Tetrahalidometallate(II) Ionic Liquids with More than One Metal: The Effect of Bromide versus Chloride.

Fifteen N-butylpyridinium salts - five monometallic [C4 Py]2 [MBr4 ] and ten bimetallic [C4 Py]2 [M0.5 a M0.5 b Br4 ] (M=Co, Cu, Mn, Ni, Zn) - were synthesized, and their structures and thermal and electrochemical properties were studied. All the compounds are ionic liquids (ILs) with melting points between 64 and 101 °C. Powder and single-crystal X-ray diffraction show that all ILs are isostructural. The electrochemical stability windows of the ILs are between 2 and 3 V. The conductivities at room temperature are between 10-5 and 10-6  S cm-1 . At elevated temperatures, the conductivities reach up to 10-4  S cm-1 at 70 °C. The structures and properties of the current bromide-based ILs were also compared with those of previous examples using chloride ligands, which illustrated differences and similarities between the two groups of ILs.

Tuning radiative lifetimes in semiconductor quantum dots.

Photonic devices stand to benefit from the development of chromophores with tunable, precisely controlled spontaneous emission lifetimes. Here, we demonstrate a method to continuously tune the radiative emission lifetimes of a class of chromophores by varying the density of electronic states involved in the emission process. In particular, we examined the peculiar composition-dependent electronic structure of copper doped CdZnSe quantum dots. It is shown that the nature and density of electronic states involved with the emission process is a function of copper inclusion level, providing a very direct handle for controlling the spontaneous lifetimes. The spontaneous emission lifetimes are estimated by examining the ratios of emission lifetimes to absolute quantum yields and also measured directly by ultrafast luminescence upconversion experiments. We find excellent agreement between these classes of experiments. This scheme enables us to tune spontaneous emission lifetimes by three orders of magnitude from ∼15 ns to over ∼7 µs, which is unprecedented in existing lumophores.

Optical Transparency Enabled by Anomalous Stokes Shift in Visible Light-Emitting CuAlS2-Based Quantum Dots.

We observe and study the anomalous Stokes shift of CuAlS2/CdS quantum dots. While all known I-III-VI2 semiconductor core/shell quantum dots show Stokes shifts in excess of 100 meV, the shift associated with CuAlS2/CdS quantum dots is uniquely large, even exceeding 1.4 eV in some cases. CuAlS2/CdS quantum dots are thus associated with cross sections less than 10-17 cm2 under the emission maximum. We investigate this anomaly using spectroscopic techniques and ascribe it to the existence of a strong type-II offset between CuAlS2 and CdS layers. Besides their strong Stokes shift, CuAlS2/CdS quantum dots also exhibit high quantum yields (63%) as well as long emission lifetimes (∼1500 ns). Because of the combined existence of these properties, CuAlS2/CdS quantum dots can act as tunable, transparent emitters over the entire visible spectrum. As a demonstration of their potential, we describe the construction of a wide area transparent lighting device with waveguided optical excitation and a clear aperture of 7.5 cm2.

Why Does CuFeS2 Resemble Gold?

While several potential applications of CuFeS2 quantum dots have already been reported, doubts regarding their optical and physical properties persist. In particular, it is unclear if the quantum dot material is metallic, a degenerately doped semiconductor, or else an intrinsic semiconductor material. Here we examine the physical properties of CuFeS2 quantum dots in order to address this issue. Specifically, we study the bump that is observed in the optical spectra of these quantum dots at ∼500 nm. Using a combination of structural and optical characterization methods, ultrafast spectroscopy, as well as electronic structure calculations, we ascertain that the unusual purple color of CuFeS2 quantum dots as well the golden luster of CuFeS2 films arise from the existence of a plasmon resonance in these materials. While the presence of free carriers causes this material to resemble gold, surface treatments are also described to suppress the plasmon resonance altogether.

Optical Signatures of Impurity-Impurity Interactions in Copper Containing II-VI Alloy Semiconductors.

We study the optical properties of copper containing II-VI alloy quantum dots (CuxZnyCd1-x-ySe). Copper mole fractions within the host are varied from 0.001 to 0.35. No impurity phases are observed over this composition range, and the formation of secondary phases of copper selenide are observed only at xCu > 0.45. The optical absorption and emission spectra of these materials are observed to be a strong function of xCu, and provide information regarding composition induced impurity-impurity interactions. In particular, the integrated cross section of optical absorption per copper atom changes sharply (from 1 × 10 -2 nm3 to 4 × 10 -2 nm3) at xCu = 0.12, suggesting a composition induced change in local electronic structure. These materials may serve as model systems to understand the electronic structure of I-III-VI2 semiconductor compounds.

Behavior of Methylammonium Dipoles in MAPbX3 (X = Br and I).

Dielectric constants of MAPbX3 (X = Br, I) in the 1 kHz-1 MHz range show strong temperature dependence near room temperature, in contrast to the nearly temperature-independent dielectric constant of CsPbBr3. This strong temperature dependence for MAPbX3 in the tetragonal phase is attributed to the MA+ dipoles rotating freely within the probing time scale. This interpretation is supported by ab initio molecular dynamics simulations on MAPbI3 that establish these dipoles as randomly oriented with a rotational relaxation time scale of ∼7 ps at 300 K. Further, we probe the intriguing possibility of transient polarization of these dipoles following a photoexcitation process with important consequences on the photovoltaic efficiency, using a photoexcitation pump and second harmonic generation efficiency as a probe with delay times spanning 100 fs-1.8 ns. The absence of a second harmonic signal at any delay time rules out the possibility of any transient ferroelectric state under photoexcitation.

CuFeS2 Quantum Dots and Highly Luminescent CuFeS2 Based Core/Shell Structures: Synthesis, Tunability, and Photophysics.

We report the synthesis of copper iron sulfide (CuFeS2) quantum dots (QDs). These materials exhibit a tunable band gap that spans the range 0.5-2 eV (600-2500 nm). Although the as-prepared material is nonemissive, CuFeS2/CdS core/shell structures are shown to exhibit quantum yields that exceed 80%. Like other members of the I-III-VI2 family QDs, CuFeS2 based nanoparticles exhibit a long-lived emission that is significantly red-shifted compared to the band gap. CuFeS2 QDs are unique in terms of their composition. In particular, these QDs are the only band-gap-tunable infrared chromophore composed entirely of elements with atomic numbers less than 30.