Silver nanostructure arrays abundant in sub-5 nm gaps as highly Raman-enhancing substrates

Two types of highly Raman-enhancing arrays substrates were fabricated using anodic aluminum oxide (AAO) templates by controlling the AAO template temperature and evaporated silver thickness during e-beam evaporating: complex patterned Ag nanoparticle arrays abundant in sub-5 nm gaps (type I); hexagonal Ag nanopore arrays (type II). The surface enhanced Raman scattering (SERS) enhancement factors (EF) of both substrates are estimated experimentally to exceed 10⁵, especially that of type I reaches 10⁷ due to the existence of numerous sub-5 nm gaps. The simulation using finite-difference time-domain (FDTD) method confirmed that gap effect has significantly improved the substrates’ SERS activity.     

Nonlinear optical properties of periodic gold nanoparticle arrays

Periodic Au nanoparticle arrays were fabricated on silica substrates using nanosphere lithography. The identical single-layer masks were prepared by self-assembly of polystyrene nanospheres with radius R = 350 nm. The structural characterization of nanosphere masks and periodic particle arrays was investigated by atomic force microscopy. The nonlinear optical properties of the Au nanoparticle arrays were determined using a single beam z-scan method at a wavelength of 532 nm with laser duration of 55 ps. The results show that periodic Au nanoparticle arrays exhibit a fast third-order nonlinear optical response with the nonlinear refractive index and nonlinear absorption coefficient being n₂ = 6.09 × 10⁻⁶ cm²/kW and β = −1.87 × 10⁻⁶ m/W, respectively.     

Nonlinear optical properties of Au/ZnO nanoparticle arrays

The triangular-shaped Au/ZnO nanoparticle arrays were fabricated on fused quartz substrate using nanosphere lithography. The structural characterization of the Au/ZnO nanoparticle arrays was investigated by atomic force microscopy. The absorption peak due to the surface plasmon resonance of Au particles at the wavelength of about 570 nm was observed. The nonlinear optical properties of the nanoparticle arrays were measured using the z-scan method at a wavelength of 532 nm with pulse duration of 10 ns. The real and imaginary part of third-order nonlinear optical susceptibility, Re χ⁽³⁾ and Im χ⁽³⁾, were determined to be 1.15 × 10⁻⁶ and −5.36 × 10⁻⁷ esu, respectively. The results show that the Au/ZnO nanoparticle arrays have great potential for future optical devices.     

膜结构对金纳米线阵列表面增强拉曼散射的影响

金纳米线阵列作为表面增强拉曼散射的基底能够产生有效的增强效应,金纳米线阵列通过金线之间的电场耦合产生增强的拉曼信号。在实验中,制备出金纳米线阵列与金纳米刷,两种样品结构不同,金纳米刷的一面带有金膜。用巯基吡啶作为探针分子,金纳米刷的SERS实验显示出很好的增强效应,增强因子为106,不同位点的SERS谱具有区域不均一的特征。而相同实验条件下的金纳米线阵列的增强因子只有102。光学吸收谱表明这两种结构均发生了共振吸收增强电场,对其结构的分析表明,这两种结构具有不同的电场局域化分布,同时金纳米刷中金线上端强烈的电场耦合,这是其具有更好的增强效用的原因。同时,4-MP的表面增强拉曼谱的变化特征体现了化学增强效应的影响。     

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.     

Plasmon resonance modulated photoluminescence and Raman spectroscopy of diindenoperylene organic semiconductor thin film

In a comparison between a bare diindenoperylene (DIP) film and a DIP film spin-coated with a layer of gold nanoparticles, we have investigated the influence of plasmon resonances in the gold particles on spectroscopic properties of the molecular film. Under off-resonant excitation with a laser at 633 nm, the bare DIP film showed only weak photoluminescence (PL) and Raman signals, but after spin-coating gold nanoparticles on such a DIP film, we found an enhancement of both the PL and Raman signals by a factor of about 3, whereas no enhancement could be observed when the same sample was excited with laser light of 488 nm. This difference reveals that at 633 nm, plasmon resonances in the gold nanoparticles are excited, leading in turn to an enhancement of PL and Raman signals of the weakly absorbing DIP film via coupling between plasmons in the gold particles and exciton-polaritons in the molecular film. For the laser at 488 nm, due to a much larger absorption coefficient of DIP, excitons in the molecular film are directly excited, out-weighing the influence of an off-resonant coupling to the plasmon resonances in the gold particles occurring at much lower energy.     

Fabrication and applications of ultraflexible nanostructures using dielectric heating-assisted nanoimprint on PVC films

We developed dielectric heating-assisted nanoimprint method for rapid fabrication of ultraflexible nanostructures. Using spin-coating polyvinyl-chloride (PVC) film on the glass slide, the dielectric heating on PVC film helped the pattern transfer from the mold to PVC film in few seconds. Various kinds of nanostructures were successfully made on PVC films with about 20-μm thickness. We demonstrated the applications of ultraflexible metallic nanostructures for bending measurement using surface plasmon resonance (SPR) and surface enhanced Raman scattering (SERS) on the curved surfaces. For measuring bending angles using SPR on capped nanowire arrays, the minimum detection angle was 2.4 × 10⁻³ degree under 0.02 nm wavelength resolution. For SERS measurement, the nanorod arrays on a curved substrate can increase SERS signals for two times as compared to planar SERS substrate.     

Nanoparticle composites: FePt with wide-band-gap semiconductor

We present a simple way to synthesize FePt and ZnO (wide-band-gap semiconductor) nanoparticle composites. The FePt nanoparticles were fabricated using the method reported by Sun et al. By controlling the heating rate, 3 nm FePt nanoparticles were synthesized. Well-dispersed FePt and ZnO nanoparticle composites were prepared by further adding zinc acetate and oleyl amine into the 3 nm FePt nanoparticle dispersion. By controlling the molar ratio of the FePt and zinc acetate, FePt and ZnO nanoparticle composites with different FePt particle fractions were obtained. The intensity of photo luminescence spectra of the nanoparticle composites increases very much with decreasing FePt particle fraction, whereas the peak position shifts a little. After annealing at 550 °C for half an hour, the nanoparticle composites become magnetically hard or semi-hard with coercivity much dependent on the FePt particle volume fraction. The coercivity of the composites increases with annealing temperature. The composites hold the promise of applications in new generation recording and/or optical devices.     

Failure behavior of ITO diffusion barrier between electroplating Cu and Si substrate annealed in a low vacuum

A structure of Cu/ITO(10 nm)/Si was first formed and then annealed at various temperatures for 5 min in a rapid thermal annealing furnace under 10⁻² Torr pressure. In Cu/ITO(10 nm)/Si structure, the ITO(10 nm) film was coated on Si substrate by sputtering process and the Cu film was deposited on ITO film by electroplating technique. The various Cu/ITO(10 nm)/Si samples were characterized by a four-point probe, a scanning electron microscope, an X-ray diffractometer, and a transmission electron microscope. The results showed that when the annealing temperature increases near 600 °C the interface between Cu and ITO becomes unstable, and the Cu₃Si particles begin to form; and when the annealing temperature increases to 650 °C, a good many of Cu₃Si particles about 1 μm in size form and the sheet resistance of Cu/ITO(10 nm)/Si structure largely increases.     

Very high coercivities of top-layer diffusion Au/FePt thin films

The Au/FePt samples were prepared by depositing a gold cap layer at room temperature onto a fully ordered FePt layer, followed by an annealing at 800 °C for the purpose of interlayer diffusion. After the deposition of the gold layer and the high-temperature annealing, the gold atoms do not dissolve into the FePt Ll₀ lattice. Compared with the continuous FePt film, the TEM photos of the bilayer Au(60 nm)/FePt(60 nm) show a granular structure with FePt particles embedded in Au matrix. The coercivity of Au(60 nm)/FePt(60 nm) sample is 23.5 kOe, which is 85% larger than that of the FePt film without Au top layer. The enhancement in coercivity can be attributed to the formation of isolated structure of FePt ordered phase.     

气/液界面自组装金纳米粒子薄膜作为SERS基底检测三聚氰胺

采用气/液界面自组装方法制备金纳米粒子薄膜作为SERS基底,其结构规整、均匀,利用此基底对三聚氰胺实现高灵敏的半定量分析。此SERS基底的制备是直接于水相合成的金纳米粒子中加人正十二硫醇,金纳米粒子通过硫醇修饰后由亲水性转变成疏水性质,在相界面上自组装为致密金纳米粒子单层膜结构。这种SERS基底不仅制备方法简单,而且应用范围广,除了检测三聚氰胺还可以拓展到其他的非极性的分子如多环芳烃等高灵敏的半定量分析。     

Surface-enhanced Raman spectroscopy based on ordered nanocap arrays

We fabricated the Ag cap array for surface-enhanced Raman scattering (SERS) by Ag deposition onto two dimensional polystyrene colloid sphere templates, and 4-mercaptopyridine (4-MPy) was used as the probing molecule. When the colloids with different size were chosen as the substrate for 20 nm Ag deposition, the film on 100 nm colloids gave the significant enhancement. SERS intensity increased with the increase of Ag thickness. When 20 nm Ag film was coated by Ta, the SERS signals decreased with the increase of Ta thickness, indicating the main effect from the top of cap structure. When Co layer was added under the Ag film, the SERS intensity decreased with the increase of Co thickness because the Co layer affects electromagnetic and plasmon resonance.     

聚甲基丙烯酸甲酯间隔的金纳米立方体与金膜复合结构的表面增强拉曼散射研究

金属纳米颗粒与金属薄膜的复合结构由于其局域表面等离子体和传播表面等离子体间的强共振耦合作用,可作为表面增强拉曼散射(SERS)基底,显著增强吸附分子的拉曼信号.本文提出了一种聚甲基丙烯酸甲酯(PMMA)间隔的90 nm金纳米立方体与50 nm金膜复合结构的SERS基底,通过有限元方法数值模拟,得到PMMA的最优化厚度为15 nm.实验制备了PMMA间隔层厚度为14 nm的复合结构,利用罗丹明6G (R6G)为拉曼探针分子, 633 nm的氦氖激光器作为激发光源,研究了复合结构和单一金纳米立方体的SERS效应,发现复合结构可以使探针分子产生比单一结构更强的拉曼信号.在此基础上,研究了不同浓度金纳米立方体水溶液条件下复合结构中R6G的拉曼光谱.结果表明,当金纳米立方体水溶液浓度为5.625μg/mL的条件下复合结构中R6G的拉曼信号最强,且可测量R6G的最低浓度达10~(–11) mol/L.     

Nanostructuring of thin Au films by means of short UV laser pulses

The particle size distribution, morphology and optical properties of the Au nanoparticle (NP) structures for surface enhanced Raman signal (SERS) application are investigated in dependence on their preparation conditions. The structures are produced from relatively thin Au films (10–20 nm) sputtered on fused silica glass substrate and irradiated with several pulses (6 ns) of laser radiation at 266 nm and at fluencies in the range of 160–412 mJ/cm². The SEM inspection reveals nearly homogeneously distributed, spherical gold particles. Their initial size distribution of the range of 20–60 nm broadens towards larger particle diameters with prolonged irradiation. This is accompanied by an increase in the uncovered surface of the glass substrate and no particle removal is observed. In the absorption profiles of the nanostructures, the broad peak centred at 546 nm is ascribed to resonant absorption of surface plasmons (SPR). The peak position, halfwidth and intensity depend on the shape, size and size distribution of the nanostructured particles in agreement with literature. From peak intensities of the Raman spectra recorded for Rhodamine 6G in the range of 300–1800 cm⁻¹, the relative signal enhancement by factor between 20 and 603 for individual peaks is estimated. The results confirm that the obtained structures can be applied for SERS measurements and sensing.     

Anisotropic nonlinear optical absorption of gold nanorods in a silica matrix

Nanocomposite films consisting of gold nanospheres or gold nanorods embedded in a silica matrix have been prepared using a hybrid deposition technique consisting of plasma-enhanced chemical vapor deposition of SiO₂ and co-sputtering of gold, followed by annealing at 900 °C. Subsequent irradiation with 30 MeV heavy ions (Cu⁵⁺) was used to form gold nanorods. Linear and nonlinear optical properties of this material are closely related with the surface plasmon resonance in the visible. The nonlinear absorption coefficient (α₂@532 nm) for the films containing gold nanospheres was measured by Z-scan and P-scan techniques, and it was found to be isotropic and equal to −4.8 × 10⁻² cm/W. On the contrary, gold nanorods films exhibited two distinct surface plasmon resonance absorption bands giving rise to a strong anisotropic behavior, namely a polarization-dependent linear absorption and saturable absorption. Z-scan and P-scan measurements using various light polarization directions yielded nonlinear absorption coefficient (α₂@532 nm) values varying from −0.9 × 10⁻² cm/W up to −3.0 × 10⁻² cm/W. Linearity of the P-scan method in the context of nanocomposite saturable absorption is also discussed.     

Interaction of gold nanoparticles with nanosecond laser pulses: Nanoparticle heating

Theoretical and experimental results on the heating process of gold nanoparticles irradiated by nanosecond laser pulses are presented. The efficiency of particle heating is demonstrated by in-vitro photothermal therapy of human tumor cells. Gold nanoparticles with diameters of 40 and 100 nm are added as colloid in the cell culture and the samples are irradiated by nanosecond pulses at wavelength of 532 nm delivered by Nd:YAG laser system. The results indicate clear cytotoxic effect of application of nanoparticle as more efficient is the case of using particles with diameter of 100 nm. The theoretical analysis of the heating process of nanoparticle interacting with laser radiation is based on the Mie scattering theory, which is used for calculation of the particle absorption coefficient, and two-dimensional heat diffusion model, which describes the particle and the surrounding medium temperature evolution. Using this model the dependence of the achieved maximal temperature in the particles on the applied laser fluence and time evolution of the particle temperature is obtained.     

Crystallization and surface morphology of Au/SiO2 thin films following furnace and flame annealing

A crystallization and surface evolution study of Au thin film on SiO₂ substrates following annealing at different temperatures above the eutectic point of the Au/Si system are reported. Samples were prepared by conventional evaporation of gold in a high vacuum (10⁻⁷ mbar) environment on substrates at room temperature. Thermal treatments were performed by both furnace and flame annealing techniques. Au thin films can be crystallized on SiO₂ substrates by both furnace and flame annealing. Annealing arranges the Au crystallites in the (1 1 1) plane direction and changes the morphology of the surface. Both, slow and rapid annealing result in a good background in the XRD spectra and hence clean and complete crystallization which depends more on the temperature than on the time of annealing. The epitaxial temperature for the Au/SiO₂ system decreases in the range of 350-400 °C. Furnace and flame annealing also form crystallized gold islands over the Au/SiO₂ surface. Relaxation at high temperatures of the strained Au layer, obtained after deposition, should be responsible for the initial stages of clusters formation. Gold nucleation sites may be formed at disordered points on the surface and they become islands when the temperature and time of annealing are increased. The growth rate of crystallites is highest around 360 °C. Above this temperature, the layer melts and gold diffuses from the substrate to the nucleation sites to increase the distance between islands and modify their shapes. Well above the eutectic temperature, the relaxed islands have hexagonally shaped borders. The mean crystallite diameters grow up to a maximum mean size of around 90 nm. The free activation energy for grain boundary migration above 360 °C is 0.2 eV. Therefore the type of the silicon substrate changes the mechanism of diffusion and growth of crystallites during annealing of the Au/Si system. Epitaxial Au(1 1 1) layers without formation of islands can be prepared by furnace annealing in the range of 300-310 °C and by flame annealing of a few seconds and up to 0.5 min.     

An atomic force microscopy study of DNA hairpin probes monolabelled with gold nanoparticle: Grafting and hybridization on oxide thin films

First and original results are reported regarding the surface evolution of two kinds of oxide film after covalent grafting and hybridization of hairpin oligonucleotide probes. These hairpin probes were monolabelled with a 1.4 nm gold nanoparticle. One kind of oxide film was rough Sb doped SnO₂ oxide film and the other kind was smooth SiO₂ film. Same process of covalent grafting, involving a silanization step, was performed on both oxide surfaces. Atomic force microscopy (AFM) was used to study the evolution of each oxide surface after different steps of the process: functionalization, probe grafting and hybridization. In the case of rough SnO₂ films, a slight decrease of the roughness was observed after each step whereas in the case of smooth SiO₂ films, a maximum of roughness was obtained after probe grafting. Step height measurements of grafted probes could be performed on SiO₂ leading to an apparent thickness of around 3.7 ± 1.0 nm. After hybridization, on the granular surface of SnO₂, by coupling AFM with SEM FEG analyses, dispersed and well-resolved groups of gold nanoparticles linked to DNA duplexes could be observed. Their density varied from 6.6 ± 0.3 × 10¹⁰ to 2.3 ± 0.3 × 10¹¹ dots cm⁻². On the contrary, on smooth SiO₂ surface, the DNA duplexes behave like a dense carpet of globular structures with a density of 2.9 ± 0.5 × 10¹¹ globular structures cm⁻².     

银纳米颗粒阵列的表面增强拉曼散射效应研究

利用具有高密度拉曼热点的金属纳米结构作为表面增强拉曼散射(SERS)基底,可以显著增强吸附分子的拉曼信号.本文通过阳极氧化铝模板辅助电化学法沉积制备了高密度银(Ag)纳米颗粒阵列;利用扫描电子显微镜和反射谱表征了样品的结构形貌和表面等离激元特性;用1, 4-苯二硫醇(1, 4-BDT)为拉曼探针分子,研究了Ag纳米颗粒阵列的SERS效应.通过优化沉积时间,制备出高SERS探测灵敏度的Ag纳米颗粒阵列,检测极限可达10~(-13)mol/L;时域有限差分法模拟结果证实了纳米颗粒间存在强的等离激元耦合作用,且发现纳米颗粒底端的局域场增强更大.研究结果表明Ag纳米颗粒阵列可作为高效的SERS基底.     

A study of the properties and microstructure of Ni81Fe19 ultrathin films with MgO

The anisotropic magnetoresistance (AMR) of a Ta (5 nm)/MgO (3 nm)/Ni₈₁Fe₁₉ (10 nm)/MgO (2 nm)/Ta (3 nm) film with MgO-Nano Oxide Layer (NOL) increases dramatically from 1.05% to 3.24% compared with a Ta (5 nm)/Ni₈₁Fe₁₉ (10 nm)/Ta (3 nm) film without the MgO-NOL layer after annealing at 380 °C for 2 h. Although the MgO destroys the NiFe (1 1 1) texture, it enhances the specular electron scattering of the conduction electrons at the NOL interface and suppresses the interface reactions and diffusion at the Ta/NiFe and NiFe/Ta interfaces. The NiFe (1 1 1) texture was formed after the annealing, resulting in a higher AMR ratio. X-ray photoelectron spectroscope results show that Mg and Mg²⁺ were present in the MgO_x films.