Thermally Activated Upconversion Near-Infrared Photoluminescence from Carbon Dots Synthesized via Microwave Assisted Exfoliation.

Upconversion near-infrared (NIR) fluorescent carbon dots (CDs) are important for imaging applications. Herein, thermally activated upconversion photoluminescence (UCPL) in the NIR region, with an emission peak at 784 nm, which appears under 808 nm continuous-wave laser excitation, are realized in the NIR absorbing/emissive CDs (NIR-CDs). The NIR-CDs are synthesized by microwave-assisted exfoliation of red emissive CDs in dimethylformamide, and feature single or few-layered graphene-like cores. This structure provides an enhanced contact area of the graphene-like plates in the core with the electron-acceptor carbonyl groups in dimethylformamide, which contributes to the main NIR absorption band peaked at 724 nm and a tail band in 800-850 nm. Temperature-dependent photoluminescence spectra and transient absorption spectra confirm that the UCPL of NIR-CDs is due to the thermally activated electron transitions in the excited state, rather than the multiphoton absorption process. Temperature dependent upconversion NIR luminescence imaging is demonstrated for NIR-CDs embedded in a polyvinyl pyrrolidone film, and the NIR upconversion luminescence imaging in vivo using NIR-CDs in a mouse model is accomplished.

Doping Lanthanide into Perovskite Nanocrystals: Highly Improved and Expanded Optical Properties.

Cesium lead halide (CsPbX3) perovskite nanocrystals (NCs) have demonstrated extremely excellent optical properties and great application potentials in various optoelectronic devices. However, because of the anion exchange, it is difficult to achieve white-light and multicolor emission for practical applications. Herein, we present the successful doping of various lanthanide ions (Ce3+, Sm3+, Eu3+, Tb3+, Dy3+, Er3+, and Yb3+) into the lattices of CsPbCl3 perovskite NCs through a modified hot-injection method. For the lanthanide ions doped perovskite NCs, high photoluminescence quantum yield (QY) and stable and widely tunable multicolor emissions spanning from visible to near-infrared (NIR) regions are successfully obtained. This work indicates that the doped perovskite NCs will inherit most of the unique optical properties of lanthanide ions and deliver them to the perovskite NC host, thus endowing the family of perovskite materials with excellent optical, electric, or magnetic properties.

Electrostatic Assembly Guided Synthesis of Highly Luminescent Carbon-Nanodots@BaSO4 Hybrid Phosphors with Improved Stability.

Carbon nanodots (CNDs)@BaSO4 hybrid phosphors are fabricated in an easy and low-cost process by sequentially assembling Ba2+ and SO42- ions onto the surface of carbon nanodots through electrostatic attraction. CNDs act as the nucleus to attract these reactive ions and provide the luminescent centers in the hybrid phosphors. This strategy is versatile for a variety of negatively charged CNDs with different emission colors. The advantage of the resultant hybrid phosphors is that their luminescence exhibits excellent thermal and photostability, as well as remarkable resistance to strong acid/alkali and common organic solvents. These merits allow for the fabrication of CNDs-based light-emitting diodes using the CNDs@BaSO4 hybrid phosphors as a color conversion layer.

Plasmonic Ag@oxide nanoprisms for enhanced performance of organic solar cells.

Localized surface plasmon resonance (LSPR), light scattering, and lowering the series resistance of noble metal nanoparticles (NPs) provide positive effect on the performance of photovoltaic device. However, the exciton recombination on the noble metal NPs accompanying above influences will deteriorate the performance of device. In this report, surface-modified Ag@oxide (TiO2 or SiO2 ) nanoprisms with 1-2 nm shell thickness are developed. The thin film composed of P3HT/Ag@oxides and P3HT:PCBM/Ag@oxides is investigated by absorption, photoluminescence (PL), and transient absorption spectroscopy. The results show a significant absorption, PL enhancement, and long-lived photogenerated polaron in the P3HT/Ag@TiO2 film, indicating the increase of photogenerated exciton population by LSPR of Ag nanoprisms. In the case of P3HT/Ag nanoprisms, partial PL quench and relatively short-lived photogenerated polaron are observed. That indicates that the oxides layer can effectively avoid the exciton recombination. When the Ag@oxide nanoprisms are introduced into the active layer of P3HT:PCBM photovoltaic devices, about 31% of power conversion efficiency enhancement is obtained relative to the reference cell. All these results indicate that Ag@oxides can enhance the performance of the cell, at the same time the ultrathin oxide shell prevents from the exciton recombination.

Towards the design of efficient quantum dot light-emitting diodes by controlling the exciton lifetime.

Time-resolved photoluminescence and electroluminescence measurements were used to explore the emission characteristics of excitons in quantum dot light-emitting diodes (QD-LEDs). It is found that the lifetime of excitons in the QDs can be varied by adjusting the distance between the excitons and metal Al mirror, which is due to the effect of local density of optical states (LDOS) on the exciton decay rate. QD-LEDs with different hole transport layer (HTL) thickness, i.e., different distance between QDs and Al reflective anode, have been fabricated and it is found that the HTL thickness affects the device efficiency performance greatly, and the optimal HTL thickness for the red QD-LED (emission peak is at 621 nm) is 80 nm. These results shed light on the factors affecting the efficiency and efficiency roll-off in QD-LEDs, thus may provide a clue for high performance QD-LEDs.

Photocarrier recombination dynamics in ternary chalcogenide CuInS2 quantum dots.

Photocarrier recombination dynamics in ternary chalcogenide CuInS2 quantum dots (CIS QDs) was studied by means of femtosecond transient-absorption (TA) and nanosecond time-resolved photoluminescence (PL) spectroscopy. Under strong excitation, the TA dynamics in CIS QDs is well described by a simple rate equation including single-carrier trapping, free-to-bound recombination, and trap-assisted Auger recombination. Under weak excitation, on the other hand, the PL decays of the QDs are composed of a short-lived component caused by surface trapping and a long-lived one caused by free-to-bound recombination. It is found that the surface trapping accelerates markedly with decreasing QD size while the free-to-bound radiative recombination hardly depends on the QD size. Besides this, we observed both a decrease in the PL lifetimes and a dynamic spectral redshift, which are attributed to the surface trapping and the coexistent inhomogeneous broadening in CIS QDs. The spectral redshift becomes less pronounced in CIS/ZnS core/shell QDs because of the suppression of the fast nonradiative recombination caused by the passivation of the surface traps. These results give clear evidence that the free-to-bound model is appropriate for interpreting the optical properties of CIS QDs.

Towards efficient photoinduced charge separation in carbon nanodots and TiO2 composites in the visible region.

In this work, photoinduced charge separation behaviors in non-long-chain-molecule-functionalized carbon nanodots (CDs) with visible intrinsic absorption (CDs-V) and TiO2 composites were investigated. Efficient photoinduced electron injection from CDs-V to TiO2 with a rate of 8.8 × 10(8) s(-1) and efficiency of 91% was achieved in the CDs-V/TiO2 composites. The CDs-V/TiO2 composites exhibited excellent photocatalytic activity under visible light irradiation, superior to pure TiO2 and the CDs with the main absorption band in the ultraviolet region and TiO2 composites, which indicated that visible photoinduced electrons and holes in such CDs-V/TiO2 composites could be effectively separated. The incident photon-to-current conversion efficiency (IPCE) results for the CD-sensitized TiO2 solar cells also agreed with efficient photoinduced charge separation between CDs-V and the TiO2 electrode in the visible range. These results demonstrate that non-long-chain-molecule-functionlized CDs with a visible intrinsic absorption band could be appropriate candidates for photosensitizers and offer a new possibility for the development of a well performing CD-based photovoltaic system.

Efficient inverted quantum-dot light-emitting devices with TiO2/ZnO bilayer as the electron contact layer.

We have demonstrated an efficient inverted CdSe/CdS/ZnS core/shell quantum-dot light-emitting device (QD-LED) using a solution-processed sol-gel TiO2 and ZnO nanoparticle composite layer as an electron-injection layer with controllable morphology and investigated the electroluminescence mechanism. The introduction of the ZnO layer can lead to the formation of spin-coated uniform QD films and fabrication of high-luminance QD-LEDs. The TiO2 layer improves the balance of charge injection due to its lower electron mobility relative to the ZnO layer. These results offer a practicable platform for the realization of a trade-off between the luminance and efficiency in the inverted QD-LEDs with TiO2/ZnO composites as the electron contact layer.

Efficient white light emitting diodes based on Cu-doped ZnInS/ZnS core/shell quantum dots.

We report the fabrication of efficient white light-emitting diodes (WLEDs) based on Cu : ZnInS/ZnS core/shell quantum dots (QDs) with super large Stokes shifts. The composition-controllable Cu : ZnInS/ZnS QDs with a tunable emission from deep red to green were prepared by a one-pot noninjection synthetic approach. The high performance Cu : ZnInS QD-WLEDs with the colour rendering index up to 96, luminous efficacy of 70-78 lm W(-1), and colour temperature of 3800-5760 K were successfully fabricated by integration of red and green Cu-doped QDs. Negligible energy transfer between Cu-doped QDs was clearly found by measuring the photoluminescence lifetimes of the QDs, consistent with the small spectral overlap between QD emission and absorption. The experimental results indicated low toxic Cu : ZnInS/ZnS QDs could be suitable for solid state lighting.

Making Patterned Single Defects in MoS2 Thermally with the MoS2/Au Moiré Interface.

Normally, it is hard to regulate thermal defects precisely in their host lattice due to the stochastic nature of thermal activation. Here, we demonstrate a thermal annealing way to create patterned single sulfur vacancy (VS) defects in monolayer molybdenum disulfide (MoS2) with about 2 nm separations at subnanometer accuracy. Theoretically, we reveal that the S-Au interface coupling reduces the energy barriers in forming VS defects and that explains the overwhelming formation of interface VS defects. We also discover a phonon regulation mechanism by the moiré interface that effectively condenses the Γ-point out-of-plane acoustic phonons of monolayer MoS2 to its TOP moiré sites, which has been proposed to trigger moiré-patterned thermal VS formation. The high-throughput nanoscale patterned defects presented here may contribute to building scalable defect-based quantum systems.

Evolution of the Electronic Properties of Tellurium Crystals with Plasma Irradiation Treatment.

Tellurium exhibits exceptional intrinsic electronic properties. However, investigations into the modulation of tellurium's electronic properties through physical modification are notably scarce. Here, we present a comprehensive study focused on the evolution of the electronic properties of tellurium crystal flakes under plasma irradiation treatment by employing conductive atomic force microscopy and Raman spectroscopy. The plasma-treated tellurium experienced a process of defect generation through lattice breaking. Prior to the degradation of electronic transport performance due to plasma irradiation treatment, we made a remarkable observation: in the low-energy region of hydrogen plasma-treated tellurium, a notable enhancement in conductivity was unexpectedly detected. The mechanism underlying this enhancement in electronic transport performance was thoroughly elucidated by comparing it with the electronic structure induced by argon plasma irradiation. This study not only fundamentally uncovers the effects of plasma irradiation on tellurium crystal flakes but also unearths an unprecedented trend of enhanced electronic transport performance at low irradiation energies when utilizing hydrogen plasma. This abnormal trend bears significant implications for guiding the prospective application of tellurium-based 2D materials in the realm of electronic devices.

Cadmium-free quantum dot light emitting devices: energy-transfer realizing pure blue emission.

In this study, deep blue, pure electroluminescence (EL) at 441.5 nm from a ZnSe/ZnS quantum dot light-emitting device (QD-LED) is obtained by using poly (4-butylphenyl-diphenyl-amine) (poly-TPD) as the hole-transport layer (HTL) to open up the channel for energy transfer from poly-TPD to QDs. The emission originating from HTL is observed in the QD-LED with N,N'-bis (tolyl)-N,N'-diphenyl-1,1'-biphenyl-4,4'-diamine functionalized with two styryl groups (2-TPD) as the HTL due to inefficient energy-transfer from 2-TPD to QDs. The poly-TPD based device exhibits color-saturated blue emission with a narrow spectral bandwidth of full width at half maximum (~17.2 nm). These results explore the operating mechanism of the QD EL and signify a remarkable progress in deep blue QD-LEDs based on environmental-friendly QD materials.

Efficient full-color emitting carbon-dot-based composite phosphors by chemical dispersion.

Realizing full-color emission plays a key role in exploring the luminescence mechanisms of carbon dots (CDots) and promoting the applications of CDots in light-emitting diodes (LEDs). Herein, a synthesis strategy for full-color emitting CDots was developed through the solvothermal reaction of citric acid and urea with a constant mass ratio but varying reactant concentrations in solvent. With the reactant concentrations increasing, a dual regulation mechanism including an enhanced nucleation growth process and subsequently increased C[double bond, length as m-dash]O/C[double bond, length as m-dash]N-related surface states should be responsible for the photoluminescence (PL) shift of CDots from blue to red. Relying on the hydrolyzation and condensation processes of 3-aminopropyltrimethoxysilane, a simple and universal method was developed by chemically dispersing the CDots into a cross-linked silica network on the surface of SiO2 nanoparticles to produce efficient full-color emitting SiO2/CDot composite phosphors with considerable PL quantum yields in the range of 30-60%. It was proved that the full-color emitting SiO2/CDot composite phosphors could be flexibly applied in packaging white LEDs, releasing pure white light at the Commission Internationale de L'Eclairage (CIE) coordinates of (0.33, 0.33) with a color rendering index (CRI) of 80.4 and a high color-rendering white light coming entirely from CDots with the CIE coordinates of (0.34, 0.36) and a CRI of 97.4, indicating promising application of the full-color emitting SiO2/CDot composite phosphors in the LED field.

[Effect of hole transporting materials on photoluminescence of CdSe core/shell quantum dots].

Photoluminescence quenching of colloidal CdSe core/shell quantum dots in the presence of hole transporting materials was studied by means of steady state and time resolved photoluminescence spectroscopy. With increasing hole transporting materials concentration in the CdSe core/shell quantum dot solution, the photoluminescence intensity and lifetime decreased gradually. The photoluminescence quenching of CdSe/ZnSe quantum dots with adding hole transporting material N,N'-bis(1-naphthyl)-N, N'-diphenyl-1,1 '-biphenyl-4, 4'-diamine (NPB) is more efficient than N,N'-diphenyl-N, N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD). And compared with CdSe core/shell quantum dots with ZnSe shell, the ZnS shell is an effective one on the surface of CdSe quantum dots for reducing photoluminescence quenching efficiency when interacting with hole transporting material TPD. Based on the analysis, there are two pathways in the photoluminescence quenching process: static quenching and dynamic quenching. The static quenching results from the decrease in the number of the emitting centers, and the dynamic quenching is caused by the hole transfer from quantum dots to hole transporting materials molecules. The efficiency of the photoluminescence quenching in CdSe core/shell quantum dots is strongly dependent on the structure of the shells and the HOMO levels of the hole transporting materials. The results are important for understanding the nature of quantum dots surface and the interaction of quantum dots and hole transporting materials.

Synthesis of green emissive carbon dots@montmorillonite composites and their application for fabrication of light-emitting diodes and latent fingerprints markers.

Multifunctional solid-state luminescent materials are strongly desired in a wide variety of applications. In this work, green emissive carbon dots@montmorillonite (g-CDs@MMT) composites were synthesized based on green emissive carbon dots and MMT clays in a convenient method by embedding g-CDs into the MMT clays. Due to the confinement of g-CDs in the layered structure of the MMT clay matrix, g-CDs are uniformly dispersed in the resulting g-CDs@MMT solid-state composites. This efficiently prevents the aggregation-induced solid-state luminescence quenching of g-CDs, and a photoluminescence quantum yield of 11% could be achieved by the g-CDs@MMT composites under a 405 nm light. Additionally, the g-CDs@MMT composites exhibit low-toxicity, excellent thermal stability, photostability, resistance to organic solvents, and a small particle size. All of these advantages enable applications in fabricating white light-emitting diodes with different color temperatures, where the g-CDs@MMT composites are applied as the color conversion layer. Furthermore, by using the g-CDs@MMT composites as a fluorescence labeling marker, the latent fingerprint detection on a variety of object surfaces could be realized.

Carbon dots produced via space-confined vacuum heating: maintaining efficient luminescence in both dispersed and aggregated states.

Aggregation-induced quenching (AIQ) of emission is an obstacle for the development of carbon dots (CDots) for solid-state luminescent devices. In this work, we introduce a method to avoid AIQ and to produce highly luminescent CDots through a space-confined vacuum heating synthesis. In the presence of CaCl2, a mixture of citric acid and urea forms an inflated foam under vacuum heating at 120 °C. Upon gradually increasing the heating temperature to 250 °C, blue emissive molecular species are first formed, and are then transformed into uniform-sized green emissive CDots through dehydration and carbonization processes taking place in the confined ultrathin spaces of the foam walls. The green luminescence of these CDots originates from conjugated sp2 domains, and these CDots exhibit a high photoluminescence quantum yield (PLQY) of 72% in ethanol solution. Remarkably, due to the existence of only one type of recombination center in these nanoparticles, AIQ does not take place in CDot-based close-packed films, which show strong emission with a PLQY of 65%. Utilizing the differences in the emission properties of vacuum heating produced CDots, CDots synthesized through microwave-assisted heating, and commercial green fluorescent organic ink (namely, excitation-dependent vs. excitation-independent emission, and different stability against photobleaching), multilevel data encryption has been demonstrated.

Surface related intrinsic luminescence from carbon nanodots: solvent dependent piezochromism.

There has been a long standing debate on the luminescence origination from carbon nanodots (CDs). Herein, we report the solvent dependent piezochromism of CDs by diamond anvil cells experiment. Red- and blue-shift piezochromism were observed in CDs with N,N-dimethylformamide and water as pressure transmitting medium (PTM) with increasing pressure from atmospheric pressure to 25 GPa, which were related to increased π-π stacking and protic-solvent-induced surface chemical structural changes, respectively. Based on theoretical modeling and structural analysis of hydrothermally treated CDs (h-CDs), the reversible and irreversible piezochromism from green emission to blue emission with water as PTM was attributed to pressure induced enhanced intermolecular hydrogen bonding and addition reaction between water molecules and surface electron withdrawing groups on the CDs, respectively. The decreased electron withdrawing ability of the surface chemical structures of CDs further affects their intrinsic luminescence. This work provides a new understanding of the piezochromic luminescence origination from CDs, which is related to the surface related intrinsic luminescence.

Efficient Red/Near-Infrared-Emissive Carbon Nanodots with Multiphoton Excited Upconversion Fluorescence.

Red/near-infrared (NIR) emissive carbon nanodots (CNDs) with photoluminescence (PL) quantum yield (QY) of 57% are prepared via an in situ solvent-free carbonization strategy for the first time. 1-Photon and 2-photon cellular imaging is demonstrated by using the CNDs as red/NIR fluorescence agent due to the high PL QY and low biotoxicity. Further study shows that the red/NIR CNDs exhibit multiphoton excited (MPE) upconversion fluorescence under excitation of 800-2000 nm, which involves three NIR windows (NIR-I, 650-950 nm; NIR-II, 1100-1350; NIR-III, 1600-1870 nm). 2-Photon, 3-photon, and 4-photon excited fluorescence of the CNDs under excitation of different wavelengths is achieved. This study develops an in situ solvent-free carbonization method for efficient red/NIR emissive CNDs with MPE upconversion fluorescence, which may push forward the application of the CNDs in bioimaging.

Red carbon dots-based phosphors for white light-emitting diodes with color rendering index of 92.

Exploration of solid-state efficient red emissive carbon dots (CDs) phosphors is strongly desired for the development of high performance CDs-based white light-emitting diodes (WLEDs). In this work, enhanced red emissive CDs-based phosphors with photoluminescence quantum yields (PLQYs) of 25% were prepared by embedding red emissive CDs (PLQYs of 23%) into polyvinyl pyrrolidone (PVP). Because of the protection of PVP, the phosphors could preserve strong luminescence under long-term UV excitation or being mixed with conventional packaging materials. By applying the red emissive phosphors as the color conversion layer, WLEDs with high color rendering index of 92 and color coordinate of (0.33, 0.33) are fabricated.

Microwave-Assisted Heating Method toward Multicolor Quantum Dot-Based Phosphors with Much Improved Luminescence.

Solid-state highly photoluminescent quantum dot (QD)-based phosphors attract great scientific interests as color converters because of an increasing demand for white-light-emitting devices. Herein, a microwave-assisted heating method is presented to fabricate multicolor QD-based phosphors within 30 s through microwave-assisted heating of the mixture of QDs and sodium silicate aqueous solution. In the composites, the formed cross-linked networks not only play as a matrix to prevent QD aggregation in solid state but also cause the variation of the refractive index around QDs and the QD surface optimization, which contributes to good stabilities and twice enhancement in photoluminescence quantum yields (69%) compared with the initial QD aqueous solution (33%). Using the QD-based phosphors as color conversion layers, white-light-emitting diodes were realized with controllable color temperature, high color purity, and high color-rendering index (90.3), which show a great potential in display and illumination. Furthermore, the luminescence lifetime of the QD-based phosphors is less than 25 ns. The potential application of the QD-based phosphors in visible light communication was also demonstrated, with the modulation bandwidth achieving 42 MHz.