Nucleobase-Specific Enhancement of Cy3 Fluorescence

We report on the role of dye–nucleobase interactions on the photophysical properties of the indocarbocyanine Cy3. The fluorescence efficiency and lifetime of Cy3 increase in the presence of all four nucleoside monophosphates. This behavior correlates with an increase in the activation energy for photoisomerization and a ∼4 nm red shift in the fluorescence spectrum. Changes are more dramatic for the purines (dAMP, dGMP) than the pyrimidines (dCMP, dTMP), and for the nonsulfonated cyanine (DiIC₂(3)) than the sulfonated dye (Cy3–SE). These results are consistent with a model in which Cy3–nucleoside π–π interactions decrease the efficiency of photoisomerization, increasing the efficiency of fluorescence. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Photostability of Cy3 and Cy5-Labeled DNA in the Presence of Metallic Silver Particles

We examined the photostability of a double-stranded DNA oligomer, covalently labeled with Cy3 or Cy5 on one strand, in the presence of metallic silver island films. In our experimental configuration a minor fraction of the labeled DNA was close to the silver particles and the remainder was distant from the particles. Proximity of the fluorophores to silver island films resulted in increased intensity. Upon continuous illumination we found a fraction of the emission that was resistant to the photobleaching. The emission spectra of the residual fractions were identical to the initial spectra. The frequency-domain lifetime measurements of this fraction revealed greatly shortened decay times. These results are consistent with the photostable fraction being close to the silver particles. This results suggest that the number of photons detected per fluorophore, prior to photobleaching, can be increased 5-fold or more by proximity to silver particles. Localization at an optimal distance from the silver surface may result in larger enhancements.     

Electromagnetic energy transport via linear chains of silver nanoparticles

We propose the idea of a subwavelength-sized light guide represented by a linear chain of spherical metal nanoparticles in which light is transmitted by electrodynamic interparticle coupling. The light-transport properties of this system are investigated by use of model calculations based on generalized Mie theory. Considering Ag particles of 50-nm diameter, we find optimum guiding conditions for an interparticle spacing of 25 nm, and a corresponding 1/e signal-damping length of 900 nm is evaluated. The proposed principle of optical energy transport may be useful for subwavelength transmission lines within integrated optics circuits and for near-field optical microscopy.     

光照法在玻璃基底上原位生长金纳米结构及其光谱性质

 以硅烷化后吸附粒径小于10 nm的金种子的玻璃片为基底,聚乙烯吡咯烷酮为还原剂,在荧光灯照射条件下还原氯金酸,制备出表面具有金纳米粒子聚集结构的基底。用原子力显微镜、扫描电镜、X射线衍射、吸收和荧光光谱研究了基底的性质。结果表明：随着光照时间增加至20 h,金种子长大为平均粒径140 nm的不规则状多晶粒子,且出现双层粒子堆叠。基底的吸收光谱上出现了由金粒子的表面等离子体激元偶极子耦合引发的强烈吸收峰,随着粒子粒径增大,耦合峰在600~800 nm波段内连续红移升高,表明耦合程度不断增强。在223 nm紫外光的激发下,基底的荧光光谱上在405 nm处出现发射峰,是由金粒子表面激发电子和空穴的复合辐射造成的,发光强度随着基底上粒子平均尺度增加而减弱。     

Dry etch damage and its effect on electronic and optical nanostructures

The creation of nano-structures in 3–5 semiconductors is currently of great interest. If the conventional route of pattern definition in a resist followed by pattern transfer is used, this implies in most cases electron beam lithography and some form of dry etching. Using electron beam lithography, patterns of 10nm width on 40nm centre to centre spacing can be transfered to metal lines on thin substrates; even on normal wafers, linewidths of 25nm on 60nm spacing are achievable with state of the art machines.If the creation of a raised structure is necessary because of the physics of the situation, it is important to consider the damage which may be introduced by dry etching. The methods by which dry etch damage can be revealed are discussed, and the ways in which it can be reduced mentioned. Progress towards understanding the microscopic nature of the damage will be reviewed. Examples are drawn from etching of GaAs/GaAlAs in Silicon tetrachloride and methane/hydrogen.     

Multicomponent periodic nanoparticle superlattices

In this article, we review the state-of-the-art in the preparation and characterization of multicomponent self-assembled superlattices of colloidal nanoparticles with core sizes in the range of 2–20 nm and interparticle spacing less than 2 nm down to intimate contact stemming from sintering. Several aspects of the field are discussed, including: structural organization, the role of particle size distribution, key interparticle forces at play, and methods of investigation of the structures. Contrary to the extensively studied colloidal crystals composed of microscale particles, the nanoparticles possess unique size-dependent properties, such as electronic, optical, or magnetic, which when combined into periodic structures can potentially lead to new collective states stemming from precise positioning of the nanocolloids. As such, we examine a number of emerging applications of this new class of metamaterials. Finally, we speculate on the potential impact of these materials, the new directions, and the challenges for the researchers.     

Plasmonic Enhancement of Single-Molecule Fluorescence Near a Silver Nanoparticle

In this short paper, we reported the enhanced fluorescence from a single fluorophore bound to a 50nm silver nanoparticle. We found that on average the Cy5 molecules bound to metal nanoparticles are approximately 15-fold brighter than that of free dyes, and that single molecule lifetimes are shorter as compared to free fluorophores. The increased emission rate is primarily the result of local plasmon enhancement. These results demonstrate that the use of fluorophore-metal interactions can increase the brightness and photostability of fluorophores for single molecule detection.     

Fluorescence properties of biochemicals in dry NaCl composite aerosol particles and in solutions

Several fluorophores, such as tryptophan, NADH, NADPH, and riboflavin are found in airborne micro-organisms. In this work, the fluorescence properties of these biochemicals were studied both in dry NaCl composite aerosol particles and in saline solutions by means of laser-induced fluorescence. Fluorescence spectra were measured from individual, airborne aerosol particles and from solutions in cuvette. The excitation wavelength was varied in steps from 210 nm to 419 nm and the fluorescence was detected within a wavelength band of 310–670 nm. For each sample, the measured fluorescence emission spectra were combined into fluorescence maps. The fluorescence maximum of riboflavin in a dry NaCl composite particle is 20 nm red-shifted compared with the solution, whereas the maxima are blue-shifted by about 25 nm for tryptophan and 15 nm for NADH and NADPH. The molecular fluorescence cross sections have significant differences between the aerosol particles and the solutions, except for tryptophan. For NADH and NADPH the cross sections are over 20 times larger in the aerosol particles than in the solutions probably as a result of partial quenching of fluorescence in solution caused by the collision or stacking with the adenine moiety. The fluorescence cross section of riboflavin is almost 60 times larger in the solution than in the dry NaCl composite aerosol. This is probably caused by the different microenvironment around the fluorophore molecule and by the concentration quenching in the particles where the fluorescing molecules are relatively close to each other.     

Characterization of the Plasmonic Fluorescence Enhancement of Poly (3-hexylthiophene) for Organic Solar Cell Applications

The dependence of surface-enhanced fluorescence of the semiconducting polymer poly (3-hexylthiophene) on the diameter of silver nanoparticles was studied. Particle suspensions with a high degree of monodispersity, ranging in diameter from 15 to 153 nm, were synthesized. Polymer films were spin-cast onto substrates containing immobilized silver particles. Fluorescence enhancement factors ranged from 0.9 to 4.9 and generally improved with increasing particle size. Normalization of the fluorescence enhancement to the number of interrogated particles showed an 800-fold increase in enhancement between the smallest and largest particles.     

Fluorescence enhancement of acridine orange in a water solution by Au nanoparticles

The surface enhanced fluorescence effect of acridine orange fluorophore in the proximity of Au nanoparticles has been investigated experimentally in the system of aqueous solution.Significant enhancement of the fluorescence intensity was observed when the system was excited with 532 nm or 442 nm CW lasers.The influence of the distances between neighboring Au particles as well as that between the fluorophore molecules and the Au surface were explored experimentally.The results demonstrated that a compact distribution of metallic particles was able to produce stronger fluorescence enhancement.Proper separation between the fluorophore molecules and the metal surface was favorable for a better enhancement.     

Thin films by regular patterns of metal nanoparticles: Tailoring the optical properties by nanodesign

Ultrathin metal films consisting of regular two-dimensional arrays of 44–95 nm sized silver nanoparticles were fabricated by electron-beam lithography. By independent variation of particle shape and interparticle distance, respectively, the film's optical extinction maximum wavelength can be tuned in a range from 460 nm to 520 nm and the bandwidth between 50 and 100 nm. The results suggests the potential of lithographically designed nanoparticle films as thin layer material with tailorable optical properties for applications in microoptics and optoelectronics.     

Optimizing surface-enhanced Raman scattering by template guided assembling of closely spaced silver nanocluster arrays

We present an easy approach to synthesize closely spaced regular arrays of silver nanoclusters, which are self-assembled by depositing gas-phase synthesized metal nanoclusters onto pre-patterned triblock copolymer templates. The array has a high particle density of about 2 ×10³ particles per μm², and an average interparticle space of about 20 nm. The surface plasmon resonance wavelength of the array is tuned due to the interparticle plasmon coupling. High SERS sensitivity for less than one layer trans-1,2-bi-(4-pyridyl) ethylene (BPE) molecule detection, with an enhancement factor of 2.6 ×10⁶, has been demonstrated for a substrate with this array. The enhanced Raman signal was found to be 5 times higher than that measured from the substrate with randomly distributed silver nanoparticles.     

Formation of superconductivity through interparticle interactions in ferrimagnetic-like Sn nanoparticle assemblies

We report on the observation of the development of superconductivity through interparticle interactions in 3, 5, 7, and 23 nm ferrimagnetic-like Sn nanoparticle assemblies. The Sn nanoparticles are fabricated using the gas condensation method. Each sample consists of a macroscopic amount of individual Sn nanoparticles without a capping molecule. Ferrimagnetism is found but no sign of superconductivity can be detected when the 3 nm particles are very loosely assembled. A reduction in the mean particle moment results when the packing fraction of the assembly is increased. Superconductivity occurs when a critical packing fraction is reached. Beyond this, the superconducting transition temperature T _C continues to increase and noticeably exceeds that of the bulk T _C. The enhancement of superconductivity by interparticle interactions has also been observed in 5, 7, and 23 nm particle assemblies, with the effect becoming less significant in larger particles. We attribute these observations to the transfer of electrons between the surface and the core regions of the nanoparticles triggered by finite size effects and interparticle interactions.     

Surface plasmon resonance in near-field coupled gold cylinder arrays fabricated by EUV-interference lithography and hot embossing

Arrays of metal nanoparticles with nanometer-scale gaps between the particles is highly interesting for plasmonic field enhancement applications. We report a simple method to fabricate arrays of closely spaced Au particles with inter-particle separation down to 20 nm. We used extreme ultraviolet interference lithography (EUV-IL) and a mechanical press to fabricate two-dimensional arrays of Au nanoparticles. Lithographically produced particle arrays were modified by hot pressing in a nanoimprint machine and the gap was varied in a range from 50 nm to below 20 nm. Optical measurement shows two resonances at 520 nm and 620 nm, with the latter gaining strength as the gap is reduced. The experimental and theoretical investigations using a FDTD algorithm demonstrate that the low-energy resonance can be assigned to a collective surface plasmon resonance arising from the strong near-field coupling between the nanoparticles. Surface Enhanced Raman Spectroscopy (SERS) experiments performed on a model molecule (BPE) show a large gain in signal intensity as a result of the reduced gaps between the particles.     

Large-scale plasmonic-SERS templates by successive growth steps

This work presents the fabrication of large-scale tunable-plasmonic surface-enhanced Raman scattering (SERS) templates and investigates their Raman enhancement. Substrates for SERS were prepared by deposition of gold nanoparticles on a glass slide followed by their growth. A plasmon shift was observed upon growing due to the formation of elongated nanoparticles and their mutual coupling. The changes in particle size, shape and interparticle distances were indicated by SEM measurements. Surface-enhanced Raman spectra of Nile blue A at a very low concentration on top of a blocking layer were measured. The overall Raman enhancement is correlated with the number of growth steps. For excitation at 532 nm four growth steps lead to maximum enhancement. Better overlap of excitation laser and the plasmon resonances upon growing increased the enhancement until four steps while further growing decreased the enhancement. At longer wavelengths excitation (633 and 785 nm) the enhancement further increased beyond the fourth growth step. This enhancement is caused by the plasmon excitation of narrower gap sizes. The proposed procedure for the SERS substrates is simple, allows covering large surface areas and plasmon band tuning from 530 nm to the near infrared in order to increase overall Raman enhancement.     

基于双表面等离子激元吸收的纳米光刻

光刻技术(lithography)是微纳结构制备的关键技术之一.受限于光的衍射极限,传统光刻方法进一步缩小特征尺寸变得越来越难.表面等离子激元(surface plasmon polariton,SPP)作为光与金属表面自由电子密度振荡相互耦合形成的一种特殊电磁形式,具有波长短、场密度大、异常色散等特点,在突破传统光学衍射极限的研究和应用中具有重要的学术和实用价值.本文针对SPP在光刻胶中的非线性吸收及其在大视场纳米光刻中的应用进行了理论和实验探索.在回顾SPP概念的基础上,阐述了双SPP吸收的概念及其应用于纳米光刻的优势,明确了该效应具有与传统双光子吸收不同的内涵和特性.在800和400nm飞秒激光的作用下,实现了基于双SPP吸收效应的周期干涉条纹,同时验证了双SPP吸收的闽值效应,通过控制曝光计量实现了图形线宽的调控,最小线宽小于真空光波长的1/10.利用SPP波长短、场增强的特点,并结合非线性吸收的闽值效应,单次曝光区域比纳米图形尺度大4 5个数量级,曝光区域的直径可达1.6 mm.同时制备出较为复杂的同心圆环结构.基于双SPP吸收独有的特性以及SPP丰富的模式,有望进一步在大光刻视场、超小尺度图形光刻技术上获得突破.     

Fabrication of Nanoimprint Stamp Using Interference Lithography

Interference lithography is used to fabricate a nanoimprint stamp, which is a key step for nanoimprint lithography. A layer of chromium in thickness of about 20 nm is deposited on the newly cleaned fused silica substrate by thermal evaporation, and a layer of positive resist in thickness of 150nm is spun on the chromium layer. Some patterns, including lines, holes and pillars, are observed on the photoresist film by exposing the resist to interference patterns and they are then transferred to the chromium layer by wet etching. Fused silica stamps are fabricated by reactive ion etching with CHF3/O2 as etchants using the chromium layer as etch mask. An atomic force microscope is used to analyse the pattern transfer in each step. The results show that regular hole patterns of fused silica, with average full width 143nm at half maximum （FWHM）, average hole depth of 76nm and spacing of 450nm, have been fabricated. The exposure method is fast, inexpensive and applicable for fabrication of nanoimprint stamps with large areas.     

Identification of single fluorescently labelled mononucleotide molecules in solution by spectrally resolved time-correlated single-photon counting

We describe a method to identify single dye-labelled mononucleotide molecules in solution with high classification probability based on confocal microscopy in combination with spectrally and time-resolved fluorescence detection with two detectors. For efficient excitation of the labelled mononucleotide molecules JA133-dUTP, JA169-dUTP, Cy5-dCTP, and JA242-dUTP a short-pulse diode laser emitting at 634 nm with a repetition rate of 64 MHz was applied. The time-resolved fluorescence signals of individual molecules were analyzed and identified by a maximum likelihood estimator (MLE). Scatter plots of spectrally and time-resolved fluorescence data demonstrated the existence of four distinct populations with symmetrical shape. The distributions of each of the mononucleotide conjugates were determined by fitting a superposition of two independent Gaussians. Taking only those single-molecule bursts which contain more than 50 photon counts, three labelled mononucleotide molecules were identified in solution by spectrally and time-resolved fluorescence spectroscopy with a probability of correct classification of ≈99%. Received: 31 March 2000 / Revised version: 31 May 2000 / Published online: 13 September 2000     

Integral fluorescence enhancement by silver nanoparticles controlled via PMMA matrix

The metal-enhanced fluorescence is measured with different thickness of emission film. Silver nanoparticles are immobilized on glass slide by chemical self-assembly method. Rhodamine B molecules are dispersed in the polymer matrix of Poly(methyl methacrylate) (PMMA), then spin coated on prepared silver particles substrate with different thickness from 15 nm to 70 nm. The enhanced fluorescence is observed depending on the thickness of emission film since the average distance between rhodamine B molecules and silver nanoparticles is altered by the PMMA matrix. The 5-fold enhancement is attained. The experiment was explained qualitatively by an integral fluorescence enhancement.     

Three‐dimensional optical laser lithography beyond the diffraction limit

Direct laser writing has become a versatile and routine tool for the mask‐free fabrication of polymer structures with lateral linewidths down to less than 100 nm. In contrast to its planar counterpart, electron‐beam lithography, direct laser writing also allows for the making of three‐dimensional structures. However, its spatial resolution has been restricted by diffraction. Clearly, linewidths and resolutions on the scale of few tens of nanometers and below are highly desirable for various applications in nanotechnology. In visible‐light far‐field fluorescence microscopy, the concept of stimulated emission depletion (STED) introduced in 1994 has led to spectacular record resolutions down to 5.6 nm in 2009. This review addresses approaches aiming at translating this success in optical microscopy to optical lithography. After explaining basic principles and limitations, possible depletion mechanisms and recent lithography experiments by various groups are summarized. Today, Abbe's diffraction barrier as well as the generalized two‐photon Sparrow criterion have been broken in far‐field optical lithography. For further future progress in resolution, the development of novel tailored photoresists in combination with attractive laser sources is of utmost importance.