Organic-inorganic hybrid perovskites are emerging low-cost emitters with very high color purity, but their low luminescent efficiency is a critical drawback. We boosted the current efficiency (CE) of perovskite light-emitting diodes with a simple bilayer structure to 42.9 candela per ampere, similar to the CE of phosphorescent organic light-emitting diodes, with two modifications: We prevented the formation of metallic lead (Pb) atoms that cause strong exciton quenching through a small increase in methylammonium bromide (MABr) molar proportion, and we spatially confined the exciton in uniform MAPbBr3 nanograins (average diameter = 99.7 nanometers) formed by a nanocrystal pinning process and concomitant reduction of exciton diffusion length to 67 nanometers. These changes caused substantial increases in steady-state photoluminescence intensity and efficiency of MAPbBr3 nanograin layers.

/pdf/overcoming-the-electroluminescence-efficiency-limitations-of-4rwp1lam48.pdf

Overcoming the electroluminescence efficiency limitations of perovskite light-emitting diodes.

When a molecule absorbs a photon of appropriate energy, a chain of photophysical events ensues, such as internal conversion or vibrational relaxation (loss of energy in the absence of light emission), fluorescence, intersystem crossing (from singlet state to a triplet state) and phosphorescence, as shown in the Jablonski diagram for organic molecules (Fig. 1). Each of the processes occurs with a certain probability, characterized by decay rate constants (k). It can be shown that the average length of time τ for the set of molecules to decay from one state to another is reciprocally proportional to the rate of decay: τ = 1/k. This average length of time is called the mean lifetime, or simply lifetime. It can also be shown that the lifetime of a photophysical process is the time required by a population of N electronically excited molecules to be reduced by a factor of e. Correspondingly, the fluorescence lifetime is the time required by a population of excited fluorophores to decrease exponentially to N/e via the loss of energy through fluorescence and other non-radiative processes. The lifetime of photophycal processes vary significantly from tens of femotoseconds for internal conversion1,2 to nanoseconds for fluorescence and microseconds or seconds for phosphorescence.1






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Figure 1


Jablonski diagram and a timescale of photophysical processes for organic molecules.

/pdf/fluorescence-lifetime-measurements-and-biological-imaging-xfalzh4w7e.pdf

Fluorescence Lifetime Measurements and Biological Imaging

We quantitatively investigate the size-dependent optical properties of colloidal PbS nanocrystals or quantum dots (Qdots), by combining the Qdot absorbance spectra with detailed elemental analysis of the Qdot suspensions. At high energies, the molar extinction coefficient epsilon increases with the Qdot volume d(3) and agrees with theoretical calculations using the Maxwell-Garnett effective medium theory and bulk values for the Qdot dielectric function. This demonstrates that quantum confinement has no influence on epsilon in this spectral range, and it provides an accurate method to calculate the Qdot concentration. Around the band gap, epsilon only increases with d(1.3), and values are comparable to the epsilon of PbSe Qdots. The data are related to the oscillator strength f(if) of the band gap transition and results agree well with theoretical tight-binding calculations, predicting a linear dependence of f(if) on d. For both PbS and PbSe Qdots, the exciton lifetime tau is calculated from f(if). We find values ranging between 1 and 3 mus, in agreement with experimental literature data from time-resolved luminescence spectroscopy. Our results provide a thorough general framework to calculate and understand the optical properties of suspended colloidal quantum dots. Most importantly, it highlights the significance of the local field factor in these systems.

/pdf/size-dependent-optical-properties-of-colloidal-pbs-quantum-2woma5parc.pdf

Size-dependent optical properties of colloidal PbS quantum dots.

Control of spontaneously emitted light lies at the heart of quantum optics. It is essential for diverse applications ranging from miniature lasers and light-emitting diodes, to single-photon sources for quantum information, and to solar energy harvesting. To explore such new quantum optics applications, a suitably tailored dielectric environment is required in which the vacuum fluctuations that control spontaneous emission can be manipulated. Photonic crystals provide such an environment: they strongly modify the vacuum fluctuations, causing the decay of emitted light to be accelerated or slowed down, to reveal unusual statistics, or to be completely inhibited in the ideal case of a photonic bandgap. Here we study spontaneous emission from semiconductor quantum dots embedded in inverse opal photonic crystals. We show that the spectral distribution and time-dependent decay of light emitted from excitons confined in the quantum dots are controlled by the host photonic crystal. Modified emission is observed over large frequency bandwidths of 10%, orders of magnitude larger than reported for resonant optical microcavities. Both inhibited and enhanced decay rates are observed depending on the optical emission frequency, and they are controlled by the crystals’ lattice parameter. Our experimental results provide a basis for all-solid-state dynamic control
of optical quantum systems.

Controlling the dynamics of spontaneous emission from quantum dots by photonic crystals

Colloidal CsPbX3 (X = Br, Cl, and I) perovskite nanocrystals (NCs) have emerged as promising phosphors and solar cell materials due to their remarkable optoelectronic properties. These properties can be tailored by not only controlling the size and shape of the NCs but also postsynthetic composition tuning through topotactic anion exchange. In contrast, property control by cation exchange is still underdeveloped for colloidal CsPbX3 NCs. Here, we present a method that allows partial cation exchange in colloidal CsPbBr3 NCs, whereby Pb2+ is exchanged for several isovalent cations, resulting in doped CsPb1–xMxBr3 NCs (M= Sn2+, Cd2+, and Zn2+; 0 50%), sh...

http://pubs.acs.org/doi/pdf/10.1021/jacs.6b13079

Highly Emissive Divalent Ion Doped Colloidal CsPb1–xMxBr3 Perovskite Nanocrystals through Cation Exchange

We present a statistical analysis of time-resolved spontaneous emission decay curves from ensembles of emitters, such as semiconductor quantum dots, with the aim of interpreting ubiquitous non-single-exponential decay. Contrary to what is widely assumed, the density of excited emitters and the intensity in an emission decay curve are not proportional, but the density is a time integral of the intensity. The integral relation is crucial to correctly interpret non-single-exponential decay. We derive the proper normalization for both a discrete and a continuous distribution of rates, where every decay component is multiplied by its radiative decay rate. A central result of our paper is the derivation of the emission decay curve when both radiative and nonradiative decays are independently distributed. In this case, the well-known emission quantum efficiency can no longer be expressed by a single number, but is also distributed. We derive a practical description of non-single-exponential emission decay curves in terms of a single distribution of decay rates; the resulting distribution is identified as the distribution of total decay rates weighted with the radiative rates. We apply our analysis to recent examples of colloidal quantum dot emission in suspensions and in photonic crystals, and we find that this important class of emitters is well described by a log-normal distribution of decay rates with a narrow and a broad distribution, respectively. Finally, we briefly discuss the Kohlrausch stretched-exponential model, and find that its normalization is ill defined for emitters with a realistic quantum efficiency of less than 100%.

/pdf/statistical-analysis-of-time-resolved-emission-from-1zfsym9fsd.pdf

Statistical analysis of time-resolved emission from ensembles of semiconductor quantum dots: Interpretation of exponential decay models

We studied the rate of spontaneous emission from colloidal CdSe and CdTe nanocrystals at room temperature. The decay rate, obtained from luminescence decay curves, increases with the emission frequency in a supralinear way. This dependence is explained by the thermal occupation of dark exciton states at room temperature, giving rise to a strong attenuation of the rate of emission. The supralinear dependence is in agreement with the results of tight-binding calculations.

/pdf/frequency-dependent-spontaneous-emission-rate-from-cdse-and-ruultnpquv.pdf

A.F. van Driel

Papers

Statistical analysis of time-resolved emission from ensembles of semiconductor quantum dots: Interpretation of exponential decay models

Frequency-Dependent Spontaneous Emission Rate from CdSe and CdTe Nanocrystals: Influence of Dark States

Macroporous germanium by electrochemical deposition

Hot carrier luminescence during porous etching of GaP under high electric field conditions

Controlling spontaneous emission by photonic crystals