Blue Light Emitting Defective Nanocrystals Composed of Earth-Abundant Elements.

Copper-based ternary (I-III-VI) chalcogenide nanocrystals (NCs) are compositionally-flexible semiconductors that do not contain lead (Pb) or cadmium (Cd). Cu-In-S NCs are the dominantly studied member of this important materials class and have been reported to contain optically-active defect states. However, there are minimal reports of In-free compositions that exhibit efficient photoluminescence (PL). Here, we report a novel solution-phase synthesis of ≈4 nm defective nanocrystals (DNCs) composed of copper, aluminum, zinc, and sulfur with ≈20 % quantum yield and an attractive PL maximum of 450 nm. Extensive spectroscopic characterization suggests the presence of highly localized electronic states resulting in reasonably fast PL decays (≈1 ns), large vibrational energy spacing, small Stokes shift, and temperature-independent PL linewidth and PL lifetime (between room temperature and ≈5 K). Furthermore, density functional theory (DFT) calculations suggest PL transitions arise from defects within a CuAl5 S8 crystal lattice, which supports the experimental observation of highly-localized states. The results reported here provide a new material with unique optoelectronic characteristics that is an important analog to well-explored Cu-In-S NCs.

Zinc Thiolate Enables Bright Cu-Deficient Cu-In-S/ZnS Quantum Dots.

Copper indium sulfide (CIS) colloidal quantum dots (QDs) are a promising candidate for commercially viable QD-based optical applications, for example as colloidal photocatalysts or in luminescent solar concentrators (LSCs). CIS QDs with good photoluminescence quantum yields (PLQYs) and tunable emission wavelength via size and composition control are previously reported. However, developing an understanding and control over the growth of electronically passivating inorganic shells would enable further improvements of the photophysical properties of CIS QDs. To improve the optical properties of CIS QDs, the focus is on the growth of inorganic shells via the popular metal-carboxylate/alkane thiol decomposition reaction. 1) The role of Zn-carboxylate and Zn-thiolate on the formation of ZnS shells on Cu-deficient CIS (CDCIS) QDs is studied, 2) this knowledge is leveraged to yield >90% PLQY CDCIS/ZnS core/shell QDs, and 3) a mechanism for ZnS shells grown from zinc-carboxylate/alkane thiol decomposition is proposed.

PbS Nanocrystal Emission Is Governed by Multiple Emissive States.

Lead chalcogenide colloidal nanocrystals (NCs) are promising materials for solution processable optoelectronics. However, there is little agreement on the identity and character of PbS NC emission for different degrees of quantum confinement-a critical parameter for realizing applications for these nanocrystals. In this work, we combine ensemble and single NC spectroscopies to interrogate preparations of lead sulfide NCs. We use solution photon correlation Fourier spectroscopy (S-PCFS) to measure the average single NC linewidth of near-infrared-emitting PbS quantum dots and find it to be dominated by homogeneous broadening. We further characterize PbS NCs using temperature-dependent linear and time-resolved emission spectroscopy which demonstrate that a kinetically accessed defect state dominates room temperature emission of highly confined emitting NCs. These experiments, taken together, demonstrate that the linewidth and Stokes shift of PbS NCs are the result of emission from two states: a thermally accessed defect-with an energetically pinned charge carrier-and an inhomogeneously broadened band-edge state.

Single Nanocrystal Spectroscopy of Shortwave Infrared Emitters.

Short-wave infrared (SWIR) emitters are at the center of ground-breaking applications in biomedical imaging, next-generation optoelectronic devices, and optical communications. Colloidal nanocrystals based on indium arsenide are some of the most promising SWIR emitters to date. However, the lack of single-particle spectroscopic methods accessible in the SWIR has prevented advances in both nanocrystal synthesis and fundamental characterization of emitters. Here, we demonstrate an implementation of a solution photon correlation Fourier spectroscopy (s-PCFS) experiment utilizing the SWIR sensitivity and time resolution of superconducting nanowire single-photon detectors to extract single-particle emission linewidths from colloidal indium arsenide/cadmium selenide (InAs/CdSe) core/shell nanocrystals emissive from 1.2 to 1.6 µm. We show that the average single InAs/CdSe nanocrystal fluorescence linewidth is, remarkably, as narrow as 52 meV, similar to what has been observed in some of the most narrowband nanostructured emitters in the visible region. Additionally, the single nanocrystal fluorescence linewidth increases with increasing shell thickness, suggesting exciton-phonon coupling as the dominant emission line-broadening mechanism in this system. The development of the SWIR s-PCFS technique has enabled measurements of spectral linewidths of colloidal SWIR-emissive NCs in solution and provides a platform to study the single NC spectral characteristics of SWIR emitters.

Correction: Colloidal atomic layer deposition growth of PbS/CdS core/shell quantum dots.

Correction for 'Colloidal atomic layer deposition growth of PbS/CdS core/shell quantum dots' by Michel Nasilowski et al., Chem. Commun., 2017, 53, 869-872.

Colloidal atomic layer deposition growth of PbS/CdS core/shell quantum dots.

Traditionally, PbS/CdS quantum dots (QDs) have been synthesized via a cation exchange method, making fine control over shell growth challenging. We show here that colloidal atomic layer deposition (c-ALD) allows for the sequential growth of single monolayers of the shell, thus creating a 'true' CdS shell on PbS QDs.