Slipping-Free Halide Perovskite Supercrystals from Supramolecularly-Assembled Nanocrystals.

Supramolecularly assembled high-order supercrystals (SCs) help control the dielectric, electronic, and excitonic properties of semiconductor nanocrystals (NCs) and quantum dots (QDs). Ligand-engineered perovskite NCs (PNCs) assemble into SCs showing shorter excitonic lifetimes than strongly dielectric PNC films showing long photoluminescence (PL) lifetimes and long-range carrier diffusion. Monodentate to bidentate ligand exchange on ≈ 8 nm halide perovskite (APbX3 ; A:Cs/MA, X:Br/I) PNCs generates mechanically stable SCs with close-packed lattices, overlapping electronic wave functions, and higher dielectric constant, providing distinct excitonic properties from single PNCs or PNC films. From Fast Fourier Transform (FFT) images, time-resolved PL, and small-angle X-ray scattering, structurally and excitonically ordered large SCs are identified. An Sc shows a smaller spectral shift (<35 meV) than a PNC film (>100 meV), a microcrystal (>100 meV), or a bulk crystal (>100 meV). Also, the exciton lifetime (<10 ns) of an SC is excitation power-independent in the single exciton regime 〈N〉<1, comparable to an isolated PNC. Therefore, bidentate-ligand-assisted SCs help overcome delayed exciton or carrier recombination in halide perovskite nanocrystal assemblies or films.

Thermodynamically and Kinetically Controlled Nucleation and Growth of Halide Perovskite Single Crystals.

Halide perovskites are ideal for next-generation optical devices and photovoltaics. Although perovskite single-crystals show reproducible optoelectronic properties, significant variations in the crystal size, anisotropy, density, defects, photoluminescence (PL), and carrier lifetime affect the sample properties and device performances. Homogenous size and shape FA/MAPbBr3 single microcrystals (MCs) with controlled edge lengths, crystal densities, PL lifetimes, and PL intensities are prepared by thermodynamically controlling and kinetically separating the crystal nucleation-growth processes using optimum N-cyclohexyl-2-pyrrolidone (CHP) concentration. The crystal growth kinetics at different CHP concentrations and temperatures are estimated spectroscopically by measuring the concentration of Pb (II). High-density cubic MCs with a homogenous size distribution, high PL intensities, and long PL lifetimes are obtained within minutes at high temperatures by the controlled addition of the pyrrolidone derivative. Conversely, the crystal size nonlinearly increases with time at low temperatures. The isotropically grown high-density single crystals at controlled nucleation-growth rates at 190 °C with 20% CHP show the highest PL intensity and the longest PL lifetimes. This method offers thermodynamic and kinetic control of perovskite single-crystal growth with shape control.

Nanomaterials for Fluorescence and Multimodal Bioimaging.

Bioconjugated nanomaterials replace molecular probes in bioanalysis and bioimaging in vitro and in vivo. Nanoparticles of silica, metals, semiconductors, polymers, and supramolecular systems, conjugated with contrast agents and drugs for image-guided (MRI, fluorescence, PET, Raman, SPECT, photodynamic, photothermal, and photoacoustic) therapy infiltrate into preclinical and clinical settings. Small bioactive molecules like peptides, proteins, or DNA conjugated to the surfaces of drugs or probes help us to interface them with cells and tissues. Nevertheless, the toxicity and pharmacokinetics of nanodrugs, nanoprobes, and their components become the clinical barriers, underscoring the significance of developing biocompatible next-generation drugs and contrast agents. This account provides state-of-the-art advancements in the preparation and biological applications of bioconjugated nanomaterials and their molecular, cell, and in vivo applications. It focuses on the preparation, bioimaging, and bioanalytical applications of monomodal and multimodal nanoprobes composed of quantum dots, quantum clusters, iron oxide nanoparticles, and a few rare earth metal ion complexes.

Halide Perovskite Single Crystals and Nanocrystal Films as Electron Donor-Acceptor Heterojunctions.

Halide perovskites are materials for future optical displays and solar cells. Electron donor-acceptor perovskite heterostructures with distinguishing halide compositions are promising for transporting and harvesting photogenerated charge carriers. Combined e-beam lithography and anion exchange are promising to develop such heterostructures but challenging to prepare multiple heterojunctions at desired locations in single crystals. We demonstrate swift laser trapping-assisted band gap engineering at the desired locations in MAPbBr3 microrods, microplates, or nanocrystal thin films. The built-in donor-acceptor double and multi-heterojunction structures let us transport and trap photogenerated charge carriers from wide-band gap bromide to narrow-band gap iodide domains. We discuss the charge carrier transport and trapping mechanisms from the viewpoints of engineered bands and band continuity. This work offers a convenient method for designing single-, double- and multi-heterojunction donor-acceptor halide perovskites for photovoltaic, photonic, and electronic applications.

Excitation-Wavelength-Dependent Functionalities of Temporally Controlled Sensing and Generation of Singlet Oxygen by a Photoexcited State Engineered Rhodamine 6G-Anthracene Conjugate.

The present study provides design guidance for unique multipotent molecules that sense and generate singlet oxygen (1 O2 ). A rhodamine 6G-aminomethylanthracene-linked donor-acceptor molecule (RA) is designed and synthesized for demonstrating wavelength-dependent functionalities as follows; (i) RA acts as a conventional fluorogenic 1 O2 sensor molecule like the commercially available reagent, singlet oxygen sensor green (SOSG), when it absorbs ultraviolet (UV)-visible light and reacts with 1 O2 . (ii) RA acts as a temporally controlled 1 O2 sensing reagent under the longer wavelength (∼700 nm) photosensitization. RA enters an intermediate state after capturing 1 O2 and does not become strongly fluorescent until it is exposed to UV, blue, or green light. (iii) RA acts as an efficient photosensitizer to generate 1 O2 under green light illumination. The spin-orbit charge transfer mediated intersystem crossing (SOCT-ISC) process achieves this function, and RA shows a potential cancer-killing effect on pancreatic cancer cells. The wavelength-switchable functionalities in RA offer to promise molecular tools to apply 1 O2 in a spatiotemporal manner.

Synthesis, optoelectronic properties and applications of halide perovskites.

Halide perovskites have emerged as a class of most promising and cost-effective semiconductor materials for next generation photoluminescent, electroluminescent and photovoltaic devices. These perovskites have high optical absorption coefficients and exhibit narrow-band bright photoluminescence, in addition to their halide-dependent tuneable bandgaps, low exciton binding energies, and long-range carrier diffusion. These properties make these perovskites superior to classical semiconductors such as silicon. Most importantly, the simple synthesis of perovskites in the form of high quality films, single crystals, nanocrystals and quantum dots has attracted newcomers to develop novel perovskites with unique optoelectronic properties for optical and photovoltaic applications. Here, we comprehensively review recent advances in the synthesis and optoelectronic properties of films, microcrystals, nanocrystals and quantum dots of lead halide and lead-free halide perovskites. Followed by the classification of synthesis, we address the ensemble and single particle properties of perovskites from the viewpoints of the confinement and transport of charge carriers or excitons. Further, we correlate the charge carrier properties of perovskite films, microcrystals, nanocrystals and quantum dots with the crystal structure and size, halide composition, temperature, and pressure. Finally, we illustrate the emerging applications of perovskites to solar cells, LEDs, and lasers, and discuss the ongoing challenges in the field.

Photoinduced Betaine Generation for Efficient Photothermal Energy Conversion.

The conversion of solar energy to thermal, chemical, or electrical energy attracts great attention in chemistry and physics. There has been a considerable effort for the efficient extraction of photons throughout the entire solar spectrum. In this work light energy was efficiently harvested by using a long-lived betaine photogenerated from an acridinium-based electron donor-acceptor dyad. The photothermal energy-conversion efficiency of the dyad is significantly enhanced by simultaneous illumination with blue (420-440 nm) and yellow (>480 nm) light in comparison with the sum of the conversion efficiencies for individual illumination with blue or yellow light. The enhanced photothermal effect is due to the photogenerated betaine, which absorbs longer-wavelength light than the dyad, and thus the dyad-betaine combination is promising for efficient photothermal energy conversion. The mechanisms of betaine generation and energy conversion are discussed on the basis of steady-state and transient spectral measurements.

Nonradiative Energy Transfer through Distributed Bands in Piezochemically Synthesized Cesium and Formamidinium Lead Halide Perovskites.

Repeated absorption of emitted photons, also called photon recycling, in large crystals and thick films of perovskites leads to delayed photoluminescence (PL) and decrease of PL intensity. The role of distinct band gaps, which act as donors and acceptors of energy, and nonradiative energy transfer on such delayed, low intensity emission is yet to be rationalized. Here we report delayed emission by nonradiative energy transfer across a distribution of energy states in close-packed crystallites of cesium lead bromide CsPbBr3 , formamidinium lead bromide FAPbBr3 , or the mixed halide FAPb(BrI)3 perovskite synthesized in the form of thick pellets by the piezochemical method. The PL lifetime of the bromide-rich domain in the mixed halide pellet is considerably decreased when compared with a pure FAPbBr3 pellet. Here the domains with higher bromide composition act as the energy donor, whereas the iodide-rich domains are the acceptors. Time-resolved PL measurements of CsPbBr3 , FAPbBr3 , and the mixed halide FAPb(BrI)3 perovskite pellets help us to clarify the role of nonradiative energy transfer on photon recycling.

Blinking Beats Bleaching: The Control of Superoxide Generation by Photo-ionized Perovskite Nanocrystals.

Moisture- or oxidation-induced degradation is a major challenge in the advancement of perovskites-based technology. The oxidation is caused by electron transfer from a photo-excited perovskite nanocrystal to oxygen and the formation of superoxide that disintegrates the perovskite structure. In air, the emission intensity of a methylammonium lead iodide (MAPbI3 ) perovskite nanocrystal continuously decreases, whereas a nanocrystal in argon or a polymer shows exceptionally stable emission intensity. Surprisingly, in air, the emission intensity of a nanocrystal with long-lived OFF states completely recovers after the OFF state. This property, along with the rate of non-radiative relaxation that exceeds the rate of electron transfer suggest that the perovskite nanocrystals produce and react with superoxide in the excited neutral state, but not in the ionized state. In other words, the ultrafast non-radiative relaxation in the ionized state hinders electron transfer to oxygen and prevents oxidation of perovskites.

Crystallization of Methylammonium Lead Halide Perovskites by Optical Trapping.

Single crystals of organolead halide perovskites attract much attention to electrooptical and photovoltaic applications. They are usually prepared in precursor solutions incubated at controlled temperatures or under optimized vapor atmosphere conditions, and thus, multiple perovskite crystals are nucleated all over the solution. Multiple nucleation of crystals prevents efficient use of precursors in the preferential growth of large single crystals. An innovative approach is presented for spatiotemporally controlled, selective nucleation and growth of single crystals of lead halide perovskites by optical trapping with a focused laser beam. Upon such trapping in unsaturated precursor solutions, nucleation of MAPbX3 (MA=CH3 NH3 + ; X=Cl- , Br- , or I- ) is induced at the focal spot through increase in the concentration of perovskite precursors in the focal volume. The rate at which the nucleated crystal grows depends upon whether the perovskite absorbs the trapping laser or not. These findings suggest that optical trapping would be useful to prepare various perovskite single crystals and modify their optical and electronic properties; thereby, offering new methods for engineering of perovskite crystals.

Influence of Zn on the photoluminescence of colloidal (AgIn)xZn2(1-x)S2 nanocrystals.

We study the effect of Zn on the photophysical properties of a family of group I-III-VI nanocrystals (NCs), namely in solid solutions of (AgIn)xZn2(1-x)S2 (ZAIS). We focus on the comparison of the photoluminescence (PL) properties of ZAIS NCs of comparable sizes and different amounts of Zn. This approach helps us to decouple the effects of size and varying chemical composition of the NCs which both influence the PL properties. We show that in the presence of Zn new radiative centers are generated which improve the NC quality in terms of PL quantum yield. However, an amount of Zn beyond a particular limit places the radiative recombination centers close to each other, leading to undesired interactions among charge carriers and non-radiative transitions. Proximity between the energy levels of these radiative centers and the conduction band leads to non-radiative localized-delocalized transitions, as evidenced from temperature dependent absorption, PL and lifetime measurements.

Channeling Exciton Migration into Electron Transfer in Formamidinium Lead Bromide Perovskite Nanocrystal/Fullerene Composites.

Hydrophobically capped nanocrystals of formamidinium lead bromide (FAPbBr3 ) perovskite (PNC) show bright and stable fluorescence in solution and thin-film states. When compared with isolated PNCs in a solution, close-packed PNCs in a thin film show extended fluorescence lifetime (ca. 4.2 µs), which is due to hopping or migration of photogenerated excitons among PNCs. Both fluorescence quantum efficiency and lifetime decrease in a PNC thin film doped with fullerene (C60 ), which is attributed to channeling of exciton migration into electron transfer to C60 . On the other hand, quenching of fluorescence intensity of a PNC solution is not accompanied by any change in fluorescence lifetime, indicating static electron transfer to C60 adsorbed onto the hydrophobic surface of individual PNCs. Exciton migration among close-packed PNCs and electron transfer to C60 places C60 -doped PNC thin films among cost-effective antenna systems for solar cells.

Chemical modifications and bioconjugate reactions of nanomaterials for sensing, imaging, drug delivery and therapy.

As prepared nanomaterials of metals, semiconductors, polymers and carbon often need surface modifications such as ligand exchange, and chemical and bioconjugate reactions for various biosensor, bioanalytical, bioimaging, drug delivery and therapeutic applications. Such surface modifications help us to control the physico-chemical, toxicological and pharmacological properties of nanomaterials. Furthermore, introduction of various reactive functional groups on the surface of nanomaterials allows us to conjugate a spectrum of contrast agents, antibodies, peptides, ligands, drugs and genes, and construct multifunctional and hybrid nanomaterials for the targeted imaging and treatment of cancers. This tutorial review is intended to provide an introduction to newcomers about how chemical and bioconjugate reactions transform the surface of nanomaterials such as silica nanoparticles, gold nanoparticles, gold quantum clusters, semiconductor quantum dots, carbon nanotubes, fullerene and graphene, and accordingly formulate them for applications such as biosensing, bioimaging, drug and gene delivery, chemotherapy, photodynamic therapy and photothermal therapy. Nonetheless, controversial reports and our growing concerns about toxicity and pharmacokinetics of nanomaterials suggest the need for not only rigorous in vivo experiments in animal models but also novel nanomaterials for practical applications in the clinical settings. Further reading of original and review articles cited herein is necessary to buildup in-depth knowledge about the chemistry, bioconjugate chemistry and biological applications of individual nanomaterials.

Auger ionization beats photo-oxidation of semiconductor quantum dots: extended stability of single-molecule photoluminescence.

Despite the bright and tuneable photoluminescence (PL) of semiconductor quantum dots (QDs), the PL instability induced by Auger recombination and oxidation poses a major challenge in single-molecule applications of QDs. The incomplete information about Auger recombination and oxidation is an obstacle in the resolution of this challenge. Here, we report for the first time that Auger-ionized QDs beat self-sensitized oxidation and the non-digitized PL intensity loss. Although high-intensity photoactivation insistently induces PL blinking, the transient escape of QDs into the ultrafast Auger recombination cycle prevents generation of singlet oxygen ((1) O2 ) and preserves the PL intensity. By the detection of the NIR phosphorescence of (1) O2 and evaluation of the photostability of single QDs in aerobic, anaerobic, and (1) O2 scavenger-enriched environments, we disclose relations of Auger ionization and (1) O2 -mediated oxidation to the PL stability of single QDs, which will be useful during the formulation of QD-based single-molecule imaging tools and single-photon devices.

Photosensitizer-singlet oxygen sensor conjugated silica nanoparticles for photodynamic therapy and bioimaging.

Intracellular singlet oxygen (1O2) generation and detection help optimize the outcome of photodynamic therapy (PDT). Theranostics programmed for on-demand phototriggered 1O2 release and bioimaging have great potential to transform PDT. We demonstrate an ultrasensitive fluorescence turn-on sensor-sensitizer-RGD peptide-silica nanoarchitecture and its 1O2 generation-releasing-storing-sensing properties at the single-particle level or in living cells. The sensor and sensitizer in the nanoarchitecture are an aminomethyl anthracene (AMA)-coumarin dyad and a porphyrin or CdSe/ZnS quantum dots (QDs), respectively. The AMA in the dyad quantitatively quenches the fluorescence of coumarin by intramolecular electron transfer, the porphyrin or QD moiety generates 1O2, and the RGD peptide facilitates intracellular delivery. The small size, below 200 nm, as verified by scanning electron microscopy and differential light scattering measurements, of the architecture within the 1O2 diffusion length enables fast and efficient intracellular fluorescence switching by the tandem ultraviolet (UV)-visible or visible-near-infrared (NIR) photo-triggering. While the red emission and 1O2 generation by the porphyrin are continually turned on, the blue emission of coumarin is uncaged into 230-fold intensity enhancement by on-demand photo-triggering. The 1O2 production and release by the nanoarchitecture enable spectro-temporally controlled cell imaging and apoptotic cell death; the latter is verified from cytotoxic data under dark and phototriggering conditions. Furthermore, the bioimaging potential of the TCPP-based nanoarchitecture is examined in vivo in B6 mice.

Dual-color photoluminescence modulation of zero-dimensional hybrid copper halide microcrystals.

Zero-dimensional hybrid copper(I) halides (HCHs) are attractive due to their interesting photoluminescence (PL) properties and the high abundance and low toxicity of copper. In this study, we report green-red dual emission from rhombic 1-butyl-1-methyl piperidinium copper bromide [(Bmpip)2Cu2Br4] microcrystals (MCs) prepared on borosilicate glass. The structure and elemental composition of the MCs are characterized by single crystal X-ray diffraction analysis, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. Interestingly, MCs prepared on an ITO-coated glass plate show an intense green emission compared to the dual emission on a bare glass or plastic substrate. Furthermore, the intensity of the green emission from the MC is enormously increased by powdering using a conductive material, suggesting the deactivation of the red-emitting state by a charge transfer interaction with the conductor. These findings open a new strategy to suppress the self-trapping of excitons by longitudinal optical phonons and control the dual emitting states in HCHs.

Transfer of 2D Films: From Imperfection to Perfection.

Atomically thin 2D films and their van der Waals heterostructures have demonstrated immense potential for breakthroughs and innovations in science and technology. Integrating 2D films into electronics and optoelectronics devices and their applications in electronics and optoelectronics can lead to improve device efficiencies and tunability. Consequently, there has been steady progress in large-area 2D films for both front- and back-end technologies, with a keen interest in optimizing different growth and synthetic techniques. Parallelly, a significant amount of attention has been directed toward efficient transfer techniques of 2D films on different substrates. Current methods for synthesizing 2D films often involve high-temperature synthesis, precursors, and growth stimulants with highly chemical reactivity. This limitation hinders the widespread applications of 2D films. As a result, reports concerning transfer strategies of 2D films from bare substrates to target substrates have proliferated, showcasing varying degrees of cleanliness, surface damage, and material uniformity. This review aims to evaluate, discuss, and provide an overview of the most advanced transfer methods to date, encompassing wet, dry, and quasi-dry transfer methods. The processes, mechanisms, and pros and cons of each transfer method are critically summarized. Furthermore, we discuss the feasibility of these 2D film transfer methods, concerning their applications in devices and various technology platforms.

Bio-catalytic nanoparticle shaping for preparing mesoscopic assemblies of semiconductor quantum dots and organic molecules.

We report a unique bio-catalytic nanoparticle shaping (BNS) method for preparing a variety of mesoscopic particles by a facile process. For example, the BNS method affords mesoscopic QD assembly dispersions. Large-size sedimentations (>1 µm) of QDs are first formed using oligo-L-lysine linkers. These then undergo controlled enzymatic cleavage of the linkers using trypsin, which surprisingly leads to mesoscopic particles about 84 nm in size with a narrow size distribution. A detailed mechanism of the BNS method is investigated using tetrakis(4-carboxyphenyl)porphyrin (TCPP), instead of QDs, as a probe molecule. Interestingly, the BNS method can also be applied to other combinations of enzymes and enzymatically degradable linkers, such as hyaluronidase with hyaluronan. As a potential application, the mesoscopic particles of QDs and oligo-lysine exhibit their ability to act as a drug delivery carrier originating from the features of both QDs and oligo-lysine. The BNS method demonstrates the universality and versatility of preparing mesoscopic particles and opens new doors for studying QD assemblies and molecular-based mesoscopic particles.

Quantitative analysis of condensation/decondensation status of pDNA in the nuclear sub-domains by QD-FRET.

Recent studies indicate that controlling the nuclear decondensation and intra-nuclear localization of plasmid DNA (pDNA) would result in an increased transfection efficiency. In the present study, we established a technology for imaging the nuclear condensation/decondensation status of pDNA in nuclear subdomains using fluorescence resonance energy transfer (FRET) between quantum dot (QD)-labeled pDNA as donor, and rhodamine-labeled polycations as acceptor. The FRET-occurring pDNA/polycation particle was encapsulated in a nuclear delivery system; a tetra-lamellar multifunctional envelope-type nano device (T-MEND), designed to overcome the endosomal membrane and nuclear membrane via step-wise fusion. Nuclear subdomains (i.e. heterochromatin and euchromatin) were distinguished by Hoechst33342 staining. Thereafter, Z-series of confocal images were captured by confocal laser scanning microscopy. pDNA in condensation/decondensation status in heterochromatin or euchromatin were quantified based on the pixel area of the signals derived from the QD and rhodamine. The results obtained indicate that modulation of the supra-molecular structure of polyrotaxane (DMAE-ss-PRX), a condenser that is cleaved in a reductive environment, conferred euchromatin-preferred decondensation. This represents the first demonstration of the successful control of condensation/decondensation in specific nuclear sub-domain via the use of an artificial DNA condenser.

Singlet-oxygen-sensitizing near-infrared-fluorescent multimodal nanoparticles.

Nanoprobes based on quantum clusters (QC) with near-infrared fluorescence, magnetic-resonance-imaging contrast, and singlet-oxygen-sensitized intracellular fluorescence are studied. The generation of singlet oxygen and singlet-oxygen-sensitized fluorescence uncaging by magnetic and NIR-emitting nanoparticles are exploited for multimodal bioimaging in vitro.