Ultra-Confined Visible-Light-Emitting Colloidal Indium Arsenide Quantum Dots.

Indium arsenide quantum dots, which typically emit in the near-infrared, have been utilized in various optoelectronics and biomedical applications, such as covert illumination, optical communication, and deep-tissue imaging. While theory predicts that further quantum confinement through size reduction could enable visible light emission, systems with larger optical bandgaps have not been realized. Here, we report a method of preparing highly luminescent, visible-light-emitting In(Zn)As/ZnSe/ZnS QD, using a low-temperature nanocluster synthesis approach. Each QD contains an ultraconfined In(Zn)As nanocluster and fluoresces at tunable wavelengths between 538 and 640 nm with a high photoluminescence quantum efficiency of 58%. We confirm, through DFT and spectroscopic analysis, that the strong confinement effects in the few-atom-wide In(Zn)As nanoclusters are responsible for the significant spectral shift from the near-infrared to the visible region. These findings suggest that broader-than-expected optical tuning may now be achievable in other quantum-confined semiconductor systems, which could lead to a wider scope of functional applications in optoelectronics.

Efficient light-emitting diodes based on nanocrystalline perovskite in a dielectric polymer matrix.

Electroluminescence in light-emitting devices relies on the encounter and radiative recombination of electrons and holes in the emissive layer. In organometal halide perovskite light-emitting diodes, poor film formation creates electrical shunting paths, where injected charge carriers bypass the perovskite emitter, leading to a loss in electroluminescence yield. Here, we report a solution-processing method to block electrical shunts and thereby enhance electroluminescence quantum efficiency in perovskite devices. In this method, a blend of perovskite and a polyimide precursor dielectric (PIP) is solution-deposited to form perovskite nanocrystals in a thin-film matrix of PIP. The PIP forms a pinhole-free charge-blocking layer, while still allowing the embedded perovskite crystals to form electrical contact with the electron- and hole-injection layers. This modified structure reduces nonradiative current losses and improves quantum efficiency by 2 orders of magnitude, giving an external quantum efficiency of 1.2%. This simple technique provides an alternative route to circumvent film formation problems in perovskite optoelectronics and offers the possibility of flexible and high-performance light-emitting displays.

Non-Toxic CuInS2 /ZnS Colloidal Quantum Dots for Near-Infrared Light-Emitting Diodes.

Ternary CuInS2 quantum dots (QDs) with photoluminescence that is tunable from the visible to the near-infrared (NIR) region are promising light-emitters for consumer electronics due to the absence of toxic elements such as Pb, Cd, or As. Despite the compelling performance of visible-light-emitting CuInS2 QDs, reports on NIR emission remain limited, with modest efficiencies at wavelengths beyond 900 nm. In this work, the facile synthesis of NIR-emitting CuInS2 /ZnS QDs is reported. A combination of two sulfur precursors w as used in the synthesis, comprising 1-dodecanethiol (DDT) and hexamethyldisilathiane (HMDS). The reactive HMDS facilitates faster nucleation and leads to a higher density of emissive Cu-deficiency sites. The resulting QDs exhibit high photoluminescence quantum efficiency (PLQE) of 65% at a long emission wavelength of 920 nm. Using these QDs, NIR light-emitting diodes (LED) are fabricated, which attain an external quantum efficiency (EQE) of 8.2%. This efficiency is comparable to the best reported PbS and InAs QD LEDs, and the emission wavelength exceeds that of lead iodide perovskites. This work thus marks one of the first reports of efficient NIR LEDs based on environmentally benign CuInS2 QDs and may open up promising new applications in consumer electronic products.

Efficient Short-Wave Infrared Light-Emitting Diodes Based on Heavy-Metal-Free Quantum Dots.

Short-wave infrared (SWIR) light emission is important for a diverse range of modern applications, such as eye-safe depth sensing, light detection and ranging (LiDAR), facial recognition, eye tracking, optical communication, and health-monitoring technologies. However, there are a very limited number of known semiconductors that can emit efficiently in the SWIR spectral range. Presently, SWIR light-emitting diodes (LEDs) based on colloidal quantum dots (CQD) are dominated by lead chalcogenide systems, despite the presence of heavy metal and modest efficiencies. Here, a highly efficient SWIR LED based on heavy-metal-free indium arsenide (InAs) core-shell CQDs is presented. In the LED design, the implementation of an otherwise hole-transporting poly(vinylcarbazole) (PVK) layer on the electron-injecting side of the device stack leads to a surprising enhancement in device performance, giving remarkably high external quantum efficiencies (EQEs) of 13.3% at 1006 nm. Single-carrier device and optical investigations reveal the origins of enhancement to be the electronic decoupling of the CQD layer with the electron-injecting zinc oxide (ZnO) layer, which mitigates luminescence quenching and improves charge balance. This work marks one of the highest efficiencies reported for heavy-metal-free solution-processed LEDs in the SWIR spectral region, and can find significant applications in emerging consumer electronic technologies.

Tuning the Emission Wavelength of Lead Halide Perovskite NCs via Size and Shape Control.

The advent of lead halide perovskite nanocrystals (NCs), which are easily synthesized, ultralow-cost materials and have an impeccable luminous efficiency, has drastically changed the future perspective of semiconductor quantum dot devices. Although the band gap energy of lead perovskite NCs can be tuned by the halide composition, the instability problem prevails for mixed-halide perovskite NCs, caused by phase segregation due to ion migration when an external electric field or light is applied. To avoid this problem and obtain the stable emission of RGB primary colors, in this study, two synthesis pathways of pure-halide perovskite NCs are proposed. One approach is the modified hot injection method with "centrifugation of a frozen eutectic mixture" to separate small NCs efficiently, and the other is the "low-temperature mixing and heat-up method" for target materials including CsPbI3, CsPbBr3, and CH(NH2)2PbBr3 (FAPbBr3). The emission wavelength of FAPbBr3 is tuned ion-stoichiometrically, unlike Cs perovskites. These various synthesis pathways of pure-halide perovskite NCs enable the efficient production of high-quality perovskite NCs and allow precise tuning of the emission color to the desired wavelength. Although there are still several "gaps" remaining in the available emission wavelength, the new methodology proposed in this study could potentially be employed for manufacturing more stable perovskite NC-based optoelectronic devices.

Impact of the Structural Modification of Diamondoid Cd(II) MOFs on the Nonlinear Optical Properties.

A change in the degree of interpenetration (DOI) in metal-organic frameworks (MOFs) prompted by heat, pressure, or exchange of solvents is a fascinating phenomenon that can potentially impact the functional properties of MOFs. Structural transformation involving two noncentrosymmetric MOFs with different DOIs provides a rare opportunity to manipulate their optical properties. Herein, we report an unusual single-crystal-to-single-crystal (SCSC) transformation of a noncentrosymmetric 7-fold interpenetrated diamondoid (dia) Cd(II) MOF into another noncentrosymmetric but 8-fold interpenetrated dia MOF upon the removal of guest solvents. A hydrogen-bond network formed between the lattice solvents and linker trans-2-(4-pyridyl)-4-vinylbenzoate (pvb) in a 7-fold interpenetrated noncentrosymmetric MOF results in a significant increase in the two-photon absorption cross-section (11 times) as compared to that in the desolvated 8-fold interpenetrated MOF. Also, an increase in the DOI in the noncentrosymmetric crystals strengthened the π···π interaction between the individual diamondoid networks and enhanced the second-order nonlinear optical (NLO) coefficient (deff) by 4.5 times. These results provide a way to manipulate the optical properties of MOFs using a combined strategy of the formation of hydrogen bonds and interpenetration for access to tunable single-crystal NLO devices in an SCSC manner. By changing the experimental conditions, another dia Cd(II) MOF with 4-fold interpenetration can be isolated. In this centrosymmetric MOF, the olefin groups in the backbone of the ligand (pvb) undergo a [2 + 2] cycloaddition reaction quantitatively under UV light but in a non-SCSC fashion.

Transparent near-infrared perovskite light-emitting diodes.

Mobile and wearable devices are increasingly reliant on near-infrared (NIR) covert illumination for facial recognition, eye-tracking or motion and depth sensing functions. However, these small devices offer limited spatial real estate that is typically already occupied by their full-area electronic color displays. Here, we report a transparent perovskite light-emitting diode (LED) that could be overlaid across a color display to provide an efficient and high-intensity NIR illumination. Our transparent devices are constructed with an ITO/AZO/PEIE/FAPbI3/poly-TPD/MoO3/Al/ITO/Ag/ITO architecture, and offer a high average transmittance of more than 55% across the visible spectral region. In particular, our Al/ITO/Ag/ITO top transparent electrode was designed to offer a combination low sheet resistance and low plasma damage upon electrode deposition. The devices emit at 799 nm with a high total external quantum efficiency of 5.7% at a current density of 5.3 mA cm-2 and a high radiance of 1.5 W sr-1 m-2, and possess a large functional device area of 120 mm2. The efficient performance is ideal for battery-powered wearable devices, and could enable advanced security and sensing features on future smart-watches, phones, gaming consoles and augmented or virtual reality headsets.

Thermodynamic Control in the Synthesis of Quantum-Confined Blue-Emitting CsPbBr3 Perovskite Nanostrips.

Size control is critical in the synthesis of quantum-confined semiconductor nanocrystals, otherwise known as quantum dots. The achievement of size-uniformity and narrow spectral line-width in quantum dots conventionally relies on a very precise kinetic control of the reactions, where reaction time plays a significant role in defining the final crystal sizes and distribution. Here, we show that synthesis of quantum-confined perovskite nanostrips could be achieved through a thermodynamically controlled reaction, using a low-temperature and ligand-rich approach. The nanostrip growth proceeds through an initial one-dimensional (1D) nanorod stage, followed by the lateral widening of the rod to form a two-dimensional (2D) nanostrip. The spectral characteristics of the final product remain unchanged after prolonged reaction, indicating no signs of crystal ripening and confirming the thermodynamic nature of this reaction. The CsPbBr3 perovskite nanostrips were highly uniform and emit at a deep-blue wavelength of 462 nm with a remarkably narrow line-width of 13 nm. This corresponds to color coordinates of (0.136, 0.049) on the CIE 1931 color space, which fulfils the stringent Rec. 2020 standard for next-generation color displays. The well-passivated nanostrips also possess negligible defects and provide a near-unity photoluminescence quantum yield at 94%. Crucially, the achievement of blue emission through a pure-halide perovskite circumvents the problems of spectral instability that are frequently experienced in mixed-halide perovskite systems. The convenience and scalability of our thermodynamic approach, coupled with the excellent optical attributes, would likely enable these quantum-confined perovskite systems to be the preferred method toward color control in trichromatic display applications.

Color Patterning of Luminescent Perovskites via Light-Mediated Halide Exchange with Haloalkanes.

Lead halide perovskite possesses a semiconductor bandgap that is readily tunable by a variation in its halide composition. Here, a photo-activated halide exchange process between perovskite nanocrystals and molecular haloalkanes is reported, which enables the perovskite luminescence to be controllably shifted across the entire visible spectrum. Mechanistic investigations reveal a mutual exchange of halogens between the perovskite crystal surface and a chemisorbed haloalkane, yielding nanocrystals and haloalkanes with mixed halide contents. Exchange kinetics studies involving primary, secondary, and tertiary haloalkanes show that the rate of reaction is governed by the activation barrier in the breakage of the covalent carbon-halogen (CX) bond, which is a function of the CX bond energy and carbon radical stability. Employing this halide exchange approach, a micrometer-scale trichromatic patterning of perovskites is demonstrated using a light-source-integrated inkjet printer and tertiary haloalkanes as color-conversion inks. The haloalkanes volatilize after halide exchange and leave no residues, thereby offering significant processing advantage over conventional salt-based exchange techniques. Beyond the possible applications in new-generation micro-LED and electroluminescent quantum dot displays, this work exemplifies the rich surface and photochemistry of perovskite nanocrystals, and could lead to further opportunities in perovskite-based photocatalysis and photochemical sensing.

Magneto-Fluorescent Perovskite Nanocomposites for Directed Cell Motion and Imaging.

The ability for a magnetic field to penetrate biological tissues without attenuation has led to significant interest in the use of magnetic nanoparticles for biomedical applications. In particular, active research is ongoing in the areas of magnetically guided drug delivery and magnetic hyperthermia treatment. However, the difficulties in tracing these optically nonactive magnetic nanoparticles hinder their usage in medical research or treatment. Here, a new perovskite-based magneto-fluorescent nanocomposite that allows the in situ, real-time optical visualization of magnetically induced cellular movements is reported. A swelling-deswelling technique is employed to capture a cesium lead halide perovskite and magnetite nanoparticles within a biocompatible polyvinylpyrrolidone matrix, to produce a water-dispersible composite that possesses a combination of strong magnetic response and intense fluorescence. The wavelength-tunability of perovskite nanocrystals is taken advantage of to demonstrate simultaneous multicolor fluorescent tagging of cancer stem cells. The magneto-directed motion of the cancer stem cells through a microfluidic channel is also imaged as a proof-of-concept toward an optically traceable magnetic manipulation of biological systems. These dual-functional nanocomposites could find promising applications in advanced biotechnologies, such as in optogenetics, cellular separation, and drug delivery studies.

Perovskite-Initiated Photopolymerization for Singly Dispersed Luminescent Nanocomposites.

Metal halide perovskites have demonstrated rich photophysics and remarkable potential in photovoltaic and electroluminescent devices. However, the photoactivity of perovskite semiconductors in chemical processes remains relatively unexplored. Here, a general approach toward the synthesis of luminescent perovskite-polymer nanocomposites is reported, whereby perovskite nanocrystals are used as photoinitiators in the polymerization of vinyl monomers. The white-light illumination of a perovskite-monomer mixture triggers a free-radical chain-growth polymerization process, giving rise to high molecular weight polymers of ≈200 kDa. The in situ growth of polymer chains from the perovskite crystal surface allows the formation of individually dispersed nanocrystal cores within an encapsulating polymer matrix, and leads to a significant threefold enhancement in photoluminescence quantum yield. This photoluminescence enhancement is attributed to the spatial separation of the perovskite nanocrystals and hence the deactivation of energy transfer to dark crystals. The resulting perovskite-polymer nanocomposites exhibit excellent stability against moisture and are shown to be useful as functional downconversion phosphor films for luminescent displays and lighting.

Tunable Near-Infrared Luminescence in Tin Halide Perovskite Devices.

Infrared emitters are reasonably rare in solution-processed materials. Recently, research into hybrid organo-lead halide perovskite, originally popular in photovoltaics,1-3 has gained traction in light-emitting diodes (LED) due to their low-cost solution processing and good performance.4-9 The lead-based electroluminescent materials show strong colorful emission in the visible region, but lack emissive variants further in the infrared. The concerns with the toxicity of lead may, additionally, limit their wide-scale applications. Here, we demonstrate tunable near-infrared electroluminescence from a lead-free organo-tin halide perovskite, using an ITO/PEDOT:PSS/CH3NH3Sn(Br1-xIx)3/F8/Ca/Ag device architecture. In our tin iodide (CH3NH3SnI3) LEDs, we achieved a 945 nm near-infrared emission with a radiance of 3.4 W sr(-1) m(-2) and a maximum external quantum efficiency of 0.72%, comparable with earlier lead-based devices. Increasing the bromide content in these tin perovskite devices widens the semiconductor bandgap and leads to shorter wavelength emissions, tunable down to 667 nm. These near-infrared LEDs could find useful applications in a range of optical communication, sensing and medical device applications.

Highly Efficient Perovskite Nanocrystal Light-Emitting Diodes Enabled by a Universal Crosslinking Method.

The preparation of highly efficient perovskite nanocrystal light-emitting diodes is shown. A new trimethylaluminum vapor-based crosslinking method to render the nanocrystal films insoluble is applied. The resulting near-complete nanocrystal film coverage, coupled with the natural confinement of injected charges within the perovskite crystals, facilitates electron-hole capture and give rise to a remarkable electroluminescence yield of 5.7%.

Size-Dependent Photon Emission from Organometal Halide Perovskite Nanocrystals Embedded in an Organic Matrix.

In recent years, organometal halide perovskite materials have attracted significant research interest in the field of optoelectronics. Here, we introduce a simple and low-temperature route for the formation of self-assembled perovskite nanocrystals in a solid organic matrix. We demonstrate that the size and photoluminescence peak of the perovskite nanocrystals can be tuned by varying the concentration of perovskite in the matrix material. The physical origin of the blue shift of the perovskite nanocrystals' emission compared to its bulk phase is also discussed.

Enhanced performance in fluorene-free organometal halide perovskite light-emitting diodes using tunable, low electron affinity oxide electron injectors.

Fluorene-free perovskite light-emitting diodes (LEDs) with low turn-on voltages, higher luminance and sharp, color-pure electroluminescence are obtained by replacing the F8 electron injector with ZnO, which is directly deposited onto the CH3NH3PbBr3 perovskite using spatial atmospheric atomic layer deposition. The electron injection barrier can also be reduced by decreasing the ZnO electron affinity through Mg incorporation, leading to lower turn-on voltages.

Interfacial control toward efficient and low-voltage perovskite light-emitting diodes.

High-performance perovskite light-emitting diodes are achieved by an interfacial engineering approach, leading to the most efficient near-infrared devices produced using solution-processed emitters and efficient green devices at high brightness conditions.

Bright light-emitting diodes based on organometal halide perovskite.

Solid-state light-emitting devices based on direct-bandgap semiconductors have, over the past two decades, been utilized as energy-efficient sources of lighting. However, fabrication of these devices typically relies on expensive high-temperature and high-vacuum processes, rendering them uneconomical for use in large-area displays. Here, we report high-brightness light-emitting diodes based on solution-processed organometal halide perovskites. We demonstrate electroluminescence in the near-infrared, green and red by tuning the halide compositions in the perovskite. In our infrared device, a thin 15 nm layer of CH3NH3PbI(3-x)Cl(x) perovskite emitter is sandwiched between larger-bandgap titanium dioxide (TiO2) and poly(9,9'-dioctylfluorene) (F8) layers, effectively confining electrons and holes in the perovskite layer for radiative recombination. We report an infrared radiance of 13.2 W sr(-1) m(-2) at a current density of 363 mA cm(-2), with highest external and internal quantum efficiencies of 0.76% and 3.4%, respectively. In our green light-emitting device with an ITO/PEDOT:PSS/CH3NH3PbBr3/F8/Ca/Ag structure, we achieved a luminance of 364 cd m(-2) at a current density of 123 mA cm(-2), giving external and internal quantum efficiencies of 0.1% and 0.4%, respectively. We show, using photoluminescence studies, that radiative bimolecular recombination is dominant at higher excitation densities. Hence, the quantum efficiencies of the perovskite light-emitting diodes increase at higher current densities. This demonstration of effective perovskite electroluminescence offers scope for developing this unique class of materials into efficient and colour-tunable light emitters for low-cost display, lighting and optical communication applications.

Suppressing recombination in polymer photovoltaic devices via energy-level cascades.

An energy cascading structure is designed in a polymer photovoltaic device to suppress recombination and improve quantum yields. By the insertion of a thin polymer interlayer with intermediate energy levels, electrons and holes can effectively shuttle away from each other while being spatially separated from recombination. An increase in open-circuit voltage and short-circuit current are observed in modified devices.