Magnetic Polaron States in Photoluminescent Carbon Dots Enable Hydrogen Peroxide Photoproduction.

Photoactivation of aspartic acid-based carbon dots (Asp-CDs) induces the generation of spin-separated species, including electron/hole (e- /h+ ) polarons and spin-coupled triplet states, as uniquely confirmed by the light-induced electron paramagnetic resonance spectroscopy. The relative population of the e- /h+ pairs and triplet species depends on the solvent polarity, featuring a substantial stabilization of the triplet state in a non-polar environment (benzene). The electronic properties of the photoexcited Asp-CDs emerge from their spatial organization being interpreted as multi-layer assemblies containing a hydrophobic carbonaceous core and a hydrophilic oxygen and nitrogen functionalized surface. The system properties are dissected theoretically by density functional theory in combination with molecular dynamics simulations on quasi-spherical assemblies of size-variant flakelike model systems, revealing the importance of size dependence and interlayer effects. The formation of the spin-separated states in Asp-CDs enables the photoproduction of hydrogen peroxide (H2 O2 ) from water and water/2-propanol mixture via a water oxidation reaction.

Bright, Magnetic NIR-II Quantum Dot Probe for Sensitive Dual-Modality Imaging and Intensive Combination Therapy of Cancer.

Improving the effectiveness of cancer therapy will require tools that enable more specific cancer targeting and improved tumor visualization. Theranostics have the potential for improving cancer care because of their ability to serve as both diagnostics and therapeutics; however, their diagnostic potential is often limited by tissue-associated light absorption and scattering. Herein, we develop CuInSe2@ZnS:Mn quantum dots (QDs) with intrinsic multifunctionality that both enable the accurate localization of small metastases and act as potent tumor ablation agents. By leveraging the growth kinetics of a ZnS shell on a biocompatible CuInSe2 core, Mn doping, and folic acid functionalization, we produce biocompatible QDs with high near-infrared (NIR)-II fluorescence efficiency up to 31.2%, high contrast on magnetic resonance imaging (MRI), and preferential distribution in 4T1 breast cancer tumors. MRI-enabled contrast of these nanoprobes is sufficient to timely identify small metastases in the lungs, which is critically important for preventing cancer spreading and recurrence. Further, exciting tumor-resident QDs with NIR light produces both fluorescence for tumor visualization through radiative recombination pathways as well as heat and radicals through nonradiative recombination pathways that kill cancer cells and initiate an anticancer immune response, which eliminates tumor and prevents tumor regrowth in 80% of mice.

Uncovering the Role of Trioctylphosphine on Colloidal and Emission Stability of Sb-Alloyed Cs2NaInCl6 Double Perovskite Nanocrystals.

Doping and compositional tuning of Cs2AInCl6 (A = Ag, Na) double perovskite nanocrystals (PNCs) is considered a promising strategy toward the development of light-emitting sources for applications in solution-processed optoelectronic devices. Oleic acid and oleylamine are by far the most often used surface capping ligands for PNCs. However, the undesirable desorption of these ligands due to proton-exchange reaction during isolation and purification processing results in colloidal and structural instabilities. Thus, the improvement of colloidal and optical stability of PNCs represents one of the greatest challenges in the field. Here, we report a trioctylphosphine-mediated synthesis and purification method toward Sb-alloyed Cs2NaInCl6 PNCs with excellent stability and optical features. Nuclear magnetic resonance spectroscopy enabled one to explain the role of trioctylphosphine and to reveal the reaction mechanism during crystal nucleation and growth. Under the optimized reaction conditions, in situ-generated trioctylphosphonium chloride and benzoyl trioctylphosphonium chloride serve as highly reactive halide sources, while benzoyl trioctylphosphonium and oleylammonium cations together with the oleate anion serve as surface capping ligands, which are bound strongly to the PNC surface. The tightly bound ionic pair of oleylammonium oleate and benzoyl trioctylphosphonium chloride/oleate ligands allows one to obtain monodispersed bright-blue-emitting PNCs with high photoluminescence quantum yields exceeding 50% at an optimum Sb content (0.5%), which also exhibit long-term colloidal stability. The approach based on dual cationic ligand passivation of double PNCs opens the doors for applications in other systems with a potential to achieve higher stability along with superior optical properties.

Carbon Dots Detect Water-to-Ice Phase Transition and Act as Alcohol Sensors via Fluorescence Turn-Off/On Mechanism.

Highly fluorescent carbon nanoparticles called carbon dots (CDs) have been the focus of intense research due to their simple chemical synthesis, nontoxic nature, and broad application potential including optoelectronics, photocatalysis, biomedicine, and energy-related technologies. Although a detailed elucidation of the mechanism of their photoluminescence (PL) remains an unmet challenge, the CDs exhibit robust, reproducible, and environment-sensitive PL signals, enabling us to monitor selected chemical phenomena including phase transitions or detection of ultralow concentrations of molecular species in solution. Herein, we report the PL turn-off/on behavior of aqueous CDs allowing the reversible monitoring of the water-ice phase transition. The bright PL attributable to molecular fluorophores present on the CD surface was quenched by changing the liquid aqueous environment to solid phase (ice). Based on light-induced electron paramagnetic resonance (LEPR) measurements and density functional theory (DFT) calculations, the proposed kinetic model assuming the presence of charge-separated trap states rationalized the observed sensitivity of PL lifetimes to the environment. Importantly, the PL quenching induced by freezing could be suppressed by adding a small amount of alcohols. This was attributed to a high tendency of alcohol to increase its concentration at the CD/solvent interface, as revealed by all-atom molecular dynamics simulations. Based on this behavior, a fluorescence "turn-on" alcohol sensor for exhaled breath condensate (EBC) analysis has been developed. This provided an easy method to detect alcohols among other common interferents in EBC with a low detection limit (100 ppm), which has a potential to become an inexpensive and noninvasive clinically useful diagnostic tool for early stage lung cancer screening.

Pressure-Modulated Broadband Emission in 2D Layered Hybrid Perovskite-Like Bromoplumbate.

Two-dimensional (2D) layered hybrid bromoplumbate perovskites are promising candidates for solution-processed light-emitting materials. Here, we report the synthesis and characterization of two novel layered bromoplumbates: (4BrPhMA)2PbBr4 (1) and (4BrPhA)6Pb3Br12 (2), where 4BrPhMA is (4-bromophenyl)methylammonium and 4BrPhA is (4-bromophenyl) ammonium. Despite similar optical absorption, these materials show remarkably different photoluminescence properties: 1 emits a narrow exciton band at ca. 395 nm with a very small bandwidth (particularly at low temperatures of 15-50 K) and Stokes shift, while 2 exhibits a broad emission at ca. 560 nm with a large Stokes shift, both at low and ambient temperatures. However, under several kbar of hydrostatic pressure, the broad emission diminishes and a new band reversibly develops at ca. 395 nm, similar to that in 1. Our results emphasize organic layer flexibility as an important design factor for this class of perovskite-like materials featuring broadband emission.

Purple-emissive carbon dots enhance sensitivity of Si photodetectors to ultraviolet range.

In this work, we achieved the synthesis of purple-emissive carbon dots (p-CDs) by a simple and highly reproducible route using folic acid as the sole precursor. The emission of the p-CDs is located around 390 nm, and is independent of the excitation wavelength with a high photoluminescence quantum yield of 54.6%, thus complementing an emission color palette of brightly emitting carbon dots with purple. The purple-emissive CDs are highly stable in both the colloidal state and in polymer films. A carbon dot luminescence down-shifting layer is used to sensitize a Si photodetector to the UV range. As an example, p-CDs with an excitation maximum at 330 nm were integrated into a Si photodetector, resulting in an improvement in the photoresponsivity in a UV range from 0.8 to 2.5 mA W-1, with a relative enhancement of 203.8%. This work is a cheap, scalable, and environmentally friendly way to create purple-emissive carbon dots, which enhance the photoresponsivity of commercial photodetectors in the UV range, thus being suitable for optical power meters, optical wireless communication systems, sunlight sensors, spectrophotometers, or radiation detectors.

A carbon dot-based tandem luminescent solar concentrator.

Luminescent solar concentrators (LSCs) are light-management devices and are used for harvesting and concentrating solar light from a large area to their edges. Being semitransparent devices, LSCs show great promise for future utilization in glass walls of urban buildings as environmentally friendly photovoltaic power plants. The development of cheap and eco-safe materials, the extension of the LSC operation range, and the enhancement of the optical efficiency are the key challenges, which need to be solved in order to transform energetically passive buildings into self-sustainable units. Herein, a large area (64 cm2) tandem LSC fabricated using entirely eco-friendly highly emissive blue, green, and red carbon dots is demonstrated, with an internal optical quantum efficiency of 23.6% and an external optical quantum efficiency of 2.3%, while maintaining a high transparency across the visible spectrum. This opens up a new direction for the application of carbon dots in advanced solar light harvesting technologies.

Manganese-Mediated Growth of ZnS Shell on KMnF3:Yb,Er Cores toward Enhanced Up/Downconversion Luminescence.

Epitaxially growing a semiconductor shell on the surface of upconversion nanocrystals to form a core/shell structure is believed to be a promising strategy to improve the luminescent efficiency of lanthanide ions doped in particle cores and, meanwhile, enriches the optical properties of the resulting nanocrystals. However, liquid-phase synthesis of such core/shell-structured nanocrystals comprised of a lanthanide ion-doped core and semiconductor shell remains challenging because of the chemical incompatibilities between lanthanides and the most intermediate gap semiconductors. In this context, the successful growth of ZnS shell on a KMnF3 core codoped with Yb3+/Er3+ ions is reported to enhance the upconversion luminescence of Er3+ ions. The underlying core/shell formation mechanism is elucidated in detail combining the hard-soft acid-base theory with structural analysis of the resulting nanocrystals. Quite unexpectedly, Mn2+ diffusion across the core/shell interface occurs during ZnS shell growth, giving rise to Mn2+ emission from the ZnS shell. Thus, the resulting core/shell particles exhibited unique up/downconversion luminescence from doped lanthanide metal ions and transition-metal ions, respectively. By manipulating the ion diffusion and shell growth kinetics, the upconversion and downconversion luminescent performance of KMnF3:Yb,Er@ZnS nanocrystals are further optimized and the related mechanisms are discussed. Further, temperature-dependent upconversion and downconversion photoluminescence properties of KMnF3:Yb,Er@ZnS nanocrystals show potential for ratiometric luminescence temperature sensing.

Carbon Dot Fluorescence-Lifetime-Encoded Anti-Counterfeiting.

Carbon dots (CDs) rank among the most promising luminescent nanomaterials for anti-counterfeiting application owing to their high fluorescence quantum yield and nontoxicity. Herein, we report a novel, high-level security performance anti-counterfeiting strategy achieved by fluorescence-lifetime-encoded CD fluorescent inks. CD-inks have identical steady-state emission properties, but they have distinctive and well-separated fluorescence lifetimes, allowing authentication of security tags using exclusively fluorescence lifetime imaging. A proof-of-concept anti-counterfeiting tag using CD-based lifetime-encoded inks is demonstrated. The developed CD lifetime-based anti-counterfeit technology is awaited to be applicable to a wide spectrum of security-protecting purposes. Furthermore, the presented method can be easily extended to integrate fluorescence-lifetime-encoded CDs in multichannel bioimaging, high-throughput flow cytometry, and optical data storage.

Graphitic Nitrogen Triggers Red Fluorescence in Carbon Dots.

Carbon dots (CDs) are a stable and highly biocompatible fluorescent material offering great application potential in cell labeling, optical imaging, LED diodes, and optoelectronic technologies. Because their emission wavelengths provide the best tissue penetration, red-emitting CDs are of particular interest for applications in biomedical technologies. Current synthetic strategies enabling red-shifted emission include increasing the CD particle size (sp2 domain) by a proper synthetic strategy and tuning the surface chemistry of CDs with suitable functional groups (e.g., carboxyl). Here we present an elegant route for preparing full-color CDs with well-controllable fluorescence at blue, green, yellow, or red wavelengths. The two-step procedure involves the synthesis of a full-color-emitting mixture of CDs from citric acid and urea in formamide followed by separation of the individual fluorescent fractions by column chromatography based on differences in CD charge. Red-emitting CDs, which had the most negative charge, were separated as the last fraction. The trend in the separation, surface charge, and red-shift of photoluminescence was caused by increasing amount of graphitic nitrogen in the CD structure, as was clearly proved by XPS, FT-IR, Raman spectroscopy, and DFT calculations. Importantly, graphitic nitrogen generates midgap states within the HOMO-LUMO gap of the undoped systems, resulting in significantly red-shifted light absorption that in turn gives rise to fluorescence at the low-energy end of the visible spectrum. The presented findings identify graphitic nitrogen as another crucial factor that can red-shift the CD photoluminescence.

Growth mechanism of strongly emitting CH3NH3PbBr3 perovskite nanocrystals with a tunable bandgap.

Metal halide perovskite nanocrystals are promising materials for a diverse range of applications, such as light-emitting devices and photodetectors. We demonstrate the bandgap tunability of strongly emitting CH3NH3PbBr3 nanocrystals synthesized at both room and elevated (60 °C) temperature through the variation of the precursor and ligand concentrations. We discuss in detail the role of two ligands, oleylamine and oleic acid, in terms of the coordination of the lead precursors and the nanocrystal surface. The growth mechanism of nanocrystals is elucidated by combining the experimental results with the principles of nucleation/growth models. The proposed formation mechanism of perovskite nanocrystals will be helpful for further studies in this field and can be used as a guide to improve the synthetic methods in the future.The development of perovskite nanocrystals is limited by poor mechanistic understanding of their growth. Here, the authors systematically study the ligand-assisted reprecipitation synthesis of CH3NH3PbBr3 nanocrystals, revealing the effect of precursor and ligand concentrations on bandgap tunability.

Carbon Dot Nanothermometry: Intracellular Photoluminescence Lifetime Thermal Sensing.

Nanoscale biocompatible photoluminescence (PL) thermometers that can be used to accurately and reliably monitor intracellular temperatures have many potential applications in biology and medicine. Ideally, such nanothermometers should be functional at physiological pH across a wide range of ionic strengths, probe concentrations, and local environments. Here, we show that water-soluble N,S-co-doped carbon dots (CDs) exhibit temperature-dependent photoluminescence lifetimes and can serve as highly sensitive and reliable intracellular nanothermometers. PL intensity measurements indicate that these CDs have many advantages over alternative semiconductor- and CD-based nanoscale temperature sensors. Importantly, their PL lifetimes remain constant over wide ranges of pH values (5-12), CD concentrations (1.5 × 10-5 to 0.5 mg/mL), and environmental ionic strengths (up to 0.7 mol·L-1 NaCl). Moreover, they are biocompatible and nontoxic, as demonstrated by cell viability and flow cytometry analyses using NIH/3T3 and HeLa cell lines. N,S-CD thermal sensors also exhibit good water dispersibility, superior photo- and thermostability, extraordinary environment and concentration independence, high storage stability, and reusability-their PL decay curves at temperatures between 15 and 45 °C remained unchanged over seven sequential experiments. In vitro PL lifetime-based temperature sensing performed with human cervical cancer HeLa cells demonstrated the great potential of these nanosensors in biomedicine. Overall, N,S-doped CDs exhibit excitation-independent emission with strongly temperature-dependent monoexponential decay, making them suitable for both in vitro and in vivo luminescence lifetime thermometry.

Self-Assembly of Electron Donor-Acceptor-Based Carbazole Derivatives: Novel Fluorescent Organic Nanoprobes for Both One- and Two-Photon Cellular Imaging.

In this study, we report fluorescent organic nanoprobes with intense blue, green, and orange-red emissions prepared by self-assembling three carbazole derivatives into nanorods/nanoparticles. The three compounds consist of two or four electron-donating carbazole groups linked to a central dicyanobenzene electron acceptor. Steric hindrance from the carbazole groups leads to noncoplanar 3D molecular structures favorable to fluorescence in the solid state, while the donor-acceptor structures endow the molecules with good two-photon excited emission properties. The fluorescent organic nanoprobes exhibit good water dispersibility, low cytotoxicity, superior resistance against photodegradation and photobleaching. Both one- and two-photon fluorescent imaging were shown in the A549 cell line. Two-photon fluorescence imaging with the fluorescent probes was demonstrated to be more effective in visualizing and distinguishing cellular details compared to conventional one-photon fluorescence imaging.

Impact of D2O/H2O Solvent Exchange on the Emission of HgTe and CdTe Quantum Dots: Polaron and Energy Transfer Effects.

We have studied light emission kinetics and analyzed carrier recombination channels in HgTe quantum dots that were initially grown in H2O. When the solvent is replaced by D2O, the nonradiative recombination rate changes highlight the role of the vibrational degrees of freedom in the medium surrounding the dots, including both solvent and ligands. The contributing energy loss mechanisms have been evaluated by developing quantitative models for the nonradiative recombination via (i) polaron states formed by strong coupling of ligand vibration modes to a surface trap state (nonresonant channel) and (ii) resonant energy transfer to vibration modes in the solvent. We conclude that channel (i) is more important than (ii) for HgTe dots in either solution. When some of these modes are removed from the relevant spectral range by the H2O to D2O replacement, the polaron effect becomes weaker and the nonradiative lifetime increases. Comparisons with CdTe quantum dots (QDs) served as a reference where the resonant energy loss (ii) a priori was not a factor, also confirmed by our experiments. The solvent exchange (H2O to D2O), however, is found to slightly increase the overall quantum yield of CdTe samples, probably by increasing the fraction of bright dots in the ensemble. The fundamental study reported here can serve as the foundation for the design and optimization principles of narrow bandgap quantum dots aimed at applications in long wavelength colloidal materials for infrared light emitting diodes and photodetectors.

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.

Efficient emission facilitated by multiple energy level transitions in uniform graphitic carbon nitride films deposited by thermal vapor condensation.

Graphitic carbon nitride (g-CN) films are important components of optoelectronic devices, but current techniques for their production, such as drop casting and spin coating, fail to deliver uniform and pinhole-free g-CN films on solid substrates. Here, versatile, cost-effective, and large-area growth of uniform and pinhole-free g-CN films is achieved by using a thermal vapor condensation method under atmospheric pressure. A comparison of the X-ray diffraction and Fourier transform infrared data with the calculated infrared spectrum confirmed the graphitic build-up of films composed of tri-s-triazine units. These g-CN films possess multiple active energy states including π*, π, and lone-pair states, which facilitate their efficient (6% quantum yield in the solid state) photoluminescence, as confirmed by both experimental measurements and theoretical calculations.

Carbon dot hybrids with oligomeric silsesquioxane: solid-state luminophores with high photoluminescence quantum yield and applicability in white light emitting devices.

We present a simple approach towards highly efficient solid-state luminophores with strong deep blue emission and a record high photoluminescence quantum yield of 60% by embedding water-soluble N,S-co-doped carbon dots into a polyhedral oligomeric silsesquioxane (POSS) matrix.

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.

Synthesis, solution-processed thin film transistors and solid solutions of silylethynylated diazatetracenes.

Silylethynylated diazatetracenes were synthesized in a more efficient way and applied as n-type semiconductors in solution-processed thin film transistors with an electron mobility of 0.65 cm(2) V(-1) s(-1). Co-crystallization of these diazatetracenes with silylethynylated tetracene resulted in solid solutions, which exhibited interesting electrical and optical properties.

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.