Electrons and photons can coexist as a single entity called a surface plasmon—an elementary excitation found at the interface between a conductor and an insulator. Because of their hybrid electric and photonic nature, plasmons allow photons to be precisely controlled on the nanoscale. Plasmons are evident in the vivid hues of rose windows, which derive their color from small metallic nanoparticles embedded in the glass. They also provide the basis for color-changing biosensors (such as home pregnancy tests), photothermal cancer treatments, improved photovoltaic cell efficiencies, and nanoscale lasers. While surface plasmons were first identified nearly 55 years ago, many of their exciting applications are yet to come. This issue of MRS Bulletin reviews the progress and promise of plasmonics—from the characterization tools that have allowed nanometer-scale probing of plasmons to the new materials that may enable low-loss, active, and quantum plasmonics. Within reach are applications ranging from integrated plasmonic circuits for nanophotonic computation to plasmonic optical tweezers for manipulation of nano-sized particles and proteins.

This article is based on the Fred Kavli Distinguished Lectureship in Nanoscience presentation given by Harry Atwater (California Institute of Technology) on April 5, 2010 at the Materials Research Society Spring Meeting in San Francisco, CA. The Kavli Foundation supports scientific research, honors scientific achievement, and promotes public understanding of scientists and their work. Its particular focuses are astrophysics, nanoscience, and neuroscience.

Solar energy is currently enjoying substantial growth and investment, owing to worldwide sensitivity to energy security and climate change. Solar energy is an inexhaustible resource and is in abundant supply on all continents of the world. The power density of sunlight (~1000 W/m2) and the efficiency of photovoltaic devices (~10–25%) are high enough so that land use does not limit photovoltaic deployment at the terawatt scale. However solar photovoltaics are currently too expensive to achieve parity with other forms of electricity generation based on fossil fuels. This is largely due to the cost (and for some cases, the abundance) of materials used in photovoltaic modules and systems, and the cost of deploying in current form. This economic and social context has created the present situation where there is widespread interest in photovoltaic technology for power generation, but the cumulative installed world capacity for photovoltaics is <50 GW, and it appears to be very challenging for photovoltaics to play a very substantial role in large-scale (terawatt) electricity generation in the short term.

InP/Si engineered substrates formed by wafer bonding and layer transfer have the potential to significantly reduce the cost and weight of III-V compound semiconductor solar cells. InP/Si substrates were prepared by He implantation of InP prior to bonding to a thermally oxidized Si substrate and annealing to exfoliate an InP thin film. Following thinning to remove damage caused by the implantation and exfoliation from the surface of the InP transferred film, InGaAs solar cells lattice-matched to bulk InP were grown on those substrates using metal-organic chemical vapor deposition. The photovoltaic current-voltage characteristics of the InGaAs cells fabricated on the wafer-bonded InP/Si substrates were comparable to those synthesized on commercially available epi-ready InP substrates, thus providing an initial demonstration of wafer-bonded InP/Si substrates as an alternative to bulk InP substrates for solar cell applications.

Since the development of the light microscope in the 16th century, optical device size and performance have been limited by diffraction. Optoelectronic devices of today are much bigger than the smallest electronic devices for this reason. Achieving control of light—material interactions for photonic device applications at the nanoscale requires structures that guide electromagnetic energy with subwavelength-scale mode confinement. By converting the optical mode into nonradiating surface plasmons, electromagnetic energy can be guided in structures with lateral dimensions of less than 10% of the free-space wavelength. A variety of methods—including electron-beam lithography and self-assembly—have been used to construct both particle and planar plasmon waveguides. Recent experimental studies have confirmed the strongly coupled collective plasmonic modes of metallic nanostructures. In plasmon waveguides consisting of closely spaced silver rods, electromagnetic energy transport over distances of 0.5 m has been observed. Moreover, numerical simulations suggest the possibility of multi-centimeter plasmon propagation in thin metallic stripes. Thus, there appears to be no fundamental scaling limit to the size and density of photonic devices, and ongoing work is aimed at identifying important device performance criteria in the subwavelength size regime. Ultimately, it may be possible to design an entire class of subwavelength-scale optoelectronic components (waveguides, sources, detectors, modulators) that could form the building blocks of an optical device technology—a technology scalable to molecular dimensions, with potential imaging, spectroscopy, and interconnection applications in computing, communications, and chemical/biological detection.

We have investigated the low-temperature epitaxial growth of thin silicon films by hotwire chemical vapor deposition (HWCVD). Using reflection high energy electron diffraction (RHEED) and transmission electron microscopy (TEM), we have found conditions for epitaxial growth at low temperatures achieving twinned epitaxial growth up to 6.8 μm on Si(100) substrates at a substrate temperature of 230°C. This opens the possibility of growing high quality films on low cost substrates. The H2:SiH4 dilution ratio was set to 50:1 for all growths. Consistent with previous results, the epitaxial thickness is found to decrease with an increase in the substrate temperature.

The fabrication of low temperature polycrystalline silicon with lifetimes close to single crystalline silicon, but with internal surface passivation similar to that observed in deposited microcrystalline silicon, is a promising direction for thin film polycrystalline silicon photovoltaics. To achieve this, large grains with passivated grain boundaries and intragranular defects are required. We investigate the low-temperature (250-550°C) epitaxial growth of thin silicon films by hot-wire chemical vapor deposition (HWCVD) on Si(100) substrates and large-grained polycrystalline silicon template layers formed by selective nucleation and solid phase epitaxy (SNSPE). Using reflection high energy electron diffraction (RHEED) and transmission electron microscopy (TEM), we have observed epitaxial, twinned epitaxial, mixed epitaxial/polycrystalline and polycrystalline phases in the 50 nm–15 μm thickness regime. HWCVD growth on Si(100) was performed using a mixture of diluted silane (4% in He) and hydrogen at a H2/SiH4 ratio of 50:1 at substrate temperatures from 300–475°C. We will discuss the relationship between the microstructure and photoconductive decay lifetimes of these undoped layers on Si(100) and SNSPE templates as well as their suitability for use in thin-film photovoltaic applications.

We report results pertinent to the high total dose tolerance of Si nanocrystal non-volatile memory cells. The nc-Si FETs made by ion implantation retained virtually unchanged write / erase characteristics, typical for the two-state devices, to cumulative doses exceeding 15 Mrad(Si).

Layer transfer of thin BaTiO3 films onto silicon-based substrates has been investigated. H+ and He+ ion implantation created a buried sacrificial layer in the BaTiO3 single crystals. Thermodynamics and kinetics of cavity nucleation and growth at the bonding interface have been investigated and single crystal thin film layers were transferred onto amorphous Si3N4 and Pt substrates. We have found that defects generated by ion implantation in ferroelectric materials can be significantly recovered with the subsequent annealing for layer splitting. Also, after high dose ion implantation, the films remain single crystal and stoichiometry. Finally, characterization proves the layer-transferred thin films are ferroelectrically active, with domains and piezoresponse similar to bulk crystals.

We investigate the optical properties of arrays of closely spaced metal nanoparticles in view of their potential to guide electromagnetic energy with a lateral mode confinement below the diffraction limit of light. Finite-difference time-domain simulations of short arrays of noble metal nanospheres show that electromagnetic pulses at optical frequencies can propagate along the arrays due to near-field interactions between plasmon-polariton modes of adjacent nanoparticles. Near-field microscopy enables the study of energy transport in these plasmon waveguides and shows experimental evidence for energy propagation over a distance of 0.5 νm for plasmon waveguides consisting of spheroidal silver particles fabricated using electron beam lithography.

A study of the interfacial properties of wafer bonded InP/Si is presented. The electrical properties are measured by bonding InP to Si with different doping concentrations and by measuring the current voltage characteristics of the bonded pairs. Two different kinds of structures are studied: 1) n+InP doped to 3×1018 cm-3 bonded with n+Si doped to 1×1019 cm-3, and 2) n+InP doped to 3×1018 cm-3 bonded with p-Si doped to 6×1014 cm-3. After a 350°C anneal, structure 1 shows low resistive ohmic behavior while structure 2 is rectifying due to its higher sensitivity to interfacial chemistry. Indeed, both the reverse and forward current are reduced by annealing in structure 2, suggesting the formation of an interfacial barrier during annealing. This hypothesis is supported by High Resolution Transmission Electron Microscopy combined with Fourier Transform Infrared Spectroscopy, which indicate the formation of an amorphous interfacial oxide from the reaction of adsorbed water trapped at the InP/Si interface.

A study of the interfacial properties of wafer bonded InP/Si is presented. The electrical properties are measured by bonding InP to Si with different doping concentrations and by measuring the current voltage characteristics of the bonded pairs. Two different kinds of structures are studied: 1) n+InP doped to 3×1018 cm-3 bonded with n+Si doped to 1×1019 cm-3, and 2) n+InP doped to 3×1018 cm-3 bonded with p-Si doped to 6×1014 cm-3. After a 350°C anneal, structure 1 shows low resistive ohmic behavior while structure 2 is rectifying due to its higher sensitivity to interfacial chemistry. Indeed, both the reverse and forward current are reduced by annealing in structure 2, suggesting the formation of an interfacial barrier during annealing. This hypothesis is supported by High Resolution Transmission Electron Microscopy combined with Fourier Transform Infrared Spectroscopy, which indicate the formation of an amorphous interfacial oxide from the reaction of adsorbed water trapped at the InP/Si interface.

We have performed a comparative study of oxide- and nonoxide-passivated silicon nanocrystals to probe the role of the silicon/oxygen interface in low coverage, non-interacting silicon nanocrystal systems. Ensembles of Si nanocrystals characterized by a narrow distribution and diameters of 2–5 nm were synthesized by ion implantation into SiO2 films followed by a high-temperature anneal in Ar. The nanocrystals were removed from the SiO2 film matrix and deposited on Si substrates using a chemical etch in HF, leaving a hydrogen-terminated surface. A natural oxide layer grows on these surfaces in air. We characterized the morphology of the samples with atomic force microscopy (AFM) and the spectroscopic properties with photoluminescence (PL) and X-Ray photoelectron spectroscopy. We found that the PL energy of Si nanocrystals can be shifted by particle size reduction and hydrogen or oxygen termination. Further, PL peak energy shifts upon etching and oxidation were consistent with the model of Wolkin et al. that proposes that for very small radii, a silicon-oxygen double bond will produce deep interface states which red shift the luminescence.

We study the influence of optical near-field interactions on the dipole surface plasmon resonance of Au nanoparticles in closely spaced particle arrays using finite-difference timedomain simulations. In particular, the resonance energies of the collective plasmon-polariton modes are determined for longitudinal and transverse polarization for different particle array lengths and inter-particle spacings of 50 nm Au spheres in air. The obtained results are set in context with recent publications suggesting the possibility to use ordered arrays of closely spaced noble metal nanoparticles as plasmon waveguides for electromagnetic energy below the diffraction limit of light.

Silicon nitride films have been grown by hot-wire chemical vapor deposition and film properties have been characterized as a function of SiH4/NH3 flow ratio. Quadrupole mass spectrometry measurements revealed that NH3 should be present in large excess relative to SiH4 (<10), due to its lower decomposition probability on the wire. Silicon nitride films were produced with refractive indices ranging from 1.8-2.5 and H-content from 9-18 atomic % as the flow ratio increased from 1% to 8%. Fourier Transform Infrared Spectroscopy revealed a change from predominantly N-H to Si-H bonding as the flow ratio increases beyond 6%. Subsequent annealing studies showed different kinetics for H release from Si versus N. Films grown with a low SiH4/NH3 ratio were found to oxidize readily (23 atomic %), while larger ratios yielded no oxygen incorporation.

We report on the layer transfer of thin ferroelectric materials onto silicon substrates. H+ and He+ ion implantation created a buried sacrificial layer in the c-cut BaTiO3 and LiNbO3 single crystals. Bubble formation and thermodynamics of cavity at the bonding interface have been investigated, and single crystal thin film layers were transferred onto crystalline silicon substrates. We have found that defects generated by ion implantation in ferroelectric materials can be significantly recovered with the subsequent annealing for layer splitting.

Wire-desorbed radicals present during hot-wire chemical vapor deposition growth have been measured by quadrupole mass spectrometry. For wire temperatures in excess of 1500 K, Si is the predominant radical desorbed from a new wire, with a minor contribution from SiH3. Aged wires showed profoundly different radical desorption kinetics, consistent with evaporation of Si from liquid silicon. It is proposed that this aging is related to silicide formation at the surface of the wire.

Quantitative understanding of charging and discharging of Si nanocrystals in SiO2 films on Si substrate is essential to their application in floating gate nonvolatile memory devices. Charge imaging by atomic force microscopy (AFM) or electrostatic force microscopy (EFM) can provide qualitative information on such system, while a further step is needed. We have developed a generalized method of images, which can solve Poisson equation for multiple dielectric layers, to simulate the charge imaging of Si nanocrystals by non-contact mode AFM under different sample geometries. Simulated images can be compared with experimental images thoroughly to estimate the total amount and distributions of trapped charges, which is also useful in the study of time evolution of charges or dissipation problems.

We used a previously reported kinematical electron scattering model1 to develop a RHEED based method for performing quantitative analysis of mosaic polycrystalline thin film in-plane and out-of-plain grain orientation distributions. RHEED based biaxial texture measurements are compared to X-Ray and transmission electron microscopy measurements to establish the validity of the RHEED analysis method. In situ RHEED analysis reveals that the out-of-plane orientation distribution starts out very broad, and then decreases during IBAD MgO growth. Other results included evidence that the in-plane orientation distribution narrows, the grain size increases, and the film roughens as film thickness increases during IBAD MgO growth. Homoepitaxy of MgO improves the biaxial texture of the IBAD layer, making X-ray measurements of IBAD films with an additional homoepitaxial layer not quantitatively representative of the IBAD layer. Systematic offsets between RHEED analysis and X-ray measurements of biaxial texture, coupled with evidence that biaxial texture improves with increasing film thickness, indicate that RHEED is a superior technique for probing surface biaxial texture.

We apply a rate-equation pair binding model of nucleation kinetics [1] to the nucleation of Si islands grown by hot-wire chemical vapor deposition on SiO2 substrates. Previously, we had demonstrated an increase in grain size of polycrystalline Si films with H2 dilution from 40 nm using 100 mTorr of 1% SiH4 in He to 85 nm with the addition of 20 mTorr H2. [2] This increase in grain size is attributed to atomic H etching of Si monomers rather than stable Si clusters during the early stages of nucleation, decreasing the nucleation density. Atomic force microscopy (AFM) measurements show that the nucleation density increases sublinearly with time at low coverage, implying a fast nucleation rate until a critical density is reached, after which grain growth begins. The nucleation density decreases with increasing H2 dilution (H2:SiH4), which is an effect of the etching mechanism, and with increasing temperature, due to enhanced Si monomer diffusivity on SiO2. From temperature-dependent measurements, we estimate the activation energy for surface diffusion of Si monomers on SiO2 to be 0.47 ± 0.09 eV. Simulations of the temperature-dependent supercritical cluster density lead to an estimated activation energy of 0.42 eV ± 0.01 eV and a surface diffusion coefficient prefactor of 0.1 ± 0.03 cm2/s. H2-dilution-dependent simulations of the supercritical cluster density show an approximately linear relationship between the H2 dilution and the etch rate of clusters.

We propose a method for replicating patterns with a resolution well below the diffraction limit, using broad beam illumination and standard photoresist. In particular it is shown that visible exposure (λ=410 nm) of silver nanoparticles in close proximity to a thin film of g-line resist (AZ 1813) can produce selectively exposed areas with a diameter smaller than λ/20. The technique relies on the local field enhancement around metal nanostructures when illuminated at the surface plasmon resonance frequency. The method can be extended to various metals, photosensitive layers, and particle shapes.