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Bismuth-based halide perovskites are nontoxic alternatives to widely studied lead-based perovskites for optoelectronic applications. Here, we synthesized Cs 2 NaBiCl 6 thin films and attempted to synthesize Cs 2 NaBiBr 6 using physical vapor deposition. While Cs 2 NaBiCl 6 forms a stable cubic structure with a 3.4 eV band gap and could be synthesized successfully, Cs 2 NaBiBr 6 does not form and is unstable with respect to dissociation into Cs 3- x Na x Bi 2 Br 9 and Cs 3- x Na x BiBr 6 . Furthermore, the close X-ray diffraction patterns of Cs 3- x Na x Bi 2 Br 9 and Cs 2 NaBiBr 6 raise doubts about the previous reports of the latter's formation based on X-ray diffraction alone.

Pyrite FeS 2 has extraordinary potential as a low-cost, nontoxic, sustainable photovoltaic but has underperformed dramatically in prior solar cells. The latter devices focus on heterojunction designs, which are now understood to suffer from problems associated with FeS 2 surfaces. Simpler homojunction cells thus become appealing but have not been fabricated due to the historical inability to understand and control doping in pyrite. While recent advances have put S-vacancy and Co-based n -doping of FeS 2 on a firm footing, unequivocal evidence for bulk p -doping remains elusive. Here, we demonstrate the first unambiguous and controlled p -type transport in FeS 2 single crystals doped with phosphorus (P) during chemical vapor transport growth. P doping is found to be possible up to at least ∼100 ppm, inducing ∼10 18 holes/cm 3 at 300 K, while leaving the crystal structure and quality unchanged. As the P doping is increased in crystals natively n -doped with S vacancies, the majority carrier type inverts from n to p near ∼25 and ∼55 ppm P, as detected by Seebeck and Hall effects, respectively. Detailed temperature- and P-doping-dependent transport measurements establish that the P acceptor level is 175 ± 10 meV above the valence band maximum, explain details of the carrier inversion, elucidate the relative mobility of electrons and holes, reveal mid-gap defect levels, and unambiguously establish that the inversion to p -type occurs in the bulk and is not an artifact of hopping conduction. Such controlled bulk p -doping opens the door to pyrite p-n homojunctions, unveiling new opportunities for solar cells based on this extraordinary semiconductor.

Cs 2 AgInBr 6 is among the lead-free halide perovskites of interest, predicted by first-principles calculations to be stable with a direct band gap, but there has been only one report of its synthesis. Herein we report the formation of Cs 2 AgInBr 6 thin films through thermal evaporation of CsBr, AgBr, and InBr 3 and subsequent annealing between 130 °C and 250 °C. Cs 2 AgInBr 6 appears stable in this temperature range. However, Cs 2 AgInBr 6 thin films are thermodynamically unstable at room temperature, remaining cubic only long enough to be characterized but not long enough to be useful for practical devices. Cs 2 AgInBr 6 decomposed into Cs 2 AgBr 3 , Cs 3 In 2 Br 9 , AgBr, and InBr 3 upon cooling from 130 °C to 250 °C to room temperature. This conclusion did not depend on illumination, film thickness, annealing environment, or details of the film formation, pointing to an intrinsic thermodynamic instability of the material. Optical absorption measurements may be interpreted as Cs 2 AgInBr 6 having a direct band gap of 1.57 ± 0.1 eV.

When excited by photons with energies greater than 2.2 eV, the bandgap energy, Yb-doped Cs 2 AgBiBr 6 thin films synthesized via physical vapor deposition emit strong near-infrared luminescence centered at ∼1.24 eV via the Yb 3+ 2 F 5/2 → 2 F 7/2 electronic transition. Robust, reproducible, and stable photoluminescence quantum yields (PLQY) as high as 82.5% are achieved with Cs 2 AgBiBr 6 films doped with 8% Yb. This high PLQY indicates facile and efficient energy transfer from the perovskite host, Cs 2 AgBiBr 6 , to Yb, making Cs 2 AgBiBr 6 the most promising lead-free down-conversion material.

Advances in the synthesis and characterization of colloidal magnetic nanoparticles (NPs) have yielded great gains in the understanding of their complex magnetic behavior, with implications for numerous applications. Recent work using Ni NPs as a model soft ferromagnetic system, for example, achieved quantitative understanding of the superparamagnetic blocking temperature-particle diameter relationship. This hinged, however, on the critical assumption of a ferromagnetic NP volume lower than the chemical volume due to a non-ferromagnetic dead shell indirectly deduced from magnetometry. Here, we determine both the chemical and magnetic average internal structures of Ni NP ensembles via unpolarized, half-polarized, and fully polarized small-angle neutron scattering (SANS) measurements and analyses coupled with X-ray diffraction and magnetometry. The postulated nanometric magnetic dead shell is not only detected but conclusively identified as a non-ferromagnetic Ni phosphide derived from the trioctylphosphine commonly used in hot-injection colloidal NP syntheses. The phosphide shell thickness is tunable via synthesis temperature, falling to as little as 0.5 nm at 170 °C. Temperature- and magnetic field-dependent polarized SANS measurements additionally reveal essentially bulk-like ferromagnetism in the Ni core and negligible interparticle magnetic interactions, quantitatively supporting prior modeling of superparamagnetism. These findings advance the understanding of synthesis-structure-property relationships in metallic magnetic NPs, point to a simple potential route to ligand-free stabilization, and highlight the power of the currently available suite of polarized SANS measurement and analysis capabilities for magnetic NP science and technology.

Many envisioned applications of semiconductor nanocrystals (NCs), such as thermoelectric generators and transparent conductors, require metallic (nonactivated) charge transport across an NC network. Although encouraging signs of metallic or near-metallic transport have been reported, a thorough demonstration of nonzero conductivity, σ, in the 0 K limit has been elusive. Here, we examine the temperature dependence of σ of ZnO NC networks. Attaining both higher σ and lower temperature than in previous studies of ZnO NCs ( T as low as 50 mK), we observe a clear transition from the variable-range hopping regime to the metallic regime. The critical point of the transition is distinctly marked by an unusual power law close to σ ∝ T 1/5 . We analyze the critical conductivity data within a quantum critical scaling framework and estimate the metal-insulator transition (MIT) criterion in terms of the free electron density, n , and interparticle contact radius, ρ.

Searching for alternatives to lead-containing metal halide perovskites, we explored the properties of indium-based inorganic double perovskites Cs 2 InMX 6 with M = Cu, Ag, Au and X = Cl, Br, I, and of its organic-inorganic hybrid derivative MA 2 InCuCl 6 (MA = CH 3 NH 3 + ) using computation within Kohn-Sham density functional theory. Among these compounds, Cs 2 InCuCl 6 and MA 2 InCuCl 6 were found to be potentially promising candidates for solar cells. Calculations with different functionals provided the direct band gap of Cs 2 InCuCl 6 between 1.05 and 1.73 eV. In contrast, MA 2 InCuCl 6 exhibits an indirect band gap between 1.31 and 2.09 eV depending on the choice of exchange-correlation functional. Cs 2 InCuCl 6 exhibits a much higher absorption coefficient than that calculated for c-Si and CdTe, common semiconductors for solar cells. Even MA 2 InCuCl 6 is predicted to have a higher absorption coefficient than c-Si and CdTe across the visible spectrum despite the fact that it is an indirect band gap material. The intrinsic charge carrier mobilities for Cs 2 InCuCl 6 along the L-Γ path are predicted to be comparable to those for MAPbI 3 . Finally, we carried out calculations of the band edge positions for MA 2 InCuCl 6 and Cs 2 InCuCl 6 to offer guidance for solar cell heterojunction design and optimization. We conclude that Cs 2 InCuCl 6 and MA 2 InCuCl 6 are promising semiconductors for photovoltaic and optoelectronic applications.

Orthorhombic tin monosulfide (SnS) consists of layers of covalently bound Sn and S atoms held together by weak van der Waals forces and is a stable two-dimensional material with potentially useful properties in emerging applications such as valleytronics. Large-scale sustainable synthesis of few-layer (e.g., 1-10 layers) SnS is a challenge, which also slows progress in understanding their properties as a function of number of layers. Herein we describe solvothermal synthesis of SnS in water or ethylene glycol. The latter yields a flower-like morphology where the petals are SnS nanoplates and sonication and separation of these flowers via differential centrifugation yields 1-10 layer SnS nanoplates. The direct optical absorption edges of these SnS nanoplates blue-shift due to quantum confinement from 1.33 to 1.88 eV as the thickness (number of layers) is decreased from ∼5 nm (10 layers) to ∼2 nm (4 layers).

Pyrite FeS 2 has long been considered a potential earth-abundant low-cost photovoltaic material for thin-film solar cells but has been plagued by low power conversion efficiencies and open-circuit voltages. Recent efforts have identified a lack of understanding and control of doping, as well as uncontrolled surface conduction, as key roadblocks to the development of pyrite photovoltaics. In particular, while n-type bulk behavior in unintentionally doped single crystals and thin films is speculated to arise from sulfur vacancies (V S ), proof remains elusive. Here, we provide strong evidence, from extensive electronic transport measurements on high-quality crystals, that V S are deep donors in bulk pyrite. Otherwise identical crystals grown via chemical vapor transport under varied S vapor pressures are thoroughly characterized structurally and chemically, and shown to exhibit systematically different electronic transport. Decreased S vapor pressure during growth leads to reduced bulk resistivity, increased bulk Hall electron density, reduced transport activation energy, onset of positive temperature coefficient of resistivity, and approach to an insulator-metal transition, all as would be expected from increased V S donor density. Impurity analyses show that these trends are uncorrelated with metal impurity concentration and that extracted donor densities significantly exceed total impurity concentrations, directly evidencing a native defect. Well-controlled, wide-range n-doping of pyrite is thus achieved via the control of V S concentration, with substantial implications for photovoltaic and other applications. The location of the V S state within the gap, the influence of specific impurities, unusual aspects to the insulator-metal transition, and the influence of doping on surface conduction are also discussed.

Semiconductor quantum dots synthesized using rapid mixing of precursors by injection into a hot solution of solvents and surfactants have surface ligands that sterically stabilize the dispersions in nonpolar solvents. Often, these ligands are exchanged to disperse the quantum dots in polar solvents, but quantitative studies of quantum dot surfaces before and after ligand exchange are scarce. We studied exchanging trioctylphosphine (TOP) and trioctylphosphine oxide (TOPO) ligands on as-synthesized CdSe quantum dots dispersed in hexane with a 2000 g/mol thiolated poly(ethylene glycol) (PEG) polymer. Using infrared spectroscopy we quantify the absolute surface concentration of TOP/TOPO and PEG ligands per unit area before and after ligand exchange. While 50-85% of the TOP/TOPO ligands are removed upon ligand exchange, only a few are replaced with PEG. Surprisingly, the remaining TOP/TOPO ligands outnumber the PEG ligands, but these few PEG ligands are sufficient to disperse the quantum dots in polar solvents such as chloroform, tetrahydrofuran, and water. Moreover, as-synthesized quantum dots once easily dispersed in hexane are no longer dispersible in nonpolar solvents after ligand exchange. A subtle coverage-dependent balance between attractive PEG-solvent interactions and repulsive TOP/TOPO-solvent interactions determines the dispersion stability.

Networks of ligand-free semiconductor nanocrystals (NCs) offer a valuable combination of high carrier mobility and optoelectronic properties tunable via quantum confinement. In principle, maximizing carrier mobility entails crossing the insulator-metal transition (IMT), where carriers become delocalized. A recent theoretical study predicted that this transition occurs at nρ 3 ≈ 0.3, where n is the carrier density and ρ is the interparticle contact radius. In this work, we satisfy this criterion in networks of plasma-synthesized ZnO NCs by using intense pulsed light (IPL) annealing to tune n and ρ independently. IPL applied to as-deposited NCs increases ρ by inducing sintering, and IPL applied after the NCs are coated with Al 2 O 3 by atomic layer deposition increases n by removing electron-trapping surface hydroxyls. This procedure does not substantially alter NC size or composition and is potentially applicable to a wide variety of nanomaterials. As we increase nρ 3 to at least twice the predicted critical value, we observe conductivity scaling consistent with arrival at the critical region of a continuous quantum phase transition. This allows us to determine the critical behavior of the dielectric constant and electron localization length at the IMT. However, our samples remain on the insulating side of the critical region, which suggests that the critical value of nρ 3 may in fact be significantly higher than 0.3.

Thin polycrystalline films of the solar absorber copper-zinc-tin-sulfide (CZTS) were formed by annealing coatings deposited on molybdenum-coated soda lime glass via ultrasonic spraying of aerosol droplets from colloidal CZTS nanocrystal dispersions. Production of uniform continuous nanocrystal coatings with ultrasonic spraying requires that the evaporation time is longer than the aerosol flight time from the spray nozzle to the substrate such that the aerosol droplets still have low enough viscosity to smooth the impact craters that form on the coating surface. In this work, evaporation was slowed by adding a high boiling point cosolvent, cyclohexanone, to toluene as the dispersing liquid. We analyzed, quantitatively, the effects of the solvent composition on the aerosol and coating drying dynamics using an aerosol evaporation model. Annealing coatings in sulfur vapor converts them into polycrystalline films with micrometer size grains, but the grains form continuous films only when Na is present during annealing to enhance grain growth. Continuous films are easier to form when the average nanocrystal size is 15 nm: using larger nanocrystals (e.g., 20 nm) sacrifices film continuity.

Nonthermal plasmas have emerged as a viable synthesis technique for nanocrystal materials. Inherently solvent and ligand-free, nonthermal plasmas offer the ability to synthesize high purity nanocrystals of materials that require high synthesis temperatures. The nonequilibrium environment in nonthermal plasmas has a number of attractive attributes: energetic surface reactions selectively heat the nanoparticles to temperatures that can strongly exceed the gas temperature; charging of nanoparticles through plasma electrons reduces or eliminates nanoparticle agglomeration; and the large difference between the chemical potentials of the gaseous growth species and the species bound to the nanoparticle surfaces facilitates nanocrystal doping. This paper reviews the state of the art in nonthermal plasma synthesis of nanocrystals. It discusses the fundamentals of nanocrystal formation in plasmas, reviews practical implementations of plasma reactors, surveys the materials that have been produced with nonthermal plasmas and surface chemistries that have been developed, and provides an overview of applications of plasma-synthesized nanocrystals.

Metal oxide semiconductor nanocrystals (NCs) exhibit localized surface plasmon resonances (LSPRs) tunable within the infrared (IR) region of the electromagnetic spectrum by vacancy or impurity doping. Although a variety of these NCs have been produced using colloidal synthesis methods, incorporation and activation of dopants in the liquid phase has often been challenging. Herein, using Al-doped ZnO (AZO) NCs as an example, we demonstrate the potential of nonthermal plasma synthesis as an alternative strategy for the production of doped metal oxide NCs. Exploiting unique, thoroughly nonequilibrium synthesis conditions, we obtain NCs in which dopants are not segregated to the NC surfaces and local doping levels are high near the NC centers. Thus, we achieve overall doping levels as high as 2 × 10(20) cm(-3) in NCs with diameters ranging from 12.6 to 3.6 nm, and for the first time experimentally demonstrate a clear quantum confinement blue shift of the LSPR energy in vacancy- and impurity-doped semiconductor NCs. We propose that doping of central cores and heavy doping of small NCs are achievable via nonthermal plasma synthesis, because chemical potential differences between dopant and host atoms-which hinder dopant incorporation in colloidal synthesis-are irrelevant when NC nucleation and growth proceed via irreversible interactions among highly reactive gas-phase ions and radicals and ligand-free NC surfaces. We explore how the distinctive nucleation and growth kinetics occurring in the plasma influences dopant distribution and activation, defect structure, and impurity phase formation.

The use of pyrite FeS2 as an earth-abundant, low-cost, nontoxic thin film photovoltaic hinges on improved understanding and control of certain physical and chemical properties. Phase stability, phase purity, stoichiometry, and defects, are central in this respect, as they are frequently implicated in poor solar cell performance. Here, phase-pure polycrystalline pyrite FeS2 films, synthesized by ex situ sulfidation, are subject to systematic reduction by vacuum annealing (to 550 °C) to assess phase stability, stoichiometry evolution, and their impact on transport. Bulk probes reveal the onset of pyrrhotite (Fe(1-δ)S) around 400 °C, rapidly evolving into the majority phase by 425 °C. This is supported by X-ray photoelectron spectroscopy on (001) crystals, revealing surface Fe(1-δ)S formation as low as 160 °C, with rapid growth near 400 °C. The impact on transport is dramatic, with Fe(1-δ)S minority phases leading to a crossover from diffusive transport to hopping (due to conductive Fe(1-δ)S nanoregions in an FeS2 matrix), followed by metallicity when Fe(1-δ)S dominates. Notably, the crossover to hopping leads to an inversion of the sign, and a large decrease in magnitude of the Hall coefficient. By tracking resistivity, magnetotransport, magnetization, and structural/chemical parameters vs annealing, we provide a detailed picture of the evolution in properties with stoichiometry. A strong propensity for S-deficient minority phase formation is found, with no wide window where S vacancies control the FeS2 carrier density. These findings have important implications for FeS2 solar cell development, emphasizing the need for (a) nanoscale chemical homogeneity, and (b) caution in interpreting carrier types and densities.

A three-step method to create dense polycrystalline semiconductor thin films from nanocrystal liquid dispersions is described. First, suitable substrates are coated with nanocrystals using aerosol-jet printing. Second, the porous nanocrystal coatings are compacted using a weighted roller or a hydraulic press to increase the coating density. Finally, the resulting coating is annealed for grain growth. The approach is demonstrated for making polycrystalline films of copper zinc tin sulfide (CZTS), a new solar absorber composed of earth-abundant elements. The range of coating morphologies accessible through aerosol-jet printing is examined and their formation mechanisms are revealed. Crack-free albeit porous films are obtained if most of the solvent in the aerosolized dispersion droplets containing the nanocrystals evaporates before they impinge on the substrate. In this case, nanocrystals agglomerate in flight and arrive at the substrate as solid spherical agglomerates. These porous coatings are mechanically compacted, and the density of the coating increases with compaction pressure. Dense coatings annealed in sulfur produce large-grain (>1 μm) polycrystalline CZTS films with microstructure suitable for thin-film solar cells.

Thin films comprising semiconductor nanocrystals are emerging for applications in electronic and optoelectronic devices including light emitting diodes and solar cells. Achieving high charge carrier mobility in these films requires the identification and elimination of electronic traps on the nanocrystal surfaces. Herein, we show that in films comprising ZnO nanocrystals, an electron acceptor trap related to the presence of OH on the surface limits the conductivity. ZnO nanocrystal films were synthesized using a nonthermal plasma from diethyl zinc and oxygen and deposited by inertial impaction onto a variety of substrates. Surprisingly, coating the ZnO nanocrystals with a few nanometres of Al2O3 using atomic layer deposition decreased the film resistivity by seven orders of magnitude to values as low as 0.12 Ω cm. Electron mobility as high as 3 cm(2) V(-1) s(-1) was observed in films comprising annealed ZnO nanocrystals coated with Al2O3.

Nonthermal plasmas can produce high quality nanocrystals in a continuous process without requiring solvents. A nonthermal plasma process is demonstrated to synthesize stoichiometric Cu2S nanocrystals, which show no signs of oxidation by spectrophotometry after 2 months in the ambient when stabilized with oleylamine and dispersed in toluene.

Copper zinc tin sulfide (CZTS) thin films were deposited from homogeneous solutions of precursors and directly onto conductive films via selective thermolysis by microwave heating. Microwave energy is absorbed strongly by conductive films, which enables preferential heating to a sufficiently high temperature for the deposition of CZTS exclusively on the conductive layer without homogeneous nucleation of CZTS in the liquid phase or heterogeneous nucleation of CZTS on uncoated portions of substrates.

Cu(2)ZnSnS(4) (CZTS) nanocrystals sterically stabilized with oleic acid and oleylamine ligands and dispersed in nonpolar organic liquids have been extracted into, and electrostatically stabilized in, polar liquids by covering their surfaces with S(2-).

Pyrite FeS2 is receiving a resurgence of interest as a uniquely attractive thin film solar absorber based on abundant, low-cost, nontoxic elements. Here we address, via ex situ sulfidation synthesis, the long-standing problem of understanding conduction and doping in FeS2 films, an elusive prerequisite to successful solar cells. We find that an abrupt improvement in crystallinity at intermediate sulfidation temperatures is accompanied by unanticipated crossovers from intergranular hopping to conventional transport, and, remarkably, from hole-like to electron-like Hall coefficients. The hopping is found to occur between a small volume fraction of conductive nanoscopic sulfur-deficient grain cores (beneath our X-ray diffraction detection limits), embedded in nominally stoichiometric FeS2. In addition to placing constraints on the conditions under which useful properties can be obtained from FeS2 synthesized in diffusion-limited situations, these results also emphasize that FeS2 films are not universally p-type. Indeed, with no knowledge of the active transport mechanism we demonstrate that the Hall coefficient alone is insufficient to determine the sign of the carriers. These results elucidate the possible transport mechanisms in thin film FeS2 in addition to their influence on the deduced carrier type, an enabling advancement with respect to understanding and controlling doping in pyrite films.

Single-crystalline anatase nanorods and nanoflakes were grown on transparent conducting fluorine-doped tin oxide (FTO) substrates through hydrolysis of titanium tetrachloride (TiCl(4)) followed by heating to 450 °C.

Zinc cadmium sulfide (ZnxCd1-xS) thin films grown through chemical bath deposition are used in chalcopyrite solar cells as the buffer layer between the n-type zinc oxide and the p-type light absorbing chalcopyrite film. To optimize energetic band alignment and optical absorption, advanced solar cell architectures require the ability to manipulate x as a function of distance from the absorber-ZnCdS interface. Herein, we investigate the fundamental factors that govern the evolution of the composition as a function of depth in the film. By changing the initial concentrations of Zn and Cd salts in the bath, the entire range of overall compositions ranging from primarily cubic ZnS to primarily hexagonal CdS could be deposited. However, films are inhomogeneous and x varies significantly as function of distance from the film-substrate interface. Films with high overall Zn concentration (x > 0.5) exhibit a Cd-rich layer near the film-substrate interface because Cd is more reactive than Zn. This layer is typically beneath a nearly pure ZnS film that forms after the Cd-rich layers are deposited and Cd is depleted in the bath. In films with high overall Cd concentration (x < 0.5) the Zn concentration rises towards the film's surface. Fortunately, these gradients are favorable for solar cells based on low band gap chalcopyrite films.

Starting with metal dithiocarbamate complexes, we synthesize colloidal Cu(2)ZnSnS(4) (CZTS) nanocrystals with diameters ranging from 2 to 7 nm. Structural and Raman scattering data confirm that CZTS is obtained rather than other possible material phases. The optical absorption spectra of nanocrystals with diameters less than 3 nm show a shift to higher energy due to quantum confinement., (This journal is © The Royal Society of Chemistry 2011)

Fast separation and spatial control of electrons and holes after photogeneration is important in photocatalysis. Ideally, after photogeneration, electrons and holes must be segregated to different parts of the photocatalyst to take part in separate oxidation and reduction reactions. One way to achieve this is by building junctions into the catalyst with built-in chemical potential differences that tend to separate the electron and the hole into two different regions of the catalyst. In this work, we sought to accomplish this by controllably forming junctions between different phases of TiO(2). A synthesis method has been developed to prepare TiO(2)-B core and anatase shell core-shell nanowires. We control the anatase phase surface coverage on the TiO(2)-B core and show that the maximum photocatalytic activity is obtained when the solution containing the reactants can contact both the anatase and TiO(2)-B phases. The photocatalytic activity drops both with bare TiO(2)-B nanowires and with completely anatase covered TiO(2)-B nanowires. In contrast, nanowires partially covered with anatase phase gives the highest photocatalytic activity. The improved photocatalytic activity is attributed to the effective electron-hole separation at the junction between the anatase and TiO(2)-B phases.

Polycrystalline anatase TiO(2) films with high-reactivity {001} facets were grown on transparent conductive fluorine-doped tin dioxide substrates. The hydrothermal synthesis method relied on capping and stabilization of the high-energy {001} surfaces with hydrofluoric acid (HF), which was generated in situ through hydrolysis of TiF(4)., (This journal is © The Royal Society of Chemistry 2011)

To understand diffusion processes occurring inside Fe catalysts during multiwall carbon nanotube (MWCNT) growth, catalysts were studied using atomic-resolution scanning transmission electron microscopy combined with electron energy-loss spectroscopy. Nanotube walls emanate from structurally modified and chemically complex catalysts that consist of cementite and a 5 nm amorphous FeOx cap separated by a 2-3 nm thick carbon-rich region that also contains Fe and O (a-C:FexOy). Nonuniform distribution of carbon atoms throughout the catalyst base reveals that carbon molecules from the gas phase decompose near the catalyst multisection junction, where the MWCNT walls terminate. Formation of the a-C:FexOy region provides the essential carbon source for MWCNT growth. Two different carbon diffusion mechanisms are responsible for the growth of the inner and outer walls of each MWCNT.

We provide an experimental test of the universal behavior arising in simulations of the electrophoretic collision of a long DNA molecule with an isolated, thin post. Our experiments take advantage of a robust protocol to embed matrices of circa 100 nm radius ZnO nanowires in a microfluidic channel. The density and height of the nanowires are easily controlled by the seeding and growth conditions. Single-molecule videomicroscopy of λ-DNA electrophoresis in a sparse nanowire array shows that the average holdup time decays exponentially with the impact parameter, in agreement with simulations. Only at the largest electric field studied here does the hooking probability approach that for an infinitesimally thin post., (Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We examined the structure, morphology, and orientation of catalyst nanoparticles used for seeding and growing multiwall carbon nanotubes (MWCNTs) by plasma enhanced chemical vapor deposition in CH4/H2 gas mixtures. Iron catalyst nanocrystals are converted to Fe3C in CH4/H2 plasmas and the MWCNTs grow from Fe3C nanocrystals. Initially faceted and equiaxed catalyst nanocrystals are distorted and elongated significantly once a tubular CNT structure is formed around the catalyst particles. Eventually, catalysts deform into elongated tear-drop shapes. Once this morphology forms, CNT structures produced are straight and have uniform diameters. Surprisingly, the Fe3C nanocrystals located inside the base of well-graphitized nanotubes do not exhibit a preferred orientation relative to the nanotube axis. Catalyst nanocrystals in a variety of orientations relative to the nanotube axis still produce well-graphitized nanotubes with similar diameters and structures.

In typical semiconductor solar cells, photons with energies above the semiconductor bandgap generate hot charge carriers that quickly cool before all of their energy can be captured, a process that limits device efficiency. Although fabricating the semiconductor in a nanocrystalline morphology can slow this cooling, the transfer of hot carriers to electron and hole acceptors has not yet been thoroughly demonstrated. We used time-resolved optical second harmonic generation to observe hot-electron transfer from colloidal lead selenide (PbSe) nanocrystals to a titanium dioxide (TiO2) electron acceptor. With appropriate chemical treatment of the nanocrystal surface, this transfer occurred much faster than expected. Moreover, the electric field resulting from sub-50-femtosecond charge separation across the PbSe-TiO2 interface excited coherent vibrations of the TiO2 surface atoms, whose motions could be followed in real time.

We report a new type of excitonic solar cell based on planar heterojunctions between PbSe semiconductor nanocrystals and thin ZnO films. These solar cells generate large photocurrents and higher photovoltages compared to Schottky cells assembled with similar nanocrystal films. When illuminated with 100 mW/cm(2) simulated AM1.5 spectrum, these solar cells exhibit short-circuit currents between 12 and 15 mA/cm(2), open-circuit voltages up to 0.45 V, and a power conversion efficiency of 1.6%. The photovoltage depends on the size of the nanocrystals, increasing linearly with their effective band gap energy.

Contrary to expectations, the electron transport rate in dye-sensitized solar cells made from single-crystal rutile titanium dioxide nanowires is found to be similar to that measured in dye-sensitized solar cells made from titanium dioxide nanoparticles.

Thin films of colloidal PbSe quantum dots can exhibit very high carrier mobilities when the surface ligands are removed or replaced by small molecules, such as hydrazine. Charge transport in such films is governed by the electronic exchange coupling energy (beta) between quantum dots. Here we show that two-dimensional quantum dot arrays assembled on a surface provide a powerful system for studying this electronic coupling. We combine optical spectroscopy with atomic force microscopy to examine the chemical, structural, and electronic changes that occur when a submonolayer of PbSe QDs is exposed to hydrazine. We find that this treatment leads to strong and tunable electronic coupling, with the beta value as large as 13 meV, which is 1 order of magnitude greater than that previously achieved in 3D QD solids with the same chemical treatment. We attribute this much enhanced electronic coupling to reduced geometric frustration in 2D films. The strongly coupled quantum dot assemblies serve as both charge and energy sinks. The existence of such coupling has serious implications for electronic devices, such as photovoltaic cells, that utilize quantum dots.

Dye-sensitized solar cells (DSSCs) made from oriented, one-dimensional semiconductor nanostructures such as nanorods, nanowires, and nanotubes are receiving attention because direct connection of the point of photogeneration with the collection electrode using such structures may improve the cell performance. Specifically, oriented single-crystalline TiO(2) nanorods or nanowires on a transparent conductive substrate would be most desirable, but achieving these structures has been limited by the availability of synthetic techniques. In this study, a facile, hydrothermal method was developed for the first time to grow oriented, single-crystalline rutile TiO(2) nanorod films on transparent conductive fluorine-doped tin oxide (FTO) substrates. The diameter, length, and density of the nanorods could be varied by changing the growth parameters, such as growth time, growth temperature, initial reactant concentration, acidity, and additives. The epitaxial relation between the FTO substrate and rutile TiO(2) with a small lattice mismatch plays a key role in driving the nucleation and growth of the rutile TiO(2) nanorods on FTO. With TiCl(4)-treatment, a light-to-electricity conversion efficiency of 3% could be achieved by using 4 mum-long TiO(2) nanorod films as the photoanode in a DSSC.

We report the synthesis of oriented single crystalline titanium dioxide (TiO(2)) nanowire arrays on titanium foil. The synthesis method relies on the ability to grow single crystal sodium titanate (Na(2)Ti(2)O(5).H(2)O) nanowires on titanium foil through a novel alkali hydrothermal growth process. Following growth, the Na(2)Ti(2)O(5).H(2)O nanowires are converted to protonated bititanate (H(2)Ti(2)O(5).H(2)O) nanowires through an ion-exchange reaction without changing their morphology or crystal structure. Finally, the protonated bititanate nanowires are converted to single crystalline anatase TiO(2) nanowires through a topotactic transformation by calcination. These three sequential steps yield a carpet of 2-50 microm long single crystalline nanowires oriented in the [100] direction and primarily normal to the titanium foil. Even longer nanowires can be grown. The single crystal TiO(2) nanowire arrays on flexible titanium substrate may be used in photocatalytic and photovoltaic devices such as dye-sensitized solar cells and may enhance their performance by providing fast electron transport. The nanowires can also be used as templates for producing hierarchical nanostructures such as nanowires decorated with nanoparticles on their periphery or nanotubes with walls made of nanoparticles.

Mesoporous films made of titanium dioxide nanowires are desirable for dye-sensitized solar cells because nanowires provide direct conduction pathways for photogenerated electrons. Anatase titanium dioxide nanowires with polycrystalline microstructure were synthesized on titanium foil using a three-step process. First, the top surface of the titanium foil was transformed to Na(2)Ti(2)O(4)(OH)(2) nanotubes through hydrothermal oxidation in NaOH. Next, the Na(2)Ti(2)O(4)(OH)(2) nanotubes were converted to H(2)Ti(2)O(4)(OH)(2) nanotubes by ion exchange. Finally, the H(2)Ti(2)O(4)(OH)(2) nanotubes were converted to polycrystalline anatase nanowires through a topotactic transformation. The film morphology evolution, crystal structure transformations and growth mechanism are described in detail. Titanium foil reacts with NaOH to form Na(2)Ti(2)O(4)(OH)(2) sheets, which exfoliate and spiral into nanotubes. The Na(2)Ti(2)O(4)(OH)(2) nanotubes are immersed in HCl solution to replace the Na(+) ions with H(+) ions. During the topotactic transformation of H(2)Ti(2)O(4)(OH)(2) nanotubes to anatase TiO(2) nanowires, the sheets made of edge bonded TiO(6) octahedra in the H(2)Ti(2)O(4)(OH)(2) nanotubes dehydrate and move towards each other to form anatase crystals oriented along the nanotube axis which creates a polycrystalline nanowire. These mesoporous TiO(2) nanowire films were suitable for use as dye-sensitized solar cell photoanodes.

We combine CdSe semiconductor nanocrystals (or quantum dots) and single-crystal ZnO nanowires to demonstrate a new type of quantum-dot-sensitized solar cell. An array of ZnO nanowires was grown vertically from a fluorine-doped tin oxide conducting substrate. CdSe quantum dots, capped with mercaptopropionic acid, were attached to the surface of the nanowires. When illuminated with visible light, the excited CdSe quantum dots injected electrons across the quantum dot-nanowire interface. The morphology of the nanowires then provided the photoinjected electrons with a direct electrical pathway to the photoanode. With a liquid electrolyte as the hole transport medium, quantum-dot-sensitized nanowire solar cells exhibited short-circuit currents ranging from 1 to 2 mA/cm2 and open-circuit voltages of 0.5-0.6 V when illuminated with 100 mW/cm2 simulated AM1.5 spectrum. Internal quantum efficiencies as high as 50-60% were also obtained.

An important concern in the deposition of thin hydrogenated amorphous silicon () films is to obtain smooth surfaces. Herein, we combine molecular-dynamics simulations with first-principles density functional theory calculations to elucidate the smoothening mechanism of plasma deposited thin films. We show that the deposition precursor may diffuse rapidly on the film surface via overcoordinated surface Si atoms and incorporate into the film preferentially in surface valleys, with activation barriers for incorporation dependent on the local surface morphology. Experimental data on smoothening and precursor diffusion are accounted for.

Hydrogenated amorphous and nanocrystalline silicon films manufactured by plasma deposition techniques are used widely in electronic and optoelectronic devices. The crystalline fraction and grain size of these films determines electronic and optical properties; the nanocrystal nucleation mechanism, which dictates the final film structure, is governed by the interactions between the hydrogen atoms of the plasma and the solid silicon matrix. Fundamental understanding of these interactions is important for optimizing the film structure and properties. Here we report the mechanism of hydrogen-induced crystallization of hydrogenated amorphous silicon films during post-deposition treatment with an H(2) (or D(2)) plasma. Using molecular-dynamics simulations and infrared spectroscopy, we show that crystallization is mediated by the insertion of H atoms into strained Si-Si bonds as the atoms diffuse through the film. This chemically driven mechanism may be operative in other covalently bonded materials, where the presence of hydrogen leads to disorder-to-order transitions.

Surfaces covered with polyethylene glycol (PEG; HO-(CH(2)-CH(2)-O)(n)-H) have been shown to be biocompatible because PEG's properties yield nonimmunogenicity, nonantigenicity, and protein rejection. To produce a biocompatible surface coating, we have developed a method for grafting PEG onto activated silica films. We first deposited an amorphous silica film by plasma-enhanced chemical vapor deposition from SiH(4) and O(2) gases, which provided the flexibility to coat diverse materials with different chemistries and shapes. The silica films were activated by exposure to water plasma, increasing the number of silanol groups (Si-OH) on their surface. The surface silanol groups were then chemically reacted with the hydroxyl end of PEG to form an ester bond, Si-O-C, and to cover the surface with PEG. The surface reactions were monitored using attenuated total reflection Fourier transform infrared spectroscopy. The vibrational absorption bands of the C-O and -CH(2) bonds increased with time and saturated, indicating that PEG was adsorbed to saturation coverage on the surface. Simultaneously, the Si-OH absorption band decreased, showing that the surface silanols reacted with PEG and were depleted. The PEG-covered surfaces were physically characterized by atomic force microscopy, Auger electron spectroscopy, ellipsometry, and contact angle measurements. These characterization techniques provided additional evidence for the existence of chemically bonded PEG on the surfaces. Efficacy of protein rejection on PEG-covered surfaces was studied through measurements of the fluorescence intensity of Texas red-labeled bovine serum albumin brought in contact with such surfaces in solution. Significantly less protein adsorption was observed on surfaces covered with PEG compared to uncovered surfaces., (Copyright 2000 John Wiley & Sons, Inc.)