金属氧化物半导体气敏材料抗湿性能提升策略

金属氧化物半导体气体传感器是目前研究和应用最为广泛的气体传感器之一,具有高灵敏、长寿命和低成本等优点。然而,金属氧化物半导体气敏材料在湿润环境中会与水蒸气发生相互作用,导致传感器的基线电阻发生漂移,气敏性能受到显著影响,成为传感器应用中面临的瓶颈问题。针对该问题,研究者们从抑制水的表面吸附、水与氧的竞争吸附及调控水与吸附氧的反应三个方面开发了一些金属氧化物半导体气敏材料的抗湿性能提升策略,从而提升金属氧化物半导体气敏材料的抗湿性。本文对水蒸气的影响机理进行了分析,对三类抗湿提升策略的未来发展提出展望,有望为金属氧化物半导体气敏材料抗湿性能的提升提供解决思路与方法指导。     

Tin Oxide Based Hybrid Nanostructures for Efficient Gas Sensing

Tin oxide as a semiconductor metal oxide has revealed great potential in the field of gas sensing due to its porous structure and reduced size. Especially for tin oxide and its composites, inherent properties such as high surface areas and their unique semiconducting properties with tunable band gaps make them compelling for sensing applications. In combination with the general benefits of metal oxide nanomaterials, the incorporation of metal oxides into metal oxide nanoparticles is a new approach that has dramatically improved the sensing performance of these materials due to the synergistic effects. This review aims to comprehend the sensing mechanisms and the synergistic effects of tin oxide and its composites in achieving high selectivity, high sensitivity and rapid response speed which will be addressed with a full summary. The review further vehemently highlights the advances in tin oxide and its composites in the gas sensing field. Further, the structural components, structural features and surface chemistry involved in the gas sensing are also explained. In addition, this review discusses the SnO₂ metal oxide and its composites and unravels the complications in achieving high selectivity, high sensitivity and rapid response speed. The review begins with the gas sensing mechanisms, which are followed by the synthesis methods. Further key results and discussions of previous studies on tin metal oxide and its composites are also discussed. Moreover, achievements in recent research on tin oxide and its composites for sensor applications are then comprehensively compiled. Finally, the challenges and scope for future developments are discussed.     

氧化锌薄膜/锡掺杂玻璃光波导元件及其对氯苯的气敏性研究

建立了玻璃光波导气敏元件检测氯苯气体的方法.采用浸渍-提拉法将ZnO敏感膜固定在锡掺杂玻璃光波导表面,研制出了检测氯苯气体的ZnO薄膜/锡掺杂玻璃光波导气敏元件,并用该玻璃光波导气敏元件对挥发性有机气体进行了检测.实验结果表明,在室温下,气敏元件对氯苯气体有明显的响应,而对相同浓度的其它挥发性有机气体的响应相对较小,对...     

Atmospheric pressure chemical vapour deposition of fluorine‐doped tin(IV) oxide from fluoroalkyltin precursors

Perfluoroalkytin compounds R_(4−n)Sn(R_f)_n (R = Me, Et, Bu, R_f = C₄F₉, n = 1; R = Bu, R_f = C₄F₉, n = 2, 3; R = Bu, R_f = C₆F₁₃, n = 1) have been synthesized, characterized by ¹H, ¹³C, ¹⁹F and ¹¹⁹Sn NMR, and evaluated as precursors for the atmospheric pressure chemical vapour deposition of fluorine‐doped SnO₂ thin films. All precursors were sufficiently volatile in the range 84–136 °C and glass substrate temperatures of ca 550 °C to yield high‐quality films with ca 0.79–2.02% fluorine incorporation, save for Bu₃SnC₆F₁₃, which incorporated <0.05% fluorine. Films were characterized by X‐ray diffraction, scanning electron microscopy, thickness, haze, emissivity, and sheet resistance. The fastest growth rates and highest quality films were obtained from Et₃SnC₄F₉. An electron diffraction study of Me₃SnC₄F₉ revealed four conformations, of which only the two of lowest abundance showed close F Sn contacts that could plausibly be associated with halogen transfer to tin, and in each case it was fluorine attached to either the γ‐ or δ‐carbon atoms of the R_f chain. Copyright © 2005 John Wiley & Sons, Ltd.     

热解法制备纳米sno2及气敏性能

在不同温度下热解SnC2O4制备出纳米SnO2。利用XRD、红外光谱测试技术研究了SnO2的形貌、结构及晶粒生长过程,对它们的气敏性能进行了研究。结果表明,随着热解温度的不同,获得的颗粒尺寸不同。机理研究显示:650℃以上或650℃以下SnO2颗粒生长的方式不同。当热处理温度<650℃时,晶核生长以表面扩散为主,晶粒生长缓慢;在650℃以上热解时,晶粒以晶界迁移进行粒子生长,生长比较迅速。热解温度对气敏灵敏度影响很大,对响应恢复时间影响不大。热解法合成的SnO2纳米材料具有较好的酒敏性能,650℃热处理所得样品的气敏性能最佳,在灵敏度、响应恢复时间上表现优良。     

Nd2O3掺杂对SnO2气敏性质的影响

SnO_2是目前应用最广的一种气敏材料。我们曾经报道掺入La_2O_3,CeO_2,Pr_6O_(11),和Nd_2O_3后可使半导体元件的灵敏度提高,尤以对乙醇、乙醚、丙酮为显著。掺Nd_2O_3元件对乙炔的灵敏度也有提高。本文考察了SnO_2粒度和被测气氛的物化性质对掺Nd_2O_3元件灵敏度的影响。SnO_2采用水解SnCl_4法制备,纯度经光谱分析测定合格,试样用标准筛分目。在SnO_2中加1wt%Nd_2O_3(光谱纯)和适量水及甲基纤维素,混磨15分钟。将制成的悬浊液滴在一对铂     

聚吡咯/二氧化锡杂化材料的制备及气敏性研究

化学氧化法制备了聚吡咯(PPy)，并进行了元素分析、TG-DTA分析、FTIR测试。讨论了氧化剂用量对PPy气敏性的影响。用机械共混法制备了含不同聚吡咯的聚吡咯/二氧化锡杂化材料，研究其低温下对有毒气体NH₃、H₂S、NO的敏感性。结果表明，相同条件下聚吡咯/二氧化锡杂化材料的气敏性和稳定性均优于聚吡咯、二氧化锡。60 ℃时，当聚吡咯/二氧化锡杂化材料中聚吡咯的质量分数为5%时，其对体积分数为0.05%的H₂S的灵敏度(V_g/ V_a)达到了104.52，且响应恢复时间短。文章讨论了气体与敏感元件的相互作用机制。这一研究有助于开发低能耗、灵敏度高的气敏元件。     

Fabrication of a gas sensor using pentacene thin films as a detector

Highly sensitive gas sensors for both acidic and basic gases were fabricated based on conducting thin films of polyacene compounds. Gas sensors formed with pentacene thin films deposited on various kinds of substrates were found to exhibit high sensitivity in detecting subppm concentrations of NO₂ or Cl₂ by monitoring the conductivity of the thin film. Improvements in the conductance and duration period for detection were achieved by changing the shape of electrodes and substrate. The sensors with PEN thin films initially doped with iodine could detect ppm concentrations of ammonia gas, since iodine molecules were dedoped upon exposure to ammonia, causing the reduction of the conductivity.     

Y2O3薄膜/锡掺杂玻璃光波导气敏元件及其气敏性

采用溶胶-凝胶法将氧化钇(Y2O3)敏感膜固定在锡掺杂玻璃光波导表面,研制出了Y2O3薄膜/锡掺杂玻璃光波导气敏元件,并对挥发性有机气体进行了检测.通过XRD测试对敏感薄膜的结构及晶粒尺寸进行了表征.实验结果表明,在室温下Y2O3薄膜/锡掺杂玻璃光波导气敏元件对二甲苯、氯苯气体有较好的选择性响应,其响应浓度范围为l×10-3 ～1×10-5(V/V).Y2O3薄膜/锡掺杂玻璃光波导气敏元件具有灵敏度高、成本低、响应速度快、制作工艺简单和可逆性好等优点.     

XPS Study of the Corrosion Protection of Fluorozirconate Glasses Dip-Coated with SnO2 Transparent Thin Films

Tin oxide nanoparticles prepared by an aqueous sol–gel method were deposited by dip-coating on fluorozirconate glass, ZBLAN (53%ZrF₄-20%BaF₂-4%LaF₃-3%AlF₃-20%NaF) to improve its resistance against wet corrosion. The aqueous leaching of uncoated and SnO₂-coated fluorozirconate glass was studied by X-ray photoemission spectroscopy (XPS) and it was shown that even an ultra thin tin dioxide film provides good protection of the glass surface against the bulk propagation of the hydrolytic attack.     

光波导二氧化氮气敏传感元件的研究

本文用离子交换法制备K+交换玻璃光波导元件,并在其表面固定纳米级敏感层酞菁铜(CuPc)薄膜,利用光波导气体检测系统对NO2气体进行测试.结果表明,该传感元件常温下对NO2等气体有快速、可逆的响应,并具有重现性好,灵敏度高等特点.     

Functionalized Nanogap for DNA Read-Out: Nucleotide Rotation and Current-Voltage Curves

Functionalized nanogaps embedded in nanopores show a strong potential for enhancing the detection of biomolecules, their length, type, and sequence. This detection is strongly dependent on the features of the target biomolecules, as well as the characteristics of the sensing device. In this work, through quantum-mechanical calculations, we elaborate on representative such aspects for the specific case of DNA detection and read-out. These aspects include the influence of single DNA nucleotide rotation within the nanogap and the current-voltage (I-V) characteristics of the nanogap. The results unveil a distinct variation in the electronic current across the functionalized device for the four natural DNA nucleotides with the applied voltage. These also underline the asymmetric response of the rotating nucleotides on this applied voltage and the respective variation in the rectification ratio of the device. The electronic tunneling current across the nanogap can be further enhanced through the proper choice of an applied bias voltage. We were able to correlate the enhancement of this current to the nucleotide rotation dynamics and a shift of the electronic transmission peaks towards the Fermi level. This nucleotide specific shift further reveals the sensitivity of the device in reading-out the identity of the DNA nucleotides for all different configurations in the nanogap. We underline the important information that can be obtained from both the I-V curves and the rectification characteristics of the nanogap device in view of accurately reading-out the DNA information. We show that tuning the applied bias can enhance this detection and discuss the implications in view of novel functionalized nanopore sequencers.     

New s-Block Metal Pyridinedicarboxylate Network Structures through Gas-Phase Thin-Film Synthesis

The combined atomic and molecular layer deposition (ALD/MLD) technique offers a unique way to build—both known and previously unknown—crystalline coordination polymer materials directly from gaseous precursors in a high-quality thin-film form. Here, we demonstrate the ALD/MLD of crystalline Li-, Na-, and K-based 3,5-pyridinedicarboxylate (3,5-PDC) thin films; the Li₂-3,5-PDC films are of the known Li-ULMOF-4 crystal structure whereas the other as-deposited crystalline films possess structures not previously reported. Another exciting possibility offered by ALD/MLD is the deposition of well-defined but amorphous metal–organic thin films, such as our Mg-, Ca-, Sr-, and Ba-based 3,5-PDC films, which can then be crystallized into water-containing structures through a post-deposition humidity treatment. All together, the new metal–organic structures realized in this study through ALD/MLD comprise a majority of the (anhydrous and water-containing) members of the s-block metal 3,5-pyridinedicarboxylate family.     

Nanofibrous polyaniline thin film prepared by plasma‐induced polymerization technique for detection of NO2 gas

A nanofibrous polyaniline (PANI) thin film was fabricated using plasma‐induced polymerization method and explored its application in the fabrication of NO₂ gas sensor. The effects of substrate position, pressure, and the number of plasma pulses on the PANI film growth rate were monitored and an optimum condition for the PANI thin film preparation was established. The resulting PANI film was characterized with UV–visible spectrophotometer, FTIR, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The PANI thin film possessed nanofibers with a diameter ranging from 15 to 20 nm. The NO₂ gas sensing behavior was studied by measuring the change in electrical conductivity of PANI film with respect to NO₂ gas concentration and exposure time. The optimized sensor exhibited a sensitivity factor of 206 with a response time of 23 sec. The NO₂ gas sensor using nanofibrous PANI thin film as sensing probe showed a linear current response to the NO₂ gas concentration in the range of 10–100 ppm. Copyright © 2009 John Wiley & Sons, Ltd.     

Characterization of N-cyclohexylmethacrylamide LB thin films for room temperature vapor sensor application

This study reports the synthesis, characterization and gas sensing applications of N-cyclohexylmethacrylamide (NCMA) monomer material using FT-IR, ¹H and ¹³C NMR, UV-visible spectroscopy, Quartz Crystal Microbalance (QCM) and Langmuir-Blodgett (LB) thin film deposition techniques. The thin film deposition conditions of NCMA monomer material, which are prepared by LB film technique, are characterized by UV-visible spectroscopy and QCM system. The sensing behaviors of the LB film with respect to volatile organic compounds (VOCs) at room temperature are investigated. Surface pressure change as a function of surface area of NCMA molecule at the water surface shows a well-organized and stable monolayer at 18 mN m^?1 surface pressure value for LB film deposition. Transfer ratio values are found to be ≥ 0.94 for quartz glass and ≥ 0.93 for quartz crystal substrate. The typical frequency shift per layer is obtained 20.10 Hz/layer and the deposited mass onto a quartz crystal is calculated as 824.62 ng/layer. The sensing responses of the LB films against chloroform, dichloromethane, acetone, toluene, benzene and ethanol are measured by QCM system. The sensitivities of the NCMA LB film sensor are determined between 0.085 and 0.029 Hz ppm^?1. Sensitivities with detection limits are between 35.29 and 100.33 ppm against organic vapors. These results can be concluded that the monomer LB film sample is found to be significantly more sensitive to chloroform and dichloromethane vapors than others organic vapors used in this work. This material may find potential applications in the development of room temperature organic vapor sensing.     

SnOx Thin Film Gas Sensors Prepared by Plasma Deposition from Tetrabutyltin

Amorphous ultrafine tin-containing organic thin films have been prepared by means of radio frequency (RF) glow-discharge plasma polymerization of tetrabutyltin (TBT). After being annealed, the films turned into ultrafine SnOx thin films, which possessed high gas sensitivity. The influences of the thermal annealing process on the film's composition, microstructure, and gas sensitivity to such reductive gases as EtOH, H ₂ , CH ₄ , and CO were investigated, and the effects of doping silver into the film on its gas sensitivity were also discussed in detail. By doping with Ag, the sensitivity and selectivity of the film obviously increased, the optimum operating temperature decreased, and the film color apparently changed. Based on these facts, the catalysis mechanism of doped Ag is addressed.     

Photoactive Thin-Film Structures of Curcumin,TiO2 and ZnO

Curcumin is known as a biologically active compound and a possible antimicrobial agent. Here, we combine it with TiO₂ and ZnO semiconductors, known for their photocatalytic properties, with an eye towards synergistic photo-harvesting and/or antimicrobial effects. We deposit different nanoscale multi-layer structures of curcumin, TiO₂ and ZnO, by combining the solution-based spin-coating (S-C) technique and the gas-phase atomic layer deposition (ALD) and molecular layer deposition (MLD) thin-film techniques. As one of the highlights, we demonstrate for these multi-layer structures a red-shift in the absorbance maximum and an expansion of the absorbance edge as far as the longest visible wavelength region, which activates them for the visible light harvesting. The novel fabrication approaches introduced here should be compatible with, e.g., textile substrates, opening up new horizons for novel applications such as new types of protective masks with thin conformal antimicrobial coatings.     

Synthesis,Characterization, and Thin-Film Transistor Response of Benzo[i]pentahelicene-3,6-dione

Organic semiconductors hold the promise of simple, large area solution deposition, low thermal budgets as well as compatibility with flexible substrates, thus emerging as viable alternatives for cost-effective (opto)-electronic devices. In this study, we report the optimized synthesis and characterization of a helically shaped polycyclic aromatic compound, namely benzo[i]pentahelicene-3,6-dione, and explored its use in the fabrication of organic field effect transistors. In addition, we investigated its thermal, optical absorption, and electrochemical properties. Finally, the single crystal X-ray characterization is reported.     

Study on Combined Optical and Electrochemical Analysis Using Indium‐tin‐oxide‐coated Optical Fiber Sensor

In this work an optical fiber sensor, where a lossy‐mode resonance (LMR) effect was obtained due to indium tin oxide (ITO) thin overlay, has been simultaneously applied as a working electrode in a 3‐electrode cyclic voltammetry electrochemical setup. Since LMR conditions highly depend on refractive index of a surrounding medium, an LMR‐based sensor was applied for optical investigations of electrolyte's properties at the ITO surface. We have found that the optical response of the sensor highly depends on the applied potential and its changes, as well as the properties of the investigated electrolyte, i. e., its composition and presence of a redox probe. Both optical and electrochemical response of the ITO‐LMR sensor to various concentrations of phosphate‐buffered saline (PBS), NaCl and Na₂SO₄, as well as scan rate were investigated and discussed. We have found that the responses in optical and electrical domains differ significantly and may deliver supplementary information about the investigated analyte.