Laser-Driven Growth of Semiconductor Nanowires from Colloidal Nanocrystals.

Semiconductor nanowire production through vapor- and solution-based processes has propelled nanowire systems toward a wide range of technological applications. Although vapor-based nanowire syntheses enable precise control over nanowire composition and phase, they typically employ batch processes with specialized pressure management systems, limiting throughput. Solution-based nanowire growth processes have improved scalability but can require even more extensive pressure and temperature management systems. Here, we demonstrate a solution-based nanowire growth process that utilizes the large Young-Laplace interfacial surface pressures and collective heating effects of colloidal metal nanocrystals under irradiation to drive nanowire growth photothermally. Laser irradiation of a solution containing metal nanocrystals and semiconductor precursors facilitates rapid heating, precursor decomposition, and nanowire growth on a benchtop in simple glassware under standard conditions, potentially enabling a range of solution-based experiments including in-line combinatorial identification of optimized reaction parameters, in situ measurements, and the production of nanowires with complex compositions.

Solid-state laser refrigeration of a composite semiconductor Yb:YLiF4 optomechanical resonator.

Photothermal heating represents a major constraint that limits the performance of many nanoscale optoelectronic and optomechanical devices including nanolasers, quantum optomechanical resonators, and integrated photonic circuits. Here, we demonstrate the direct laser refrigeration of a semiconductor optomechanical resonator >20 K below room temperature based on the emission of upconverted, anti-Stokes photoluminescence of trivalent ytterbium ions doped within a yttrium-lithium-fluoride (YLF) host crystal. Optically-refrigerating the lattice of a dielectric resonator has the potential to impact several fields including scanning probe microscopy, the sensing of weak forces, the measurement of atomic masses, and the development of radiation-balanced solid-state lasers. In addition, optically refrigerated resonators may be used in the future as a promising starting point to perform motional cooling for exploration of quantum effects at mesoscopic length scales, temperature control within integrated photonic devices, and solid-state laser refrigeration of quantum materials.

Optically oriented attachment of nanoscale metal-semiconductor heterostructures in organic solvents via photonic nanosoldering.

As devices approach the single-nanoparticle scale, the rational assembly of nanomaterial heterojunctions remains a persistent challenge. While optical traps can manipulate objects in three dimensions, to date, nanoscale materials have been trapped primarily in aqueous solvents or vacuum. Here, we demonstrate the use of optical traps to manipulate, align, and assemble metal-seeded nanowire building blocks in a range of organic solvents. Anisotropic radiation pressure generates an optical torque that orients each nanowire, and subsequent trapping of aligned nanowires enables deterministic fabrication of arbitrarily long heterostructures of periodically repeating bismuth-nanocrystal/germanium-nanowire junctions. Heat transport calculations, back-focal-plane interferometry, and optical images reveal that the bismuth nanocrystal melts during trapping, facilitating tip-to-tail "nanosoldering" of the germanium nanowires. These bismuth-semiconductor interfaces may be useful for quantum computing or thermoelectric applications. In addition, the ability to trap nanostructures in oxygen- and water-free organic media broadly expands the library of materials available for optical manipulation and single-particle spectroscopy.

Photothermal Heating and Cooling of Nanostructures.

A vast range of insulating, semiconducting, and metallic nanomaterials have been studied over the past several decades with the aim of understanding how continuous-wave or pulsed laser radiation can influence their chemical functionality and local environment. Many fascinating observations have been made during laser irradiation including, but not limited to, the superheating of solvents, mass-transport-mediated morphology evolution, photodynamic therapy, morphology dependent resonances, and a range of phase transformations. In addition to laser heating, recent experiments have demonstrated the laser cooling of nanoscale materials through the emission of upconverted, anti-Stokes photons by trivalent rare-earth ions. This Focus Review outlines the analytical modeling of photothermal heat transport with an emphasis on the experimental validation of anti-Stokes laser cooling. This general methodology can be applied to a wide range of photothermal applications, including nanomedicine, photocatalysis, and the synthesis of new materials. The review concludes with an overview of recent advances and future directions for anti-Stokes cooling.

Nanowire heating by optical electromagnetic irradiation.

The dissipative absorption of electromagnetic energy by 1D nanoscale structures at optical frequencies is applicable to several important phenomena, including biomedical photothermal theranostics, nanoscale photovoltaic materials, atmospheric aerosols, and integrated photonic devices. Closed-form analytical calculations are presented for the temperature rise within infinite circular cylinders with nanometer-scale diameters (nanowires) that are irradiated at right angles by a continuous-wave laser source polarized along the nanowire's axis. Solutions for the heat source are compared to both numerical finite-difference time domain (FDTD) simulations and well-known Mie scattering cross sections for infinite cylinders. The analysis predicts that the maximum temperature increase is affected not only by the cylinder's composition and porosity but also by morphology-dependent resonances (MDRs) that lead to significant spikes in the local temperature at particular diameters. Furthermore, silicon nanowires with high thermal conductivities are observed to exhibit extremely uniform internal temperatures during electromagnetic heating to 1 part in 10(6), including cases where there are substantial fluctuations of the internal electric-field source term that generates the Joule heating. For a highly absorbing material such as carbon, much higher temperatures are predicted, the internal temperature distribution is nonuniform, and MDRs are not encountered.

Interpretation of uptake coefficient data obtained with flow tubes.

The uptake of trace gases such as OH and HO2 radicals, NH3, ClONO2, N2O5, ozone, and many other gases by water, aqueous solutions of acids, and salts has been reported by numerous investigators using a variety of techniques. Reported uptake coefficients vary greatly, ranging from 10(-8) to 1. This paper describes a new analysis of uptake data obtained in flow tubes that consolidates data obtained for various flow rates and trace gas concentrations. Previous analyses, which have been often used, are shown to be limiting cases or special cases of the analysis outlined here. Of particular emphasis are results for wetted-wall columns and trace gas uptake by aerosol entrained in flow tubes. In the absence of aerosol, the analysis is shown to predict the decrease in trace gas concentration due to bulk chemical reaction and/or reaction at the tube wall or gas-liquid interface. Uptake coefficients for OH and HO2 radicals on water in wetted-wall tubes are shown to range from 0.01 to 1, and on sulfuric acid, they vary from 0.008 to 0.03. For O3 on a water film doped with a scavenger, the uptake coefficient is found to be 0.0008. Uptake coefficients determined by different techniques are compared.

A genetic approach for controlling the binding and orientation of proteins on nanoparticles.

Although silver nanoparticles are excellent surface enhancers for Raman spectroscopy, their use to probe the conformation of large proteins at interfaces has been complicated by the fact that many polypeptides adsorb weakly or with a random orientation to colloidal silver. To address these limitations, we sought to increase binding affinity and control protein orientation by fusing a silver-binding dodecapeptide termed Ag4 to the C-terminus of maltose-binding protein (MBP), a well-characterized model protein with little intrinsic silver binding affinity. Quartz crystal microbalance measurements conducted with the MBP-Ag4 fusion protein revealed that its affinity for silver (Kd approximately 180 nM) was at least 1 order of magnitude higher than a control protein, MBP2, containing a non-silver-specific C-terminal extension. Under our experimental conditions, MBP-Ag4 SERS spectra exhibited 2-4 fold higher signal-to-background relative to MPB2 and contained a number of amino acid-assigned vibrational modes that were either weak or absent in control experiments performed with MBP2. Changes in amino acid-assigned peaks before and after MBP-Ag4 bound maltose were used to assess protein orientation on the surface of silver nanoparticles. The genetic route described here may prove useful to study the orientation of other proteins on a variety of SERS-active surfaces, to improve biosensors performance, and to control functional nanobiomaterials assembly.

Surface-enhanced Raman spectroscopy of soft-landed polyatomic ions and molecules.

Surface-enhanced Raman spectroscopy (SERS) was used to detect and characterize polyatomic cations and molecules that were electrosprayed into the gas phase and soft-landed in vacuum on plasma-treated silver substrates. Organic dyes such as crystal violet and Rhodamine B, the nucleobase cytosine, and nucleosides cytidine and 2'-deoxycytidine were immobilized by soft landing on plasma-treated metal surfaces at kinetic energies ranging from near thermal to 200 eV. While enhancing Raman scattering 10(5)-10(6)-fold, the metal surface effectively quenches the fluorescence that does not interfere with the Raman spectra. SERS spectra from submonolayer amounts of soft-landed compounds were sufficiently intense and reproducible to allow identification of Raman active vibrational modes for structure assignment. Soft-landed species appear to be microsolvated on the surface and bound via ion pairing or pi-complexation to the Ag atoms and ions in the surface oxide layer. Comparison of spectra from soft-landed and solution samples indicates that the molecules survive soft landing without significant chemical damage even when they strike the surface at hyperthermal collision energies.

Bioaerosol detection and characterization by surface-enhanced Raman spectroscopy.

Instrumentation has been developed to detect and characterize airborne pollen and bacteria rapidly by injecting a bioaerosol into a nanocolloidal suspension of silver particles using a micropump. The biological particles were mixed with the silver colloid in order to deposit the metallic particles on the surface of the bioanalyte. The silver/bioanalyte suspension was pumped through a light scattering cuvette, and the enhanced Raman spectrum was recorded. Surface-enhanced Raman spectra are presented for tree pollen (cottonwood and redwood pollen) and a bacterium (Escherichia coli), and the E. coli spectra are compared with results obtained from the literature and with results obtained previously by mixing various concentrations of the bioanalyte with the silver colloid. Although the system has not been optimized to maximize the Raman spectra, it is shown spectra can be obtained rapidly. Some assignments of the chemical bonds associated with the spectra are based on previously published results for bacteria and pollen.

Detection of bacteria by surface-enhanced Raman spectroscopy.

The detection and identification of dilute bacterial samples by surface-enhanced Raman spectroscopy has been explored by mixing aqueous suspensions of bacteria with a suspension of nanocolloidal silver particles. An estimate of the detection limit of E. coli was obtained by varying the concentration of bacteria. By correcting the Raman spectra for the broad librational OH band of water, reproducible spectra were obtained for E. coli concentrations as low as approximately 10(3) cfu/mL. To aid in the assignment of Raman bands, spectra for E. coli in D(2)O are also reported.

Comparison of psychro-active arctic marine bacteria and common mesophillic bacteria using surface-enhanced Raman spectroscopy.

Psychro-active bacteria, important constituents of polar ecosystems, have a unique ability to remain active at temperatures below 0 degrees C, yet it is not known to what extent the composition of their outer cell surfaces aids in their low-temperature viability. In this study, aqueous suspensions of five strains of Arctic psychro-active marine bacteria (PAMB) (mostly sea-ice isolates), were characterized by surface-enhanced Raman spectroscopy (SERS) and compared with SERS spectra from E. coli and P. aerigunosa. We find the SERS spectra of the five psychro-active bacterial strains are similar within experimental reproducibility. However, these spectra are significantly different from the spectra of P. aeruginosa and E. coli. We find that the relative intensities of many of the common peaks show the largest differences reported so far for bacterial samples. An indication of a peak was found in the PAMB spectra that has been identified as characteristic of unsaturated fatty acids and suggests that the outer membranes of the PAMB may contain unsaturated fatty acids. We find that using suspensions of silver colloid particles greatly intensifies the Raman peaks and quenches the fluorescence from bacterial samples. This technique is useful for examination of specific biochemical differences among bacteria.

Surface-enhanced Raman spectroscopy of bacteria and pollen.

A technique for distinguishing biological material based on surface-enhanced Raman scattering (SERS) is reported in this work. Of particular interest is biological material that can be airborne. Silver colloidal particles with diameters in the range 10 to 20 nm and with a characteristic ultraviolet-visible (UV-VIS) absorption band at 400 nm were used to obtain SERS spectra of Escherichia coli, Pseudomonas aeruginosa, and Salmonella typhimurium bacteria and a number of tree and grass pollens (Cupressus arizonica (cypress), Sequoia sempervirens (redwood), Populus deltoides (cottonwood), Poa pratensis (Kentucky bluegrass), and Anthoxanthum odoratum (sweet vernal grass)). While differences in the SERS spectra among the bacteria were small, we found that the pollen spectra we analyzed could readily be distinguished from the bacteria spectra, and there were significant differences between pollen from different families. In order to obtain reproducible results, we studied the parameters controlling the interaction between the analyte and the nanoscale metallic surface. Our results show that the volume ratio of analyte to colloidal particles must be within a narrow range of values to optimize the signal-to-noise ratio of the SERS spectra and minimize the fluorescence from the analyte. Also, we found that the time-dependent behavior of colloidal/bacterial suspensions (or adsorption rate of the silver colloid particles on the bacteria) is strongly dependent on pH, density of bacteria in solution, and even, to some extent, the type of bacteria.

Mass transfer from an oscillating microsphere.

The enhancement of mass transfer from single oscillating aerocolloidal droplets having initial diameters approximately 40 microm has been measured using electrodynamic levitation to trap and oscillate a droplet evaporating in nitrogen gas. The frequency and amplitude of the oscillation were controlled by means of ac and dc fields applied to the ring electrodes of the electrodynamic balance (EDB). Elastic light scattering was used to size the droplet. It is shown that the mass transfer process for a colloidal or aerocolloidal particle oscillating in the Stokes flow regime is governed by a Peclet number for oscillation and a dimensionless oscillation parameter that represents the ratio of the diffusion time scale to the oscillation time scale. Evaporation rates are reported for stably oscillating droplets that are as much as five times the rate for evaporation in a stagnant gas. The enhancement is substantially larger than that predicted by quasi-steady-flow mass transfer.