Subdiffraction‐limited chemical imaging of patterned phthalocyanine films using tip‐enhanced near‐field optical microscopy

A tip‐enhanced near‐field optical microscope, based on a shear‐force atomic force microscope with plasmonic tip coupled to an inverted, confocal optical microscope, has been constructed for nanoscale chemical (Raman) imaging of surfaces. The design and validation of the instrument, along with its application to near‐field Raman mapping of patterned organic thin films (coumarin‐6 and Cu(II) phthalocyanine), are described. Lateral resolution of the instrument is estimated at 50 nm (better than λ/10), which is roughly dictated by the size of the plasmonic tip apex. Additional observations, such as the distance scaling of Raman enhancement and the inelastic scattering background generated by the plasmonic tip, are presented. Copyright © 2016 John Wiley & Sons, Ltd.     

Measurement of water film thickness by laser-induced fluorescence and Raman imaging

We present two non-intrusive, laser-based imaging techniques for the quantitative measurement of water fluid film thickness. The diagnostics methods are based on laser-induced fluorescence (LIF) of the organic tracer ethyl acetoacetate added to the liquid in sub-percent (by mass) concentration levels, and on spontaneous Raman scattering of liquid water, respectively, both with excitation at 266 nm. Signal intensities were calibrated with measurements on liquid layers of known thickness in a range between 0 and 500 μm. Detection via an image doubler and appropriate filtering in both light paths enabled the simultaneous detection of two-dimensional liquid film thickness information from both methods. The thickness of water films on transparent quartz glass plates was determined with an accuracy of 9% for the tracer LIF and 15% for the Raman scattering technique, respectively. The combined LIF/Raman measurements also revealed a preferential evaporation of the current tracer during the time-resolved recording of film evaporation.     

一种基于荧光信号的海面厚油膜评估方法

油膜厚度是海面溢油污染评估分析的一个重要指标,激光诱导荧光(LIF)技术是目前最有效的海面溢油探测技术之一,基于LIF探测技术的油膜厚度反演算法当下仅有适用于薄油膜(≤10~20 μm)的评估方法,而对于较厚油膜(>20 μm)的评估目前尚无有效的反演算法。鉴于此,提出一种基于LIF技术适用于较厚油膜的反演算法,该算法采用油膜荧光信号反演油膜厚度,推导了油膜厚度反演公式,并给出了基于该反演算法的油膜厚度评估方法。首先采用最大类间方差算法(Otsu)选取合适的荧光光谱波段,然后根据选取波段内每个波长的光谱数据反演油膜厚度,最后采用反演油膜厚度的平均值作为油膜厚度评估结果。研究了该算法的适用范围,给出了该算法有效评估范围最大值与测量相对误差的关系,并结合消光系数给出了在多种测量误差条件下不同消光系数油品有效评估范围的最大值。通过实验对本文方法进行了验证,选用原油和白油的混合油(1∶50)作为实验油品,以波长为405 nm的激光作为激发光源,采集波长范围为420～750 nm,采集了海水背景荧光和拉曼散射光光谱、实验油品的荧光特征光谱和多种不同厚度的较厚油膜的荧光光谱。采用Otsu算法选取420～476 nm波段评估油膜厚度,在实验油品油膜厚度≤800 μm时,该算法对油膜厚度的评估具有较高的精度,平均误差为10.5%;在油膜厚度>800 μm时,平均误差为28.8%,评估误差较大且随油膜厚度的增加快速变大,该实验结果与利用测量相对误差和消光系数的分析结果一致。实验结果表明,该方法可以实现对海面较厚油膜厚度的有效评估,并可以根据测量相对误差和消光系数判断评估结果的有效性。     

融合拉曼散射光和荧光信号反演海面溢油厚度的算法研究

随着海洋溢油问题的日益严重,多种遥感技术被用于海面溢油监测,其中激光诱导荧光(LIF)技术是目前被认为最有效的海面溢油探测技术之一。Hoge等基于LIF技术提出了一种利用拉曼散射光评估薄油膜厚度的积分反演算法并广泛应用于海面溢油探测,针对该算法存在误差较大的问题,提出一种融合拉曼散射光和荧光信号评估海面溢油厚度的反演算法。首先利用拉曼散射光信号反演油膜厚度,然后利用该反演结果计算获取溢油油品的荧光特征光谱,最后利用荧光信号反演油膜厚度。文中推导了利用荧光信号反演油膜厚度的算法,给出了油品荧光特征光谱的逼近算法,并给出了利用荧光信号反演油膜厚度的误差分析。通过实验对该方法进行了验证,选用原油和柴油为实验油品,以波长405 nm的激光作为激发光源,采集波长范围为420～700 nm,采集了海水的背景荧光和拉曼散射光信号、实验油品2,5,10和20 μm等不同厚度油膜的光谱信号。将采集数据分为训练集和测试集,利用训练集数据采用梯度下降法获取油品的荧光特征光谱,利用测试集数据分别采用积分拉曼法和该方法反演油膜厚度。采用积分拉曼法,原油不同厚度油膜反演结果的平均误差分别为12.6%,4.6%,4.4%和2.3%,柴油不同厚度油膜反演结果的平均误差分别为14.0%,7.0%,4.2%和3.6%;采用本文方法,原油不同厚度油膜反演结果的平均误差分别为2.5%,2.2%,1.2%和1.1%,柴油不同厚度油膜反演结果的平均误差分别为3.0%,2.4%,2.7%和1.6%。实验结果表明,2 μm油膜反演结果的误差降低最多,原油和柴油2 μm油膜的反演结果误差分别由12.6%和14.0%降低为2.5%和3.0%,其他厚度油膜反演结果的误差也有较大程度的降低,油膜厚度反演结果的误差均小于3%,采用本文算法可以有效提高油膜厚度反演结果的精度。     

Study on solid structure of pentacene thin films using Raman imaging

We present a 532‐nm excited Raman imaging study of pentacene thin films (thickness, 2, 5, 10, 20, 50, 100, and 150 nm) prepared on an SiO₂ surface. The structure of the pentacene films has been investigated by images and histograms of the ratio (R) of intensity of the 1596‐cm⁻¹ band (b_3g) to that of the 1533‐cm⁻¹ band (a_g), which can be used as a marker of solid‐state phases: 1.54‐nm and 1.44‐nm phases. The Raman images showed that island‐like 1.44‐nm phase domains are grown on the 1.54‐nm phase layer from 50 nm, and all the surface of the 1.54‐nm phase layer is covered with the 1.44‐nm phase layer from 100 nm. The structural disorders have been discussed on the basis of the full width at half maximum of a band in the histogram of the R values for each film. Copyright © 2012 John Wiley & Sons, Ltd.     

Molecular orientation analysis of organic thin films by z‐polarization Raman microscope

Polarization‐dependent Raman microscopy is a powerful technique to perform both structural and chemical analyses with submicron spatial resolution. In conventional Raman microscopy, the polarization measurements are limited only in the direction parallel to the sample plane. In this work, we overcome the limit of conventional measurements by controlling the incident polarization by a spatially modulated waveplate. In this method, the polarization perpendicular to the sample surface (z‐polarization) can be detected together with the parallel polarization (xy‐polarization). Because of this unique polarization control, our Raman microscope has the ability to image the molecular orientation, together with the molecular analysis. Here, we have investigated thin films of pentacene molecules that are widely studied as an organic semiconductor material. The orientations of pentacene molecules are imaged with a spatial resolution of 300 nm. Our results clearly indicate that the lamellar grains show the lower tilt angles compared to the neighboring islands, which has not been proved in conventional methods. The substrate effects and the thickness dependence of the film are also studied. These results provide knowledge about the relationship between the devise performance and the film structures, which is indispensable for future device exploitations. Copyright © 2012 John Wiley & Sons, Ltd.     

Far ultraviolet optical properties of MgF2 films deposited by ion-beam sputtering and their application as protective coatings for Al

Thin films of MgF₂ deposited by evaporation is a material widely used for its transparency in the far ultraviolet (FUV) down to ∼115 nm. In this paper the optical properties of ion-beam sputtered (IBS) MgF₂ in the FUV are investigated and compared with MgF₂ films deposited by evaporation. A slightly higher transparency at the 121.6-nm, H Lyman α line was obtained for IBS MgF₂ films compared to films deposited by evaporation, which makes IBS MgF₂ a promising protective material for Al reflective coatings. Experimental work on Al films that were protected with a thin evaporated MgF₂ film followed by an IBS MgF₂ film to produce a protective coating with optimum thickness showed a reflectance at 121.6 nm that was higher by about 3% compared to an Al film protected with an all-evaporated MgF₂ film.     

Ultra‐thin (002)‐oriented Al‐doped zinc oxide transparent electrode grown on oxygen‐controlled homo‐seed layer

Highly (002)‐oriented Al‐doped zinc oxide (AZO) thin films with the thickness of less than 200 nm have been deposited on an oxygen‐controlled homo‐seed layer at 200 °C by DC magnetron sputtering. With the homo‐seed layer being employed, the full‐width at half maximum (FWHM) of the (002) diffraction peak for the AZO ultra‐thin films decreased from 0.33° to 0.22°, and, the corresponding average grain size increased from 26.8 nm to 43.0 nm. The XRD rocking curves revealed that the AZO ultra‐thin film grown on the seed layer deposited in atmosphere of O₂/Ar of 0.09 exhibited the most excellent structural order. The AZO ultra‐thin film with homo‐seed layer reached a resistivity of 4.2 × 10^–4 Ω cm, carrier concentration of 5.2 × 10²⁰ cm^–3 and mobility of 28.8 cm² V^–1 s^–1. The average transmittance of the AZO ultra‐thin film with homo‐seed layer reached 85.4% in the range of 380–780 nm including the substrate. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Preparation and characterization of alkyl sulfate and alkylbenzene sulfonate surfactants/TiO2 hybrid thin films by the liquid phase deposition (LPD) method

Hybrid titanium oxide thin films containing surfactants, sodium dodecyl benzylsulfonate and sodium dodecyl sulfate, have been prepared by a novel liquid-phase deposition method. It is a new attempt to prepare organic–inorganic hybrid thin film by this method which usually be applied in preparing metal oxide thin film before. The two kinds of surfactants/TiO₂ hybrid thin films were characterized by means of FT-IR, SEM, XRD, fluorescence X-ray, ICP–AES and Raman spectroscopy, and showed noticeable differences in surface top view and particle diameter, cross-section image and thickness, deposited amount of Ti, XRD patterns and Raman shift. The reasons giving rise to above differences of the two kinds composite thin films has been discussed. The deposition mechanism of organic–inorganic hybrid thin film has been also presumed. The use of this processing parameter may open up a new way to the preparing of the organic–inorganic hybrid thin film.     

钼掺杂氧化锌薄膜的结构、光学和表面等离子体特性研究

室温下,通过直流磁控反应溅射在石英衬底上制备一系列钼掺杂氧化锌薄膜。分别采用X射线衍射(XRD)、原子力显微镜(AFM)、分光光度计及拉曼光谱仪研究了钼掺杂浓度对氧化锌薄膜结构、表面形貌、光学性能和表面等离子体特性的影响。XRD测试结果表明,零掺杂氧化锌薄膜结晶良好,呈c轴择优取向,掺杂后薄膜缺陷增多,结晶质量下降,当掺杂浓度达到3.93 Wt%时,薄膜由c轴择优取向的晶态转变为非晶态。AFM测试结果表明非晶态掺钼氧化锌薄膜表面光滑,粗糙度最低可达489 pm。透射光谱表明所有薄膜样品在可见光范围(400～760 nm)平均透过率均达到80%,禁带宽度随着掺杂浓度的提高从3.28 eV单调增加至3.60 eV。吸收光谱表明氧化锌薄膜表面等离子体共振吸收峰随钼掺杂量的增大发生蓝移,而拉曼光谱表明Mo重掺杂时ZnO薄膜表面拉曼散射信号强度显著降低。通过Mo掺杂获得非晶态氧化锌薄膜,拓宽了氧化锌薄膜材料的应用领域,同时研究了Mo掺杂浓度对氧化锌薄膜表面等离子体的调控作用,这对制备氧化锌基光子器件具有重要参考价值。     

Aperture based Raman spectroscopy on SiGe film structures with high spatial resolution

We have investigated silicon–germanium (SiGe) line structures employing metallic apertures in combination with Raman spectroscopy to obtain high‐spatial strain resolution below the diffraction limit. The apertures were cut into specifically shaped electrochemically etched tungsten tips, which were adjusted within the Raman laser beam on the sample surface by a tuning fork atomic force microscope. With this setup, line structures on patterned SiGe films with a center‐to‐center distance down to 200 nm were resolved in the Raman scans, evidently indicating a resolution clearly below the far‐field Raman resolution of about 600 nm for the used instrument. This setup allows improved local strain analysis by Raman spectroscopy and shows potential for further near‐field Raman applications. Copyright © 2008 John Wiley & Sons, Ltd.     

Full X-ray pattern analysis of vacuum deposited pentacene thin films

Pentacene thin films with thicknesses ranging from 10 nm to 180 nm are investigated by specular X-ray diffraction in the reflectivity regime and in the wide angular regime. The results of the reflectivity measurements show a clear shift of the 001 reflection of the thin film phase depending on the layer thickness. It is shown that this shift can be explained by the dynamical scattering theory. The wide angular regime measurements show the 00L of the thin film phase. Williams-Hall plots are used to extract information on the crystallite size and mean micro strain of the thin film phase. The crystallite size is in good agreement with the results obtained by the reflectivity measurements. From this it can be concluded that the thin film phase crystallites are extended over the entire film thickness down to the substrate. Additionally an increase of the micro strain with increasing film thickness is observed.     

CRYSTAL GROWTH OF ISOTACTIC POLYSTYRENE IN ULTRATHIN FILMS: FILM THICKNESS DEPENDENCE

The film thickness dependence of crystal growth is investigated for isotactic polystyrene (it-PS) in thin films for thicknesses from 20 down to 4 nm. The single crystals of it-PS grown at 180°C in the ultrathin films show a morphology typical of diffusion-controlled growth: dense branching morphology and fractal seaweed. The characteristic length of the morphology, i.e., the width of the branch, increases with decreasing film thickness. The thickness dependence of the crystal growth rate shows a crossover around the lamellar thickness of 8 nm. The thickness dependences of the growth rate and morphology are discussed in terms of the diffusion of chain molecules in thin films.     

Ag-BaO薄膜在垂直表面电场作用下的光吸收增强

Ag-BaO薄膜是金属纳米微粒埋藏于半导体介质中的功能复合薄膜,它具有超快的光电时间响应,可以检测超短激光脉冲,在Ag-BaO薄膜表面加入垂直电场,可以提高薄膜的光电发射效率,在垂直表面电场作用下近紫外波段光吸收有较明显增强现象,在波长λ=303nm处15V电压作用下光吸收增强6.5%,30V电压作用下增强18%。这种光吸收增强是由于在电场作用下,薄膜的能带结构发生倾斜,以及在强电场下能级分裂。光吸收涉及被激发电子在倾斜能带间隧穿几率的增加,和被激发电子在这些分裂能级间的跃迁。     

Crystallization of Poly(Ethylene Oxide) in Thin Films

Crystallization of poly(ethylene oxide) (PEO) in thin films was studied using hot-stage polarized optical microscopy. Isothermal linear crystal growth rates were measured for various film thicknesses at various degrees of undercooling. At a given crystallization temperature, the linear crystal growth rate decreased exponentially with decreasing film thickness below a film thickness of 80 nm. Films showed similar spherulitic morphology down to a film thickness of 30 nm. Control experiments on hydrophilic and hydrophobic surfaces showed that surface chemistry affects stability of the polymer films and causes a competition between crystallization and dewetting.     

Investigations of the sorption behaviour of amorphous nitrogen-rich carbon nitride films as sensitive layers for cantilever-based chemical sensors

We present investigations of the sorption behaviour of amorphous nitrogen-rich carbon nitride films (CN_x) towards water vapour and volatile organic compounds, for example methanol, ethanol, i-propanol and acetone, in order to evaluate their potential as sensitive layers for cantilever-based chemical sensor applications. The CN_x films were deposited by inductively coupled plasma chemical vapour deposition (ICP-CVD) utilizing transport reactions from a solid carbon source. In order to study the influence of the thickness of the sensitive layer on its sensitivity and selectivity, two series of cantilevers coated with 120 nm and 240 nm CN_x films were prepared. We found that the variation of the film thickness affected the sorption process of the CN_x film quantitatively as well as qualitatively. For thin films (120 nm), the sensor dynamic responses (frequency shift) increased with increasing molecular weight of the analytes. The largest responses were observed towards acetone and i-propanol ; here, the cantilever acted as a resonant microbalance. When the film thickness was increased from 120 to 240 nm, the analytes with higher dipole moments caused stronger response signals. In this case we observed, for example, an increase of the sensitivity towards methanol by a factor of more than three. The performance of the cantilever-based sensors functionalised with CN_x coatings was compared to that of organic polymers, and the observed peculiarities were explained by the chemical nature of the sensitive materials. PACS 81.05.-t; 85.85.+j; 07.07.Df     

氧化钛薄膜调控金属铜的表面等离子体共振特性研究

提出了一种利用氧化钛薄膜对金属铜薄膜表面等离子体共振特性调制的想法。实验中首先使用电子束蒸发制备一批同等厚度的氧化钛薄膜,再利用磁控溅射方法在氧化钛薄膜上沉积厚度为5～80 nm不等的金属铜薄膜。测试结果表明,氧化钛膜层对不同厚度的金属铜薄膜表面等离子体共振增强具有不同调制效果,金属铜薄膜厚度小于20 nm时,底层的氧化钛薄膜对Cu薄膜表面等离子体共振增强效果显著,且随着金属Cu膜层厚度增加表面等离子体共振峰发生蓝移,而当金属铜膜层的厚度超过20 nm时,共振增强效果因金属Cu薄膜消光能力的上升而开始减弱。     

Stress evolution and lattice distortion induced by thickness variation and lattice misfit in La0.67Sr0.33MnO3−δ films

La_0.67Sr_0.33MnO_3?δ thin films with different thicknesses are prepared in order to investigate the structural variation induced by film thickness and lattice misfit. The X-ray diffraction results show the in-built stress evolution from a full strained thin layer (～10 nm) to a completely relaxed thick layer (～150 nm), which can be well explained by the Poisson effect. Raman spectroscopy measurements reveal the complicated correlation between the Jahn–Teller (JT) distortion and film thickness. Important octahedron modes reflecting JT distortion are completely caused by the relaxed layer. It is observed that broad JT bands are formed in the films with large thickness of the relaxed layer and the residual stress in the layer leads to an obvious blue shift. In contrast, for films with the thin relaxed layer, JT modes are present as a sharper structure and move to low frequency, indicating towards a much better oxygen stoichiometry.     

Controlling molecular orientation of OMBE grown 6P thin films on mica(0 0 1)

The growth of para-sexiphenyl thin films by organic molecular beam epitaxy (OMBE) on mica(0 0 1) was investigated. The morphology of the films was qualitatively and quantitatively analyzed by atomic-force microscopy. Synchrotron radiation was used in order to extract information about orientation of the individual molecules with respect to the substrate. Controlling the growth environment inside the growth chamber allowed to reproduce one-dimensional film morphologies with partially oriented crystallite chains usually obtained by hot wall epitaxy (HWE). Following a dedicated pregrowth procedure results in terraces of upright standing molecules so far not obtained. Phase imaging was used to clearly distinguish film and substrate.     

Growth of SrTiO3 on Si(001) by hybrid molecular beam epitaxy

We report the heteroepitaxial growth of SrTiO₃ thin films on Si(001) by hybrid molecular beam epitaxy (hMBE). Here, elemental strontium and the metal‐organic precursor titanium tetraisopropoxide (TTIP) were co‐supplied in the absence of additional oxygen. The carbonization of pristine Si surfaces during native oxide removal was avoided by freshly evaporating Sr into the hMBE reactor prior to loading samples. Nucleation, growth and crystallization behavior as well a structural properties and film surfaces were characterized for a series of 46‐nm‐thick SrTiO₃ films grown with varying Sr to TTIP fluxes to study the effect of non‐stoichiometric growth conditions on film lattice parameter and surface morphology. High quality SrTiO₃ thin films with epitaxial relationship (001)SrTiO₃ || (001)Si and [110]SrTiO₃ || [100]Si were demonstrated with an amorphous layer of around 4 nm thickness formed at the SrTiO₃/Si interface. The successful growth of high quality SrTiO₃ thin films with atomically smooth surfaces using a thin film technique with scalable growth rates provides a promising route towards heterogeneous integration of functional oxides on Si. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)