Aditya Mohite

Intraband conductivity response in graphene observed using ultrafast infrared-pump visible-probe spectroscopy

Graphene, a monolayer of carbon atoms arranged in a hexagonal pattern, provides a unique two-dimensional (2D) system exhibiting exotic phenomena such as quantum Hall effects, massless Dirac quasiparticle excitations and universal absorption&conductivity. The linear energy-momentum dispersion relation in graphene also offers the opportunity to mimic the physics of far-away relativistic particles like neutron stars and white dwarfs. In this letter, we perform a counterintuitive ultrafast pump-probe experiment with high photon energies to isolate the Drude-like intraband dynamics of photoexcited carriers. We directly demonstrate the relativistic nature of the photoexcited Dirac quasiparticles by observing a nonlinear scaling of the response with the density of photoexcited carriers. This is in striking contrast to the linear scaling that is usually observed in conventional materials. Our results also indicate strong electron-phonon coupling in graphene, leading to a sub-100 femtosecond thermalization between high energy photoexcited carriers and optical phonons.

Light-induced lattice expansion leads to high-efficiency perovskite solar cells

Light relaxes hybrid perovskites Ion migration in organic-inorganic perovskite solar cells limits device stability and performance. Tsai et al. found that a cesium-doped lead triiodide perovskite with mixed organic cations underwent a uniform lattice expansion after 180 min of exposure at 1 sun of illumination. This structural change reduced the energy barriers for charge carriers at the contacts of solar cells. The resulting increase in power conversion efficiency from 18.5 to 20.5% was maintained for more than 1500 hours of illumination. Science, this issue p. 67 Light-induced lattice expansion improves crystallinity and relaxes lattice strain in organic-inorganic perovskite films. Light-induced structural dynamics plays a vital role in the physical properties, device performance, and stability of hybrid perovskite–based optoelectronic devices. We report that continuous light illumination leads to a uniform lattice expansion in hybrid perovskite thin films, which is critical for obtaining high-efficiency photovoltaic devices. Correlated, in situ structural and device characterizations reveal that light-induced lattice expansion benefits the performances of a mixed-cation pure-halide planar device, boosting the power conversion efficiency from 18.5 to 20.5%. The lattice expansion leads to the relaxation of local lattice strain, which lowers the energetic barriers at the perovskite-contact interfaces, thus improving the open circuit voltage and fill factor. The light-induced lattice expansion did not compromise the stability of these high-efficiency photovoltaic devices under continuous operation at full-spectrum 1-sun (100 milliwatts per square centimeter) illumination for more than 1500 hours.

Scaling law for excitons in 2D perovskite quantum wells

Ruddlesden–Popper halide perovskites are 2D solution-processed quantum wells with a general formula A2A’n-1MnX3n+1, where optoelectronic properties can be tuned by varying the perovskite layer thickness (n-value), and have recently emerged as efficient semiconductors with technologically relevant stability. However, fundamental questions concerning the nature of optical resonances (excitons or free carriers) and the exciton reduced mass, and their scaling with quantum well thickness, which are critical for designing efficient optoelectronic devices, remain unresolved. Here, using optical spectroscopy and 60-Tesla magneto-absorption supported by modeling, we unambiguously demonstrate that the optical resonances arise from tightly bound excitons with both exciton reduced masses and binding energies decreasing, respectively, from 0.221u2009m0 to 0.186u2009m0 and from 470u2009meV to 125u2009meV with increasing thickness from n equals 1 to 5. Based on this study we propose a general scaling law to determine the binding energy of excitons in perovskite quantum wells of any layer thickness.Hybrid 2D layered perovskites are solution-processed quantum wells whose optoelectronic properties are tunable by varying the thickness of the inorganic slab. Here Blancon et al. work out a general behavior for dependence of the excitonic properties in layered 2D perovskites.

Design principles for electronic charge transport in solution-processed vertically stacked 2D perovskite quantum wells

State-of-the-art quantum-well-based devices such as photovoltaics, photodetectors, and light-emission devices are enabled by understanding the nature and the exact mechanism of electronic charge transport. Ruddlesden–Popper phase halide perovskites are two-dimensional solution-processed quantum wells and have recently emerged as highly efficient semiconductors for solar cell approaching 14% in power conversion efficiency. However, further improvements will require an understanding of the charge transport mechanisms, which are currently unknown and further complicated by the presence of strongly bound excitons. Here, we unambiguously determine that dominant photocurrent collection is through electric field-assisted electron–hole pair separation and transport across the potential barriers. This is revealed by in-depth device characterization, coupled with comprehensive device modeling, which can self-consistently reproduce our experimental findings. These findings establish the fundamental guidelines for the molecular and device design for layered 2D perovskite-based photovoltaics and optoelectronic devices, and are relevant for other similar quantum-confined systems.Solution-processed two-dimensional perovskite quantum-well-based optoelectronic devices have attracted great research interest but their electrical transport is poorly understood. Tsai et al. reveal that the potential barriers of the quantum wells dominate the transport properties in solar cell devices.

Probing Intraband Conductivity Dynamics in Graphene

We use ultrafast optical spectroscopy to investigate intraband conductivity dynamics in a graphene monolayer grown by chemical vapor deposition, revealing the effect of the conical band structure on two-dimensional Dirac quasiparticles.

Hybrid graphene metasurfaces for high-speed mid-infrared light modulation and single-pixel imaging

During the past decades, major advances have been made in both the generation and detection of infrared light; however, its efficient wavefront manipulation and information processing still encounter great challenges. Efficient and fast optoelectronic modulators and spatial light modulators are required for mid-infrared imaging, sensing, security screening, communication and navigation, to name a few. However, their development remains elusive, and prevailing methods reported so far have suffered from drawbacks that significantly limit their practical applications. In this study, by leveraging graphene and metasurfaces, we demonstrate a high-performance free-space mid-infrared modulator operating at gigahertz speeds, low gate voltage and room temperature. We further pixelate the hybrid graphene metasurface to form a prototype spatial light modulator for high frame rate single-pixel imaging, suggesting orders of magnitude improvement over conventional liquid crystal or micromirror-based spatial light modulators. This work opens up the possibility of exploring wavefront engineering for infrared technologies for which fast temporal and spatial modulations are indispensable.Metamaterials: mid-infrared modulatorUltrafast modulators and spatial light modulators (SLMs) for mid-infrared light have been realized by the use of an electrically-tunable graphene on a silicon-integrated metasurface. The modulators designed and built by Beibei Zeng and coworkers from Los Alamos National Laboratory, Duke University and Arizona State University in the US offer a depth of modulation of 90% and a modulation speed exceeding 1 GHz. The modulator consists of a sandwich structure consisting of an array of gold nanoantennas, a layer of graphene, atop a thin dielectric film of Al2O3, an amorphous-Si layer and a rear reflector made of gold. The structure also features gate and drain electrodes to electrically tune the device. When constructed into a 6x6 pixel array the modulators allow the realization of a SLM for proof-of-principle high frame rate single-pixel imaging in the mid-IR.

Two-Dimensional Halide Perovskites Incorporating Straight Chain Symmetric Diammonium Ions, (NH3CmH2mNH3)(CH3NH3)n−1PbnI3n+1 (m = 4–9; n = 1–4)

Low-dimensional halide perovskites have recently attracted intense interest as alternatives to the three-dimensional (3D) perovskites because of their greater tunability and higher environmental stability. Herein, we present the new homologous 2D series (NH3C mH2 mNH3)(CH3NH3) n-1Pb nI3 n+1 ( m = 4-9; n = 1-4), where m represents the carbon-chain number and n equals layer-thickness number. Multilayer ( n > 1) 2D perovskites incorporating diammonium cations were successfully synthesized by the solid-state grinding method for m = 4 and 6 and by the solution method for m = 7-9. Structural characterization by single-crystal X-ray diffraction for the m = 8 and m = 9 series ( n = 1-4) reveals that these compounds adopt the Cc space group for even n members and Pc for odd n members. The optical bandgaps are 2.15 eV for two-layer ( n = 2), 2.01 eV for three-layer ( n = 3), and 1.90 eV for four-layer ( n = 4). The materials exhibit excellent solution processability, and casting thin-films of the n = 3 members was successfully accomplished. The films show a clear tendency for the higher- m members to have preferred orientation on the glass substrate, with m = 8 exhibiting almost perfect vertical layer orientation and m = 9 displaying both vertical and parallel layer orientation, as confirmed by grazing-incidence wide-angle X-ray scattering (GIWAXS) measurements. The vertical layer orientation for the (NH3C8H16NH3)(CH3NH3)2Pb3I10 member results in the best thermal, light, and air stability within this series, thus showing excellent potential for solar cell applications.