Daniel Webber

Simultaneous observation of free and defect-bound excitons in CH 3 NH 3 PbI 3 using four-wave mixing spectroscopy

Solar cells incorporating organic-inorganic perovskite, which may be fabricated using low-cost solution-based processing, have witnessed a dramatic rise in efficiencies yet their fundamental photophysical properties are not well understood. The exciton binding energy, central to the charge collection process, has been the subject of considerable controversy due to subtleties in extracting it from conventional linear spectroscopy techniques due to strong broadening tied to disorder. Here we report the simultaneous observation of free and defect-bound excitons in CH3NH3PbI3 films using four-wave mixing (FWM) spectroscopy. Due to the high sensitivity of FWM to excitons, tied to their longer coherence decay times than unbound electron- hole pairs, we show that the exciton resonance energies can be directly observed from the nonlinear optical spectra. Our results indicate low-temperature binding energies of 13 meV (29 meV) for the free (defect-bound) exciton, with the 16 meV localization energy for excitons attributed to binding to point defects. Our findings shed light on the wide range of binding energies (2–55 meV) reported in recent years.

Four-Wave Mixing in Perovskite Photovoltaic Materials Reveals Long Dephasing Times and Weaker Many-Body Interactions than GaAs

Perovksite semiconductors have shown promise for low-cost solar cells, lasers and photodetectors, yet their fundamental photophysical properties are not well understood. Recent observations of a low exciton binding energy and evidence of hot phonon effects in the room temperature phase suggest that perovskites are much closer to inorganic semiconductors than the absorber layers in traditional organic photovoltaics, signaling the need for experiments that shed light on the placement of perovskite materials within the spectrum of semiconductors used in optoelectronics and photovoltaics. Here we use four-wave mixing (FWM) to contrast the coherent optical response of CH3NH3PbI3 thin films and crystalline GaAs. At carrier densities relevant for solar cell operation, our results show that carriers interact surprisingly weakly via the Coulomb interaction in perovskite, much weaker than in inorganic semiconductors. These weak many-body effects lead to a dephasing time in CH3NH3PbI3 ∼ 3× longer than in GaAs. Our r...

Observation of the exciton and Urbach band tail in low-temperature-grown GaAs using four-wave mixing spectroscopy

Four-wave mixing (FWM) spectroscopy reveals clear signatures associated with the exciton, free carrier inter-band transitions, and the Urbach band tail in low-temperature-grown GaAs, providing a direct measure of the effective band gap as well as insight into the influence of disorder on the electronic structure. The ability to detect (and resolve) these contributions, in contrast to linear spectroscopy, is due to an enhanced sensitivity of FWM to the optical joint density of states and to many-body effects. Our experiments demonstrate the power of FWM for studying the near-band-edge optical properties and coherent carrier dynamics in low-temperature-grown semiconductors.

Role of strain on the coherent properties of GaAs excitons and biexcitons

Polarization-dependent two-dimensional Fourier-transform spectroscopy (2DFTS) is performed on excitons in strained bulk GaAs layers probing the coherent response for differing amounts of strain. Biaxial tensile strain lifts the degeneracy of heavy-hole (HH) and light-hole (LH) valence states, leading to an observed splitting of the associated excitons at low temperature. Increasing the strain increases the magnitude of the HH/LH exciton peak splitting, induces an asymmetry in the off-diagonal coherences, increases the difference in the HH and LH exciton homogenous linewidths, and increases the inhomogeneous broadening of both exciton species. All results arise from strain-induced variations in the local electronic environment, which is not uniform along the growth direction of the thin layers. For cross-linear polarized excitation, wherein excitonic signals give way to biexcitonic signals, the high-strain sample shows evidence of bound LH, HH, and mixed biexcitons.

Role of many-body effects in the coherent dynamics of excitons in low-temperature-grown GaAs

Femtosecond four-wave mixing experiments on low-temperature-grown (LT-) GaAs indicate a polarization-dependent nonlinear optical response at the exciton, which we attribute to Coulomb-mediated coupling between excitons and electron-hole pairs simultaneously excited by the broad-bandwidth laser pulses. Strong suppression of the exciton response through screening by carriers injected by a third pump pulse was observed, an effect that is transient due to rapid carrier trapping. Our findings highlight the need to account for the complex interplay of disorder and many-body effects in the design of ultrafast optoelectronic devices using this material.

Measurement of coherence decay in GaMnAs using femtosecond four-wave mixing.

The application of femtosecond four-wave mixing to the study of fundamental properties of diluted magnetic semiconductors ((s,p)-d hybridization, spin-flip scattering) is described, using experiments on GaMnAs as a prototype III-Mn-V system. Spectrally-resolved and time-resolved experimental configurations are described, including the use of zero-background autocorrelation techniques for pulse optimization. The etching process used to prepare GaMnAs samples for four-wave mixing experiments is also highlighted. The high temporal resolution of this technique, afforded by the use of short (20 fsec) optical pulses, permits the rapid spin-flip scattering process in this system to be studied directly in the time domain, providing new insight into the strong exchange coupling responsible for carrier-mediated ferromagnetism. We also show that spectral resolution of the four-wave mixing signal allows one to extract clear signatures of (s,p)-d hybridization in this system, unlike linear spectroscopy techniques. This increased sensitivity is due to the nonlinearity of the technique, which suppresses defect-related contributions to the optical response. This method may be used to measure the time scale for coherence decay (tied to the fastest scattering processes) in a wide variety of semiconductor systems of interest for next generation electronics and optoelectronics.

Carrier diffusion in thin-film CH3NH3PbI3 perovskite measured using four-wave mixing

We report the application of femtosecond four-wave mixing (FWM) to the study of carrier transport in solution-processed CH3NH3PbI3. The diffusion coefficient was extracted through direct detection of the lateral diffusion of carriers utilizing the transient grating technique, coupled with simultaneous measurement of decay kinetics exploiting the versatility of the boxcar excitation beam geometry. The observation of exponential decay of the transient grating versus interpulse delay indicates diffusive transport with negligible trapping within the first nanosecond following excitation. The in-plane transport geometry in our experiments enabled the diffusion length to be compared directly with the grain size, indicating that carriers move across multiple grain boundaries prior to recombination. Our experiments illustrate the broad utility of FWM spectroscopy for rapid characterization of macroscopic film transport properties.

Signatures of four-particle correlations associated with exciton-carrier interactions in coherent spectroscopy on bulk GaAs

Transient four-wave mixing studies of bulk GaAs under conditions of broad bandwidth excitation of primarily interband transitions have enabled four-particle correlations tied to degenerate (exciton-exciton) and nondegenerate (exciton-carrier) interactions to be studied. Real two-dimensional Fourier-transform spectroscopy (2DFTS) spectra reveal a complex response at the heavy-hole exciton emission energy that varies with the absorption energy, ranging from dispersive on the diagonal, through absorptive for low-energy interband transitions to dispersive with the opposite sign for interband transitions high above band gap. Simulations using a multilevel model augmented by many-body effects provide excellent agreement with the 2DFTS experiments and indicate that excitation-induced dephasing (EID) and excitation-induced shift (EIS) affect degenerate and nondegenerate interactions equivalently, with stronger exciton-carrier coupling relative to exciton-exciton coupling by approximately an order of magnitude. These simulations also indicate that EID effects are three times stronger than EIS in contributing to the coherent response of the semiconductor.

Control of the Urbach band tail and interband dephasing time with post-growth annealing in low-temperature-grown GaAs

Femtosecond four-wave mixing experiments on low-temperature-grown (LT-) GaAs for a range of post-growth annealing temperatures indicate that the Urbach band tail abruptly diminishes above 550°C due to the conversion of As-related point defects to As clusters and that the interband dephasing time is limited by scattering with As point defects for annealing temperatures below 550°C. In addition, we observe a complex interplay of polarization source terms associated with the exciton and Urbach band tail for annealing temperatures below 550°C. These experiments shed light on the carrier dynamics and ultrafast nonlinear optical properties of LT-GaAs.

Four-wave mixing response of solution-processed CH3NH3PbI3 thin films

The interest in perovskite-based solar cell absorber materials has skyrocketed in recent years due to the rapid rise in solar cell efficiency and the potential for cost reductions tied to solution-processed device fabrication. Due to complications associated with the presence of strong static and dynamic disorder in these organic-inorganic materials, the fundamental photophysical behavior of photo-excited charge carriers remains unclear. We apply four-wave mixing spectroscopy to study the charge carrier dynamics in CH3NH3PbI3 thin films. Our experiments reveal two discrete optical transitions below the band gap of the semiconductor with binding energies of 13 meV and 29 meV, attributed to free and defect-bound excitons respectively.