基于DNA自组装的金属纳米结构制备及相关纳米光子学研究

纳米光子学是研究光在纳米尺度下的行为以及光和纳米材料相互作用的一门科学.金属纳米材料凭借其独特的表面等离子体效应,可以在衍射极限以下对光进行传递和聚焦,因而是纳米光子学研究的重点.大量研究表明,通过调控金属纳米材料的形貌和成分可以控制表面等离子体的性质,从而对光进行可控调节.近年来,随着DNA纳米技术的发展,又为纳米光子学的发展带来了新的机遇.首先,人们发现不同的DNA序列可以调控金属纳米颗粒的成长,从而影响金属纳米颗粒的形貌和成分.此外,利用DNA自组装技术,可以将金属纳米颗粒组装成为有序可控的纳米结构.因此,基于DNA的纳米光子学研究近年来发展十分迅速.在此背景下,本文对相关研究进行归纳与总结,以期吸引更多研究人员的关注,推动该领域的进一步发展.本文首先介绍了金属纳米结构基于表面等离体实现突破光学衍射极限的原理,然后按照DNA对金属纳米结构的形貌或成分影响方式的不同分成若干部分,对基于DNA的纳米光子学做了系统的综述,最后展望了未来可能的发展方向.     

Electron beam induced surface activation: a method for the lithographic fabrication of nanostructures via catalytic processes

In focused electron beam induced processing (FEBIP), the very narrow electron beam of a scanning electron microscope or transmission electron microscope is used to locally modify matter on the nanometer scale. Recently, the family of FEBIP could be considerably expanded by the technique of focused electron beam induced surface activation (EBISA). In EBISA, the surface itself gets chemically activated by the impact of the electron beam without the presence of precursor molecules. In the second EBISA processing step, the surface is exposed to a precursor molecule which is then catalytically decomposed at the pre-irradiated/activated areas and eventually continues to grow autocatalytically upon prolonged precursor dosage. In this way, electron irradiation and precursor dosage are effectively separated. One of the advantages is that, due to the autocatalytic growth, the size of the corresponding nanostructures can be controlled by the precursor dosage and corresponding electron proximity effects can be omitted. Another advantage is the parallel processing of the pre-irradiated regions during precursor dosage. This bears the potential to significantly reduce the fabrication times for larger deposits compared to the classical electron beam induced deposition approach, in which precursor molecules are sequentially dissociated by the impact of the electron. The fundamentals and apparent further developments as well as the potential and challenges of the comparably new EBISA technique, and more general of catalytic effects in FEBIP are presented and discussed.     

Parallel fabrication of atomic nanostructures

A new approach to fabrication of atomic nanostructures for atomic nanooptics is reported, which is based on the use of one-, two-, and three-dimensional spatial localization of laser fields at the nanoscale level, and fabrication of atomic nanostructures on a surface is demonstrated.     

Hexagonal boron nitride film substrate for fabrication of nanostructures

The fabrication of material with an atomic scale manipulation requires the suitable advanced substrate for epitaxial growth without the effect by the substrate lattice structure. Hexagonal boron nitride (h-BN) can be the advanced substrate for atomic manipulation due to van der Waals’ gap with little attractive force along to c axis. We have successfully synthesized h-BN layer on the co-deposited Cu/BN film by surface segregation phenomena using helicon wave plasma enhanced radio frequency (rf) magnetron sputtering system. Auger electron spectroscopy (AES) and X-ray photon spectroscopy (XPS) analysis showed that the h-BN composite segregated on the surface of Cu/BN film covered over 95% of the film annealed at 900 K for 30 min. Atomic forces microscopy (AFM) and scanning tunneling microscopy (STM) analysis showed that attractive force on the film surface is uniformly distributed to an extent of 2nN and that the h-BN surface can be a good electric insulator like sintered h-BN plate.     

Plasmon-enhanced fluorescence near metallic nanostructures: biochemical applications

Amplification of fluorescence is a nanoscale phenomenon which is particularly pronounced in close proximity to metal nanostructures. Due to its sharp distance dependence, it is ideally suited to monitor biorecognition reactions. Using this effect we have been able to demonstrate ultrasensitive bioassays. Two types of metal nanostructures have been employed, nanometric silver islands deposited over an ultrathin metal mirror and silver fractal structures. For the first type, metal mirrors (aluminum, gold, or silver protected with a thin silica layer) were coated with SIFs and an immunoassay (model assay for rabbit IgG or myoglobin immunoassay) was performed on this surface using fluorescently labeled antibodies. Our results show that SIFs alone (on a glass surface not coated with metal) enhance the immunoassay signal approximately 3 to 10-fold. Using a metal mirror instead of glass as support for SIFs leads to up to 50-fold signal enhancement. The second type of metal nanostructures, silver fractals, were produced by electrochemical reduction of silver nitrate deposited on sapphire covered with a thin conductive film of indium tin oxide. These structures were used as a substrate for a model rabbit IgG bioassay. The fluorescence resulting from the binding of antibody labeled with Rhodamine was highly nonuniform with distinctive hot spots. These highly fluorescent regions were correlated with areas of higher Ag thickness and coverage. Such high values of fluorescence amplification in both types of nanostructures have been interpreted by using time-resolved fluorescence data and by considering the radiative properties of plasmons in the environments which promote plasmon coupling. PACS 87.64.Ni; 81.07.-b; 87.14.-g     

Planar self-aligned imprint lithography for coplanar plasmonic nanostructures fabrication

Nanoimprint lithography (NIL) is a cost-efficient nanopatterning technology because of its promising advantages of high throughput and high resolution. However, accurate multilevel overlay capability of NIL required for integrated circuit manufacturing remains a challenge due to the high cost of achieving mechanical alignment precision. Although self-aligned imprint lithography was developed to avoid the need of alignment for the vertical layered structures, it has limited usage in the manufacture of the coplanar structures, such as integrated plasmonic devices. In this paper, we develop a new process of planar self-alignment imprint lithography (P-SAIL) to fabricate the metallic and dielectric structures on the same plane. P-SAIL transfers the multilevel imprint processes to a single-imprint process which offers higher efficiency and less cost than existing manufacturing methods. Such concept is demonstrated in an example of fabricating planar plasmonic structures consisting of different materials.     

The fabrication of 3-D nanostructures by a low- voltage EBL

Three-dimensional (3-D) structures are used in many applications, including the fabrication of opto-electronic and bio-MEMS devices. Among the various fabrication techniques available for 3-D structures, nano imprint lithography (NIL) is preferred for producing nanoscale 3-D patterns because of its simplicity, relatively short processing time, and high manufacturing precision. For efficient replication in NIL, a precise 3-D stamp must be used as an imprinting tool. Hence, we attempted the fabrication of original 3-D master molds by low-voltage electron beam lithography (EBL). We then fabricated polydimethylsiloxane (PDMS) stamps from the original 3-D mold via replica molding with ultrasonic vibration.First, we experimentally analyzed the characteristics of low-voltage EBL in terms of various parameters such as resist thickness, acceleration voltage, aperture size, and baking temperature. From these e-beam exposure experiments, we found that the exposure depth and width were almost saturated at 3 kV or lesser, even when the electron dosage was increased. This allowed for the fabrication of various stepped 3-D nanostructures at a low voltage. In addition, by using line-dose EBL, V-groove patterns could be fabricated on a cured electron resist (ER) at a low voltage and low baking temperature. Finally, the depth variation could be controlled to within 10 nm through superposition exposure at 1 kV. From these results, we determined the optimum electron beam exposure conditions for the fabrication of various 3-D structures on ERs by low-voltage EBL. We then fabricated PDMS stamps via the replica molding process.     

Electrochemical template-assisted fabrication of CdS micro/nanostructures

One-dimensional (1D) cadmium sulphide (CdS) nanostructures, including micro/nanorods, and nanostructures resembling flowers and cactus have been synthesized by electrochemical template deposition technique, using polycarbonate membranes, by controlling various reaction parameters. These 1D CdS nanostructures were characterized structurally through the X-ray diffraction (XRD) studies and morphologically through scanning electron microscopy (SEM). It was found that apart from the dimensions of the pores of the templates, the geometrical morphologies of the CdS 1D nanostructures were significantly influenced by the synthesizing parameters also. The optical characterization has been done by UV–visible absorption and room-temperature photoluminescence (PL) studies.     

缓慢沉淀法制备ZnS纳米结构

使用两个直径不同的试管按照不同的方向套在一起的方法实现了ZnS 的缓慢沉淀,在两个试管中扩散过来的反应离子的补充下制备核壳结构的ZnS 纳米晶. 利用透射电子显微镜（TEM）,选区电子衍射分析（SAED）对样品的形貌和结构进行分析. 改变反应溶液的浓度和浓度比观察所得到样品形貌的改变,并从Zn2+和S2-两种离子与生成ZnS 单体之间所建立的平衡的角度,应用Ostwald 熟化效应等对样品形貌产生的原因进行了分析.     

Femtosecond laser fabrication of nanostructures in silica glass

A femtosecond laser beam focused inside fused silica and other glasses can modify the refractive index of the glass. Chemical etching and atomic-force microscope studies show that the modified region can have a sharp-tipped cone-shaped structure with a tip diameter as small as 100 nm. Placing the structure near the bottom surface of a silica glass sample and applying a selective chemical etch to the bottom surface produces clean, circular, submicrometer-diameter holes. Holes spaced as close to one another as 1.4 microm are demonstrated.     

Electrochemical template-assisted fabrication of CdS micro/nanostructures

One-dimensional (1D) cadmium sulphide (CdS) nanostructures, including micro/nanorods, and nanostructures resembling flowers and cactus have been synthesized by electrochemical template deposition technique, using polycarbonate membranes, by controlling various reaction parameters. These 1D CdS nanostructures were characterized structurally through the X-ray diffraction (XRD) studies and morphologically through scanning electron microscopy (SEM). It was found that apart from the dimensions of the pores of the templates, the geometrical morphologies of the CdS 1D nanostructures were significantly influenced by the synthesizing parameters also. The optical characterization has been done by UV–visible absorption and room-temperature photoluminescence (PL) studies.     

Large scale fabrication of nitrogen vacancy-embedded diamond nanostructures for single-photon source applications

Some color centers in diamond can serve as quantum bits which can be manipulated with microwave pulses and read out with laser,even at room temperature.However,the photon collection efficiency of bulk diamond is greatly reduced by refraction at the diamond/air interface.To address this issue,we fabricated arrays of diamond nanostructures,differing in both diameter and top end shape,with HSQ and Cr as the etching mask materials,aiming toward large scale fabrication of single-photon sources with enhanced collection efficiency made of nitrogen vacancy(NV) embedded diamond.With a mixture of O_2 and CHF_3 gas plasma,diamond pillars with diameters down to 45 nm were obtained.The top end shape evolution has been represented with a simple model.The tests of size dependent single-photon properties confirmed an improved single-photon collection efficiency enhancement,larger than tenfold,and a mild decrease of decoherence time with decreasing pillar diameter was observed as expected.These results provide useful information for future applications of nanostructured diamond as a single-photon source.     

Metallic nanostructures in a polymer matrix and substrate fabrication and structural characterization

Metal nanostructures are of considerable interest in the field of plasmonics and metamaterials and could have a wider impact if they are successfully embedded in a stable, inert and flexible polymer matrix. Fabrication of such structures is challenging for a variety of reasons including thermal stability, material compatibility with processing steps and general handling of material. In this work we have demonstrated the fabrication of metal nanostructures and embedded them in a polymer. Furthermore, these structures were fabricated on a flexible polymer membrane and detached from a carrier substrate. Characterization of these structures was performed with SEM, TEM and EDS.     

Ion beam sputtering for progressive reduction of nanostructures dimensions

An ion beam-based dry etching method has been developed for the progressive reduction of the dimensions of prefabricated nanostructures. The method has been successfully applied to aluminum nanowires and aluminum single electron transistors (SET). The method is based on removal of material from the structures when exposed to energetic argon ions, and it was shown to be applicable to the same sample many times. Electrical measurements, and samples imaged in-between the sputtering sessions, clearly indicated that the dimensions (the cross-section of the nanowires and the area of the tunnel junctions in SET) were progressively reduced without noticeable degradation of the sample structure. We were able to reduce the effective diameter of aluminum nanowires from 65 nm down to 30 nm, whereas the tunnel junction area has been reduced by 40%. PACS 74.40.+k, 68.65.La, 73.23.Hk, 61.80.Jh     

圆锥磁绝缘传输线的横向空间电荷流

根据电磁场基本理论及电子运动守恒方程，导出圆锥传输线横向空间电荷流的数值模型和磁绝缘临界条件。通过数值计算，讨论了电压及圆锥几何结构参数等对横向空间电荷流和磁绝缘性能的影响。电压较高时,无磁场的空间电荷流较大，而磁绝缘性能更好。在传输线的三个几何参数中，几何因子对传输性能影响最大。     

Numerical synthesis of metallic nanostructures for enhancing the emission of a dipole through surface plasmon coupling

In this study, we numerically synthesize a two-dimensional metallic nanostructure consisting of a Au half-space and two separate Ag elliptical cylinders by the simulated annealing (SA) method. The simulated nanostructure is so designed that the surface plasmon polariton (SPP) and the localized surface plasmon (LSP) are simultaneously excited at their common resonant wavelength (535 nm), leading to the enhancement of emission of a nearby dipole source. This enhancement effect is more significant than that of the case where only one of the SPP and LSP is excited. In numerically synthesizing a metallic nanostructure, we try to maximize both the downward emission (in the direction away from the metallic structure) and the emission efficiency. A cost function is defined as some combination of the downward emission and the emission efficiency. We adjust the simulated structure by SA to minimize the cost function at a designated resonant wavelength, and calculate and analyze the spectra of downward emission and emission efficiency for the optimal structure. Other structures are also investigated for comparison. From numerical simulations, it is demonstrated that the enhancement of dipole emission is better for optimization at wavelength 535 nm than at other wavelengths. Note that the downward emission and the emission efficiency can reach maxima almost simultaneously when the SPP and the LSP couple effectively at a common resonant wavelength. This implies that the lighting efficiency of green light-emitting diodes (LEDs) can be increased by the coupling effect at a common resonant wavelength of SPP and LSP.     

非晶合金的高通量制备与表征

非晶合金是一种不同于传统合金材料的新型合金,其突出的机械、物理、化学等性能在工程应用领域备受关注.作为一种具有无序原子结构的新型合金,非晶合金中蕴含的丰富的物理现象在基础研究领域也备受瞩目.非晶合金往往由多个组元构成,这给成分优化和性能调制带来了巨大的挑战.材料基因组方法是最近发展起来的新方法,通过高通量制备和结构表征以及性能筛选有望加快新型非晶合金材料的探索,在高通量表征中获得的大量实验数据可以帮助人们理解非晶合金中的科学问题.本文主要介绍高通量制备和表征在非晶合金中的应用,通过列举典型案例,展示通过高通量方法探索新型非晶合金材料的作用.     

Charge distributions in metallic alloys: a charge-excess functional theory approach

The distribution of local charge (DLC) excesses in metallic alloys, previously obtained as a result of the analysis of order N electronic structure calculations, is derived from a variational principle. A phenomenological charge-excess functional theory is obtained which is determined by three concentration dependent, material specific parameters that can be obtained from ab initio calculations. The theory requires modest computational efforts and reproduces with an excellent accuracy the DLC and the electrostatic energies of ordered, substitutionally disordered, or segregating metallic alloys and, hence, can be considered an efficient approach alternative to conventional electronic structure calculations. The substantial reduction of computing time opens new perspectives for the understanding of metallic systems and their mechanical properties.     

Lithography-free fabrication of large-area plasmonic nanostructures using colloidal gold nanoparticles

We report simple and efficient fabrication of large-area gold nanostructures using solution-processible gold nanoparticles, where lithography and vacuum evaporation techniques are not involved in the fabrication processes. These gold nanoisland structures exhibit strong particle plasmon resonance that is characterized by optical extinction spectroscopy in the visible spectral range. The tunability of the optical response is realized by controlling the annealing temperature and by changing the concentration of the colloidal solutions of gold nanoparticles. This enables a low-cost route for exploiting new photonic devices, biosensors, and optoelectronic devices with localized field-enhancement.