Matthew T. Klug

Tunable localized surface plasmon-enabled broadband light harvesting enhancement for high-efficiency panchromatic dye- sensitized solar cells

In photovoltaic devices, light harvesting (LH) and carrier collection have opposite relations with the thickness of the photoactive layer, which imposes a fundamental compromise for the power conversion efficiency (PCE). Unbalanced LH at different wavelengths further reduces the achievable PCE. Here, we report a novel approach to broadband balanced LH and panchromatic solar energy conversion using multiple-core-shell structured oxide-metal-oxide plasmonic nanoparticles. These nanoparticles feature tunable localized surface plasmon resonance frequencies and the required thermal stability during device fabrication. By simply blending the plasmonic nanoparticles with available photoactive materials, the broadband LH of practical photovoltaic devices can be significantly enhanced. We demonstrate a panchromatic dye-sensitized solar cell with an increased PCE from 8.3% to 10.8%, mainly through plasmon-enhanced photoabsorption in the otherwise less harvested region of solar spectrum. This general and simple strategy also highlights easy fabrication, and may benefit solar cells using other photoabsorbers or other types of solar-harvesting devices.

A low viscosity, low boiling point, clean solvent system for the rapid crystallisation of highly specular perovskite films

Perovskite-based photovoltaics have, in recent years, become poised to revolutionise the solar industry. While there have been many approaches taken to the deposition of this material, one-step spin-coating remains the simplest and most widely used method in research laboratories. Although spin-coating is not recognised as the ideal manufacturing methodology, it represents a starting point from which more scalable deposition methods, such as slot-dye coating or ink-jet printing can be developed. Here, we introduce a new, low-boiling point, low viscosity solvent system that enables rapid, room temperature crystallisation of methylammonium lead triiodide perovskite films, without the use of strongly coordinating aprotic solvents. Through the use of this solvent, we produce dense, pinhole free films with uniform coverage, high specularity, and enhanced optoelectronic properties. We fabricate devices and achieve stabilised power conversion efficiencies of over 18% for films which have been annealed at 100 °C, and over 17% for films which have been dried under vacuum and have undergone no thermal processing. This deposition technique allows uniform coating on substrate areas of up to 125 cm2, showing tremendous promise for the fabrication of large area, high efficiency, solution processed devices, and represents a critical step towards industrial upscaling and large area printing of perovskite solar cells.

Versatile Three-Dimensional Virus-Based Template for Dye-Sensitized Solar Cells with Improved Electron Transport and Light Harvesting

By genetically encoding affinity for inorganic materials into the capsid proteins of the M13 bacteriophage, the virus can act as a template for the synthesis of nanomaterial composites for use in various device applications. Herein, the M13 bacteriophage is employed to build a multifunctional and three-dimensional scaffold capable of improving both electron collection and light harvesting in dye-sensitized solar cells (DSSCs). This has been accomplished by binding gold nanoparticles (AuNPs) to the virus proteins and encapsulating the AuNP-virus complexes in TiO2 to produce a plasmon-enhanced and nanowire (NW)-based photoanode. The NW morphology exhibits an improved electron diffusion length compared to traditional nanoparticle-based DSSCs, and the AuNPs increase the light absorption of the dye-molecules through the phenomenon of localized surface plasmon resonance. Consequently, we report a virus-templated and plasmon-enhanced DSSC with an efficiency of 8.46%, which is achieved through optimizing both the NW morphology and the concentration of AuNPs loaded into the solar cells. In addition, we propose a theoretical model that predicts the experimentally observed trends of plasmon enhancement.

Tailoring metal halide perovskites through metal substitution: influence on photovoltaic and material properties

We present herein an experimental screening study that assesses how partially replacing Pb in methylammonium lead triiodide perovskite films with nine different alternative, divalent metal species, B′ = {Co, Cu, Fe, Mg, Mn, Ni, Sn, Sr, and Zn}, influences photovoltaic performance and optical properties. Our findings indicate the perovskite film is tolerant to most of the considered homovalent metal species with lead–cobalt compositions yielding the highest power conversion efficiencies when less than 6% of the Pb2+ ions are replaced. Through subsequent materials characterisation, we demonstrate for the first time that partially substituting Pb2+ at the B-sites of the perovskite lattice is not restricted to Group IV elements but is also possible with at least Co2+. Moreover, adjusting the molar ratio of Pb:Co in the mixed-metal perovskite affords new opportunities to tailor the material properties while maintaining stabilised device efficiencies above 16% in optimised solar cells. Specifically, crystallographic analysis reveals that Co2+ incorporates into the perovskite lattice and increasing its concentration can mediate a crystal structure transition from the cubic to tetragonal phase at room-temperature. Likewise, Co2+ substitution continually modifies the perovskite work function and band edge energies without either changing the band gap or electronically doping the intrinsic material. By leveraging this orthogonal dimension of electronic tunability, we achieve remarkably high open-circuit voltages up to 1.08 V with an inverted device architecture by shifting the perovskite into a more favourable energetic alignment with the PEDOT:PSS hole transport material.

Environmentally responsible fabrication of efficient perovskite solar cells from recycled car batteries

Organolead halide perovskite solar cells (PSCs) show great promise as a new large-scale and cost-competitive photovoltaic technology. Power conversion efficiencies over 15% to 19% have been achieved within 18 to 24 months of development, and thus perovskite materials have attracted great attention in photovoltaic research. However, the manufacture of PSCs raises environmental concerns regarding the over-production of raw lead ore, which has harmful health and ecological effects. Herein, we report an environmentally responsible process to fabricate efficient PSCs by reusing car batteries to simultaneously avoid the disposal of toxic battery materials and provide alternative, readily available lead sources for PSCs. Perovskite films, assembled using materials sourced from either recycled battery materials or high-purity commercial reagents, show the same material characteristics (i.e., crystallinity, morphology, optical absorption, and photoluminescence properties) and identical photovoltaic performance (i.e., photovoltaic parameters and resistances of electron recombination), indicating the practical feasibility of recycling car batteries for lead-based PSCs.

A Universal Deposition Protocol for Planar Heterojunction Solar Cells with High Efficiency Based on Hybrid Lead Halide Perovskite Families

A robust and expedient gas quenching method is developed for the solution deposition of hybrid perovskite thin films. The method offers a reliable standard practice for the fabrication of a non-exhaustive variety of perovskites exhibiting excellent film morphology and commensurate high performance in both regular and inverted structured solar cell architectures.

Assembly of a Bacteriophage-Based Template for the Organization of Materials into Nanoporous Networks

M13 bacteriophages are assembled via a covalent layer-by-layer process to form a highly nanoporous network capable of organizing nanoparticles and acting as a scaffold for templating metal-oxides. The morphological and optical properties of the film itself are presented as well as its ability to organize and disperse metal nanoparticles.

Assembly of Viral Hydrogels for Three-Dimensional Conducting Nanocomposites

M13 bacteriophages act as versatile scaffolds capable of organizing single-walled carbon nanotubes and fabricating three-dimensional conducting nanocomposites. The morphological, electrical, and electrochemical properties of the nanocomposites are presented, as well as its ability to disperse and utilize single-walled carbon nanotubes effectively.

The Effects of Doping Density and Temperature on the Optoelectronic Properties of Formamidinium Tin Triiodide Thin Films

Optoelectronic properties are unraveled for formamidinium tin triiodide (FASnI3 ) thin films, whose background hole doping density is varied through SnF2 addition during film fabrication. Monomolecular charge-carrier recombination exhibits both a dopant-mediated part that grows linearly with hole doping density and remnant contributions that remain under tin-enriched processing conditions. At hole densities near 1020 cm-3 , a strong Burstein-Moss effect increases absorption onset energies by ≈300 meV beyond the bandgap energy of undoped FASnI3 (shown to be 1.2 eV at 5 K and 1.35 eV at room temperature). At very high doping densities (1020 cm-3 ), temperature-dependent measurements indicate that the effective charge-carrier mobility is suppressed through scattering with ionized dopants. Once the background hole concentration is nearer 1019 cm-3 and below, the charge-carrier mobility increases with decreasing temperature according to ≈T-1.2 , suggesting that it is limited mostly by intrinsic interactions with lattice vibrations. For the lowest doping concentration of 7.2 × 1018 cm-3 , charge-carrier mobilities reach a value of 67 cm2 V-1 s-1 at room temperature and 470 cm2 V-1 s-1 at 50 K. Intraexcitonic transitions observed in the THz-frequency photoconductivity spectra at 5 K reveal an exciton binding energy of only 3.1 meV for FASnI3 , in agreement with the low bandgap energy exhibited by this perovskite.

Quantum Electromechanical Processes in Plasmonic Nanostructures

Summary form only given. We present analysis of electromechanical effects associated with collective optical excitation of electrons in plasmonic nanoparticles, with emphasis on the enhanced transfer of angular momentum and nonlinear hydrodynamics such as vortex pairs.