Near-Field and Polarized Evanescent Field Excited Fluorescence of Self-Organized Particle Arrays of Organic Dye

A wetting/dewetting process was utilized to prepare self-organized organic dye particles of micrometer and submicrometer size. Near-field scanning optical microscopy successfully identified near-field excited near-field fluorescence from single particles. The majority of the small particles with diameters around 2 mm or less, however, did not show fluorescence under near-field observation. In contrast, far-field fluorescence, when excited by a polarized evanescent field, was observed, with the intensity depending on the excitation polarization, indicating that molecules' transition moment within dye particles was oriented parallel to the substrate surface. Single particle fluorescence spectrum consistently showed an identical sharp peak with a large redshift, indicating that the particles were composed of identical dye aggregates similar to J-aggregates. These observations suggest that the near-field at the probe tip was polarized parallel to the probe axis. Another observation, that molecules were oriented in a similar direction among adjacent particles, suggests that the dewetting process contributed to the alignment of the molecular direction among adjacent particles, which further proves that the present specimen was formed by a self-organizing mechanism.     

Magneto-optic Fluorescence Behavior of Anthracene and Its Derivatives in a Diluted Magnetic Fluid Solution.

Variations in the fluorescence in the intensities of anthracene derivatives under a magnetic field were investigated in the presence of a dilute magnetic fluid. When excitation was carried out with light that was polarized parallel to the magnetic field, the intensity of the fluorescence that was polarized paralell to the magnetic field decreased by about 10%. Although the fluorescence intensities of most of the anthracene derivatives showed a similar decrease in magnitude, that of 9,10-dimethylanthracene showed a large decrease. On the other hand, fluorescence increased when excitation and fluorescence were perpendicular to the magnetic field. The obtained phenomena can be explaned by the formation of anisotropic assembly of magnetic fluid particles in the solution.     

Imaging contrast under aperture tip–nanoantenna array interaction

Periodic arrays of paired and single gold nanorods were imaged in the near field using reflection and transmission modes of a near-field scanning optical microscope at various wavelengths and polarizations of light in the visible range. The paired nanorods act like nanoantenna, and an array of them was initially designed as a negative-index material for the near infrared. Reverse contrast in reflection and transmission images is observed under illumination from the small aperture of a metal-coated fiber probe. By changing the relative orientation of the rods to the polarization, the reverse contrast switches to the normal contrast of near-field imaging. Coupling between the aperture and the nanorod array makes the contrast higher. Transmission through the aperture is enhanced if the aperture probe is positioned between the nanorods. The average near-field transmission exhibits an opposite sign of anisotropy relative to the far-field case. Aperture probes with larger diameters always show normal imaging contrast. The results demonstrate that the broad angular spectra of small-aperture sources play a crucial role in near-field interactions with nanorod arrays. The results also show that angular redistributions of these spectra after transmission or reflection from the nanorod array are likely due to excitation of localized and propagating plasmons.     

Spatial photoselection of single molecules on the surface of spherical microcavities

We show that ultrasensitive microdroplet-stream fluorescence techniques combined with surfactant forms of Rhodamine dyes can be used to probe single molecules on the surfaces of spherical microcavities. Individual octadecyl Rhodamine B molecules, shown previously by ensemble measurements to be localized and oriented at the surfaces of liquid microspheres, were spatially photoselected primarily along great circles lying perpendicular or parallel to the detection axis by use of polarized laser excitation. A polarization dependence is observed in the distribution of single-molecule fluorescence amplitudes that can be interpreted qualitatively in terms of position-dependent fluorescence-collection efficiencies.     

Scanning near-field optical images of ordered polystyrene particle layers in transmission and luminescence excitation modes

Scanning near-field optical images of hexagonally close-packed layers of polystyrene spherical particles with a diameter of 1.0 microm have been investigated. The layers were composed of particles that were doped either totally or partially with an organic fluorescent dye. Observations were made in the transmission and luminescence excitation modes with a scanning near-field optical microscope (SNOM) with a spatial resolution shorter than the wavelength of light. The patterns observed in the SNOM images are significantly dependent on the microstructures of layers, that is, the layers are either single or double layered, and the particles are either totally or partially doped. These results are discussed in terms of specific modes of electromagnetic waves transmitting across and along the layers after the local excitation at the tip end of the scanning microprobe.     

Scanning plasmon near-field microscopy on dye clusters

A scanning plasmon near-field microscope has been used to image dye clusters on a silver surface. This demonstrates the potential of optical near-field microscopy for the investigation of surfaces and non-conducting adsorbate layers. Images recorded in parallel with the conventional scanning tunneling microscope show the underlying conductive substrate.     

Investigation of the spontaneous emission rate of perylene dye molecules encapsulated into three-dimensional nanofibers via FLIM method

The decay dynamics of perylene dye molecules encapsulated in polymer nanofibers produced by electrospinning of polymethyl methacrylate are investigated using a confocal fluorescence lifetime imaging microscopy technique. Time-resolved experiments show that the fluorescence lifetime of perylene dye molecules is enhanced when the dye molecules are encapsulated in a three-dimensional photonic environment. It is hard to produce a sustainable host with exactly the same dimensions all the time during fabrication to accommodate dye molecules for enhancement of spontaneous emission rate. The electrospinning method allows us to have a control over fiber diameter. It is observed that the wavelength of monomer excitation of perylene dye molecules is too short to cause enhancement within nanofiber photonic environment of 330 nm diameters. However, when these nanofibers are doped with more concentrated perylene, in addition to monomer excitation, an excimer excitation is generated. This causes observation of the Purcell effect in the three-dimensional nanocylindrical photonic fiber geometry.     

Dewetting observations of ultrathin metallic films

Ultrathin metallic films like CoFe, Ta, Cu, Cr, and NiFe are widely used in magnetic devices such as magnetic random access memory (MRAM) and magnetic recording heads. Dewetting corrosions were often observed after O₂ plasma ashing in MRAM fabrications. The surface stability of these films was then examined. The results show that dewetting takes place when CoFe or Cu films are exposed to air after an O₂ plasma process. In contrast to the dewetting reported so far in organic or metallic liquid films on solid substrates, the observed dewetting does not occur in a liquid state but in a solid state. Several in situ and ex situ process methods were examined to control the dewetting. It is found that after ashing, the immediate immersion of wafer into acetone and ultrasonic cleaning some minutes after opening chamber can greatly suppress the occurrence of dewettings. Process examinations show that the heating is unimportant for the formation of the dewetting, while moisture in air may play an important role in the formation of the dewetting, acting as a necessary catalyst. Several dewetting patterns were observed, and the pattern shape depends not only on the thickness of the film, but also on the plasma parameters. Possible mechanisms responsible for the formation of these patterns are discussed.     

Electromagnetic interaction of fluorophores with designed two-dimensional silver nanoparticle arrays

We study the fluorescence enhancement of dye molecules adsorbed on regular two-dimensional arrays of designed silver nanoparticles. The silver particles show two orthogonal optical resonances at different wavelengths because of their elongated shape. The short-wavelength resonance was designed to fit to the absorption maximum of the fluorophore. When the excitation light drives the short-wavelength resonance, the measured fluorescence intensity is strongly enhanced compared to that for the orthogonal particle orientation. This shows directly a strong electromagnetic coupling between the nanoparticles and the fluorophore. Additionally enhanced photochemical bleaching is observed due to the interaction of fluorophores with the particles. Using a rate model describing the fluorescence enhancement and the bleaching enhancement, an average value for the particle-induced increase in the radiative fluorescence rate is obtained, together with a lower limit for the averaged particle-induced field intensity enhancement factor. Received: 3 July 2001 / Revised version: 3 September 2001 / Published online: 15 October 2001     

Morphology and bilayer integrity of small liposomes during aerosol generation by air-jet nebulisation

Small liposome suspensions (hydrodynamic diameter, 80–130 nm) were nebulised, and the resulting changes in morphology and bilayer integrity were found to be related to surface properties controlled by bilayer composition. Four separate liposome compositions (or liposome types) were investigated using three different phospholipids with unique properties. Morphological changes were studied using light scattering and imaging of liposomes before and after nebulisation, and structural integrity was investigated on the basis of the retention of an encapsulated dye (probe molecule). Nebulisation generated droplets contained liposomes. The liposome particles generated on droplet evaporation had a hollow structure as evidenced by electron imaging, indicating that the lipid bilayer does not collapse on evaporation. The particles of all compositions had mobility diameters between 50 and 90 nm, 1.4–1.6 times smaller than their diameters (hydrodynamic) measured before nebulisation, implying considerable volume shrinkage. Liposomes that had polymer-conjugated lipids covering their external surface underwent aggregation during nebulisation, evidenced by increased diameter after nebulisation. Incorporation of charged lipids reduced nebulisation-induced aggregation, but induced greater membrane rupture during aerosol generation, causing leakage of encapsulated probe molecules. Incorporation of both cholesterol and charged lipids prevented aggregation, but also preserved bilayer integrity, evidenced by the maximum retention of encapsulated dye observed in these conditions (>85%). The findings suggest that liposome bilayer composition can be manipulated to improve the efficiency of liposome aerosol delivery.     

Near-Field Birefringence Response of Liquid Crystal Molecules in Thickness Direction of Liquid Crystal Thin Film Orientated by Shear Force

Information of molecular orientation in nematic liquid crystal （LC） is attractive and important for applications in the field of display devices. We demonstrate a novel method using a birefringence scanning near-field optical microscope （Bi-SNOM） with a probe which is inserted into the LC thin film to detect the molecular orientation from its birefringence responses in the thickness direction of the LC thin film. The probe is laterally vibrated when going forward into the LC thin film, and the retardation and azimuth angle are recorded as the probe going down. Firstly, the thickness of the LC thin film is measured by the shear force detection. Since the shear force acts as a stimulation to reorientate the LC molecules above the substrate surface, we can detect the molecular orientation caused by a polyimide alignment substrate and the effect to molecular orientation caused by vibration of fibre probe. As a result, the orientation profiling of the LC film in depth direction is obtained in both the cases that the direction of probe vibrating is vertical/parallel to the rubbing direction of the alignment film. Furthermore, the thickness of completely orientated layers just above the substrate surface can also be obtained by either vibrating probe or no-vibrating probe. Ultimately, the LC thin film can be modelled in thickness direction from all the results using this method.     

Fabrication of a Near-Field Optical Fiber Probe with a Nanometric Metallized Protrusion

We have developed a novel probe with a nanometric metallized protrusion extending through a subwavelength aperture to increase optical near-field excitation and collection efficiencies. The apex diameter of the fabricated metallized protrusion was 35 nm. The Intensity distribution of the optical near-field at the apex of the probe was measured by scanning another probe across the apex, and it was observed that strong optical near-field was generated at the apex of the metallized protrusion. The width of the intensity distribution was 150 nm including instrumental resolution. Probes with spherical and ellipsoidal metallized protrusion were also fabricated, by which enhancement of the optical near-field is expected due to localized plasmon excitation.     

Using gold colloid nanoparticles to modulate the surface enhanced fluorescence of Rhodamine B

Enhanced fluorescence from Rhodamine B (RB) mixed with gold colloids has been observed under ultraviolet irradiation. Spectroscopic studies show that with the increasing gold colloids content, the fluorescence of RB at about 590 nm increases firstly and then decreases with slight red shift. These features observed in the experiment can be explained by the local electric field enhancement via surface plasmon resonance (SPR) of gold nanoparticles. Fluorescence enhancement is obtained when the emission frequency of RB lies within the bandwidth of local field enhancement from gold nanoparticles. Theoretical calculation results show that the local field band red shifts obviously with increase the thickness of dye shell which capped on gold particle, whereas the fluorescence band of RB is fixed around 590 nm. Therefore, the red shift and non-monotonic change of fluorescence intensity from RB is attributed to the dye shell dependent red shift of local field band of gold particles.     

Fluorescence spectra of Rhodamine 6G for high fluence excitation laser radiation

Fluorescence spectral changes of Rhodamine 6G in ethanol and glycerol solutions and deposited as a film on a silica surface have been studied using a wide range of pumping field fluence at 532 nm at room temperature. Blue shift of the fluorescence spectra and fluorescence quenching of the dye molecule in solution are observed at high excitation fluence values. Such effects are not reported for the film sample. The effects are interpreted as the result of population redistribution in the solute-solvent molecular system induced by the high fluence field and the fluence dependence of the radiationless decay mechanism.     

扫描近场光学显微镜的光耦合偶极子模型

为了研究扫描近场光学显微镜中探针和粗糙样品表面的耦合相互作用,提出了一种光耦合偶极子模型.在该模型中,探针和样品突起都由光极化偶极子表示,在准静态电磁场近似的情况下样品表面的诱导极化效应由影像偶极子表示,应用偶极子辐射理论可以得到系统的自洽场方程.此模型提供了一种直观分析扫描近场光学显微镜中探针和样品相互作用机理的方法.在此基础上,进一步讨论了金属样品的近场成像特点和其特有的局域光学共振现象.数值结果表明：不同于一般的介质样品,金属样品的近场图像与入射光频率直接相关,改变入射光的频率,获得的样品近场图像的形状和对比度都会发生变化.特别是当入射光频率处于样品极化共振范围内时,金属纳米粒子的极化率会出现光极化共振,这样就可以获得样品粒子的最大有效尺寸,为提高系统的分辨率提供了一条重要途径.     

Internal reflection mode scanning near-field optical microscopy with the tetrahedral tip on metallic samples

An internal reflection mode is introduced for scanning near-field optical microscopy (SNOM) with the tetrahedral tip. A beam of light is coupled into the tip and the light specularly reflected out of the tip is detected as a photosignal for SNOM. An auxiliary STM mode is used to control the distance during the scanning process and to record the topography of the sample simultaneously with the SNOM image. Images were obtained of different metallic samples which show a contrast in the order of 10% of the total reflected photosignal. In images of metallic samples an inverted contrast is consistently obtained compared to images previously obtained of comparable samples in a transmission mode. The contrast shows a pronounced dependence on the polarization of the incident beam with respect to the orientation of the edges of the tip. In the case of gold surfaces, the photosignal as a function of distance between the tip and the surface shows a pronounced peak in the near-field range of 0–20 nm which is tentatively attributed to the excitation of surface plasmons on the gold surface. The pronounced near-field effects and the strong contrast in the near-field images and the resolution well below 50 nm are an indication of a highly efficient coupling of the incident beam to a local excitation of the tip apex which is essential for the function of the tip as a probe for SNOM. Received: 17 May 1999 / Accepted: 18 May 1999 / Published online: 21 October 1999     

近场显微干涉成像中的探测角度和偏振问题研究

用偶极子耦合系统来模拟近场干涉测量中的探针样品关系,并利用各电场分量之间的组合方程组精确计算出其可能探测到的强度和相位像。结果显示,近场干涉所测量到的近场像的分辨力和探测器的方位及参考光的偏振方向之间有较强的依赖关系,随着探测器位置不同或者参考光偏振方向的变化,同一样品在同一照明条件下所得到的图像也会发生明显的改变。在倏逝波照明的情况下,近场像的精确度随着探测器相对于样品视角的增大而改善,且在不同偏振方向的近场像中,只有偏振方向垂直于样品表面的像能真实反映样品的细节分布,且同时具有足够的强度分布。     

The timescale of spinodal dewetting at a polymer/polymer interface

We investigate the dynamics of spinodal dewetting in liquid-liquid polymer systems. Dewetting of poly(methyl-methacrylate) (PMMA) thin films on polystyrene (PS) “substrates” is followed in situ using neutron reflectivity. By following the development of roughness at the PS/PMMA interface and the PMMA surface we extract characteristic growth times for the dewetting process. These characteristic growth times are measured as a function of the molecular weight of the two polymers. By also carrying out experiments in the regime where the dynamics are independent of the PS molecular weight, we are able to use dewetting to probe the scaling of the PMMA thin film viscosity with temperature and molecular weight. We find that this scaling reflects bulk behaviour. However, absolute values are low compared to bulk viscosities, which we suggest may be due in part to slippage at the polymer/polymer interface. Received 25 June 2001 and Received in final form 5 December 2001     

The molecular aggregation of pyronin Y in natural bentonite clay suspension

The molecular aggregation and spectroscopic properties of Pyronin Y (PyY) in the suspension containing natural bentonite clay were studied using molecular absorption, steady-state and time-resolved fluorescence spectroscopy techniques. Interaction between the clay particles and the cationic dye compounds in aqueous solution resulted in significant changes in spectral properties of PyY compared to its molecular behavior in deionized water at the same concentration. These changes were due to the formation of dimer and aggregate of PyY in the clay suspension as well as the presence of the dye monomer. The H-type aggregates of PyY in the clay suspension were identified by the observation of a blue-shifted absorption band of the dye compared to that of its monomer. In spite of diluted dye concentrations, the H-aggregate of PyY in the clay suspension was formed. The intensive aggregation in the clay suspension attributed to the localized high dye concentration on the negatively charged clay surfaces. Adsorption sites of PyY on the clay particles were discussed by deconvulated absorption and excitation spectra. Fluorescence spectroscopy studies revealed that the fluorescence intensity of PyY in the clay suspension is decreased by H-aggregates drastically. Moreover, the presence of H-aggregates in the clay suspension resulted in the decrease of fluorescence lifetime and quantum yield of PyY compared to those in deionized water.     

飞秒荧光亏蚀光谱技术研究液相体系取向弛豫

溶液中分子的快速弛豫过程直接反映了溶液中溶质和周围溶剂分子间的相互作用[1- 3 ] .在液相体系中分子取向通常是随机分布的 .当溶质分子被线偏振光激发至激发态时 ,其分子取向将由原来各向同性的球形分布瞬间变成各向异性的椭球分布 .由于溶质分子周围大量溶剂分子的存在 ,通过二者之间相互作用 ,激发态溶质分子在一定方向上的取向优势将很快弛豫掉 .这种溶液中的取向弛豫过程通常是几个到几百皮秒[1- 3 ] .飞秒分辨荧光亏蚀光谱原理和实验方法见文献[4 - 7] .当溶液中的溶质分子被线偏振飞秒激光脉冲激发至电子激发态时 ,经过一定的延迟…