time-resolved-photoluminescence-spectroscopy-semiconductor

Time-Resolved Photoluminescence Spectroscopy of Semiconductor Nanocrystals and Other Fluorophores

Time-resolved photoluminescence (TRPL) is a key technique for understanding the photophysics of semiconductor nanocrystals and light-emitting materials in ...

University of Alberta

Ensembles of iron nanocrystals up to 25 nm in diameter embedded in SiO(2) were found to exhibit an ultrafast magnetic response to a transient out-of-plane magnetic field. The response time varies as a function of in-plane bias magnetic field with the fastest rise times, as short as 26 ps, observed for both zero and high bias fields (140 kA/m). Analytical modeling and micromagnetic simulations confirm that magnetostatic interactions between nanoparticles play an important role in the dynamic response.

Ultrafast dynamics of a ferromagnetic nanocomposite.

We investigate the spontaneous emission modifications when ensembles of quantum dots (QDs) with differing emission frequencies and finite Lorentzian linewidths are coupled to a microcavity. Using contour integrals we develop a general expression for the rate enhancement when neither the emitter nor the cavity resonance can be treated as a delta function. We show that the ensemble cavity-coupled luminescence lifetimes are generally suppressed in the case of spherical cavities and that the spontaneous emission dynamics of the cavity coupled component becomes increasingly stretched as the coupling factor increases. The Q-factor measured from the luminescence spectrum can be much lower than the intrinsic cavity Q-factor, and is in many practical situations limited by the QD spectral width. The mode spectrum observed in the photoluminescence (PL) spectrum can be largely determined by the QD emission linewidth, permitting this parameter to be extracted without requiring single-particle spectroscopy. In the case of Si-QDs, the linewidth cannot be significantly greater than 10 meV in order to observe spherical cavity resonances in the PL spectrum.

Modification of ensemble emission rates and luminescence spectra for inhomogeneously broadened distributions of quantum dots coupled to optical microcavities.

The luminescence dynamics in ensembles of nanocrystals are complicated by a variety of processes, including the size-dependence of the radiative and non-radiative rates in inhomogeneous broadened samples and interparticle interactions. This results in a non-exponential decay, which for the specific case of silicon nanocrystals (SiNCs) has been widely modeled with a Kohlrausch or "stretched exponential" (SE) function. We first derive the population decay function for a luminescence decay following exp[- (t/τ)]. We then compare the distributions and mean times calculated by assuming that either the luminescence decay or the population decay follows this function and show that the results are significantly different for β much below 1. We then apply these two types of SE functions as well as other models to the luminescence decay data from two thermally grown SiNC samples with different mean sizes. The mean lifetimes are strongly dependent on the experimental setup and the chosen fitting model, none of which appears to adequately describe the ensemble decay dynamics. Frequency-resolved spectroscopy (FRS) techniques are then applied to SiNCs in order to extract the lifetime distribution directly. The rate distribution has a half width of ~ 0.5 decades and mainly resembles a somewhat high-frequency-skewed lognormal function. The combination of TRS and FRS methods appear best suited to uncovering the luminescence dynamics of NC materials having a broad emission spectrum.

Reappraising the Luminescence Lifetime Distributions in Silicon Nanocrystals.

Ratiometric photoluminescent detection of the toxicologically potent organophosphate ester nerve agents paraoxon (PX) and parathion (PT) using the complementary optical and chemical properties of the long Stokes shift green fluorescent protein variant, mAmetrine1.2 (mAm), and red-emitting silicon-based quantum dots (SiQDs) is reported. PX and PT selectively quench SiQD photoluminescence (PL) through a dynamic quenching mechanism, thereby, facilitating the development of a ratiometric sensor platform that shows micromolar limits of detection for PX and PT and that is unaffected by the presence of common inorganic and organic interferents. As a part of the present study, we also demonstrate that the paper-based sensors derived from mAm and SiQDs detect PX and PT at concentrations as low as 5 μM using a readily available commercial color analysis smartphone "app". The ratiometric sensor reported herein can potentially be used for the convenient and rapid on-site detection and quantification of PX and PT in real-world samples.

Ratiometric Detection of Nerve Agents by Coupling Complementary Properties of Silicon-Based Quantum Dots and Green Fluorescent Protein.

Leading edge p-i-n type halide perovskite solar cells (PSCs) severely underperform n-i-p PSCs. p-i-n type PSCs that use PEDOT:PSS hole transport layers (HTLs) struggle to generate open-circuit photovoltage values higher than 1 V. NiO HTLs have shown greater promise in achieving high  values albeit inconsistently. In this report, a NiO nanomesh with Ni defect grown by the hydrothermal method was used to obtain PSCs with  values that consistently exceeded 1.10 V (champion  = 1.14 V). A champion device photoconversion efficiency of 17.75% was observed. Density functional theory modeling was used to understand the interfacial properties of the NiO/perovskite interface. The PCE of PSCs constructed using the Ni-doped NiO nanomesh HTL was ∼34% higher than that of conventional compact NiO-based perovskite solar cells. A suite of characterization techniques such as transmission electron microscopy, field emission scanning electron microscopy, intensity-modulated photocurrent spectroscopy, intensity-modulated photovoltage spectroscopy, time-resolved photoluminescence, steady-state photoluminescence, and Kelvin probe force microscopy provided evidence of better film quality, enhanced charge transfer, and suppressed charge recombination in PSCs based on hydrothermally grown NiO nanostructures.

Consistently High  Values in p-i-n Type Perovskite Solar Cells Using Ni-Doped NiO Nanomesh as the Hole Transporting Layer.

We demonstrate a versatile and easily fabricated paper-based CO sensor. The sensor consists of a specially designed fluorescent color-shift chromophore infused into standard filter paper. The emission color of the resulting fluorescent paper changes upon exposure to CO due to the formation of carbonic acid, which underlies the sensing mechanism. By using a ratiometric method, the undesirable effects of photobleaching can be eliminated, leading to a stable and repeatable sensor performance. These multiuse sensors have a response time on the order of 1 min and feature low detection limits for a paper-based CO gas sensor, suggesting possible low-cost applications in smart buildings or other facilities in which CO levels are required to be continuously monitored.

An Ultrasensitive Fluorescent Paper-Based CO Sensor.

Efficient white-light-emitting single-material sources are ideal for sustainable lighting applications. Though layered hybrid lead-halide perovskite materials have demonstrated attractive broad-band white-light emission properties, they pose a serious long-term environmental and health risk as they contain lead (Pb) and are readily soluble in water. Recently, lead-free halide double perovskite (HDP) materials with a generic formula A(I)B'(III)B″(I)X (where A and B are cations and X is a halide ion) have demonstrated white-light emission with improved photoluminescence quantum yields (PLQYs). Here, we present a series of Bi/In mixed-cationic CsBiInAgCl HDP solid solutions that span the indirect to direct band-gap modification which exhibit tailorable optical properties. Density functional theory (DFT) calculations indicate an indirect-direct band-gap crossover composition when  > 0.50. These HDP materials emit over the entire visible light spectrum, centered at 600 ± 30 nm with full-width at half maxima of ca. 200 nm upon ultraviolet light excitation and a maximum PLQY of 34 ± 4% for CsBiInAgCl. Short-range structural insight for these materials is crucial to unravel the unique atomic-level structural properties which are difficult to distinguish by diffraction-based techniques. Hence, we demonstrate the advantage of using solid-state nuclear magnetic resonance (NMR) spectroscopy to deconvolute the local structural environments of these mixed-cationic HDPs. Using ultrahigh-field (21.14 T) NMR spectroscopy of quadrupolar nuclei (In, Cs, and Bi), we show that there is a high degree of atomic-level B'(III)/B″(I) site ordering (i.e., no evidence of antisite defects). Furthermore, a combination of XRD, NMR, and DFT calculations was used to unravel the complete atomic-level random Bi/In cationic mixing in CsBiInAgCl HDPs. Briefly, this work provides an advance in understanding the photophysical properties that correlate long- to short-range structural elucidation of these newly developed solid-state white-light emitting HDP materials.

Tailorable Indirect to Direct Band-Gap Double Perovskites with Bright White-Light Emission: Decoding Chemical Structure Using Solid-State NMR.

Luminescent silicon nanoparticles have been widely recognized as an alternative for metal-based quantum dots (QDs) for optoelectronics partly because of the high abundance and biocompatibility of silicon. To date, the broad photoluminescence line width (often >100 nm) of silicon QDs has been a hurdle to achieving competitive spectral purity and incorporating them into light-emitting devices. Herein we report fabrication and testing of straightforward configuration of Fabry-Pérot resonators that incorporates a thin layer of SiQD-polymer hybrid/blend between two reflective silver mirrors; remarkably these devices exhibit up-to-14-fold narrowing of SiQD emission and achieve a spectral bandwidth as narrow as ca. 9 nm. Our polymer-based, SiQD-containing Fabry-Pérot resonators also provide convenient spectral tunability, can be prepared using a variety of polymer hosts and substrates, and enable rigid as well as flexible devices.

Silicon Quantum Dot-Polymer Fabry-Pérot Resonators with Narrowed and Tunable Emissions.

We report on a fluorescent-droplet-based acid-sensing scheme that allows limits of detection below 100 pM for weak acids. The concept is based on a strong partitioning of acid from an aqueous phase into octanol droplets. Using salicylic acid as a demonstration, we show that at a high concentration, the acid partitions into the organic phase by a factor of 260, which is approximately consistent with literature values. However, at lower concentrations, we obtain a partition coefficient as high as 10, which is partly responsible for the excellent sensing performance. The enhanced equilibrium partitioning is likely due to the interaction of the dissociated acid phase with the sensor dye employed for this work. The effect of droplet size was determined, after which we derived a simple model to predict the time dependence of the color change as a function of droplet size. This work shows that color-change fluorescent-droplet-based detection is a promising avenue that can lead to exceptional sensing performance from an aqueous analyte.

Ultrasensitive Picomolar Detection of Aqueous Acids in Microscale Fluorescent Droplets.

We show a double-functional fluorescence sensing paradigm that can retrieve nanometric pH information on biological structures. We use this method to measure the extent of protonic condensation around microtubules, which are protein polymers that play many roles crucial to cell function. While microtubules are believed to have a profound impact on the local cytoplasmic pH, this has been hard to show experimentally due to the limitations of conventional sensing techniques. We show that subtle changes in the local electrochemical surroundings cause a double-functional sensor to transform its spectrum, thus allowing a direct measurement of the protonic concentration at the microtubule surface. Microtubules concentrate protons by as much as one unit on the pH scale, indicating a charge storage role within the cell via the localized ionic condensation. These results confirm the bioelectrical significance of microtubules and reveal a sensing concept that can deliver localized biochemical information on intracellular structures.

Article	Year
Ultrafast dynamics of a ferromagnetic nanocomposite. Nano letters\| PubMed ID: 15794630	2005
Modification of ensemble emission rates and luminescence spectra for inhomogeneously broadened distributions of quantum dots coupled to optical microcavities. Optics express\| PubMed ID: 20588877	2010
Reappraising the Luminescence Lifetime Distributions in Silicon Nanocrystals. Nanoscale research letters\| PubMed ID: 30488251	2018
Ratiometric Detection of Nerve Agents by Coupling Complementary Properties of Silicon-Based Quantum Dots and Green Fluorescent Protein. ACS applied materials & interfaces\| PubMed ID: 31414591	2019
Consistently High Values in p-i-n Type Perovskite Solar Cells Using Ni-Doped NiO Nanomesh as the Hole Transporting Layer. ACS applied materials & interfaces\| PubMed ID: 31904215	2020
An Ultrasensitive Fluorescent Paper-Based CO Sensor. ACS applied materials & interfaces\| PubMed ID: 32320202	2020
Tailorable Indirect to Direct Band-Gap Double Perovskites with Bright White-Light Emission: Decoding Chemical Structure Using Solid-State NMR. Journal of the American Chemical Society\| PubMed ID: 32426971	2020
Silicon Quantum Dot-Polymer Fabry-Pérot Resonators with Narrowed and Tunable Emissions. ACS applied materials & interfaces\| PubMed ID: 33983697	2021
Ultrasensitive Picomolar Detection of Aqueous Acids in Microscale Fluorescent Droplets. ACS sensors\| PubMed ID: 34936335	2022
A Nanometric Probe of the Local Proton Concentration in Microtubule-Based Biophysical Systems. Nano letters\| PubMed ID: 34962401	2022

Alkiviathes Meldrum

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