Peijun Guo

Solvent-Mediated Crystallization of CH3NH3SnI3 Films for Heterojunction Depleted Perovskite Solar Cells

Organo-lead halide perovskite solar cells have gained enormous significance and have now achieved power conversion efficiencies of ∼20%. However, the potential toxicity of lead in these systems raises environmental concerns for widespread deployment. Here we investigate solvent effects on the crystallization of the lead-free methylammonium tin triiodide (CH3NH3SnI3) perovskite films in a solution growth process. Highly uniform, pinhole-free perovskite films are obtained from a dimethyl sulfoxide (DMSO) solution via a transitional SnI2·3DMSO intermediate phase. This high-quality perovskite film enables the realization of heterojunction depleted solar cells based on mesoporous TiO2 layer but in the absence of any hole-transporting material with an unprecedented photocurrent up to 21 mA cm(-2). Charge extraction and transient photovoltage decay measurements reveal high carrier densities in the CH3NH3SnI3 perovskite device which are one order of magnitude larger than CH3NH3PbI3-based devices but with comparable recombination lifetimes in both devices. The relatively high background dark carrier density of the Sn-based perovskite is responsible for the lower photovoltaic efficiency in comparison to the Pb-based analogues. These results provide important progress toward achieving improved perovskite morphology control in realizing solution-processed highly efficient lead-free perovskite solar cells.

Metal-Free Tetrathienoacene Sensitizers for High-Performance Dye-Sensitized Solar Cells

A new series of metal-free organic chromophores (TPA-TTAR-A (1), TPA-T-TTAR-A (2), TPA-TTAR-T-A (3), and TPA-T-TTAR-T-A (4)) are synthesized for application in dye-sensitized solar cells (DSSC) based on a donor-π-bridge-acceptor (D-π-A) design. Here a simple triphenylamine (TPA) moiety serves as the electron donor, a cyanoacrylic acid as the electron acceptor and anchoring group, and a novel tetrathienoacene (TTA) as the π-bridge unit. Because of the extensively conjugated TTA π-bridge, these dyes exhibit high extinction coefficients (4.5-5.2 × 10(4) M(-1) cm(-1)). By strategically inserting a thiophene spacer on the donor or acceptor side of the molecules, the electronic structures of these TTA-based dyes can be readily tuned. Furthermore, addition of a thiophene spacer has a significant influence on the dye orientation and self-assembly modality on TiO2 surfaces. The insertion of a thiophene between the π-bridge and the cyanoacrylic acid anchoring group in TPA-TTAR-T-A (dye 3) promotes more vertical dye orientation and denser packing on TiO2 (molecular footprint = 79 Å(2)), thus enabling optimal dye loading. Using dye 3, a DSSC power conversion efficiency (PCE) of 10.1% with Voc = 0.833 V, Jsc = 16.5 mA/cm(2), and FF = 70.0% is achieved, among the highest reported to date for metal-free organic DSSC sensitizers using an I(-)/I3(-) redox shuttle. Photophysical measurements on dye-grafted TiO2 films reveal that the additional thiophene unit in dye 3 enhances the electron injection efficiency, in agreement with the high quantum efficiency.

Infrared plasmonics with indium-tin-oxide nanorod arrays.

This article reports the study of infrared plasmonics with both random and periodic arrays of indium-tin-oxide (ITO) nanorods (NR). A description is given on the synthesis, patterning, and characterization of physical properties of the ITO NR arrays. A classical scattering model, along with a 3-D finite-element-method and a 3-D finite-difference-time-domain numerical simulation method has been used to interpret the unique light scattering phenomena. It is also shown that the intrinsic plasma frequency can be varied through careful postsynthesis processing of the ITO NRs. Examples are given on how coupled plasmon resonances can be tuned through patterning of the ITO NR arrays. In addition, environment dielectric sensing has been demonstrated through the shift of the resonances as a result of index change surrounding the NRs. These initial results suggest potential for further improvement and opportunities to develop a good understanding of infrared plasmonics using ITO and other transparent conducting oxide semiconducting materials.

Materials, Interfaces, and Photon Confinement in Dye-Sensitized Solar Cells†

A series of experiments have been carried out to study the effects of materials quality, surface and interfacial modification, and photon confinement on standard dye-sensitized solar cells. For these studies, both physical and optical characterization of the materials has been performed in detail. In addition, DC and AC impedance measurements along with kinetic charge-transport modeling of experimental results have yielded information on how to systematically optimize the cell efficiency. The same kinetic model has been used to interpret the results of a series of experiments on interfacial modification studies using fluorine etching in combination with TiCl(4) surface treatment. By using specially designed photonic crystals to confine the photons in the cells, it is shown that the best cell efficiency can be further increased by about 13%.

Ultra‐Flexible, “Invisible” Thin‐Film Transistors Enabled by Amorphous Metal Oxide/Polymer Channel Layer Blends

Ultra-flexible and transparent metal oxide transistors are developed by doping In2 O3 films with poly(vinylphenole) (PVP). By adjusting the In2 O3 :PVP weight ratio, crystallization is frustrated, and conducting pathways for efficient charge transport are maintained. In2 O3 :5%PVP-based transistors exhibit mobilities approaching 11 cm(2) V(-1) s(-1) before, and retain up to ca. 90% performance after 100 bending/relaxing cycles at a radius of 10 mm.

Large optical nonlinearity of ITO nanorods for sub-picosecond all-optical modulation of the full-visible spectrum

Nonlinear optical responses of materials play a vital role for the development of active nanophotonic and plasmonic devices. Optical nonlinearity induced by intense optical excitation of mobile electrons in metallic nanostructures can provide large-amplitude, dynamic tuning of their electromagnetic response, which is potentially useful for all-optical processing of information and dynamic beam control. Here we report on the sub-picosecond optical nonlinearity of indium tin oxide nanorod arrays (ITO-NRAs) following intraband, on-plasmon-resonance optical pumping, which enables modulation of the full-visible spectrum with large absolute change of transmission, favourable spectral tunability and beam-steering capability. Furthermore, we observe a transient response in the microsecond regime associated with slow lattice cooling, which arises from the large aspect-ratio and low thermal conductivity of ITO-NRAs. Our results demonstrate that all-optical control of light can be achieved by using heavily doped wide-bandgap semiconductors in their transparent regime with speed faster than that of noble metals.

Conformal Coating of a Phase Change Material on Ordered Plasmonic Nanorod Arrays for Broadband All-Optical Switching

Actively tunable optical transmission through artificial metamaterials holds great promise for next-generation nanophotonic devices and metasurfaces. Plasmonic nanostructures and phase change materials have been extensively studied to this end due to their respective strong interactions with light and tunable dielectric constants under external stimuli. Seamlessly integrating plasmonic components with phase change materials, as demonstrated in the present work, can facilitate phase change by plasmonically enabled light confinement and meanwhile make use of the high sensitivity of plasmon resonances to the variation of dielectric constant associated with the phase change. The hybrid platform here is composed of plasmonic indium-tin-oxide nanorod arrays (ITO-NRAs) conformally coated with an ultrathin layer of a prototypical phase change material, vanadium dioxide (VO2), which enables all-optical modulation of the infrared as well as the visible spectral ranges. The interplay between the intrinsic plasmonic nonlinearity of ITO-NRAs and the phase transition induced permittivity change of VO2 gives rise to spectral and temporal responses that cannot be achieved with individual material components alone.

Atomic Layer Deposition of Metastable β-Fe2O3 via Isomorphic Epitaxy for Photoassisted Water Oxidation

We report the growth and photoelectrochemical (PEC) characterization of the uncommon bibyite phase of iron(III) oxide (β-Fe2O3) epitaxially stabilized via atomic layer deposition on an conductive, transparent, and isomorphic template (Sn-doped In2O3). As a photoanode, unoptimized β-Fe2O3 ultrathin films perform similarly to their ubiquitous α-phase (hematite) counterpart, but reveal a more ideal bandgap (1.8 eV), a ∼0.1 V improved photocurrent onset potential, and longer wavelength (>600 nm) spectral response. Stable operation under basic water oxidation justifies further exploration of this atypical phase and motivates the investigation of other unexplored metastable phases as new PEC materials.

Spray-combustion synthesis: Efficient solution route to high-performance oxide transistors

Significance Although impressive progress in solution-processed metal-oxide (MO) electronics has been achieved, fundamental science challenges remain concerning whether solution-processed MO materials and particularly technologically relevant, indium-gallium-tin-oxide (IGZO), can achieve efficient and stable charge transport characteristics when processed at low temperatures for short times and how IGZO film density, porosity, carrier mobility, and charge trapping can be manipulated. Here, we report a coating technique, spray-combustion synthesis, and demonstrate IGZO semiconductor thickness, densification, nanoporosity, electron mobility, trap densities, and bias stress stability approaching the quality of sputtered films. Metal-oxide (MO) semiconductors have emerged as enabling materials for next generation thin-film electronics owing to their high carrier mobilities, even in the amorphous state, large-area uniformity, low cost, and optical transparency, which are applicable to flat-panel displays, flexible circuitry, and photovoltaic cells. Impressive progress in solution-processed MO electronics has been achieved using methodologies such as sol gel, deep-UV irradiation, preformed nanostructures, and combustion synthesis. Nevertheless, because of incomplete lattice condensation and film densification, high-quality solution-processed MO films having technologically relevant thicknesses achievable in a single step have yet to be shown. Here, we report a low-temperature, thickness-controlled coating process to create high-performance, solution-processed MO electronics: spray-combustion synthesis (SCS). We also report for the first time, to our knowledge, indium-gallium-zinc-oxide (IGZO) transistors having densification, nanoporosity, electron mobility, trap densities, bias stability, and film transport approaching those of sputtered films and compatible with conventional fabrication (FAB) operations.

Three Dimensional Indium–Tin-Oxide Nanorod Array for Charge Collection in Dye-Sensitized Solar Cells

In this article, we report the design, fabrication, characterization, and simulation of three-dimensional (3D) dye-sensitized solar cells (DSSCs), using ordered indium-tin-oxide (ITO) nanorod (NR) arrays as the photoanode, and compare them with conventional planar (2D) DSSCs. The ITO NR array used in the 3D cell greatly improves its performance by providing shorter electron pathways and reducing the recombination rate of the photogenerated electrons. We observed a 10-20% enhancement of the energy conversion efficiency, primarily due to an increased short circuit current. This finding supports the concept of using 3D photoanodes with optically transparent and conducting nanorods for the enhancement of the energy-harvesting devices that require short charge collection distance without sacrificing the optical thickness. Thus, unlike the conventional solar cell structure, the functions for photon collection and charge transport are decoupled to allow for improved cell designs.