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Photothermal IR spectroscopy with perforated membrane micromechanical resonators

机译:具有穿孔膜微机械谐振器的光热红外光谱

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摘要

Rapid progress in nanofabrication techniques resulted in the emergence of ultrasensitive nanomechanical sensors, commonly consisting of simple vibrating structures such as cantilevers, strings or membranes that exhibit resonance behavior. The principle of operation is based on monitoring the resonance frequency shift due to various external factors, including mass, force and temperature change. The high sensitivity of nanomechanical resonators has already been exploited to create a group of photothermal spectroscopy devices capable of exceptionally fast chemical analysis of compounds on the femtogram level.Nanomechanical infrared spectroscopy (NAM-IR) originated from photothermal bilayer cantilever deflection spectroscopy and is based on the photothermal response of a nanomechanical resonator. It has already been presented with a string resonator, which was acting as sampling element and temperature sensor. The string could be considered as a single filter-fiber and guaranteed relatively high overall sampling efficiency through impaction of airborne nanoparticles on the resonator surface. When the analyte, collected by the sensor, is exposed to IR radiation it absorbs light at a certain wavelength corresponding to its specific molecular vibrations. This thermal energy heats the resonator and leads to its thermal expansion followed by a decrease of the tensile stress in the resonator. In turn it eventually causes the resonance frequency to shift towards lower values.However, further development of this approach was curbed by difficult and inefficient coupling of the IR light beam to a nanometer-sized resonator. In addition, readout of vibration was done by laser Doppler vibrometer, a precise but bulky and expensive instrument. These issues hindered a realworld application of the NAM-IR method. In order to overcome them, string resonators were replaced by membranes. A reliable sampling technique was maintained by adding perforation to membranes and thereby essentially getting membrane porous filters. Membranes gave also access to fully integrated magnetic transduction that allowed for significant shrinkage and simplification of the system.An analytical model of a locally heated membrane was developed and confirmed through FEM simulations. Then, low stress silicon nitride perforated membranes were fabricated and characterized using two different experimental setups that employed optical and magnetomotive readout. Finally, spectroscopic measurements and crystallization study of about 100 pg of the model drug ‘indomethacin’ were performed. Obtained IR spectra were in good agreement both with conventional Fourier transform IR spectroscopy (FTIR) reference and literature reports. The performance of the magnetic transduction scheme was found to be comparable to the traditionally used optical detection with a minimum sample mass required for analysis of roughly 100 fg. NAM-IR technique requires exceptionally small amount of sample and does not involve timeconsuming sample preparation. Therefore, it is a promising alternative to standard IR spectroscopy with vast possible applications for example in the pharmaceutical industry.
机译:纳米制造技术的飞速发展导致出现了超灵敏的纳米机械传感器,该传感器通常由简单的振动结构(例如悬臂,细绳或表现出共振行为的膜)组成。工作原理基于监视由于各种外部因素(包括质量,力和温度变化)引起的共振频率偏移。纳米机械共振器的高灵敏度已经被用来创建一组光热能谱设备,能够以飞克级的速度对化合物进行异常快速的化学分析。纳米机械谐振器的光热响应。已经为它提供了一个弦谐振器,该谐振器用作采样元件和温度传感器。该串可以被认为是单根过滤纤维,并且通过将空气中的纳米颗粒撞击在谐振器表面上而保证了较高的总体采样效率。当传感器收集的分析物暴露于红外辐射时,它会吸收与其特定分子振动相对应的特定波长的光。该热能加热谐振器并导致其热膨胀,随后谐振器中的张应力减小。反过来,它最终导致谐振频率向更低的值偏移。但是,由于红外光束与纳米尺寸谐振器的耦合困难且效率低下,因此该方法的进一步发展受到了限制。此外,振动的读出是通过激光多普勒测振仪完成的,这是一种精确但体积庞大且昂贵的仪器。这些问题阻碍了NAM-IR方法在现实世界中的应用。为了克服它们,弦谐振器被膜代替。通过在膜上增加穿孔,从而从根本上获得膜多孔过滤器,可以维持可靠的采样技术。膜还可以使用完全集成的磁转导,从而显着收缩和简化系统。开发了局部加热膜的分析模型,并通过FEM模拟进行了确认。然后,使用两种采用光学和磁动读数的不同实验装置,制造并表征了低应力氮化硅穿孔膜。最后,对约100 pg模型药物“吲哚美辛”进行了光谱测量和结晶研究。所获得的红外光谱与常规傅立叶变换红外光谱(FTIR)参考文献和文​​献报道都非常吻合。发现磁转导方案的性能与传统使用的光学检测相当,分析所需的最小样品质量约为100 fg。 NAM-IR技术需要非常少量的样品,并且不涉及费时的样品制备。因此,它是标准红外光谱的有希望的替代方法,具有广泛的应用前景,例如在制药行业中。

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