Direct determination of the experimentally observed penetration depth of the evanescent field via near-infrared absorptions enhanced by the off-resonance of surface plasmons

Recently, absorption-sensitive surface plasmon resonance (SPR) techniques have attracted much attention. SPR near-infrared spectroscopy (SPR-NIRS) based on the Kretschmann configuration is one of the techniques for absorption enhancement. The enhanced spectrum obtained by SPR-NIRS basically corresponds to the measurement of an NIR absorption spectrum with a very short path length. However, the path length cannot be applied for Lambert's law due to the enhanced evanescent field. A direct determination of the penetration depth of the evanescent field is carried out via NIR absorptions enhanced by the off-resonance of surface plasmons, which is a principle of SPR-NIRS. The signal intensities of the enhanced NIR spectra of micrometer-thick polymer films having various thicknesses are compared with the classic theory of penetration depth. It is confirmed that the effective depth of the SPR-NIRS measurement can be expressed by the classic theory of penetration depth of the evanescent field proposed by Harrick.     

Sensitive detection and identification of organic liquids using the second derivative of surface plasmon resonance near-infrared spectra

Sensitive detection of near-infrared (NIR) spectra of several organic liquids has been carried out by surface plasmon resonance (SPR) NIR spectroscopy. For all the liquids, 50- to 100-fold enhancements of the absorption peaks were obtained in the combination band region 4500-4000 cm(-1) using a gold film with a thickness of 14 nm. The SPR peak shows up as an unnecessary broadband peak or trend in an SPR-NIR spectrum, and it was difficult to separate it from the absorption signals. In order to remove the contribution of SPR from the raw SPR-NIR spectrum, the second-order derivative has been employed. The second derivative of the SPR-NIR spectrum was reasonably comparable to that of the corresponding transmittance spectrum. Two simple algorithms for sample identification from the second-derivative data have been proposed. One is similarity, which directly compares the second-derivative spectrum of an unknown sample with that of a known reference sample. The other is fitness, which is defined as a ratio of the common part of absorption peak wavenumbers of the sample and the reference. Although both methods are unfit for the identification of a minor component in a mixture, a major component can be definitely identified by choosing an informative wavenumber region. It was found that the wavenumber region 4250-4080 cm(-1) is especially useful for the identification of similar molecules such as normal alkanes.     

Quantitative analyses of absorption-sensitive surface plasmon resonance near-infrared spectra

Surface plasmon resonance near-infrared (SPR-NIR) spectroscopy provides 10-100 times absorption enhancement compared with the absorption in the corresponding attenuated total reflection (ATR) NIR spectra. However, analysis of the enhanced SPR-NIR spectra is not straightforward because of the substantial contribution from SPR. This paper proposes two analysis methods for concentration-dependent changes of SPR-NIR spectra from a viewpoint of change in absorption intensity. One is based on rapid scans of the SPR-NIR spectra with a fixed incident angle, and the other is based on multi-angle sequential scans. A concentration of methanol in water has successfully been determined by both methods. From the measurement of the light intensity within an absorption band of water (5230-5120 cm(-1)) at a fixed incident angle, the concentration was calibrated to an accuracy of 0.02 wt. %. In the latter multi-angle method, it has been proved that computed bottom ridges of the envelope curve of the SPR-NIR spectra are not only enhanced 30 times compared with the corresponding ATR-NIR spectra, but are also equivalent to the conventional transmittance NIR spectra in quality. The bottom ridges allow us to analyze SPR-NIR spectra in the same manner as conventional spectral analyses based on Beer's law.     

Surface plasmon resonance near-infrared spectroscopy

Near-infrared (NIR) spectroscopy is ill-suited to microanalysis because of its low absorptivity. We have developed a highly sensitive detection method for NIR spectroscopy based on absorption-sensitive surface plasmon resonance (SPR). The newly named SPR-NIR spectroscopy, which may open the way for NIR spectroscopy in microanalysis and surface science, is realized by an attachment of the Kretschmann configuration equipped with a mechanism for fine angular adjustment of incident light. The angular sweep of incident light enables us to make a tuning of a SPR peak for an absorption band of sample medium. From the dependences of wavelength, incident angle, and thickness of a gold film on the intensity of the SPR peak, it has been found that the absorbance can be enhanced by approximately 100 times compared with the absorbance obtained without the gold film under optimum conditions. This article reports the details of the experimental setup and the characteristics of absorption-sensitive SPR in the NIR region, together with some experimental results obtained by using it.     

High-density silver nanoparticle film with temperature-controllable interparticle spacing for a tunable surface enhanced Raman scattering substrate

The formation of high-density silver nanoparticles and a novel method to precisely control the spacing between nanoparticles by temperature are demonstrated for a tunable surface enhanced Raman scattering substrates. The high-density nanoparticle thin film is accomplished by self-assembling through the Langmuir-Blodgett (LB) technique on a water surface and transferring the particle monolayer to a temperature-responsive polymer membrane. The temperature-responsive polymer membrane allows producing a dynamic surface enhanced Raman scattering substrate. The plasmon peak of the silver nanoparticle film red shifts up to 110 nm with increasing temperature. The high-density particle film serves as an excellent substrate for surface-enhanced Raman spectroscopy (SERS), and the scattering signal enhancement factor can be dynamically tuned by the thermally activated SERS substrate. The SERS spectra of Rhodamine 6G on a high-density silver particle film at various temperatures is characterized to demonstrate the tunable plasmon coupling between high-density nanoparticles.     

Preparation and properties of multilayer poly(3,4-ethylenedioxythiophene) Langmuir-Blodgett film

Multilayer ultrathin film of poly(3,4-ethylene dioxythiophene) (PEDOT) was fabricated using a modified Langmuir-Blodgett (LB) method. The chemical polymerization of PEDOT occurred in the multilayer nanometer space of an as-prepared LB film by exposing the film to 3,4-ethylene dioxythiophene vapor. UV-Vis-near infrared absorption spectrum and Fourier-transform infrared spectrum techniques were applied to confirm the formation of the PEDOT ultrathin film. The results of atomic force microscopy investigation for the PEDOT LB film showed that the film surface consisted of small clusters having diameters ranging from 50 to 200 nm. X-ray photoelectron spectroscopy and secondary-ion mass spectrometry were employed to analyze the atomic composition of the PEDOT LB film and the location of the formed PEDOT. It was found that the atomic composition of the composite film was almost consistent with the theoretical value, and the PEDOT clusters were well located in different planes of the multilayer structure. The PEDOT LB film exhibited higher conductivity than conventional films and better doping/dedoping characteristics of conductivity. The sensitivity of the PEDOT LB film to NH₃ and HCl gases was also discussed.     

Cartesian-structure analysis in cast films by advanced infrared multiple-angle incidence resolution spectroscopy

Multiple-angle incidence resolution spectroscopy (MAIRS) has been improved to be an advanced algorithm so that the Cartesian structure in organic thin films can be analyzed. The infrared MAIRS technique was originally proposed as a totally new spectroscopic technique to reveal structural anisotropy in thin films on an infrared-transparent substrate, which yields both in-plane- (IP; X and Y) and out-of-plane (OP; Z)-mode spectra from an identical sample. Since this technique employs an analytical concept based on a signal decomposition of light intensity (not absorbance spectra), the algorithm intrinsically has high potential for further development. In the present study, the theoretically deduced matrix that correlates the light intensity to the angle of incidence has been modified to further decompose the IP-mode spectrum into X and Y components. As a result, anisotropic measurements of infrared spectra of thin film have become possible for the X, Y, and Z directions (Cartesian coordinate) simultaneously. With this advanced algorithm, the Cartesian structural changes in a cast film prepared on a germanium substrate have readily been analyzed, and a change from the biaxial to the uniaxial film structure with aging has spectroscopically been revealed.     

金属卟啉LB膜吸收光谱研究

采用Langmuir-Blodgett(LB)技术,在23mN/m的膜压下制备了四苯基卟啉铜(CuTPP)、四苯基卟啉锌(ZnTPP)及四苯基卟啉镍(NiTPP)超薄膜.分析了CuTPP、ZnTPP及 NiTPP 的LB膜分别对乙酸乙酯气体和四氢呋喃气体的紫外光谱变化,并通过薄膜对紫外-可见吸收光谱的变化阐述了构建有机气体-金属卟啉色谱探测阵列的可行性.实验结果表明,无论针对乙酸乙酯气体还是四氢呋喃气体,ZnTPP 薄膜光谱变化最明显,CuTPP薄膜次之,而NiTPP薄膜几乎没有光谱变化.因此认为CuTPP和ZnTPP可作为色谱阵列单元识别乙酸乙酯气体和四氢呋喃气体(THF).     

Molecular orientation analysis of a single-monolayer Langmuir-Blodgett film on a thin glass plate by infrared multiple-angle incidence resolution spectrometry

Molecular orientation analysis in a single monolayer deposited on a glass substrate has been a difficult matter, since the glass substrate absorbs infrared rays so strongly that the measurements of infrared spectra are difficult to perform, and the single monolayer is not suitable for X-ray diffraction analysis because no periodical structure is available. When a thin glass is used as the substrate, in particular, the infrared analysis becomes more difficult, since optical fringes appear strongly on the absorption spectra due to the multiple reflections in the glass. In the present study, infrared multiple-angle incidence resolution spectrometry (MAIRS) has been employed to remove the fringes from the spectra of single- and five-monolayer Langmuir-Blodgett (LB) films of cadmium stearate deposited on a thin glass plate. The MAIRS in-plane spectra gave quantitatively reliable infrared transmission spectra for both films with little fringes, which made it possible for the first time to analyze the molecular orientation in the single-monolayer LB film on glass. As a result, it has been revealed that the molecule in the single-monolayer LB film on thin glass exhibits a significantly larger molecular tilt angle than those prepared on other substrates such as gold and germanium.     

Nanophotonic crescent moon structures with sharp edge for ultrasensitive biomolecular detection by local electromagnetic field enhancement effect

We present novel gold nanophotonic crescent moon structures with a sub-10 nm sharp edge, which can enhance local electromagnetic field at the edge area. The formation of unconventional nanophotonic crescent moon structure is accomplished by using a sacrificial nanosphere template and conventional thin film deposition method, which allows an effective batch nanofabrication and precise controls of nanostructure shapes. Unique multiple scattering peaks are observed in a single gold nanocrescent moon with dark-field white light illumination. A 785 nm near-infrared (NIR) diode laser was used as the excitation source to induce the amplified scattering field on the sharp edge of the single gold nanocrescent moon. The Raman scattering spectrum of Rhodamine 6G molecules adsorbed on the single gold nanocrescent moon are characterized, and the Raman enhancement factor of single gold nanocrescent moon is estimated larger than 10(10), which suggests the potential applications of gold nanocrescent moons in ultrasensitive biomolecular detection and cellular imaging using surface enhanced Raman spectroscopy.     

Surface enhanced absorption and transmission from dye coated gold nanoparticles in thin films

Absorption spectra of gold nanoisland thin film and the composite film of gold having thin coating of Methylene Blue and Rh6G dyes have been studied. Thin gold nanoisland film shows surface plasmon resonance (SPR) peak in the visible wavelength range, which shifts to near infrared with an increase in the thickness of the film. It was found that thin film of gold consists of nanoparticles of different size and shape, particularly nanorods of noncylindrical shapes. A linear relation was found between SPR peak wavelength and the aspect ratio of the nanoparticles in gold thin film. Effective medium refractive index of the gold film is estimated to be ~2.5, which decreases with an increase in film thickness. The coating of dyes on gold films splits the SPR peak with an enhanced absorption. Enhancement in absorption of composite film is maximal when the dye absorption peak coincides with the SPR peak; otherwise enhancement in transmission is observed for all the wavelength range. Absorption amplitude of composite film peaks increase with an increase in the gold film thickness, which tend toward saturation for film thickness of ≥6 nm. A correlation shows that absorption spectra can be described by the Maxwell Garnett theory, when the gold nanoparticles have a nearly spherical shape for very thin film (≤6 nm).     

Time-resolved NIR spectroscopy for quantitative analysis of intact pharmaceutical tablets

Near-infrared (NIR) spectroscopy is a useful technique for quantitative measurements of intact tablets, but it suffers from limitations due to the fact that changes in the physical properties of a sample strongly affect the recorded spectrum. In this work, time-resolved transmission NIR spectroscopy was utilized to conduct quantitative measurements of intact tablets. The technique enables separation of the absorption properties of the sample from the scattering properties and can therefore handle changes of the physical parameters of the samples in a better way than conventional NIR transmission spectroscopy. The experiments were conducted using a pulsed Ti:sapphire laser coupled into a nonlinear photonic crystal fiber as light source. The light transmitted through the sample was measured by a time-resolving streak camera. A comparison of the results from the time-resolved technique with the results from conventional transmission NIR spectroscopy was made using tablets containing different concentrations of iron oxide and manufactured with different thicknesses. A PLS model made with data from the time-resolved technique predicted samples 5 times better than a PLS model made data from the conventional NIR transmission technique. Furthermore, an improvement to predict samples with physical properties outside those included in the calibration set was demonstrated.     

TiO2／SnO2超微粒及其复合LB膜的紫外—可见光吸收光谱的研究

用胶体化学方法制备ＴｉＯ２／ＳｎＯ２超微粒,ＴｉＯ２／ＳｎＯ２超微粒及其复合ＬＢ膜的紫外－可见光吸收光谱研究表明：ＴｉＯ２／ＳｎＯ２超微粒具有量子尺寸效应使吸收光谱发生“蓝移”;ＴｉＯ２／ＳｎＯ２超微粒／硬脂酸复合ＬＢ膜具有良好的抗紫外性能和光学透过性能。     

Transmission fourier transform Raman spectroscopy of pharmaceutical tablet cores

Transmission Fourier transform (FT) Raman spectroscopy of pharmaceutical tablet cores is demonstrated using traditional, unmodified commercial instrumentation. The benefits of improved precision over backscattering Raman spectroscopy due to increased sample volume are demonstrated. Self-absorption effects on analyte band ratios and sample probe volume are apparent, however. A survey of near-infrared (NIR) absorption spectra in the FT-Raman spectral range (approximately 0 to 3500 wavenumber shift from 1064 nm, or 1064 to 1700 nm) of molecules with a wide range of NIR-active functional groups shows that although absorption at the laser wavelength (1064 nm) is relatively small, some regions of the Raman spectrum coincide with NIR absorbances of 0.5 per cm or greater. Fortunately, the pharmaceutically important regions of the Raman shift spectrum from 0 to 600 cm(-1) and from 1400 to 1900 cm(-1) exhibit low self-absorption for most organic materials. A statistical analysis of transmission FT-Raman noise in spectra collected from different regions of a pharmaceutical tablet provides insight into both spectral distortion and reduced sampling volume caused by self-absorption.     

Thermal-changeable complex-refractive-index spectra of merocyanine aggregate films

Thermal behaviors of complex refractive index of merocyanine (MC) Langmuir-Blodgett (LB) films have been investigated with absorption spectrum measurements, which are obtained from the Kramers-Kronig (K-K) analysis. The complex-refractive-index spectra with an anomalous dispersion around a J-aggregate absorption band of MC molecules are changed by annealing temperatures. This thermal characteristic is attributed to the annealing-changeable MC J-aggregates. The MC J-aggregates in the LB films collapse in the annealing and become a monomer state. The refractive-index dispersion decreased with the collapse of MC J-aggregates. These behaviors are confirmed from the reflection spectrum measurements under the different conditions of incident light to the MC film samples.     

Growth of CdS nanoparticles in Y- and Z-type Langmuir–Blodgett thin film using 1,3-bis-(p-iminobenzoic acid)indane

Cadmium sulphide (CdS) nanoparticles were formed in 1,3-bis-(p-iminobenzoic acid)indane by exposing Cd²⁺ doped Y- and Z-type multilayered Langmuir–Blodgett (LB) films to H₂S gas. The growth of CdS nanoparticles were monitored by UV–visible spectroscopy measurements. It was observed that CdS nanoparticles in both Y- and Z-type LB films cause a blue-shift in absorption spectra. The surface morphology of LB films were characterized with atomic force microscopy DC electrical measurements were carried out for these LB films grown in a metal/LB film/metal sandwich structures with and without CdS nanoparticles. By analyzing I–V curves and assuming Schottky conduction mechanism the barrier height was found to be as 1.25 and 1.17?eV for Y-type unexposed and exposed samples; 1.18 and 1.25?eV for Z-type unexposed and exposed samples, respectively.     

Solution fabrication and photoelectrical properties of CuInS₂ nanocrystals on TiO₂ nanorod array

One-dimensional semiconductor architectures are receiving attention in preparing photovoltaic solar cells because of its superior charge transport as well as excellent light-harvesting efficiency. In this study, vertically aligned single-crystalline TiO(2) nanorods array was grown directly on transparent conductive glass (FTO), and then CuInS(2) nanocrystals were deposited on nanorods array by spin coating method to form TiO(2)/CuInS(2) heterostructure films. The resulting nanostructure assembly and composition was confirmed by field-emission scanning electron microscope (FESEM) , transmission electron microscopy (TEM), high-resolution TEM, and X-ray diffraction(XRD). Ultraviolet-visible absorption spectroscopy (UV-vis) data indicates that the absorbance of the nanocomposite film extended into the visible region compared with bare TiO(2) nanorod arrays. The surface photovoltage spectra (SPS) also showed a new and enhanced response region corresponding to the absorption spectrum. These results suggest that the novel CuInS(2) nanocrystals sensitized TiO(2) nanorod array on FTO photoelectrodes has a potential application in photovoltaic devices.     

Orientation of J-aggregate molecules in Langmuir film and Langmuir-Blodgett films of merocyanine dyes mixed with arachidic acid and n-octadecane and irradiation effect of visible light

Langmuir (L) film and Langmuir-Blodgett (LB) films of a merocyanine dyes (MC) containing C₁₈ alkyl chain mixed with arachidic acid (AA) and n-octadecane (OD) were fabricated. Surface-pressure-area isotherms of an L film and absorption spectra of LB films deposited on a substrate were measured. Amphiphilic molecular orientation in the L film and the built-up proportion of MC J-aggregates to monomer and H-aggregates in MC-LB films mixed with AA and OD were controlled by altering the molar ratio of AA and OD to MC. The built-up proportion of MC J-aggregates in LB films decreased and the J-aggregates decayed to monomer and H-aggregates by increasing the exposure power of a 608-nm monochromatic light.     

Electrical properties of a novel 1,3-bis-(p-iminobenzoic acid) indane Langmuir-Blodgett films containing ZnS nanoparticles

ZnS nanoparticles have been formed in a newly synthesized 1,3-bis-(p-iminobenzoic acid) indane (IBI) by exposing Zn2+ doped multilayered Langmuir-Blodgett (LB) film to H2S gas after the growth. The formation of ZnS nanoparticles in the LB film structure was verified by measuring UV-Visible absorption spectra. DC electrical measurements were carried out for thin films of IBI prepared in a metal/LB films/metal sandwich structure with and without ZnS nanoparticles. It was observed that ZnS nanoparticles in the LB films cause a blue-shift in the absorption spectra as well as a decrease in both capacitance and conductivity values. By analysing I-V curves and assuming a Schottky conduction mechanism the barrier height was found to be about 1.13 eV and 1.21 eV for IBI LB films without and with ZnS nanoparticles, respectively. It is thought that the presence of ZnS nanoparticles influences the barrier height at the metal-organic film interface and causes a change in electrical conduction properties of LB films.     

Langmuir-Blodgett films of Cu(II)-tetrakis (3,3-dimethylbutoxycarbonyl) phthalocyanine: a spectrophotometric and TEM analysis of their structure and morphology

Langmuir-Blodgett (LB) films of copper(II)-tetrakis (3,3-dimethylbutoxycarbonyl) phthalocyanine [Cu(dmbc)Pc] have been prepared from toluene solutions; multilayers (up to 80 layers) were deposited onto hydrophobic quartz substrates. The refractive index n and extinction coefficient κ at normal incidence have been determined from both transmission and reflection measurements carried out in the 400–800 nm spectral range. The optical absorption spectrum as a function of the incident photon energy was also registered in order to determine the optical transition type in Cu(dmbc)Pc LB films by using a band model approach. Linearly polarised light absorbance measurements were performed at room temperature in the same spectral range. The average orientation of the phthalocyanine molecular rings in the LB film, with respect to the normal to the substrate and the dipping direction, has been evaluated. We have found that such orientation differs from that determined for LB films deposited from ethyl acetate solutions.

Structural and morphological analysis were also carried out by transmission electron microscopy techniques. Small ordered domains in a low range order matrix were observed by high resolution images. The structure of the material in the substrate plane has been determined by electron diffraction performed on single ordered domains.