Charge transfer state emission dynamics in blue-emitting functionalized silicon nanocrystals

We explore the dynamics of blue emission from dodecylamine and ammonia functionalized silicon nanocrystals (Si NCs) with average diameters of ∼3 and ∼6 nm using time-resolved photoluminescence (TRPL) spectroscopy. The Si NCs exhibit nanosecond PL decay dynamics that is independent of NC size and uniform across the emission spectrum. The TRPL measurements reveal complete quenching of core state emission by a charge transfer state that is responsible for the blue PL with a radiative recombination rate of ∼5 × 10^7 s^(−1). A detailed picture of the charge transfer state emission dynamics in these functionalized Si NCs is proposed

Terahertz spectroscopy: studying carrier dynamics in semiconductor nanostructures

Understanding the ultrafast dynamics of photoexcited carriers in semiconductor nanostructures and their dependence on sample morphology is crucial for their incorporation into photonic devices. Time-resolved terahertz (THz) spectroscopy (TRTS) is an all-optical, contact-free technique that directly measures the transient mobile carrier dynamics and terahertz conductivity in materials over picosecond time scales, and is uniquely suited as a probe of conductivity in nanomaterials. Using low temperature MBE-grown silicon films as an example, we show how TRTS can be used to probe microscopic photoconductivity as well as obtain crucial insights into sample morphology. The thin silicon films consist of a mixture of amorphous and crystalline phases, and their relative content changes drastically with growth temperature. Photoexcited carrier dynamics in these films are determined by film crystallinity: in the amorphous phase, carriers are trapped in bandtail states on sub-picosecond time scales, while the carriers excited in crystalline grains remain free for tens of picoseconds. The complex THz conductivity spectra obtained from the TRTS measurements show that the long range conductivity is significantly higher in films grown at higher temperatures that contain a larger fraction of crystalline material with larger crystal grain sizes.Peer reviewed: YesNRC publication: Ye

Ultrafast carrier dynamics in silicon nanocrystal films

We have applied time-resolved THz spectroscopy to probe the transient photoexcited carrier dynamics and THz conductivity in Si nanocrystal films with varying silicon volume filling fractions and nanocrystal sizes on picosecond time scales. The THz conductivity reveals microscopic carrier motion with significant interface scattering within nanocrystals as well as percolative transport between nanocrystals. The time variation of the THz conductivity is analyzed within the framework of the Drude-Smith model, an extension of the Drude model that characterizes carrier localization in nanostructured materials. Below the percolation threshold, transport between nanocrystals is inhibited and photoexcited carriers are localized within individual nanocrystals. These films also exhibit efficient optical emission. In films with Si filling fractions above the percolation threshold, photoluminescence is suppressed and a transition from long-range inter-nanocrystal transport immediately after photoexcitation to increased carrier localization over a 50 ps time scale due to accumulation of charges at interface defect sites is observed.Peer reviewed: YesNRC publication: Ye

Ultrafast percolative transport dynamics in silicon nanocrystal films

We have applied time-resolved terahertz (THz) spectroscopy to probe ultrafast conduction dynamics of photoexcited carriers in silicon nanocrystal films with a wide range of nanocrystal sizes and concentrations. The picosecond THz conductivity reveals microscopic photocarrier motion with significant interface scattering within the nanocrystals, as well as percolative transport between nanocrystals. In films with silicon filling fractions above the percolation threshold, we observe a transition from long-range internanocrystal transport immediately after photoexcitation to increased carrier localization over a 50-ps time scale due to accumulation of charges at interface defect sites. However, in films with silicon filling fractions below the percolation threshold, transport between nanocrystals is strongly suppressed at all times. Finally, we estimate effective carrier diffusion lengths of 60 to 130 nm for the silicon nanocrystal composites with silicon filling fractions above the percolation threshold, making such films promising candidates for active layers in photovoltaic devices. \ua9 2011 American Physical Society.Peer reviewed: YesNRC publication: Ye

Equilibrium and Non-Equilibrium Free Carrier Dynamics in 2D Ti₃C₂Tₓ MXenes: THz Spectroscopy Study

MXenes is an emerging class of 2D transition metal carbides, nitrides and carbonitrides which exhibit large conductivity, ultrahigh volumetric capacitance, high threshold for light-induced damage and nonlinear optical transmittance, making them attractive candidates for a variety of optoelectronic and electrochemical applications. Here, we report on equilibrium and non-equilibrium free carrier dynamics of Ti3C2Tx gleaned from THz spectroscopic studies for the first time. Ti3C2Tx showed high (~2 x 1021 cm-3) intrinsic charge carrier density and relatively high (~34 cm2 V-1 s-1) mobility of carriers with an exceptionally large, ~46 000 cm-1 absorption in the THz range, which suggests that Ti3C2Tx is well suited for THz detection. We also demonstrate that Ti3C2Tx conductivity and THz transmission can be manipulated by photoexcitation, as absorption of near-infrared, 800 nm pulses is found to cause transient suppression of the conductivity that recovers over hundreds of picoseconds. The possibility of control over THz transmission and conductivity by photoexcitation suggests the promise for application of Ti3C2Tx Mxenes in THz modulation devices and variable electromagnetic shielding

A Novel THz Electromagnetic Interference Shielding Material: 2D Ti₃C₂T\u3csub\u3ey\u3c/sub\u3e MXene

Metallic 2D Ti3C2Ty MXene shows high electrical conductivity and strong absorption of electromagnetic radiation in the THz frequency range. We demonstrate that optical pulses (400nm and 800nm) induce transient broadband THz transparency in this MXene, which lasts for nanoseconds and is independent of temperature from 95 to 290 K. This optically controlled THz electromagnetic interference shielding material could be exploited in future THz communication systems

Ultrafast carrier dynamics and the role of grain boundaries in polycrystalline silicon thin films grown by molecular beam epitaxy

We have used time-resolved terahertz spectroscopy to study microscopic photoconductivity and ultrafast photoexcited carrier dynamics in thin, pure, non-hydrogenated silicon films grown by molecular beam epitaxy on quartz substrates at temperatures ranging from 335 degrees C to 572 degrees C. By controlling the growth temperature, thin silicon films ranging from completely amorphous to polycrystalline with minimal amorphous phase can be achieved. Film morphology, in turn, determines its photoconductive properties: in the amorphous phase, carriers are trapped in bandtail states on sub-picosecond time scales, while the carriers excited in crystalline grains remain free for tens of picoseconds. We also find that in polycrystalline silicon the photoexcited carrier mobility is carrier-density-dependent, with higher carrier densities mitigating the effects of grain boundaries on inter-grain transport. In a film grown at the highest temperature of 572 degrees C, the morphology changes along the growth direction from polycrystalline with needles of single crystals in the bulk of the film to small crystallites interspersed with amorphous silicon at the top of the film. Depth profiling using different excitation wavelengths shows corresponding differences in the photoconductivity: the photoexcited carrier lifetime and mobility are higher in the first 100-150 nm from the substrate, suggesting that thinner, low-temperature grown polycrystalline silicon films are preferable for photovoltaic applications

Ultrafast Zero-Bias Photocurrent in GeS Nanosheets: Promise for Photovoltaics

Ferroelectric semiconductors have been predicted to exhibit strong zero-bias shift current, spurring the search for ferroelectric semiconductors with band gaps in the visible range as candidates for so-called shift current photovoltaics with efficiencies not constrained by the Schockley–Queisser limit. Recent theoretical works have predicted that two-dimensional IV–VI monochalcogenides are multiferroic and capable of generating significant shift currents. Here we present experimental validation of this prediction, observing ultrafast shift currents by detecting terahertz electromagnetic pulses emitted by the photoexcited GeS nanosheets without external bias. We explore excitation fluence, orientation, and excitation polarization dependence of the terahertz emission to confirm that shift currents are indeed responsible for the observed emission. Experimental observation of zero-bias photocurrents puts GeS nanosheets forth as a promising candidate material for applications in third-generation photovoltaics based on shift current, or bulk photovoltaic effect