Ultraviolet Circularly Polarized Luminescence in Chiral Perovskite Nanoplatelet-Molecular Hybrids: Direct Binding Versus Efficient Triplet Energy Transfer.

The development of ultraviolet circularly polarized light (UVCPL) sources has the potential to benefit plenty of practical applications but remains a challenge due to limitations in available material systems and a limited understanding of the excited state chirality transfer. Herein, by constructing hybrid structures of the chiral perovskite CsPbBr3 nanoplatelets and organic molecules, excited state chirality transfer is achieved, either via direct binding or triplet energy transfer, leading to efficient UVCPL emission. The underlying photophysical mechanisms of these two scenarios are clarified by comprehensive optical studies. Intriguingly, UVCPL realized via the triple energy transfer, followed by the triplet-triplet annihilation upconversion processes, demonstrates a 50-fold enhanced dissymmetry factor glum. Furthermore, stereoselective photopolymerization of diacetylene monomer is demonstrated by using such efficient UVCPL. This study provides both novel insights and a practical approach for realizing UVCPL, which can also be extended to other material systems and spectral regions, such as visible and near-infrared.

Red-Emitting CsPbI3/ZnSe Colloidal Nanoheterostructures with Enhanced Optical Properties and Stability.

Producing heterostructures of cesium lead halide perovskites and metal-chalcogenides in the form of colloidal nanocrystals can improve their optical features and stability, and also govern the recombination of charge carriers. Herein, the synthesis of red-emitting CsPbI3/ZnSe nanoheterostructures is reported via an in situ hot injection method, which provides the crystallization conditions for both components, subsequently leading to heteroepitaxial growth. Steady-state absorption and photoluminescence studies alongside X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy analysis evidence on a type-I band alignment for CsPbI3/ZnSe nanoheterostructures, which exhibit photoluminescence quantum yield of 96% due to the effective passivation of surface defects, and an enhancement in carrier lifetime. Furthermore, the heterostructure growth of ZnSe domains leads to significant improvement in the stability of the CsPbI3 nanocrystals under ambient conditions and against thermal and UV irradiation stress.

Fine-Tuning Crystal Structures of Lead Bromide Perovskite Nanocrystals through Trace Cadmium(II) Doping for Efficient Color-Saturated Green LEDs.

Decreasing perovskite nanocrystal size increases radiative recombination due to the quantum confinement effect, but also increases the Auger recombination rate which leads to carrier imbalance in the emitting layers of electroluminescent devices. Here, we overcome this trade-off by increasing the exciton effective mass without affecting the size, which is realized through the trace Cd2+ doping of formamidinium lead bromide perovskite nanocrystals. We observe an ~2.7 times increase in the exciton binding energy benefiting from a slight distortion of the [BX6]4- octahedra caused by doping in the case of that the Auger recombination rate is almost unchanged. As a result, bright color-saturated green emitting perovskite nanocrystals with a photoluminescence quantum yield of 96 % are obtained. Cd2+ doping also shifts up the energy levels of the nanocrystals, relative to the Fermi level so that heavily n-doped emitters convert into only slightly n-doped ones; this boosts the charge injection efficiency of the corresponding light-emitting diodes. The light-emitting devices based on those nanocrystals reached a high external quantum efficiency of 29.4 % corresponding to a current efficiency of 123 cd A-1, and showed dramatically improved device lifetime, with a narrow bandwidth of 22 nm and Commission Internationale de I'Eclairage coordinates of (0.20, 0.76) for color-saturated green emission for the electroluminescence peak centered at 534 nm, thus being fully compliant with the latest standard for wide color gamut displays.

A Near-Infrared Absorbing and Emissive Quadruple Helicene Enabled by the Scholl Reaction of Perylene.

Herein, we report the synthesis, structural analysis, optical and chiroptical properties of a novel quadruple helicene, which has two [6] and two [7]helicene moieties fused in a contorted framework of 92 sp2 carbon atoms. It was synthesized by the Scholl reaction of a perylene-containing substrate with the formation of eight carbon-carbon bonds on the perylene unit in a single synthetic operation. Chemical oxidation of the quadruple helicene with tris(4-bromophenyl)ammoniumyl hexachloroantimonate resulted in an air-stable dication, which exhibits the same helicity in its four helicene moieties as unambiguously identified by single-crystal X-ray crystallography. The quadruple helicene exhibits unusual near-infrared absorption and emission with absorption and emission maxima at 848 nm and 977 nm, respectively, and its isolated enantiomers exhibit electronic circular dichroism in the near-infrared and visible-light regions.

Bright CsPbI3 Perovskite Quantum Dot Light-Emitting Diodes with Top-Emitting Structure and a Low Efficiency Roll-Off Realized by Applying Zirconium Acetylacetonate Surface Modification.

Zirconium acetylacetonate used as a co-precursor in the synthesis of CsPbI3 quantum dots (QDs) increased their photoluminescence quantum efficiency to values over 90%. The top-emitting device structure on a Si substrate with high thermal conductivity (to better dissipate Joule heat generated at high current density) was designed to improve the light extraction efficiency making use of a strong microcavity resonance between the bottom and top electrodes. As a result of these improvements, light-emitting diodes (LEDs) utilizing Zr-modified CsPbI3 QDs with an electroluminescence at 686 nm showed external quantum efficiency (EQE) of 13.7% at a current density of 108 mA cm-2, which was combined with low efficiency roll-off (maintaining an EQE of 12.5% at a high current density of 500 mA cm-2) and a high luminance of 14 725 cd m-2, and the stability of the devices being repeatedly lit (cycled on and off at high drive current density) has been greatly enhanced.

Zn-Alloyed CsPbI3 Nanocrystals for Highly Efficient Perovskite Light-Emitting Devices.

We alloyed Zn2+ into CsPbI3 perovskite nanocrystals by partial substitution of Pb2+ with Zn2+, which does not change their crystalline phase. The resulting alloyed CsPb0.64Zn0.36I3 nanocrystals exhibited an improved, close-to-unity photoluminescence quantum yield of 98.5% due to the increased radiative decay rate and the decreased non-radiative decay rate. They also showed an enhanced stability, which correlated with improved effective Goldschmidt tolerance factors, by the incorporation of Zn2+ ions with a smaller radius than the Pb2+ ions. Simultaneously, the nanocrystals switched from n-type (for CsPbI3) to nearly ambipolar for the alloyed nanoparticles. The hole injection barrier of electroluminescent LEDs was effectively eliminated by using alloyed CsPb0.64Zn0.36I3 nanocrystals, and a high peak external quantum efficiency of 15.1% has been achieved.

Synthesis of Anisotropic ZnSe Nanorods with Zinc Blende Crystal Structure.

Compared with the well-explored cadmium-based one-dimensional nanorods (NRs), it is still a challenge to produce heavy-metal-free II-VI semiconductor analogues with a controlled size, shape, and crystal structure. Herein, a synthetic strategy towards ZnSe NRs with a zinc blende crystal structure is presented, where use of the anisotropic nuclei produced via a high-temperature selenium injection favors anisotropic growth. Elongated ZnSe NRs were produced from anisotropic ZnSe nuclei, while spherical ZnSe nanocrystals were obtained starting from isotropic nuclei. The different free energy at (111) and (220) planes in anisotropic ZnSe nuclei induces the anisotropic growth of (111) plane for ZnSe NRs. Proper choice of the capping ligand (1-dodecanethiol) has an important implication for the formation of anisotropic ZnSe nuclei and also allows the control of the diameter of the final ZnSe NRs by limiting the growth of the (220) crystal plane of anisotropic ZnSe nuclei.

Synthesis and Optical Properties of Cubic Chalcopyrite/Hexagonal Wurtzite Core/Shell Copper Indium Sulfide Nanocrystals.

We report a synthetic method to produce heavy-metal-free heterophase core/shell CuInS2 nanocrystals, which comprise differently sized cores with a cubic chalcopyrite (CP) structure overgrown with hexagonal wurtzite (WZ) shells. For a given core size, CP/WZ core/shell CuInS2 nanocrystals experience shifts in both absorption and photoluminescence spectra toward the near-infrared with increasing shell thickness. Studies of the photoluminescence dynamics of these heterophase CuInS2 nanocrystals reveals behavior similar to that of the typical type II nanostructures constructed from different semiconductor materials of the same crystal structure. The interface between the CP core and the WZ shell has an important effect on the photoluminescence quantum yield.

Oxalic Acid Enabled Emission Enhancement and Continuous Extraction of Chloride from Cesium Lead Chloride/Bromide Perovskite Nanocrystals.

All-inorganic cesium lead halide perovskite nanocrystals (NCs) have demonstrated excellent optical properties and an encouraging potential for optoelectronic applications; however, mixed-halide perovskites, especially CsPb(Cl/Br)3 NCs, still show lower photoluminescence quantum yields (PL QY) than the corresponding single-halide materials. Herein, anhydrous oxalic acid is used to post-treat CsPb(Cl/Br)3 NCs in order to initially remove surface defects and halide vacancies, and thus, to improve their PL QY from 11% to 89% for the emission of 451 nm. Furthermore, due to the continuous chelating reaction with the oxalate ion, chloride anions from the mixed-halide CsPb(Cl/Br)3 perovskite NCs could be extracted, and green emitting CsPbBr3 NCs with PL QY of 85% at 511 nm emission are obtained. Besides being useful to improve the emission of CsPb(Cl/Br)3 NCs, the oxalic acid treatment strategy introduced here provides a further tool to adjust the distribution of halide anions in mixed-halide perovskites without using any halide additives.

Hydrogen Peroxide Assisted Synthesis of Highly Luminescent Sulfur Quantum Dots.

An H2 O2 -assisted top-down approach is used to synthesize brightly luminescent, color-tunable sulfur quantum dots (SQDs), with a photoluminescence quantum yield of up to 23 %. The formation of SQDs involves dissolution of bulk sulfur powder into small particles in an alkaline environment in the presence of polyethylene glycol, followed by H2 O2 -assisted etching of polysulfide species, which has the advantage of the passivation of surface states. This synthetic strategy allows us to simultaneously control the final size of SQDs, to tune their emission color, and to improve their emission quantum yield by eliminating surface traps. Down-conversion white light emitting diodes were also fabricated using blue emissive SQDs and orange emissive copper nanoclusters, with CIE color coordinates of (0.33, 0.32) and a high color rendering index of 91. The water-soluble, highly luminescent SQDs are promising luminescent materials that can be produced from abundant precursor materials.

A Building Brick Principle to Create Transparent Composite Films with Multicolor Emission and Self-Healing Function.

A cellulose paper is used impregnated with light-emitting CdTe nanocrystals and carbon dots, and filled with a polyurethane to fabricate uniform transparent composite films with bright photoluminescence of red (R), green (G), and blue (B) (RGB) colors. A building brick-like assembly method is introduced to realize RGB multicolor emission patterns from this composite material. By sectioning out individual pixels from monochrome-emissive composite sheets, the advantage of the self-healing properties of polyurethane is taken to arrange and weld them into a RGB patterned fabric by brief exposure to ethanol. This provides an approach to form single layer RGB light-emitting pixels, such as potentially required in the display applications, without the use of any lithographic or etching processing. The method can utilize a wide range of different solution-based kinds of light-emitting materials.

Aqueous Based Semiconductor Nanocrystals.

This review summarizes traditional and recent nonconventional, bioinspired, methods for the aqueous synthesis of colloidal semiconductor quantum dots (QDs). The basic chemistry concepts are critically emphasized at the very beginning as these are strongly correlated with the selection of ligands and the optimal formation of aqueous QDs and their more sophisticated structures. The synergies of biomimetic and biosynthetic methods that can combine biospecific reactivity with the robust and strong optical responses of QDs have also resulted in new approaches to the synthesis of the nanoparticles themselves. A related new avenue is the recent extension of QD synthesis to form nanoparticles endowed with chiral optical properties. The optical characteristics of QD materials and their advanced forms such as core/shell heterostructures, alloys, and doped QDs are discussed: from the design considerations of optical band gap tuning, the control and reduction of the impact of surface traps, the consideration of charge carrier processes that affect emission and energy and charge transfer, to the impact and influence of lattice strain. We also describe the considerable progress in some selected QD applications such as in bioimaging and theranostics. The review concludes with future strategies and identification of key challenges that still need to be resolved in reaching very attractive, scalable, yet versatile aqueous syntheses that may widen the scope of commercial applications for semiconductor nanocrystals.

Revealing the Formation Mechanism of CsPbBr3 Perovskite Nanocrystals Produced via a Slowed-Down Microwave-Assisted Synthesis.

We developed a microwave-assisted slowed-down synthesis of CsPbBr3 perovskite nanocrystals, which retards the reaction and allows us to gather useful insights into the formation mechanism of these nanoparticles, by examining the intermediate stages of their growth. The trends in the decay of the emission intensity of CsPbBr3 nanocrystals under light exposure are well correlated with their stability against decomposition in TEM under electron beam. The results show the change of the crystal structure of CsPbBr3 nanocrystals from a deficient and easier to be destroyed lattice to a well crystallized one. Conversely the shift in the ease of degradation sheds light on the formation mechanism, indicating first the formation of a bromoplumbate ionic scaffold, with Cs-ion infilling lagging a little behind. Increasing the cation to halide ratio towards the stoichiometric level may account for the improved radiative recombination rates observed in the longer reaction time materials.

Temperature-Dependent Exciton and Trap-Related Photoluminescence of CdTe Quantum Dots Embedded in a NaCl Matrix: Implication in Thermometry.

Temperature-dependent optical studies of semiconductor quantum dots (QDs) are fundamentally important for a variety of sensing and imaging applications. The steady-state and time-resolved photoluminescence properties of CdTe QDs in the size range from 2.3 to 3.1 nm embedded into a protective matrix of NaCl are studied as a function of temperature from 80 to 360 K. The temperature coefficient is found to be strongly dependent on QD size, with the highest sensitivity obtained for the smallest size of QDs. The emission from solid-state CdTe QD-based powders is maintained with high color purity over a wide range of temperatures. Photoluminescence lifetime data suggest that temperature dependence of the intrinsic radiative lifetime in CdTe QDs is rather weak, and it is mostly the temperature-dependent nonradiative decay of CdTe QDs which is responsible for the thermal quenching of photoluminescence intensity. By virtue of the temperature-dependent photoluminescence behavior, high color purity, photostability, and high photoluminescence quantum yield (26%-37% in the solid state), CdTe QDs embedded in NaCl matrices are useful solid-state probes for thermal imaging and sensing over a wide range of temperatures within a number of detection schemes and outstanding sensitivity, such as luminescence thermochromic imaging, ratiometric luminescence, and luminescence lifetime thermal sensing.

Highly Integrated Supercapacitor-Sensor Systems via Material and Geometry Design.

An ultimate integration strategy making use of material and geometry is applied in a proof-of-concept study. Integrated supercapacitor-sensor systems with the capability of photodetecting and strain sensing are fabricated based on multifunctional conducting polypyrrole and piezoresistive textile geometry, respectively. This integration strategy enables promising applications for self-powered smart sensory, wearable and healthcare electronics.

Insight into strain effects on band alignment shifts, carrier localization and recombination kinetics in CdTe/CdS core/shell quantum dots.

The impact of strain on the optical properties of semiconductor quantum dots (QDs) is fundamentally important while still awaiting detailed investigation. CdTe/CdS core/shell QDs represent a typical strained system due to the substantial lattice mismatch between CdTe and CdS. To probe the strain-related effects, aqueous CdTe/CdS QDs were synthesized by coating different sized CdTe QD cores with CdS shells upon the thermal decomposition of glutathione as a sulfur source under reflux. The shell growth was carefully monitored by both steady-state absorption and fluorescence spectroscopy and transient fluorescence spectroscopy. In combination with structural analysis, the band alignments as a consequence of the strain were modified based on band deformation potential theory. By further taking account of these strain-induced band shifts, the effective mass approximation (EMA) model was modified to simulate the electronic structure, carrier spatial localization, and electron-hole wave function overlap for comparing with experimentally derived results. In particular, the electron/hole eigen energies were predicted for a range of structures with different CdTe core sizes and different CdS shell thicknesses. The overlap of electron and hole wave functions was further simulated to reveal the impact of strain on the electron-hole recombination kinetics as the electron wave function progressively shifts into the CdS shell region while the hole wave function remains heavily localized in CdTe core upon the shell growth. The excellent agreement between the strain-modified EMA model with the experimental data suggests that strain exhibits remarkable effects on the optical properties of mismatched core/shell QDs by altering the electronic structure of the system.

Multiple exciton generation in cluster-free alloy Cd(x)Hg(1-x)Te colloidal quantum dots synthesized in water.

A number of different composition CdxHg1-xTe alloy quantum dots have been synthesized using a modified aqueous synthesis and ion exchange method. The benefits of good stoichiometric control and high emission quantum yield were retained whilst also ensuring that the tendency to form gel-like clusters and adsorb excess cations in the stabilizing ligand shells was mitigated using a sequestering method to remove excess ionic material during and after the synthesis. This was highly desirable for ultrafast carrier dynamics measurements, avoiding strong photocharging effects which may mask fundamental carrier signals. Transient grating measurements revealed a composition dependent carrier multiplication process which competes with phonon mediated carrier cooling to deplete the initial hot carrier population. The interplay between these two mechanisms is strongly dependent on the electron effective mass which in these alloys has a marked composition dependence and may be considerably lower than the hole effective mass. For a composition x = 0.52 we measured a maximum carrier multiplication quantum yield of 199 ± 19% with pump photon energy 3 times the bandgap energy, Eg, whilst the threshold energy is calculated to be just 2.15Eg. There is some evidence to suggest an impact ionization process analogous to the inverse Auger S mechanism seen in bulk CdxHg1-xTe.

Narrow bandgap colloidal metal chalcogenide quantum dots: synthetic methods, heterostructures, assemblies, electronic and infrared optical properties.

The chemistry, material processing and fundamental understanding of colloidal semiconductor nanocrystals (quantum dots) are advancing at an astounding rate, bringing the prospects of widespread commercialization of these novel and exciting materials ever closer. Interest in narrow bandgap nanocrystals in particular has intensified in recent years, and the results of research worldwide point to the realistic prospects of applications for these materials in solar cells, infrared optoelectronics (e.g. lasers, optical modulators, photodetectors and photoimaging devices), low cost/large format microelectronics, and in biological imaging and biosensor systems to name only some technologies. Improvements in fundamental understanding and material quality are built on a vast body of experience spread over many different methods of colloidal synthetic growth, each with their own strengths and weaknesses for different materials and sometimes with regard to particular applications. The nanocrystal growth expertise is matched by a rapidly expanding, and highly interdisciplinary, understanding of how best to assemble these materials into films or hybrid composites and thereby into useful devices, and again there are many different strategies that can be adopted. In this review we have attempted to survey and compare the recent work on colloidal synthesis, film and nanocrystal composite material fabrication, concentrating on narrow bandgap chalcogenide materials and some of their topical applications in the solar energy and biological fields. Since these applications are attracting rising interest across a wide range of disciplines, from the biological sciences, device engineering, and materials processing fields as well as the physics and synthetic chemistry communities, we have endeavoured to make the review of these narrow bandgap nanomaterials both comprehensive and accessible to newcomers to the area.

Temperature Dependence of Charge Transport Properties of Quasi-2D Chiral Perovskite Thin-Film Field-Effect Transistors.

Chiral halide perovskite materials promise both superior light response and the capability to distinguish circularly polarized emissions, which are especially common in the fluorescence spectra of organic chiral materials. Herein, thin-film field-effect transistors (FETs) based on chiral quasi-two-dimensional perovskites are explored, and the temperature dependence of the charge carrier transport mechanism over the broad temperature range (80-300 K) is revealed. A typical p-type charge transport behavior is observed for both left-handed (S-C6H5(CN2)2NH3)2(CH3NH3)n-1PbnI3n+1 and right-handed (R-C6H5(CN2)2NH3)2(CH3NH3)n-1PbnI3n+1 chiral perovskites, with maximum carrier mobilities of 1.7 × 10-5 cm2 V-1 s-1 and 2.5 × 10-5 cm2 V-1 s-1 at around 280 K, respectively. The shallow traps with smaller activation energy (0.03 eV) hinder the carrier transport over the lower temperature regime (80-180 K), while deep traps with 1 order of magnitude larger activation energy than the shallow traps moderate the charge carrier transport in the temperature range of 180-300 K. From the charge carrier mechanism point of view, impurity scattering is established as the dominant factor from 80 K until around 280 K, while phonon scattering becomes predominant up to room temperature. Responsivities of 0.15 A W-1 and 0.14 A W-1 for left-handed and right-handed chiral perovskite FET devices are obtained.

Slow Hot-Exciton Cooling and Enhanced Interparticle Excitonic Coupling in HgTe Quantum Dots.

Rapid hot-carrier/exciton cooling constitutes a major loss channel for photovoltaic efficiency. How to decelerate the hot-carrier/exciton relaxation remains a crux for achieving high-performance photovoltaic devices. Here, we demonstrate slow hot-exciton cooling that can be extended to hundreds of picoseconds in colloidal HgTe quantum dots (QDs). The energy loss rate is 1 order of magnitude smaller than bulk inorganic semiconductors, mediated by phonon bottleneck and interband biexciton Auger recombination (BAR) effects, which are both augmented at reduced QD sizes. The two effects are competitive with the emergence of multiple exciton generation. Intriguingly, BAR dominates even under low excitation fluences with a decrease in interparticle distance. Both experimental evidence and numerical evidence reveal that such efficient BAR derives from the tunneling-mediated interparticle excitonic coupling induced by wave function overlap between neighboring HgTe QDs in films. Thus, our study unveils the potential for realizing efficient hot-carrier/exciton solar cells based on HgTe QDs. Fundamentally, we reveal that the delocalized nature of quantum-confined wave function intensifies BAR. The interparticle excitonic coupling may cast light on the development of next-generation photoelectronic materials, which can retain the size-tunable confinement of colloidal semiconductor QDs while simultaneously maintaining high mobilities and conductivities typical for bulk semiconductor materials.