The influence of phosphate glass structure on results of thermal poling.

Two sodium phosphate glasses with different structure (meta- and orthophosphate ones) were thermally poled well below the glass transition temperatures. Glass with an orthophosphate structure (glass LA30) demonstrated a typical behavior of polarization current, that is, monotonic current decrease; however, in glass with a metaphosphate structure (glass LA10) the current first increased for 15-20 min and only then started monotonic decreasing. In spite of the similar sodium content, the current in LA10 glass exceeded the one in LA30 glass by about 10 times. This is explained by the capability of substituting intrinsic sodium ions by more mobile protons entering LA10 glass with a metaphosphate structure from the atmosphere. The other difference consists in the fact that the subanodic layer of LA10 glass after poling has many small cracks, while the subanodic layer of LA30 glass is crystallized. It should be emphasized that the crystallization of phosphate glasses under dc electric field below glass transition temperature is observed for the first time. In addition, after poling, no changes in the refractivity of both glasses were detected, but the generation of the second optical harmonic in LA30 glass was observed.

Poling of Glasses Using Resistive Barrier Discharge Plasma.

A technique for poling of glasses using a resistive barrier discharge plasma in the atmosphere in a gap of hundreds of microns is presented. Measurements of the polarization current, second harmonic generation, and IR spectra of poled soda-lime glass slides show that voltage sufficient to ignite plasma discharge provides efficient poling, whereas for lower voltages the poling effect is close to zero. We attributed this to the large number of hydrogen/hydronium ions generated from atmospheric water vapor by the plasma discharge in the gap, which penetrate into the glass. We also developed a simple model of poling according to Ohm's law, analyzed the temporal dependencies of the polarization current and, basing on the model, estimated mobilities of hydrogen/hydronium and sodium ions in the glass: µH = (2.4 ± 0.8) × 10-18 m2V-1s-1 and µNa = (4.8 ± 1.8) × 10-15 m2V-1s-1. The values obtained are very close to the known literature data.

Diffusive Formation of Au/Ag Alloy Nanoparticles of Governed Composition in Glass.

For the first time we show that the introduction of silver ions in the glass containing gold nanoparticles (NPs) and additional heat treatment of the glass in the air lead to the formation of Au/Ag alloy NPs. The proposed approach makes it possible to position localized surface plasmon resonance of the NPs by selecting the heat treatment temperature, which determines the silver proportion in the alloy NPs. This allows for expanding customizability of NPs for applications in surface-enhanced Raman scattering spectroscopy, catalysis and biochemistry. Developed technique benefits from the presence of silver in the glass in ionic form, which prevents the oxidation of silver and provides stable preparation of Au/Ag alloy NPs.

How Activity Series Governs Transformation of Metal Nanoparticles in Glasses.

It has been experimentally shown for the first time that metallic copper in glasses can play the role of a reducing agent for other metallic ions, in particular, resulting in the formation of metal nanoparticles. Silver ions have been introduced into an alkali silicate glass containing copper nanoparticles by ion exchange. This has resulted in the formation of silver nanoparticles accompanied by the disappearance of copper nanoparticles initially contained in the glass. Such a process has never been observed and described anywhere. The process has been explained by the redox reaction Cu0 + Ag+ → Cu+ + Ag0 taking place in silver ion exchange. It has been shown that this reaction can go only in one direction (from left to right) as a result of the relative positions of copper and silver in the activity series.

Raman Scattering Study of Amino Acids Adsorbed on a Silver Nanoisland Film.

We studied the surface-enhanced Raman spectra of amino acids D-alanine and DL-serine and their mixture on silver nanoisland films (SNF) immersed in phosphate-buffered saline (PBS) solution at millimolar amino acid concentrations. It is shown that the spectra from the amino acid solutions differ from the reference spectra for microcrystallites due to the electrostatic orientation of amino acid zwitterions by the metal nanoisland film. Moreover, non-additive peaks are observed in the spectrum of the mixture of amino acids adsorbed on SNF, which means that intermolecular interactions between adsorbed amino acids are very significant. The results indicate the need for a thorough analysis of the Raman spectra from amino acid solutions, particularly, in PBS, in the presence of a nanostructured silver surface, and may also be of interest for studying molecular properties and intermolecular interactions.

Giant Enhancement of Optical Second Harmonic in Poled Glasses by Cold Repoling.

For the first time, we demonstrated that additional poling at room temperature (cold repoling) of a soda-lime glass thermally poled in open anode configuration causes an increase of the optical second harmonic signal by more than an order of magnitude. Performed experiments allow relating this increase in the optical nonlinearity of the glass to the orientation of hydrogenated dipoles in the vicinity of the glass surface. This indicates that both frozen electric field and dipole orientation are responsible for the nonlinearity of thermally poled alkali-containing glasses. Observed dipole orientation in glasses is of interest for molecular physics and electrodynamic studies.

Power Spectral Density Analysis for Optimizing SERS Structures.

The problem of optimizing the topography of metal structures allowing Surface Enhanced Raman Scattering (SERS) sensing is considered. We developed a model, which randomly distributes hemispheroidal particles over a given area of the glass substrate and estimates SERS capabilities of the obtained structures. We applied Power Spectral Density (PSD) analysis to modeled structures and to atomic force microscope images widely used in SERS metal island films and metal dendrites. The comparison of measured and calculated SERS signals from differing characteristics structures with the results of PSD analysis of these structures has shown that this approach allows simple identification and choosing a structure topography, which is capable of providing the maximal enhancement of Raman signal within a given set of structures of the same type placed on the substrate.

Stable in Biocompatible Buffers Silver Nanoisland Films for SERS.

We investigated the stability of silver nanoisland films, which were formed on glass surface by the method of out-diffusion, in biocompatible buffers and the applicability of the films in surface enhanced Raman scattering (SERS). We have shown that silver nanoisland films are stable in one of the most widespread in biological studies buffer-phosphate buffer saline (PBS), and in 1:100 water-diluted PBS, in the PBS-based buffer, in which NaCl is replaced by the same amount of NaClO4, and in acidic phosphate buffer. At the same time, the replacement of NaCl in PBS by N(CH3)4Cl leads to the degradation of the nanoislands. It was shown that after exposure to PBS the nanoisland films provided a good SERS signal from a monolayer of 1,2-di(4-pyridyl)ethylene (BPE), which makes silver nanoisland films promising for biosensor applications. Additionally, in our experiments, we registered for the first time that silver nanoparticles formed in the bulk of the samples dissolved after exposing to PBS, while nanoislands on the glass surface stayed unchanged. We associate this phenomenon with the interaction of ions contained in PBS solution with silver, which results in the shift of corresponding chemical equilibrium.

Visualization of Spatial Charge in Thermally Poled Glasses via Nanoparticles Formation.

It is shown for the first time that the vacuum poling of soda-lime silicate glass and the subsequent processing of the glass in a melt containing silver ions results in the formation of silver nanoparticles buried in the subanodic region of the glass at a depth of 800-1700 nm. We associate the formation of nanoparticles with the transfer of electrons from negatively charged non-bridging oxygen atoms to silver ions, their reduction as well as their clustering. The nanoparticles do not form in the ion-depleted area just beneath the glass surface, which indicates the absence of a spatial charge (negatively charged oxygen atoms) in this region of the vacuum-poled glass. In consequence, the neutralization of the glass via switching of non-bridging oxygen bonds to bridging ones, which leads to the release of oxygen, should occur in parallel with the shift of calcium, magnesium, and sodium ions into the depth of the glass.

Controlled metallization of ion-exchanged glasses by thermal poling.

We present studies of the formation of silver nanoparticles (NPs) in silver-sodium ion-exchanged glasses by a combination of thermal poling and nanosecond pulsed laser irradiation at 355 nm. In poling, silver ions drift deeper into the glass and become separated from the glass surface by a poled layer depleted in cations. Performed measurements have indicated poling-induced broadening of silver ions depth distribution. Laser irradiation reduces silver ions to atomic silver via breaking silver-non-bridging oxygen (NBO) bonds, extraction of electrons from the NBO atoms and capturing these electrons and electrons generated via multi-photon absorption in the glass by silver ions. The depleted layer limits diffusion of silver atom towards glass surface and, as a consequence, formation of silver NPs on the surface of poled glasses. It is shown that thermal poling mode allows one to control formation of silver NPs of glass surface.

SERS-Active Pattern in Silver-Ion-Exchanged Glass Drawn by Infrared Nanosecond Laser.

The irradiation of silver-to-sodium ion-exchanged glass with 1.06-µm nanosecond laser pulses of mJ-range energy results in the formation of silver nanoparticles under the glass surface. Following chemical removal of ~25-nm glass layer reveals a pattern of nanoparticles capable of surface enhancement of Raman scattering (SERS). The pattern formed when laser pulses are more than half-overlapped provides up to ~105 enhancement and uniform SERS signal distribution, while the decrease of the pulse overlap results in an order of magnitude higher but less uniform enhancement.

Nonresonant Local Fields Enhance Second-Harmonic Generation from Metal Nanoislands with Dielectric Cover.

We study second-harmonic generation from gold nanoislands covered with amorphous titanium oxide (TiO_{2}) films. As the TiO_{2} thickness increases, the plasmon resonance of the nanoislands shifts away from the second-harmonic wavelength of 532 nm, diminishing the resonant enhancement of the process at this wavelength. Nevertheless, the second-harmonic signal is enhanced by up to a factor of 45 with increasing TiO_{2} thickness. This unexpected effect arises from the scaling of local fields at the fundamental wavelength of 1064 nm-which is at the far tail of the resonance-due to a change in the dielectric environment of the nanoislands.

Heat-sink free CW operation of injection microdisk lasers grown on Si substrate with emission wavelength beyond 1.3 µm.

High-performance injection microdisk (MD) lasers grown on Si substrate are demonstrated for the first time, to the best of our knowledge. Continuous-wave (CW) lasing in microlasers with diameters from 14 to 30 µm is achieved at room temperature. The minimal threshold current density of 600 A/cm2 (room temperature, CW regime, heatsink-free uncooled operation) is comparable to that of high-quality MD lasers on GaAs substrates. Microlasers on silicon emit in the wavelength range of 1320-1350 nm via the ground state transition of InAs/InGaAs/GaAs quantum dots. The high stability of the lasing wavelength (dλ/dI=0.1 nm/mA) and the low specific thermal resistance of 4×10-3°C×cm2/W are demonstrated.

2D-patterning of self-assembled silver nanoisland films.

The paper is dedicated to the recently developed by the authors technique of silver nanoisland growth, allowing self-arrangement of 2D-patterns of nanoislands. The technique employs silver out-diffusion from ion-exchanged glass in the course of annealing in hydrogen. To modify the silver ion distribution in the exchanged soda-lime glass we included the thermal poling of the ion-exchanged glass with a profiled electrode as an intermediate stage of the process. The resulting consequence consists of three steps: (i) during the ion exchange of the glass in the AgxNa1-xNO3 (x = 0.01-0.15) melt we enrich the subsurface layer of the glass with silver ions; (ii) under the thermal poling, the electric field displaces these ions deeper into the glass under the 2D profiled anodic electrode, the displacement is smaller under the hollows in the electrode where the intensity of the field is minimal; (iii) annealing in a reducing atmosphere of hydrogen results in silver out-diffusion only in the regions corresponding to the electrode hollows, as a result silver forms nanoislands following the shape of the electrode. Varying the electrode and mode of processing allows governing the nanoisland size distribution and self-arrangement of the isolated single nanoislands, pairs, triples or groups of several nanoislands-so-called plasmonic molecules.

Erratum to: Plasmonic molecules via glass annealing in hydrogen.

[This corrects the article DOI: 10.1186/1556-276X-9-606.].

Plasmonic molecules via glass annealing in hydrogen.

Growth of self-assembled metal nanoislands on the surface of silver ion-exchanged glasses via their thermal processing in hydrogen followed by out-diffusion of neutral silver is studied. The combination of thermal poling of the ion-exchanged glass with structured electrode and silver out-diffusion was used for simple formation of separated groups of several metal nanoislands presenting plasmonic molecules. The kinetics of nanoisland formation and temporal evolution of their size distribution on the surface of poled and unpoled glass are modeled. PACS: 78.67.Sc (nanoaggregates; nanocomposites); 81.16.Dn (self-assembly); 68.35.bj (surface structure of glasses); 64.60.Qb (Nucleation); 81.16.Nd (micro- and nanolithography).

Out-diffused silver island films for surface-enhanced Raman scattering protected with TiO2 films using atomic layer deposition.

We fabricated self-assembled silver nanoisland films using a recently developed technique based on out-diffusion of silver from an ion-exchanged glass substrate in reducing atmosphere. We demonstrate that the position of the surface plasmon resonance of the films depends on the conditions of the film growth. The resonance can be gradually shifted up to 100 nm towards longer wavelengths by using atomic layer deposition of titania, from 3 to 100 nm in thickness, upon the film. Examination of the nanoisland films in surface-enhanced Raman spectrometry showed that, in spite of a drop of the surface-enhanced Raman spectroscopy (SERS) signal after the titania spacer deposition, the Raman signal can be observed with spacers up to 7 nm in thickness. Denser nanoisland films show slower decay of the SERS signal with the increase in spacer thickness. PACS: 78.67.Sc (nanoaggregates; nanocomposites); 81.16.Dn (self-assembly); 74.25.nd (Raman and optical spectroscopy).

Ultrasmall microdisk and microring lasers based on InAs/InGaAs/GaAs quantum dots.

Ultrasmall microring and microdisk lasers with an asymmetric air/GaAs/Al0.98Ga0.02As waveguide and an active region based on InAs/InGaAs/GaAs quantum dots emitting around 1.3 µm were fabricated and studied. The diameter D of the microrings and microdisks was either 2 or 1.5 µm, and the inner diameter d of the microrings varied from 20% to 70% of the outer diameter D. The microring with D = 2 µm and d = 0.8 µm demonstrated a threshold pump power as low as 1.8 µW at room temperature. Lasing was observed up to 100°C owing to the use of quantum dots providing high confinement energy both for electrons and holes. Tuning spectral positions of the whispering gallery modes via changing the inner diameters of the microrings was demonstrated. PACS: 78.67.Hc; 42.55.Sa; 42.50.Pq; 78.55.Cr.

Plasmonic bandgap in random media.

We present a dispersion theory of the surface plasmon polaritons (SPP) in random metal-dielectric nanocomposite (MDN) consisting of bulk metal embedded with dielectric inclusions. We demonstrate that embedding of dielectric nanoparticles in metal results in the formation of the plasmonic bandgap due to strong coupling of the SPP at the metal-vacuum interface and surface plasmons localized at the surface of nanoinclusions. Our results show that MDN can replace metals in various plasmonic devices, which properties can be tuned in a wide spectral range. Being compatible with waveguides and other photonic structures, MDN offers high flexibility in the plasmonic system design.

Nanoscale patterning of metal nanoparticle distribution in glasses.

: We show that electric field imprinting technique allows for patterning of metal nanoparticles in the glass matrix at the subwavelength scale. The formation of glass-metal nanocomposite strips with a width down to 150 nm is demonstrated. The results of near-field microscopy of imprinted patterns are in good agreement with the performed numerical modeling. Atomic force microscopy reveals that imprinting also results in the formation of nanoscale surface profile with the height going down with the decrease of the strip width. The experiments prove the applicability of this technique for the fabrication of nanoscale plasmonic components.