Strategic Compositional Engineering in Quasi-2D Ruddlesden-Popper Perovskites to Decipher Deep Blue Emission.

Perovskites have achieved immense progression in optoelectronic device applications owing to their fascinating intrinsic properties. However, the integration of perovskites in lighting applications has been retarded due to the challenges involved in achieving their deep blue light-emitting diodes (LEDs). Unlike other color counterparts, obtaining a stable, defect-tolerant, and high-band gap perovskite material for deep blue emission is an arduous task. Moreover, the ambient stability and efficient charge injection in the device are bottlenecks for the established perovskite emissive materials. Among all the dimensional perovskite counterparts, quasi-two-dimensional perovskites (Q2DPes) with hydrophobic ligands can exhibit better stability, and also, facile tunability of the properties can overcome the associated challenges. In this paper, for the first time, we demonstrate Ruddlesden-Popper-based Q2DPes that are pure deep blue emissive in the 450 nm region, stable, and can facilitate decent charge injection in LEDs. We have also demonstrated systematic modulations in the properties of the material, concerning the organic cation concentration.

Probing the charge transfer and electron-hole asymmetry in graphene-graphene quantum dot heterostructure.

In recent years, graphene-based van der Waals (vdW) heterostructures have come into prominence showcasing interesting charge transfer dynamics which is significant for optoelectronic applications. These novel structures are highly tunable depending on several factors such as the combination of the two-dimensional materials, the number of layers and band alignment exhibiting interfacial charge transfer dynamics. Here, we report on a novel graphene based 0D-2D vdW heterostructure between graphene and amine-functionalized graphene quantum dots (GQD) to investigate the interfacial charge transfer and doping possibilities. Using a combination ofab initiosimulations and Kelvin probe force microscopy (KPFM) measurements, we confirm that the incorporation of functional GQDs leads to a charge transfer induced p-type doping in graphene. A shift of the Dirac point by 0.05 eV with respect to the Fermi level (EF) in the graphene from the heterostructure was deduced from the calculated density of states. KPFM measurements revealed an increment in the surface potential of the GQD in the 0D-2D heterostructure by 29 mV with respect to graphene. Furthermore, we conducted power dependent Raman spectroscopy for both graphene and the heterostructure samples. An optical doping-induced gating effect resulted in a stiffening of theGband for electrons and holes in both samples (graphene and the heterostructure), suggesting a breakdown of the adiabatic Born-Oppenheimer approximation. Moreover, charge imbalance and renormalization of the electron-hole dispersion under the additional influence of the doped functional GQDs is pointing to an asymmetry in conduction and carrier mobility.

Transparent, flexible MAPbI3 perovskite microwire arrays passivated with ultra-hydrophobic supramolecular self-assembly for stable and high-performance photodetectors.

The emergence of organic-inorganic hybrid perovskites (OHPs) has revolutionised the potential performance of optoelectronic devices; most perovskites are opaque and hence incompatible with transparent optoelectronics and sensitive to environmental degradation. Here, we have reported a single-step fabrication of ultra-long MAPbI3 perovskite microwire arrays over a large area using stencil lithography based on sequential vacuum sublimation. The environmental stability of MAPbI3 is empowered with a newly designed and synthesized transparent supramolecular self-assembly based on a mixture of two tripodal l-Phe-C11H23/C7F15 molecules, which showed a contact angle of 105° and served as ultra-hydrophobic passivation layers for more than 45 days in an ambient atmosphere. The MAPbI3 microwire arrays passivated with the supramolecular self-assembly demonstrated for the first time both excellent transparency of ∼89% at 550 nm and a remarkable photoresponse with a photo-switching ratio of ∼104, responsivity of 789 A W-1, detectivity of 1014 Jones, linear dynamic range of ∼122 dB, and rise time of 432 µs. Furthermore, the photodetector fabricated on a flexible PET substrate demonstrated robust mechanical flexibility even beyond 1200 bending cycles. Therefore, the scalable stencil lithography and supramolecular passivation approaches have the potential to deliver next-generation transparent, flexible, and stable optoelectronic devices.

Large-area transparent flexible guanidinium incorporated MAPbI3 microstructures for high-performance photodetectors with enhanced stability.

Unveiling the transparency and flexibility in perovskite-based photodetectors with superior photoresponse and environmental stability remains an open challenge. Here we report on guanidinium incorporated metal halide perovskite (MA1-xGuaxPbI3, x = 0 to 0.65) random percolative microstructure (RPM) fabrication using an ultra-fast spray coating technique. Remarkably, RPMs over a large area of 5 × 5 cm2 on flexible substrates with a transparency of ∼50% can be achieved with enriched environmental stability. Transparent photodetectors based on MA1-xGuaxPbI3 (x = 0.12) RPMs manifest excellent performance with a responsivity of 187 A W-1, a detectivity of 2.23 × 1012 Jones and an external quantum efficiency of 44 115%. Additionally, the photodetectors exhibited superior mechanical flexibility under a wide range of bending angles and large number of binding cycles. Integrating features including transparency, high performance, stability, flexibility and scalability within a photodetector is unmatched and holds potential for novel applications in transparent and wearable optoelectronic devices.

Vortex-Aligned Ordered Film of Crystalline Fullerene C70 Microtubes with Enhanced Photoluminescence and Photovoltaics Properties.

Crystalline fullerene C70 microtubes (FMTs) were produced employing ultrasound-assisted liquid- liquid interfacial precipitation (ULLIP) technique at the interface between fullerene C70 solution in 1,2 dichlorobenzene (DCB) and isopropanol (IPA) at 15 °C. Using the vortex-flow motion of the subphase water (also called Vortex-Langmuir-Blodgett technique), the FMTs were aligned and homogeneous films were prepared at the air-water interface. The aligned FMTs film exhibited enhanced photoluminescence (PL) with PL intensity ~5 times higher than that of the pristine C70. Moreover, the aligned FMT film showed better photovoltaics properties compared with randomly oriented FMTs and pristine C70 film obtained from the spin coating. The compact, directional orientation and proper surface coverage of the FMT film enhanced the charge transport properties in the photovoltaic device.

Resonant energy transfer in a van der Waals stacked MoS2 - functionalized graphene quantum dot composite with ab initio validation.

Graphene-based van der Waals (vdW) heterostructures can facilitate exciting charge transfer dynamics in between structural layers with the emission of excitonic quasi-particles. However, the chemical formation of such heterostructures has been elusive thus far. In this work, a simple chemical approach is described to form such van der Waals (vdW) heterostructures using few layer MoS2 sheet embedded quantum dots (QDs) and amine-functionalized graphene quantum dots (GQDs) to probe the energy transfer mechanism for tunable photoluminescence (PL). Our findings reveal an interesting non-radiative Förster-type energy transfer with the quenching of functional GQD PL intensity after GQD/MoS2 composite formation, which validates the existing charge transfer dynamics analogous to 0D and 2D systems. The non-radiative type of energy transfer characteristic from GQD into the MoS2 layer through vdW interactions has been confirmed by photoluminescence, time decay analyses and ab initio calculations with the shifting of the Fermi level in the density of states towards the conduction band in the stacked configuration. These results are encouraging for the fundamental exploration of optical properties in other chemically prepared QD/2D based heterostructures to understand the charge transfer mechanism and fingerprint luminescence quenching for future optoelectronic device and optical sensing applications.

Hierarchical heterostructure of Ag-nanoparticle decorated fullerene nanorods (Ag-FNRs) as an effective single particle freestanding SERS substrate.

A hierarchical heterostructure composed of silver nanoparticles (Ag-NPs: average diameter ∼10 nm) on fullerene nanorods (FNRs: average length ∼11 µm and average diameter ∼200 nm) was fabricated using a simple solution route. It was used as an effective single particle freestanding surface enhanced Raman scattering (SERS) substrate for the detection of target molecules (Rhodamine 6G: R6G). FNRs were formed ultra-rapidly (formation process completed in a few seconds) at a liquid-liquid interface of methanol and C60/mesitylene solution then Ag-NPs were grown directly on the surfaces of the FNRs by treatment with a solution of silver nitrate in ethanol. This unique hierarchical heterostructure allows efficient adsorption of target molecules also acting as an effective SERS substrate capable of detecting the adsorbed R6G molecules in the nanomolar concentration range. In this study, SERS spectra are acquired on an isolated single Ag-FNR for the detection of the absorbed molecule rather than from a bulk, large area film composed of silver/gold nanoparticles as used in conventional methods. Thus, this work provides a new approach for the design and fabrication of freestanding SERS substrates for molecular detection applications.

Transparent, Flexible Silicon Nanostructured Wire Networks with Seamless Junctions for High-Performance Photodetector Applications.

Optically transparent photodetectors are crucial in next-generation optoelectronic applications including smart windows and transparent image sensors. Designing photodetectors with high transparency, photoresponsivity, and robust mechanical flexibility remains a significant challenge, as is managing the inevitable trade-off between high transparency and strong photoresponse. Here we report a scalable method to produce flexible crystalline Si nanostructured wire (NW) networks fabricated from silicon-on-insulator (SOI) with seamless junctions and highly responsive porous Si segments that combine to deliver exceptional performance. These networks show high transparency (∼92% at 550 nm), broadband photodetection (350 to 950 nm) with excellent responsivity (25 A/W), optical response time (0.58 ms), and mechanical flexibility (1000 cycles). Temperature-dependent photocurrent measurements indicate the presence of localized electronic states in the porous Si segments, which play a crucial role in light harvesting and photocarrier generation. The scalable low-cost approach based on SOI has the potential to deliver new classes of flexible optoelectronic devices, including next-generation photodetectors and solar cells.

Supramolecular Aggregates of Tetraphenylethene-Cored AIEgen toward Mechanoluminescent and Electroluminescent Devices.

Luminescent materials possessing both the mechanoluminescence (MCL) and electroluminescence (EL) properties are the quest for sensing and optoelectronic applications. We report on the synthesis of a new tailor-made luminogen, 1,2-bis(4-(1-([1,1'-biphenyl]-4-yl)-2,2-diphenylvinyl)phenyl)-1,2-diphenylethene (TPE 5), using Suzuki coupling reaction with high yield. An aggregation-induced emission (AIE) active complex TPE 5 forms supramolecular spherical aggregates at the air-water interface of a Langmuir trough. As a consequence, a large enhancement of luminescence is obtained from the mono- and multilayer Langmuir-Blodgett films of TPE 5 owing to the AIE effect. The luminogen TPE 5 exhibits a reversible MCL response, displaying photoluminescence switching due to change in the crystalline states under external stimuli. The unique feature of luminescence enhancement upon aggregate formation is utilized for the fabrication of light-emitting diodes with low threshold voltage using supramolecular aggregates as the active layer. This work demonstrates an efficient strategy for obtaining controlled supramolecular aggregates of AIEgen with a potential in the dual applications of MCL and EL.

Induced Aggregation of AIE-Active Mono-Cyclometalated Ir(III) Complex into Supramolecular Branched Wires for Light-Emitting Diodes.

Aggregation-induced emission (AIE) is commonly observed in irregular bulk form. Herein, unique aggregation properties of an AIE-active complex into branched supramolecular wires are reported for the first time. Mono-cyclometalated Ir(III) complex shows in-plane J-aggregation at the air-water interface owing to the restriction of intramolecular vibration of bidentate phenylpyridinato and intramolecular rotations of monodentate triphenylphosphine ligands at air-water interface. As a consequence, a large enhancement of luminescence comparable to the solid state is obtained from the monolayers of supramolecular wires. This unique feature is utilized for the fabrication of light-emitting diodes with low threshold voltage using supramolecular wires as active layer. This study opens up the need of ordered assembly of AIE complexes to achieve optimal luminescence characteristics.

Colossal magnetoresistance in amino-functionalized graphene quantum dots at room temperature: manifestation of weak anti-localization and doorway to spintronics.

In this work, we have demonstrated the signatures of localized surface distortions and disorders in functionalized graphene quantum dots (fGQD) and consequences in magneto-transport under weak field regime (∼1 Tesla) at room temperature. Observed positive colossal magnetoresistance (MR) and its suppression is primarily explained by weak anti-localization phenomenon where competitive valley (inter and intra) dependent scattering takes place at room temperature under low magnetic field; analogous to low mobility disordered graphene samples. Furthermore, using ab-initio analysis we show that sub-lattice sensitive spin-polarized ground state exists in the GQD as a result of pz orbital asymmetry in GQD carbon atoms with amino functional groups. This spin polarized ground state is believed to help the weak anti-localization dependent magneto transport by generating more disorder and strain in a GQD lattice under applied magnetic field and lays the premise for future graphene quantum dot based spintronic applications.

Insight into the mechanism revealing the peroxidase mimetic catalytic activity of quaternary CuZnFeS nanocrystals: colorimetric biosensing of hydrogen peroxide and glucose.

Artificial enzyme mimetics have attracted immense interest recently because natural enzymes undergo easy denaturation under environmental conditions restricting practical usefulness. We report for the first time chalcopyrite CuZnFeS (CZIS) alloyed nanocrystals (NCs) as novel biomimetic catalysts with efficient intrinsic peroxidase-like activity. Novel peroxidase activities of CZIS NCs have been evaluated by catalytic oxidation of the peroxidase substrate 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of hydrogen peroxide (H2O2). CZIS NCs demonstrate the synergistic effect of elemental composition and photoactivity towards peroxidase-like activity. The quaternary CZIS NCs show enhanced intrinsic peroxidase-like activity compared to the binary NCs with the same constituent elements. Intrinsic peroxidase-like activity has been correlated with the energy band position of CZIS NCs extracted using scanning tunneling spectroscopy and ultraviolet photoelectron spectroscopy. Kinetic analyses indicate Michaelis-Menten enzyme kinetic model catalytic behavior describing the rate of the enzymatic reaction by correlating the reaction rate with substrate concentration. Typical color reactions arising from the catalytic oxidation of TMB over CZIS NCs with H2O2 have been utilized to establish a simple and sensitive colorimetric assay for detection of H2O2 and glucose. CZIS NCs are recyclable catalysts showing high efficiency in multiple uses. Our study may open up the possibility of designing new photoactive multi-component alloyed NCs as enzyme mimetics in biotechnology applications.

Demonstration of ultrarapid interfacial formation of 1D fullerene nanorods with photovoltaic properties.

We demonstrate ultrarapid interfacial formation of one-dimensional (1D) single-crystalline fullerene C60 nanorods at room temperature in 5 s. The nanorods of ∼ 11 µm in length and ∼ 215 nm in diameter are developed in a hexagonal close-pack crystal structure, contrary to the cubic crystal structure of pristine C60. Vibrational and electronic spectroscopy provide strong evidence that the nanorods are a van der Waals solid, as evidenced from the preservation of the electronic structure of the C60 molecules within the rods. Steady state optical spectroscopy reveals a dominance of charge transfer excitonic transitions in the nanorods. A significant enhancement of photogenerated charge carriers is observed in the nanorods in comparison to pristine C60, revealing the effect of shape on the photovoltaic properties. Due to their ultrarapid, large-scale, room-temperature synthesis with single-crystalline structure and excellent optoelectronic properties, the nanorods are expected to be promising for photosensitive devices applications.