Crosslinking-induced patterning of MOFs by direct photo- and electron-beam lithography.

Metal-organic frameworks (MOFs) with diverse chemistry, structures, and properties have emerged as appealing materials for miniaturized solid-state devices. The incorporation of MOF films in these devices, such as the integrated microelectronics and nanophotonics, requires robust patterning methods. However, existing MOF patterning methods suffer from some combinations of limited material adaptability, compromised patterning resolution and scalability, and degraded properties. Here we report a universal, crosslinking-induced patterning approach for various MOFs, termed as CLIP-MOF. Via resist-free, direct photo- and electron-beam (e-beam) lithography, the ligand crosslinking chemistry leads to drastically reduced solubility of colloidal MOFs, permitting selective removal of unexposed MOF films with developer solvents. This enables scalable, micro-/nanoscale (≈70 nm resolution), and multimaterial patterning of MOFs on large-area, rigid or flexible substrates. Patterned MOF films preserve their crystallinity, porosity, and other properties tailored for targeted applications, such as diffractive gas sensors and electrochromic pixels. The combined features of CLIP-MOF create more possibilities in the system-level integration of MOFs in various electronic, photonic, and biomedical devices.

Nondestructive Direct Optical Patterning of Perovskite Nanocrystals with Carbene-Based Ligand Cross-Linkers.

Microscale patterning of colloidal perovskite nanocrystals (NCs) is essential for their integration in advanced device platforms, such as high-definition displays. However, perovskite NCs usually show degraded optical and/or electrical properties after patterning with existing approaches, posing a critical challenge for their optoelectronic applications. Here we achieve nondestructive, direct optical patterning of perovskite NCs with rationally designed carbene-based cross-linkers and demonstrate their applications in high-performance light-emitting diodes. We reveal that both the photochemical properties and the electronic structures of cross-linkers need to be carefully tailored to the material properties of perovskite NCs. This method produces high-resolution (∼4000 ppi) NC patterns with preserved photoluminescent quantum efficiencies and charge transport properties. Prototype light-emitting diodes with patterned/cross-linked NC layers show a maximum luminance of over 60000 cd m-2 and a peak external quantum efficiency of 16%, among the highest for patterned perovskite electroluminescent devices. Such a material-adapted patterning method enabled by designs from a photochemistry perspective could foster the applications of perovskite NCs in system-level electronic and optoelectronic devices.

3D printing of inorganic nanomaterials by photochemically bonding colloidal nanocrystals.

3D printing of inorganic materials with nanoscale resolution offers a different materials processing pathway to explore devices with emergent functionalities. However, existing technologies typically involve photocurable resins that reduce material purity and degrade properties. We develop a general strategy for laser direct printing of inorganic nanomaterials, as exemplified by more than 10 semiconductors, metal oxides, metals, and their mixtures. Colloidal nanocrystals are used as building blocks and photochemically bonded through their native ligands. Without resins, this bonding process produces arbitrary three-dimensional (3D) structures with a large inorganic mass fraction (~90%) and high mechanical strength. The printed materials preserve the intrinsic properties of constituent nanocrystals and create structure-dictated functionalities, such as the broadband chiroptical responses with an anisotropic factor of ~0.24 for semiconducting cadmium chalcogenide nanohelical arrays.

Charge Transport Dynamics of Quasi-Type II Perovskite Janus Nanocrystals in High-Performance Photoconductors.

CsPbBr3-Pb4S3Br2 Janus nanocrystals (NCs) are the only nanomaterial where the epitaxial structure of perovskite and chalcogenide materials has been realized at the nanoscale, but their exciton dynamics mechanism has not yet been thoroughly investigated or applied in photodetection applications. This work reports an attractive device performance of perovskite photoconductors based on epitaxial CsPbBr3-Pb4S3Br2 Janus NCs, as well as the carrier relaxation and transfer mechanism of the heterojunction. By a combination of transient optical absorption and quantum dynamics simulation, it is demonstrated that the photogenerated holes on CsPbBr3 can be successfully extracted by Pb4S3Br2, while the hole transfer proceeds about three times faster than energy loss and remains "hot" for about 300 fs. This feature has favorable effects on long-range charge separation and transport; therefore, the Janus NCs photoconductors exhibit an exceptional responsivity of 34.0 A W-1 and specific detectivity of 1.26 × 1014 Jones.

Epitaxial CsPbBr3 /CdS Janus Nanocrystal Heterostructures for Efficient Charge Separation.

Epitaxial heterostructures of colloidal lead halide perovskite nanocrystals (NCs) with other semiconductors, especially the technologically important metal chalcogenides, can offer an unprecedented level of control in wavefunction design and exciton/charge carrier engineering. These NC heterostructures are ideal material platforms for efficient optoelectronics and other applications. Existing methods, however, can only yield heterostructures with random connections and distributions of the two components. The lack of epitaxial relation and uniform geometry hinders the structure-function correlation and impedes the electronic coupling at the heterointerface. This work reports the synthesis of uniform, epitaxially grown CsPbBr3 /CdS Janus NC heterostructures with ultrafast charge separation across the electronically coupled interface. Each Janus NC contains a CdS domain that grows exclusively on a single {220} facet of CsPbBr3 NCs. Varying reaction parameters allows for precise control in the sizes of each domain and readily modulates the optical properties of Janus NCs. Transient absorption measurements and modeling results reveal a type II band alignment, where photoexcited electrons rapidly transfer (within ≈9 picoseconds) from CsPbBr3 to CdS. The promoted charge separation and extraction in epitaxial Janus NCs leads to photoconductors with drastically improved (approximately three orders of magnitude) responsivity and detectivity, which is promising for ultrasensitive photodetection.

A General Approach to Stabilize Nanocrystal Superlattices by Covalently Bonded Ligands.

Self-assembled inorganic nanocrystal (NC) superlattices are powerful material platforms with diverse structures and emergent functionalities. However, their applications suffer from the low structural stability against solvents and other stimuli, due to the weak interparticle interactions. Existing strategies to stabilize NC superlattices typically require the design and incorporation of special ligands prior to self-assembly and are only applicable to superlattices of certain NCs, ligands, and structures. Here we report a general method to stabilize superlattices of various NC compositions and structures via strong, covalently bonded ligands. The core is the use of light-triggered, nitrene-based cross-linkers that do not interfere the self-assembly process while nonspecifically and effectively bonding the native ligands of NCs. The stabilized 2D and 3D superlattices of metal, semiconductor, and magnetic NCs retain their structures when being exposed to solvents of different polarities (from toluene to water) and show high thermal stability and mechanical rigidity. This can further stabilize binary NC superlattices, beyond those achievable in previous methods. Stabilized superlattices show robust and reproducible functionalities, for instance, when serving as reusable substrates for surface enhanced Raman spectroscopy. These results create more possibilities in exploiting the impressive library of NC superlattices in a broad scope of applications.

Highly Efficient White Emission from Semiconductor Ink Based on Copper Iodide Nanoclusters.

Recent developments in the perovskite field have aimed at exploring cluster-based organic-inorganic copper(I) halides as novel luminescent materials because of their low toxicity and structural diversity. However, the poor framework stability and low dispersion in solvent constitute the key challenges to their practical applications such as luminescent inks. Herein, we report the preparation of highly luminescent inks via one-pot solution synthesis, which consisted of ionic CumIn clusters (tetrabutylammonium copper iodide) coupled with polymer polyvinylpyrrolidone (PVP). Benefiting from the high-affinity PVP to stabilize and disperse the Cu-I inorganic units, the obtained hybrid nanocrystals exhibit high structural stabilitiy/photostability and good dispersion in ethanol. The characteristics of bright white light emission from inks were explored by temperature-dependent photoluminescence experiments and theoretical calculations. Attractively, the stable, highly luminescent inks show great potential for practical applications, such as anticounterfeiting and imaging identification. Our study offers a new material designing strategy that may be generalized to many other material classes.

Beyond a Linker: The Role of Photochemistry of Crosslinkers in the Direct Optical Patterning of Colloidal Nanocrystals.

Surface chemistry mediated direct optical patterning represents an emerging strategy for incorporating colloidal nanocrystals (NCs) in integrated optoelectronic platforms including displays and image sensors. However, the role of photochemistry of crosslinkers and other photoactive species in patterning remains elusive. Here we show the design of nitrene- and carbene-based photocrosslinkers can strongly affect the patterning capabilities and photophysical properties of NCs, especially quantum dots (QDs). Their role beyond physical linkers stems from structure-dictated electronic configuration, energy alignment and associated reaction kinetics and thermodynamics. Patterned QD layers with designed carbene-based crosslinkers fully preserve their photoluminescent and electroluminescent properties. Patterned light emitting diodes (QLEDs) show a maximum external quantum efficiency of ≈12 % and lifetime over 4800 h, among the highest for reported patterned QLEDs. These results would guide the rational design of photoactive species in NC patterning and create new possibilities in the monolithic integration of NCs in high-performance device platforms.

Direct optical patterning of perovskite nanocrystals with ligand cross-linkers.

Precise microscale patterning is a prerequisite to incorporate the emerging colloidal metal halide perovskite nanocrystals into advanced, integrated optoelectronic platforms for widespread technological applications. Current patterning methods suffer from some combination of limitations in patterning quality, versatility, and compatibility with the workflows of device fabrication. This work introduces the direct optical patterning of perovskite nanocrystals with ligand cross-linkers or DOPPLCER. The underlying, nonspecific cross-linking chemistry involved in DOPPLCER supports high-resolution, multicolored patterning of a broad scope of perovskite nanocrystals with their native ligands. Patterned nanocrystal films show photoluminescence (after postpatterning surface treatment), electroluminescence, and photoconductivity on par with those of conventional nonpatterned films. Prototype, pixelated light-emitting diodes show peak external quantum efficiency of 6.8% and luminance over 20,000 cd m-2. Both are among the highest for patterned perovskite nanocrystal devices. These results create new possibilities in the system-level integration of perovskite nanomaterials and advance their applications in various optoelectronic and photonic platforms.

Strong violet emission from ultra-stable strontium-doped CsPbCl3 superlattices.

Among the lead halide perovskites, the photoluminescence quantum yields (PLQYs) of perovskite quantum dots (PQDs) in the violet region are the very lowest. This is an obstacle to the optical applications across the entire visible area based on perovskite materials. Herein, we report a novel strontium (Sr)-substitution along with chlorine passivation strategy to enhance the PLQYs of CsPbCl3 PQDs. We surprisingly found that when the molar ratio of Sr2+/Pb2+ = 0.1/0.9, CsSr0.1Pb0.9Cl3 PQDs exhibit strong single-color violet emission, which is attributed to the effective passivation of chlorine defects. We further found spontaneous self-assembly of PQDs into highly emissive PSCs from the precursor in a highly concentrated solution. Moreover, by dilution of these PSCs, a few small PQD aggregates can be regained, which is similar to the PQDs formed at lower concentrations. Benefiting from the superior collective properties of individual PQDs, these highly fluorescent CsSr0.1Pb0.9Cl3 PSCs can maintain good stability even when directly immersed in water or exposed to illumination.

Trioctylphosphine-Assisted Pre-protection Low-Temperature Solvothermal Synthesis of Highly Stable CsPbBr3/TiO2 Nanocomposites.

Lead halide perovskite quantum dots (PQDs) are reported as a promising branch of perovskites, which have recently emerged as a field in luminescent materials research. However, before the practical applications of PQDs can be realized, the problem of poor stability has not yet been solved. Herein, we propose a trioctylphosphine (TOP)-assisted pre-protection low-temperature solvothermal synthesis of highly stable CsPbBr3/TiO2 nanocomposites. Due to the protection of branched ligands and the lower temperature of shell formation, these TOP-modified CsPbBr3 PQDs are successfully incorporated into a TiO2 monolith without a loss of fluorescence intensity. Because the excellent nature of both parent materials is preserved in CsPbBr3/TiO2 nanocomposites, it is found that the as-prepared CsPbBr3/TiO2 nanocomposites not only display excellent photocatalytic activity but also yield improved PL stability, enabling us to build highly stable white light-emitting diodes and to photodegrade rhodamine B.

A versatile approach for shape-controlled synthesis of ultrathin perovskite nanostructures.

Very recently, ultrathin perovskite nanostructures, with the advantages of perovskite and ultrathin properties, have received an enormous level of interest due to their many fascinating properties, such as a strong quantum confinement effect and a large specific surface area. In spite of this incredible success of perovskite nanocrystals (NCs), the development of perovskite NCs is still in its infancy, and the production of high-quality ultrathin perovskite nanostructures has been a hot topic in the fields of nanoscience and nanotechnology. Herein, we demonstrate that ultrathin CsPbBr3 perovskite nanosheets (NSs) can be obtained by a simple mixing of precursor-ligand complexes under ambient conditions. It was found that the formation of NSs is ascribed to the stepwise self-assembly of the initially formed different types of ultrathin nanostructures. Due to the disappearance of grain boundaries and protection of branched ligands, these NSs exhibit enhanced optical properties compared to other types of samples. This direct synthesis method opens up a promising road for the synthesis of ultrathin NSs and guides the fabrication of other ultrathin nanostructures.

Pressure-Driven Transformation of CsPbBrI2 Nanoparticles into Stable Nanosheets in Solution through Self-Assembly.

Very recently, two-dimensional (2D) perovskite nanosheets (PNSs), taking the advantages of perovskite as well as the 2D structure properties, have received an enormous level of interest throughout the scientific community. In spite of this incredible success in perovskite nanocrystals (NCs), self-assembly of many nanostructures in metal halide perovskites has not yet been realized, and producing highly efficient red-emitting PNSs remains challenging. In this Letter, we show that by using CsPbBrI2 perovskite nanoparticles (NPs) as a building block, PNSs can emerge spontaneously under high ambient pressure via template-free self-assembly without additional complicated operation. It is found that the formation of PNSs is ascribed to the high pressure that provides the driving force for the alignment of NPs in solution. Because of the disappearance of the grain boundaries between the adjacent NPs and increased crystallinity, these PNSs self-assembled from NPs exhibit enhanced properties compared to the initial NPs, including higher PL intensity and remarkable chemical stability toward light and water.

CB Nanoparticles Optimized 3D Wearable Graphene Multifunctional Piezoresistive Sensor Framed by Loofah Sponge.

Three-dimensional (3D) wearable piezoresistive sensors with excellent performance are urgently needed in many emerging fields. Herein, a hybrid piezoresistive sensor with 3D structure, which is framed by loofah sponge and coated with reduced graphene oxide modified with carbon black nanoparticles (rGO-CB@LS), was obtained via a facile solvothermal method. The ingenious use of loofah sponge (LS) provides a 3D highly ordered structure with excellent flexibility for the hybrid sensor, which assists the sensor free from the dependence on an organic substrate and eliminates the pollution to the environment. While the addition of carbon black (CB) nanoparticles can reduce the contact resistance between rGO sheets, improve the conductivity and sensitivity effectively, and shorten the response/recovery time of the sensor. An ultralight piezoresistive sensor, which is low cost and environmentally friendly, was obtained under the synergy of LS and rGO-CB, accompanied by high sensitivity and good stability. This novel sensor also exhibits excellent performance in detecting tiny and big human activities, demonstrating its great potential for a new generation of 3D wearable sensors.

Highly stable Na: CsPb(Br,I)3@Al2O3 nanocomposites prepared by a pre-protection strategy.

Among the leading energy materials, metal tri-halide perovskite quantum dots (PQDs) with outstanding optoelectronic properties are at the forefront of current research. However, enormous challenges remain to be addressed, including hazardous components and poor stability, before achieving practical applications of PQDs. Although there are diverse methods to improve the stability of PQDs, it is of central importance to avoid damage during operation. Herein, we develop a pre-protected strategy in which the coating combines the advantages of doping with sodium ions to jointly improve stability. Because the stable Na-rich surface acts as a defence, it protects the PQDs from damage during the coating process; therefore, they retain their initial fluorescence. When employing these Na-rich PQDs as core materials of a coating, the highly fluorescent Na: CsPb(Br,I)3@Al2O3 nanocomposites can maintain good stability even when directly immersed in water or exposed to illumination. Clearly, the combination of these features sheds light on the stabilization and applications of PQDs.

Reversible transformation between CsPbBr3 nanowires and nanoparticles.

We show that CsPbBr3 nanowires (NWs) are formed by the hierarchical arrangement of individual nanoparticles (NPs), and reversible transformation from NWs to NPs is also achieved by anion exchange.

Spray-Coated CsPbBr3 Quantum Dot Films for Perovskite Photodiodes.

Large-area film deposition and high material utilization ratio are the crucial factors for large-scale application of perovskite optoelectronics. Recently, all-inorganic halide perovskite CsPbBr3 has attracted great attention because of its high phase stability, thermal stability, and photostability. However, most reported perovskite devices were fabricated by spin-coating, suffering from a low material utilization ratio of 1% and a small coverage area. Here, we developed a spray-coating technique to fabricate a CsPbBr3 quantum dot (QD) film photodiode which had a high material utilization ratio of 32% and a deposition rate of 9 nm/s. The film growth process was studied, and substrate temperature and spray time were two key factors for the deposition of uniform and crack-free QD films. The spray-coated photodiode was demonstrated to be more suitable for working in the photodetector mode because a low dark current density of 4 × 10-4 mA cm-2 resulting from an extremely low recombination current contributed to a high detectivity of 1 × 1014 Jones. A high responsivity of 3 A W-1 was obtained at -0.7 V under 365 nm illumination, resulting from a low charge-transfer resistance and a high charge recombination resistance. We believe that the spray deposition technique will benefit the fabrication of perovskite QD film optoelectronics on a large scale.

Effect of Graphene-EC on Ag NW-Based Transparent Film Heaters: Optimizing the Stability and Heat Dispersion of Films.

To optimize the performance of silver nanowire (Ag NW) film heaters and explore the effect of graphene on a film, we introduced poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) and graphene modified with ethyl cellulose (graphene-EC) into the film. The high-quality and well-dispersed graphene-EC was synthesized from graphene obtained by electrochemical exfoliation as a precursor. The transparent film heaters were fabricated via spin-coating. With the assistance of graphene-EC, the stability of film heaters was greatly improved, and the conductivity was optimized by adjusting the Ag NW concentration. The film heaters exhibited a fast and accurate response to voltage, accompanied by excellent environmental endurance, and there was no significant performance degradation after being operated for a long period of time. These results indicate that graphene-EC plays a crucial role in optimizing film stability and heat dispersion in the film. The Ag NW/PEDOT:PSS-doped graphene-EC film heaters show a great potential in low-cost indium-tin-oxide-free flexible transparent electrodes, heating systems, and transparent film heaters.

A new route for the synthesis of a Ag nanopore-inlay-nanogap structure: integrated Ag-core@graphene-shell@Ag-jacket nanoparticles for high-efficiency SERS detection.

We present a new route for the synthesis of Ag nanopore-inlay-nanogap structures using creviced graphene-shell encapsulated Cu nanoparticles (Cu@G-NPs) as the sacrificial templates. The as-synthesized integrated Ag-core@graphene-shell@Ag-jacket nanoparticles (AgC@G@AgJ-NPs) presents "chrysanthemum" shapes that contain abundant sub-10 nm size intraparticle nanopores/nanogaps, which can generate huge enhanced electromagnetic fields to support SERS activity, resulting in an average EF > 107 due to a high-density of intraparticle and interparticle "hot spots".

Dielectrophoretic-Assembled Single and Parallel-Aligned Ag Nanowire-ZnO-Branched Nanorod Heteronanowire Ultraviolet Photodetectors.

The branched hierarchical heteronanowires have been widely studied for optoelectronics application because of their unique electronic and photonic performances. Here, we successfully synthesized Ag nanowire-ZnO-branched nanorod heteronanowires based on an improved hydrothermal method. Then we fabricated single heteronanowire across a Au electrode pair with different gap widths and parallel-aligned heteronanowires on a Au interdigitated electrode with a dielectrophoresis method, indicating the flexibility and operability of the dielectrophoresis assembly method. Increased photocurrent and shortened response time could be obtained by air-annealing and Ar-plasma post-treatments. A large responsivity of 2.5 A W-1 and a linear dynamic range of 74 dB could be obtained, indicating stable responsivity for both weak and strong illumination. The excellent photoresponse performance is attributed to the structure superiority of heteronanowires. The proposed strategy of dielectrophoresis-assembled heteronanowires provides a new opportunity to design and fabricate hierarchical nanostructure photodetectors.