力,在气体传感器领域得到了广泛研究.本文采用磁控溅射金属钨薄膜和两步热氧化工艺在二氧化硅衬底上生长出氧化钨纳米线.通过改变第二步氧化温度,研究退火温度对氧化钨纳米线气敏特性的影响.采用扫描电子显微镜、X射线衍射仪、X射线光电子能谱分析仪和透射射电子显微镜表征材料的微观特性和晶体结构,利用静态配气法测试气敏性能.研究结果表明,经过退火处理后氧化钨纳米线密度略微降低,300℃比400℃退火后的氧化钨结晶性差,对应的表面态含量多,有利于室温气体敏感性.测试NO_2的气敏性能,经过对比得出300℃退火温度下制备的氧化钨纳米线在室温下表现出较很好的气敏响应,对6 ppm(1 ppm=10~(-6))NO_2达到2.5,对检测极限0.5 ppm NO_2响应达1.37.氧化钨纳米线在室温下表现出反常的P型响应,是因为氧化钨纳米线表面被氧气吸附形成反型层,空穴取代电子成为主要载流子所致.     

SnO2/Co3O4 nanofibers using double jets electrospinning as low operating temperature gas sensor

SnO₂/Co₃O₄nanofibers(NFs)are synthesized by using a homopolar electrospinning system with double jets of positive polarity electric fields.The morphology and structure of SnO₂/Co₃O₄hetero-nanofibers are characterized by using field emission scanning electron microscope(FE-SEM),transmission electron microscope(TEM),x-ray diffraction(XRD),and x-ray photoelectron spectrometer(XPS).The analyses of SnO₂/Co₃O₄NFs by EDS and HRTEM show that the cobalt and tin exist on one nanofiber,which is related to the homopolar electrospinning and the crystallization during sintering.As a typical n-type semiconductor,Sn O₂has the disadvantages of high optimal operating temperature and poor reproducibility.Comparing with Sn O₂,the optimal operating temperature of SnO₂/Co₃O₄NFs is reduced from 350℃to 250℃,which may be related to the catalysis of Co₂O₂.The response of SnO₂/Co₃O₄to 100-ppm ethanol at 250℃is 50.9,9 times higher than that of pure Sn O₂,which may be attributed to the p–n heterojunction between the n-type Sn O₂crystalline grain and the p-type Co₂O₂crystalline grain.The nanoscale p–n heterojunction promotes the electron migration and forms an interface barrier.The synergy effects between Sn O₂and Co₂O₂,the crystalline grain p–n heterojunction,the existence of nanofibers and the large specific surface area all jointly contribute to the improved gas sensing performance.     

Performance and reliability improvement of La_2O_3/Al_2O_3 nanolaminates using ultraviolet ozone post treatment

La-based binary or ternary compounds have recently attracted a great deal of attention as a potential candidate to replace the currently used Hf-based dielectrics in future transistor and capacitor devices for sub-22 generation. However, the hygroscopic nature of La₂O₃ hampers its application as dielectrics in electron devices. To cope with this challenge, ultraviolet (UV) ozone post treatment is proposed to suppress the moisture absorption in the H₂O-based atomic layer deposition (ALD) La₂O₃/Al₂O₃ nanolaminates which is related to the residual hydroxyl/hydrogen groups after annealing. The x-ray photoelectron spectroscopy (XPS) and conductive atomic force microscopy (AFM) results indicate that the moisture absorption of the H₂O-based ALD La₂O₃/Al₂O₃ nanolaminates is efficiently suppressed after 600 ℃ annealing, and the electrical characteristics are greatly improved.     

Photoelectron spectroscopic study of Li oxides on Li over-deposited V2O5 thin film surfaces

The Li oxides species formed on Li over-deposited V₂O₅ thin film surfaces have been studied by using X-ray and UV induced photoelectron spectroscopy (XPS and UPS). The photoelectron spectroscopic data show that the Li over-deposited V₂O₅ system itself is not stable. Further chemical decomposition reactions are taken place even under UHV conditions and lead to form Li₂O and Li₂O₂ compounds on the surface. The formation of Li₂O₂ causes to arise an emission line at about 11.3 eV in the valence band spectra.     

Yb-In_2O_3纳米管的制备及其对甲醛的优异气敏性能

采用单管静电纺丝的方法成功制备了纯的与Yb掺杂的In_2O_3纳米管(Yb-In_2O_3).利用扫描电子显微镜和X射线衍射对样品的结构和形貌进行了表征,制作了基于纯In_2O_3和Yb-In_2O_3纳米管的气敏元件.研究表明,Yb-In_2O_3纳米管气敏元件在230℃下对100 ppm甲醛的灵敏度为69.8,是纯In_2O_3纳米管气敏元件对同浓度甲醛灵敏度(18.4)的3.8倍,其对100 ppm甲醛的响应恢复时间分别为4 s和84 s.并且,基于Yb-In_2O_3纳米管的气敏元件对100 ppb甲醛的灵敏度达到2.5.此外,该气敏元件还具有出色的选择性及稳定性,具备良好的实际应用前景.     

钒掺杂W18O49纳米线的室温p型电导与NO2敏感性能

钨氧化物纳米线在高灵敏度低功耗气体传感器中极具应用潜力, 且通过掺杂改性可进一步显著改善其敏感性能. 本文以WCl₆为钨源, NH₄VO₃为掺杂剂, 采用溶剂热法合成了钒掺杂的W₁₈O₄₉纳米线. 利用扫描电镜、透射电镜、X射线衍射、X射线光电子能谱仪表征了纳米线的微结构, 并利用静态气敏性能测试系统评价了掺杂纳米线的NO₂敏感性能. 研究结果表明: 五价钒离子受主掺杂进入氧化钨晶格结构, 抑制了纳米线沿轴向的生长并导致了纳米线束的二次集聚; 室温下, 钒掺杂W₁₈O₄₉纳米线接触NO₂气体后表现出反常的p型响应特性; 随工作温度逐渐升高至约110 ℃时, 发生从p型到n型的电导特性转变; 该掺杂纳米线气敏元件对浓度低至80 ppb (1 ppb=10^-9) 的NO₂气体具有明显的室温敏感响应和良好的响应稳定性. 分析并探讨了钒掺杂W₁₈O₄₉纳米线的高室温敏感特性及其p-n电导转型机理, 认为钒掺杂W₁₈O₄₉纳米线在室温下的良好敏感响应及反常p型导电性与掺杂纳米线表面高密度非稳表面态诱导的低温气体强吸附有关. 关键词： 氧化钨 纳米线 气体传感器 室温灵敏度     

高温氢退火还原V2O5制备二氧化钒薄膜及其性能的研究

过渡金属氧化物二氧化钒(VO₂)在温度340 K附近会发生金属绝缘体的转变(metal-insulator transition, MIT). 基于金属绝缘体的转变性质, VO₂薄膜材料具有很好的应用前景. 本文首先采用脉冲激光沉积制备了高质量的V₂O₅薄膜, 再通过高温氢退火还原V₂O₅薄膜制备出VO₂多晶薄膜. 研究了不同的退火温度、退火时间、退火气氛对VO₂薄膜制备的影响, 采用X射线衍射、X射线光电子能谱、变温电阻特性测量等手段对样品进行分析, 发现在H₂(5%)/Ar退火气氛下, 在一定的退火温度范围内(500–525 ℃), 退火 3 h, 得到了B相和M相共存的VO₂薄膜, 具有M相的VO₂的MIT特性, 而相同退火温度下退火时间达到4.5 h, 薄膜完全变成B相的VO₂. 通过纯Ar气氛下对B相VO₂再退火, 得到了转变温度为350 K, 电阻突变接近4个数量级的M相的VO₂薄膜. 实现了VO₂的B相和M相的相互转变. 关键词： 2薄膜')" href="#">VO₂薄膜 金属绝缘体转变 氢退火     

Chemical synthesis of zinc oxide nanorods for enhanced hydrogen gas sensing

Zinc oxide(ZnO) nanorods are prepared using equimolar solution of zinc nitrate((Zn(NO3)2) and hexamethylenetetramine(C6H12N4) by the hydrothermal technique at 80 C for 12 h. Epitaxial growth is explored by X-ray diffraction(XRD) patterns, revealing that the ZnO nanorods have a hexagonal(wurtzite) structure. Absorption spectra of ZnO are measured by UV–visible spectrometer. The surface morphology is investigated by field emission scanning electron microscopy(FESEM). The synthesized ZnO nanorods are used for detecting the 150 C hydrogen gas with a concentration over 1000 ppm. The obtained results show a reversible response. The influence of operating temperature on hydrogen gas detecting characteristic of ZnO nanorods is also investigated.     

Effect of co-doped metal caions on the properties of Y_2O_3:Eu~(3+) phosphors synthesized by gel-combustion method

Y_2O_3:Eu~(3+) phosphors co-doped with different metal cations(Li~+, Na~+, K~+, Mg~(2+), Ca~(2+)) are prepared by the gelcombustion method with Y_2O_3, Eu_2O_3, and R(NO3)x(R = Li, Na, K, Mg, Ca) serving as raw materials and glycine as fuel,calcined at 1000?C for 2h. The synthesized Y_2O_3:Eu~(3+) phosphors doped with different metal cations and doping ratios are characterized by x-ray diffractometry(XRD), fluorescence and phosphorescent spectrophotometer. The co-doping metal cations are advantageous to the development of Y_2O_3:Eu~(3+) lattice. All the samples can emit red light peaked at 611 nm under 254-nm excited. The luminescence intensities of co-doping samples are increased because the cations increase the electron transition probability of Eu~(3+) from ~5D_0 level to ~7F level. The fluorescence lifetime of Eu~(3+)(~5D_0→~7F_2) is increased by doping metal cations.     

过渡金属Cu、Cr掺杂TiO2表面氧化性气体NO2光学气敏传感特性

采用密度泛函理论（DFT）体系广义梯度近似（GGA）第一性原理平面波超软赝势方法,分析锐钛矿型TiO₂（101）表面吸附NO₂分子光学气敏传感的微观机理.结果表明：Cu和Cr原子易于掺入TiO₂（101）表面,掺杂表面能稳定地吸附NO₂分子且吸附后光学性质发生显著变化.表面吸附NO₂分子后,Cu掺杂TiO₂（101）表面对分子的吸附能最大,吸附后结构更稳定,分子与表面的距离最短.通过分析差分电荷密度和电荷布居数发现,NO₂分子与基底表面间发生电荷转移,转移电子数目：Cu掺杂表面 > Cr掺杂表面 > 无掺杂表面.对比吸收光谱和反射光谱发现,在Cu掺杂表面吸附分子后,光学性质变化最明显,说明表面与吸附分子间氧化还原能力是决定光学气敏传感性能的核心因素.在过渡金属中,Cu与Cr都有4s价电子结构,其4s电子降低了材料表面氧空位的氧化性,增加了其还原性.对于氧化性气体,可以提升表面与分子的氧化还原作用,而Cu的4s电子更加活泼,从而光学气敏传感特性更加明显.因此,Cu掺杂的TiO₂对氧化性气体是一种较好的光学气敏传感材料.     

不同退火温度的Al_2O_3:C薄膜热释光和光释光性能

α-Al_2O_3:C晶体的热释光和光释光性能优越,但其制备要求高,需高温和高还原气氛.与α-Al_2O_3:C晶体性能接近的α-Al_2O_3:C陶瓷,热释光峰不单一.本文采用两次阳极氧化法在0.5 mol/L的草酸溶液中5℃恒温制备高度均匀有序的多孔Al_2O_3:C薄膜,主要研究不同退火温度对其热释光和光释光特性的影响.结果表明,经不同温度退火后的Al_2O_3:C薄膜均为非晶结构;不同退火温度的Al_2O_3:C薄膜热释光的主发光峰约在310℃左右,符合通用级动力学模型.600℃退火后的Al_2O_3:C薄膜热释光灵敏度最强,其热释光剂量曲线在1-10 Gy范围内具有很好的线性响应,在剂量10-120 Gy范围内出现超线性响应;在相同的辐照剂量下,随着退火温度的升高(≤600℃)光释光的初始发光强度逐渐增强.不同退火温度的Al_2O_3:C薄膜光释光衰减曲线都呈典型的指数衰减且快衰减速率相比α-Al_2O_3:C晶体显著加快.600℃退火后的Al_2O_3:C薄膜光释光灵敏度最强,其光释光剂量响应曲线在1-200 Gy整体上都具有很好的剂量线性关系.与热释光相比,Al_2O_3:C薄膜的光释光具有更宽的线性剂量响应范围.此研究为Al_2O_3:C薄膜作为光释光辐射剂量材料做出了有益的探索.     

多孔CeO2膜的制备及其光谱性能

以铈箔为原料,采用阳极氧化法和热处理法制备多孔的CeO₂膜。将阳极氧化铈膜分别在400,500和800 ℃下进行热处理,分别研究阳极氧化铈膜的晶体结构、组成和表面形貌,分别研究多孔的CeO₂膜红外光谱特征吸收和热膨胀性能。阳极氧化铈膜是Ce(OH)₃,CeF₃,Ce₂O₃,CeO₂和Ce的混合膜,并吸附水和乙二醇,其中Ce(OH)₃,CeF₃,Ce₂O₃分别为六方晶型结构,CeO₂和Ce分别为立方晶型结构。阳极氧化铈膜中的Ce(OH)₃,Ce₂O₃和Ce分别在400和500 ℃进行热处理时可能分别转变为CeO₂,分别在400和500 ℃热处理后的膜为CeF₃和CeO₂的混合膜。阳极氧化铈膜中的Ce(OH)₃,CeF₃,Ce₂O₃和Ce在800 ℃进行热处理时可能分别转变为CeO₂,在800 ℃热处理后的膜为CeO₂膜。该CeO₂膜是多孔的膜,且孔为直孔,在1 600～4 000 cm-1范围内具有强吸收。该CeO₂膜在170～900 ℃范围内热膨胀系数变化不大,该膜的热稳定性较好。     

The structure of AgI-Ag2O-V2O5 glasses

Structures of 10AgI-3Ag₂O-2V₂O₅, 3AgI-3Ag₂O---2V₂O₅ and 2AgI---2Ag₂O-V₂O₅ glasses have been investigated by neutron diffraction experiments. The characteristic features of observed structure factors S(Q) in 10AgI-3Ag₂O-2V₂O₅ glass is similar to those of other superionic conducting glasses and molten AgI. From the standpoint of the pair distribution functions, it is clarified that the Ag-I and I-I correlation strength and Ag---Ag correlation length increase with increasing AgI concentration. Observed results suggest that the local AgI structure accompanied by the re-arrangement of silver ions is formed with highly doped iodide ions.     

Ce掺杂Bi2O3 光催化剂的制备、表征及其可见光催化性能

采用水热-焙烧法制备了Ce掺杂的可见光响应的Bi₂O₃光催化剂（Ce-Bi₂O₃）。利用 XRD、FT-IR、XPS和 UV-Vis对不同Ce-Bi₂O₃样品进行了表征分析,并以光催化降解金橙Ⅱ溶液为探针反应,考察了Ce-Bi₂O₃的可见光催化性能。结果表明,Ce掺杂可以减小催化剂的禁带宽度,使光谱响应范围向可见光拓展。掺杂的Ce可取代Bi₂O₃晶格中部分Bi,形成Bi-O-Ce键,并生成了少量铈铋复合氧化物（Bi_7.38Ce_0.62O_12.31）,它们的存在有效地抑制了光生电子-空穴对的复合,有助于提高Bi₂O₃的可见光催化活性。但焙烧时间过长将导致Ce-Bi₂O₃催化剂的表面发生烧结现象,致使其催化活性降低。可见光照射下的金橙Ⅱ光催化降解实验表明,经2 h焙烧后得到的Ce/Bi的量比为0.5 的Ce-Bi₂O₃催化剂具有最佳的光催化活性。     

快速吸附与脱附的声表面波H2S传感器

本文主要研究了基于SnO₂/CuO薄膜的声表面波（SAW）传感器（室温下,工作频率约为147.8 MHz）检测H₂S气体的特性。以36°YXLiTaO₃为基片制作声表面波器件,通过采用射频磁控溅射法在其表面淀积SnO₂/CuO的复合薄膜制作出H₂S气体传感器。由场发射电子扫描电镜观察薄膜,薄膜连续均匀且表面分布大量微气孔,因而具有良好的吸附性。然后本文在85℃～205℃范围内对传感器的吸附和脱附速率、灵敏度及选择性等进行了实验研究。实验结果表明,所制备的传感器在较低温度下同时具备快速吸附和脱附特性,工作在190℃时气体吸附和脱附速率最快,检测20ppm H₂S的响应和恢复时间分别为30s、15s;工作在160℃时,传感器检测20ppmH₂S的灵敏度最高,工作频率变化约230 kHz,且对于低浓度2 ppm H₂S,频率变化可达45 kHz。同时,传感器也表现出良好的重复性和选择性。