Evan Lafalce

Enhanced emissive and lasing characteristics of nano-crystalline MAPbBr3 films grown via anti-solvent precipitation

Control of the nano-scale crystal size distribution in films of organic-inorganic lead-tri-bromide perovskites is achieved through a recently reported solution-based, anti-solvent treatment method [H. Cho et al., Science 350, 1222 (2015)]. The treated films are shown to be high quality, optically smooth with excellent emissive and optical gain properties including higher photoluminescence yield and reduced threshold for laser action. The improved lasing is shown to originate from a synergistic combination of a reduction in waveguide losses and a decrease in the non-radiative decay rate of the excited state population, compared to untreated films. The net gain is increased by a factor of two upon anti-solvent treatment and reaches a respectable value of ≈300 cm−1.

Enhancement of optical gain characteristics of quantum dot films by optimization of organic ligands

This work examines how the optimization of molecular dimensions and chemical functionality of the organic ligands of quantum dots (QDs) can be explored for dramatic enhancement of the optical properties of QD films, particularly, optical gain. We show that the replacement of traditional QD organic ligands with a much shorter ligand, butylamine, yields a dense QD-packing that results in a two-fold increase in optical gain. Overall, the highly packed QD films exhibit very large net gain values (∼500 cm−1) which greatly exceed typical Cd-based QD films with traditional ligands. In addition, thresholds for amplified-spontaneous emission (ASE) down to 50 μJ cm−2 were observed, which is exceptionally low for ns-pulse pumped QD systems. Our results confirm an additional route for obtaining high optical gain using QDs, and outline a strategy for modifying the optical gain characteristics by ligand exchange without needing to modify the QD selection. Consideration of the ligands along with QD compositional design could make it possible to fabricate photonic systems with exceptionally low lasing thresholds, and offers a route toward achieving high gain using steady state pumping, an extremely difficult feat to achieve in traditional QD systems.

Electroabsorption Spectroscopy Studies of (C4H9NH3)2PbI4 Organic–Inorganic Hybrid Perovskite Multiple Quantum Wells

Two-dimensional (2D) organic-inorganic hybrid perovskite multiple quantum wells that consist of multilayers of alternate organic and inorganic layers exhibit large exciton binding energies of order of 0.3 eV due to the dielectric confinement between the inorganic and organic layers. We have investigated the exciton characteristics of 2D butylammonium lead iodide, (C4H9NH3)2PbI4 using photoluminescence and UV-vis absorption in the temperature range of 10 K to 300 K, and electroabsorption spectroscopy. The evolution of an additional absorption/emission at low temperature indicates that this compound undergoes a phase transition at ≈250 K. We found that the electroabsorption spectrum of each structural phase contains contributions from both quantum confined exciton Stark effect and Franz-Keldysh oscillation of the continuum band, from which we could determine more accurately the 1s exciton, continuum band edge, and the exciton binding energy.

Optical studies of native defects in π-conjugated donor–acceptor copolymers

We used multiple spectroscopies such as photoinduced absorption (PIA), magneto photoinduced absorption, and doping induced absorption for studying native defects in π-conjugated donor–acceptor copolymer chains of benzodithio-phene fluorinated benzotriazole. The PIA spectrum contains characteristic photoinduced absorption bands that are due to polarons and triplet exciton species, whose strengths have different dependencies on the modulation frequency, temperature, and laser excitation, as well as magnetic field response. We found that the native defects in the copolymer chains serve as efficient traps that ionize the photoexcited excitons, thereby generating charge carriers whose characteristic optical properties are similar, but not equal to those of intrachain polarons formed by doping. The native defects density is of the order of 1017 cm−3 indicating that most of the copolymer chains contain native defects upon synthesis; however, this does not preclude their used-for photovoltaic applications.

Electronic and vibrational spectroscopy studies of PffBT4T π -conjugated donor-acceptor copolymer

Abstract. We used a variety of optical spectroscopies to investigate the charge excitations and correlated infrared (IR)-active and Raman-active vibrations in poly[(difluoro-benzothiadiazol-diyl)-alt-(di(2-octyldodecyl)-quaterthiophen-diyl)], PffBT4T, a π-conjugated donor–acceptor (DA) copolymer, which, when blended with fullerene PCBM molecules, serves as an active layer in high-performance photovoltaic solar cells. The applied optical spectroscopies in films of pristine PffBT4T and PffBT4T/PCBM blend include absorption, photoluminescence, electroabsorption, photoinduced absorption (PA), and resonant Raman scattering. We found that the PffBT4T copolymer chain contains 11 strongly coupled Raman-active vibrational modes, which are renormalized upon photogeneration of charge polarons onto the chain. As the lower energy polaron absorption band overlaps with the renormalized vibrational modes, they appear in the PA spectrum as antiresonance (AR) lines superposed onto the induced polaron absorption band. We show that the Raman scattering, doping induced, and photoinduced AR spectra in PffBT4T are well explained by the amplitude mode model (AMM), where a single vibrational propagator describes the renormalized Raman modes and their related photoinduced AR intensities in detail. Surprisingly, we found that two of the IR-active modes in the pristine copolymer must be included in the AMM propagator for explaining the complete photoinduced AR spectrum. This feature is unique to DA-copolymers and indicates that some intrachain C2v symmetry breaking occurs because of the different electron affinities of the donor and acceptor moieties.

Study of spin transport in polyfluorene films

Abstract. We have investigated spin transport in films of polyfluorene, a π-conjugated polymer, using the technique of “spin pumping” from a ferromagnet substrate, namely Ni80Fe20 in a NiFe/polyfluorene/Pt trilayer device at room temperature. Pure spin current (without carrier injection) is generated in the polymer film by microwave excitation of the NiFe magnetic moment at ferromagnetic resonance conditions. The induced spin current through the ferromagnet/polymer interface crosses the polymer layer and is detected by a Pt overlayer in the device, where it is converted into electric current via the inverse spin Hall effect. We have successfully determined the spin diffusion length, λS, in the polyfluorene film by varying the polymer thickness in the trilayer structure, and found λS  =  118  ±  9  nm. We also measured the charge-carrier mobility, μ in polyfluorene film using the time-of-flight technique and found it to be affected by dispersive transport. From the obtained λS and μ values, we estimated the spin relaxation time in polyfluorene to be ∼5  μs at room temperature.

Exceptional gain for the stimulated resonant Raman scattering in the π-conjugated polymer poly(dioctylfluorene).

Stimulated resonant Raman scattering (SRRS) is observed in slab waveguides formed in thin films of the π-conjugated polymer poly(dioctylfluorene) (PFO). The presence of two distinct morphological phases with different electronic bandgaps in these films allows the output frequency of this process to be observed over a much broader range than in other organic materials. In particular, the SRRS peak is pronounced when it is spectrally located in the vicinity of the amplified spontaneous emission bands of the films, which peak at 449 and 463 nm, respectively, for the two different phases, allowing selective tuning in the range of 440-470 nm. Furthermore, the superposition of the SRRS spectral location with that of electronic gain produces an overall gain of 269  cm(-1), making this material extremely attractive for use as an active material in compact Raman lasers.