Probing the Interaction between Individual Metal Nanocrystals and Two-Dimensional Metal Oxides via Electron Energy Loss Spectroscopy.

Metal nanoparticles can photosensitize two-dimensional metal oxides, facilitating their electrical connection to devices and enhancing their abilities in catalysis and sensing. In this study, we investigated how individual silver nanoparticles interact with two-dimensional tin oxide and antimony-doped indium oxide using electron energy loss spectroscopy (EELS). The measurement of the spectral line width of the longitudinal plasmon resonance of the nanoparticles in absence and presence of 2D materials allowed us to quantify the contribution of chemical interface damping to the line width. Our analysis reveals that a stronger interaction (damping) occurs with 2D antimony-doped indium oxide due to its highly homogeneous surface. The results of this study offer new insight into the interaction between metal nanoparticles and 2D materials.

Strategically Constructed Bilayer Tin (IV) Oxide as Electron Transport Layer Boosts Performance and Reduces Hysteresis in Perovskite Solar Cells.

Nanostructured tin (IV) oxide (SnO2 ) is emerging as an ideal inorganic electron transport layer in n-i-p perovskite devices, due to superior electronic and low-temperature processing properties. However, significant differences in current-voltage performance and hysteresis phenomena arise as a result of the chosen fabrication technique. This indicates enormous scope to optimize the electron transport layer (ETL), however, to date the understanding of the origin of these phenomena is lacking. Reported here is a first comparison of two common SnO2 ETLs with contrasting performance and hysteresis phenomena, with an experimental strategy to combine the beneficial properties in a bilayer ETL architecture. In doing so, this is demonstrated to eliminate room-temperature hysteresis while simultaneously attaining impressive power conversion efficiency (PCE) greater than 20%. This approach highlights a new way to design custom ETLs using functional thin-film coatings of nanomaterials with optimized characteristics for stable, efficient, perovskite solar cells.

Visualizing Phase Segregation in Mixed-Halide Perovskite Single Crystals.

Mixed organolead halide perovskites (MOHPs), CH3 NH3 Pb(Brx I1-x )3 , have been shown to undergo phase segregation into iodide-rich domains under illumination, which presents a major challenge to their development for photovoltaic and light-emitting devices. Recent work suggested that phase-segregated domains are localized at crystal boundaries, driving investigations into the role of edge structure and the growth of larger crystals with reduced surface area. Herein, a method for growing large (30×30×1 µm3 ) monocrystalline MAPb(Brx I1-x )3 single crystals is presented. The direct visualization of the growth of nanocluster-like I-rich domains throughout the entire crystal revealed that grain boundaries are not required for this transformation. Narrowband fluorescence imaging and time-resolved spectroscopy provided new insight into the nature of the phase-segregated domains and the collective impact on the optoelectronic properties.

Controlled Growth of Monocrystalline Organo-Lead Halide Perovskite and Its Application in Photonic Devices.

Organo-lead halide perovskites (OHPs) have recently emerged as a new class of exceptional optoelectronic materials, which may find use in many applications, including solar cells, light emitting diodes, and photodetectors. More complex applications, such as lasers and electro-optic modulators, require the use of monocrystalline perovskite materials to reach their ultimate performance levels. Conventional methods for forming single crystals of OHPs like methylammonium lead bromide (MAPbBr3 ) afford limited control over the product morphology, rendering the assembly of defined microcavity nanostructures difficult. We overcame this by synthesizing for the first time (MA)[PbBr3 ]⋅DMF (1), and demonstrating its facile transformation into monocrystalline MAPbBr3 microplatelets. The MAPbBr3 microplatelets were tailored into waveguide based photonic devices, of which an ultra-low propagation loss of 0.04 dB µm-1 for a propagation distance of 100 µm was demonstrated. An efficient active electro-optical modulator (AEOM) consisting of a MAPbBr3 non-linear arc waveguide was demonstrated, exhibiting a 98.4 % PL intensity modulation with an external voltage of 45 V. This novel synthetic approach, as well as the demonstration of effective waveguiding, will pave the way for developing a wide range of photonic devices based on organo-lead halide perovskites.

Cu2ZnSnS(4x)Se(4(1-x)) solar cells from polar nanocrystal inks.

A facile ligand exchange method for dispersing Cu2ZnSnS4 (CZTS) nanocrystals (NCs) in environmentally benign polar solvents, such as ethanol or n-propanol, at high concentrations (up to 200 mg/mL) is demonstrated. This approach has been applied to CZTS nanocrystals synthesized via scalable, noninjection methods to formulate colloidally stable inks that are suitable for the solution processing of solar cell devices. Unlike other inks currently used to fabricate NC solar cells, the CZTS nanocrystal ink developed here circumvents the need for hydrazine, pyridine, or thiol coordinating solvents. By combining our polar CZTS inks with optimized selenization procedures, substrate CZTSSe solar cells have been successfully fabricated with device efficiencies of 7.7%.

Near-infrared absorbing Cu12Sb4S13 and Cu3SbS4 nanocrystals: synthesis, characterization, and photoelectrochemistry.

Herein, we present the novel synthesis of tetrahedrite copper antimony sulfide (CAS) nanocrystals (Cu12Sb4S13), which display strong absorptions in the visible and NIR. Through ligand tuning, the size of the Cu12Sb4S13 NCs may be increased from 6 to 18 nm. Phase purity is achieved through optimizing the ligand chemistry and maximizing the reactivity of the antimony precursor. We provide a detailed investigation of the optical and photoelectrical properties of both tetrahedrite (Cu12Sb4S13) and famatinite (Cu3SbS4) NCs. These NCs were found to have very high absorption coefficients reaching 10(5) cm(-1) and band gaps of 1.7 and 1 eV for tetrahedrite and famatinite NCs, respectively. Ultraviolet photoelectron spectroscopy was employed to determine the band positions. In each case, the Fermi energies reside close to the valence band, indicative of a p-type semiconductor. Annealing of tetrahedrite CAS NC films in sulfur vapor at 350 °C was found to result in pure famatinite NC films, opening the possibility to tune the crystal structure within thin films of these NCs. Photoelectrochemistry of hydrazine free unannealed films displays a strong p-type photoresponse, with up to 0.1 mA/cm(2) measured under mild illumination. Collectively these optical properties make CAS NCs an excellent new candidate for both thin film and hybrid solar cells and as strong NIR absorbers in general.

Highly efficient p-type dye-sensitized solar cells based on tris(1,2-diaminoethane)cobalt(II)/(III) electrolytes.

Co-produced: using [Co(en)(3)](2+/3+) based-electrolytes in p-type dye-sensitized solar cells (p-DSCs) gives record energy conversion efficiencies of 1.3 % and open-circuit voltages up to 709 mV under simulated sun light. The increase in photovoltage is due to the more negative redox potential of [Co(en)(3)](2+/3+) compared to established mediators.

Optimal Geometry for Plasmonic Hot-Carrier Extraction in Metal-Semiconductor Nanocrystals.

Plasmon-induced energy and charge transfer from metal nanostructures hold great potential for harvesting solar energy. Presently, the efficiencies of charge-carrier extraction are still low due to the competitive ultrafast mechanisms of plasmon relaxation. Using single-particle electron energy loss spectroscopy, we correlate the geometrical and compositional details of individual nanostructures to their carrier extraction efficiencies. By removing ensemble effects, we are able to show a direct structure-function relationship that permits the rational design of the most efficient metal-semiconductor nanostructures for energy harvesting applications. In particular, by developing a hybrid system comprising Au nanorods with epitaxially grown CdSe tips, we are able to control and enhance charge extraction. We show that optimal structures can have efficiencies as high as 45%. The quality of the Au-CdSe interface and the dimensions of the Au rod and CdSe tip are shown to be critical for achieving these high efficiencies of chemical interface damping.

A new direction in dye-sensitized solar cells redox mediator development: in situ fine-tuning of the cobalt(II)/(III) redox potential through Lewis base interactions.

Dye-sensitized solar cells (DSCs) are an attractive renewable energy technology currently under intense investigation. In recent years, one area of major interest has been the exploration of alternatives to the classical iodide/triiodide redox shuttle, with particular attention focused on cobalt complexes with the general formula [Co(L)(n)](2+/3+). We introduce a new approach to designing redox mediators that involves the application of [Co(PY5Me(2))(MeCN)](2+/3+) complexes, where PY5Me(2) is the pentadentate ligand, 2,6-bis(1,1-bis(2-pyridyl)ethyl)pyridine. It is shown, by X-ray crystallography, that the axial acetonitrile (MeCN) ligand can be replaced by more strongly coordinating Lewis bases (B) to give complexes with the general formula [Co(PY5Me(2))(B)](2+/3+), where B = 4-tert-butylpyridine (tBP) or N-methylbenzimidazole (NMBI). These commonly applied DSC electrolyte components are used for the first time to fine-tune the potential of the redox couple to the requirements of the dye through coordinative interactions with the Co(II/III) centers. Application of electrolytes based on the [Co(PY5Me(2))(NMBI)](2+/3+) complex in combination with a commercially available organic sensitizer has enabled us to attain DSC efficiencies of 8.4% and 9.2% at a simulated light intensity of 100% sun (1000 W m(-2) AM1.5 G) and at 10% sun, respectively, higher than analogous devices applying the [Co(bpy)(3)](2+/3+) redox couple, and an open circuit voltage (V(oc)) of almost 1.0 V at 100% sun for devices constructed with the tBP complex.

Attributes of direct current aperiodic and alternating current harmonic components derived from large amplitude Fourier transformed voltammetry under microfluidic control in a channel electrode.

The flow rate dependencies of the aperiodic direct current (dc) and fundamental to eighth alternating current (ac) harmonic components derived from large-amplitude Fourier transformed ac (FT-ac) voltammetry have been evaluated in a microfluidic flow cell containing a 25 µm gold microband electrode. For the oxidation of ferrocenemethanol ([FcMeOH]/[FcMeOH](+) process) in aqueous 0.1 M KNO(3) electrolyte, standard "Levich-like" dc behavior is observed for the aperiodic dc component, which enables the diffusion coefficient for FcMeOH to be obtained. In experimental studies, the first and second ac harmonic components contain contributions from the double layer capacitance current, thereby allowing details of the non-Faradaic current to be established. In contrast, the higher order harmonics and dc aperiodic component are essentially devoid of double layer capacitance contributions allowing the faradaic current dependence on flow rate to be studied. Significantly, flow rate independent data conforming to linear diffusion controlled theory are found in the sixth and higher ac harmonics at a frequency of 15 Hz and for all ac harmonics at a frequency of ≥ 90 Hz. Analysis of FT-ac voltammograms by theory based on stationary microband or planar electrode configurations confirms that stationary microband and planar electrode configurations and experimental data all converge for the higher order harmonics and establishes that the electrode kinetics are very fast (≥1 cms(-1)). The ability to locate, from a single experiment, a dc Faradaic component displaying Levich behavior, fundamental and second harmonics that contain details of the double layer capacitance, and Faradaic ac higher order harmonic currents that are devoid of capacitance, independent of the volume flow rate and also conform closely to mass transport by planar diffusion, provides enhanced flexibility in mass transport and electrode kinetic analysis and in understanding the performance of hydrodynamic electrochemical cells and reactors.

Tunable transition metal complexes as hole transport materials for stable perovskite solar cells.

Transition metal complexes offer cost-effective alternatives as hole-transport materials (HTMs) in perovskite solar cells. However, the devices suffer from low performance. We boost the power conversion efficiency of devices with transition metal complex HTMs from 2% to above 10% through energy level tuning. We further demonstrate the excellent photostability of the device based on the additive-free HTM.

Passivation by pyridine-induced PbI2 in methylammonium lead iodide perovskites.

Defects at discontinuities of the perovskite lattice limit the performance of the perovskite solar cell (PSC). Lead iodide (PbI2) and pyridine have been shown to passivate these defects. We treat methylammonium lead iodide (MAPbI3) films with pyridine solutions to investigate the effects of the two passivators. By comparing confocal fluorescence microscopy (CFM) images at 405 nm excitation and then at 559 nm excitation we demonstrate the pyridine treatment passivates and forms PbI2 crystallites which cause additional passivation.

Characterization of nonlinear background components in voltammetry by use of large amplitude periodic perturbations and fourier transform analysis.

Under most experimental conditions, a distinctly nonlinear background current is encountered in all forms of voltammetry which arises from the potential dependence of the capacitance. The nonlinear background current has been successfully modeled under large amplitude sinusoidal ac voltammetric conditions with a fourth order polynomial. The model was applied to a dummy cell containing a nonideal ceramic capacitor and commonly used electrodes. The nonlinearity in behavior of the background capacitance is particularly significant when considering the discrimination between the Faradaic and background contributions in the higher order harmonics resolved in ac voltammetry by Fourier transform-inverse Fourier transform approaches and in the simulation of the background current and hence double-layer capacitance as a function of potential. Typically, measurable background current under large amplitude conditions is detectable in the dc and fundamental to fourth harmonic components in large amplitude ac voltammetry. For analytical purposes, this background current can be corrected on a per harmonic basis without the need for any model. Background correction has been successfully applied to the first four harmonics for the oxidation of ferrocenemonocarboxylic acid over the concentration range of 5-500 microM in aqueous 0.5 M NaCl solution.

Tunable Crystallization and Nucleation of Planar CH3NH3PbI3 through Solvent-Modified Interdiffusion.

A smooth and compact light absorption perovskite layer is a highly desirable prerequisite for efficient planar perovskite solar cells. However, the rapid reaction between CH3NH3I methylammonium iodide (MAI) and PbI2 often leads to an inconsistent CH3NH3PbI3 crystal nucleation and growth rate along the film depth during the two-step sequential deposition process. Herein, a facile solvent additive strategy is reported to retard the crystallization kinetics of perovskite formation and accelerate the MAI diffusion across the PbI2 layer. It was found that the ultrasmooth perovskite thin film with narrow crystallite size variation can be achieved by introducing favorable solvent additives into the MAI solution. The effects of dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, chlorobenzene, and diethyl ether additives on the morphological properties and cross-sectional crystallite size distribution were investigated using atomic force microscopy, X-ray diffraction, and scanning electron microscopy. Furthermore, the light absorption and band structure of the as-prepared CH3NH3PbI3 films were investigated and correlated with the photovoltaic performance of the equivalent solar cell devices. Details of perovskite nucleation and crystal growth processes are presented, which opens new avenues for the fabrication of more efficient planar solar cell devices with these ultrasmooth perovskite layers.

Dipole-field-assisted charge extraction in metal-perovskite-metal back-contact solar cells.

Hybrid organic-inorganic halide perovskites are low-cost solution-processable solar cell materials with photovoltaic properties that rival those of crystalline silicon. The perovskite films are typically sandwiched between thin layers of hole and electron transport materials, which efficiently extract photogenerated charges. This affords high-energy conversion efficiencies but results in significant performance and fabrication challenges. Herein we present a simple charge transport layer-free perovskite solar cell, comprising only a perovskite layer with two interdigitated gold back-contacts. Charge extraction is achieved via self-assembled monolayers and their associated dipole fields at the metal-perovskite interface. Photovoltages of ~600 mV generated by self-assembled molecular monolayer modified perovskite solar cells are equivalent to the built-in potential generated by individual dipole layers. Efficient charge extraction results in photocurrents of up to 12.1 mA cm-2 under simulated sunlight, despite a large electrode spacing.Simplified device concepts may become important for the development of low cost photovoltaics. Lin et al. report solar cells based on interdigitated gold back-contacts and metal halide perovskites where charge extraction is assisted via a dipole field generated by self-assembled molecular monolayers.

Plasmonic Ge-doped ZnO nanocrystals.

We present the first colloidal synthesis of Ge-doped ZnO nanocrystals, which are produced by a scalable method that uses only air and moisture stable precursors. The incorporation of tetravalent Ge ions within ZnO nanocrystals generates a surface plasmon resonance in the near-mid infrared, and induces a change in morphology, from isotropic spheroidal nanocrystals to rod-like, elongated structures with a distinctive c-axis orientation.

An EPR Study of 2,3-Bis(diphenylphosphino)maleic Anhydride (BMA) Complexes and the BMA Radical Anion.

EPR spectra are reported for four metal complexes of 2,3-bis(diphenylphosphino)maleic anhydride (BMA), [Co(2)(PhCCR)(CO)(4)(eta-BMA)](-), R = Ph, H, [Co(2)(PhCCPh)(CO)(4)(&mgr;-BMA)](-), and [PhCW(CO)(2)(BMA)Cl](-), as well as the radical anions, [BMA](-) and [BPCD](-), BPCD = 4,5-bis(diphenylphosphino)cyclopentene-1,3-dione. At room temperature, all spectra are 1:2:1 triplets due to hyperfine coupling to two equivalent (31)P nuclei with coupling to two equivalent (1)H nuclei for [BPCD](-) and unresolved coupling to one or two (59)Co nuclei for the Co complexes with chelating or bridging BMA, respectively. The (31)P couplings are temperature dependent, ca. -3 and -13 mG K(-)(1) for the metal complexes and ligand radical anions, respectively. At low temperature, the spectrum of [BMA](-) shows the presence of symmetric and asymmetric PPh(2) rotational conformers, related by the thermodynamic parameters DeltaH degrees = -0.8 +/- 0.2 kJ mol(-)(1) and DeltaS degrees = 4 +/- 1 J mol(-)(1) K(-)(1) and interconverted with activation parameters DeltaH() = 18.2 +/- 0.4 kJ mol(-)(1), DeltaS() = -30 +/- 2 J mol(-)(1) K(-)(1). The temperature dependence of the (31)P couplings is explained by a negative spin-polarization contribution to and a positive contribution due to P 3s character; the latter increases with the asymmetry of the PPh(2) conformations. The range of conformations accessible to the metal complexes is less than for the ligand radical anions, and accordingly the temperature dependence is significantly smaller.

Mimicry of sputtered i-ZnO thin films using chemical bath deposition for solution-processed solar cells.

Solution processing provides a versatile and inexpensive means to prepare functional materials with specifically designed properties. The current challenge is to mimic the structural, optical, and/or chemical properties of thin films fabricated by vacuum-based techniques using solution-based approaches. In this work we focus on ZnO to show that thin films grown using a simple, aqueous-based, chemical bath deposition (CBD) method can mimic the properties of sputtered coatings, provided that the kinetic and thermodynamic reaction parameters are carefully tuned. The role of these parameters toward growing highly oriented and dense ZnO thin films is fully elucidated through detailed microscopic and spectroscopic investigations. The prepared samples exhibit bulk-like optical properties, are intrinsic in their electronic characteristics, and possess negligible organic contaminants, especially when compared to ZnO layers deposited by sol-gel or from nanocrystal inks. The efficacy of our CBD-grown ZnO thin films is demonstrated through the effective replacement of sputtered ZnO buffer layers within high efficiency solution processed Cu2ZnSnS4xSe4(1-x) solar cells.

Aqueous dye-sensitized solar cell electrolytes based on the ferricyanide-ferrocyanide redox couple.

Solar energy conversion efficiencies of over 4% have been achieved in DSCs constructed with aqueous electrolytes based on the ferricyanide-ferrocyanide redox couple, thereby avoiding the use of expensive, flammable and toxic solvents. This paradigm shift was made possible by the use of a hydrophobic organic carbazole dye.