A Strategic Approach to Design Multi-Functional RGB Luminescent Security Pigment Based Golden Ink with Myriad Security Features to Curb Counterfeiting of Passport.

Authentication and verification of the most important government issued identity proof, i.e. passport has become more complex and challenging in the last few decades due to various innovations in ways of counterfeiting by fraudsters. Here, the aim is to provide more secured ink without altering its golden appearance in visible light. In this panorama, a novel advanced multi-functional luminescent security pigment (MLSP) based golden ink (MLSI) is developed that provides an optical authentication and information encryption features to protect the legitimacy of the passport. The advanced MLSP is derived from the ratiometric combination of different luminescent materials to form a single pigment which emits red (620 nm), green (523 nm) and blue (474 nm), when irradiated via 254, 365 and 980 nm NIR wavelengths, respectively. It also includes magnetic nanoparticles to generate magnetic character recognition feature. The MLSI has been fabricated to examine its printing feasibility and stability over different substrates using the conventional screen-printing technique against harsh chemicals and under different atmospheric conditions. Hence, these advantageous multi-level security features with golden appearance in visible light is a new breakthrough toward curbing the counterfeiting of passport as well as bank cheques, government documents, pharmaceuticals, military equipment, and many more.

Wide spectral photoresponse of template assisted out of plane grown ZnO/NiO composite nanowire photodetector.

Zinc oxide (ZnO) one-dimensional nanostructures are extensively used in ultra-violet (UV) detection. To improve the optical sensing capability of ZnO, various nickel oxide (NiO) based p-n junctions have been employed. ZnO/NiO heterojunction based sensing has been limited to UV detection and not been extended to the visible region. In the present work, p-NiO/n-ZnO composite nanowire (NW) heterojunction based UV-visible photodetector is fabricated. A porous anodic aluminum oxide template based electrochemical deposition method is adopted for well separated and vertically aligned growth of composite NWs. The photoresponse is studied in an out of plane contact configuration. The fabricated photodetector shows fast response under UV-visible light with a rise and decay time of tens of ms. The wide spectral photoresponse is analyzed in terms of conduction from defect states of ZnO and interfacial defects during p-n junction formation. Light interaction with heterojunction along the length of the composite NW results in enhanced visible photoresponse of the detector and is further supported by simulation.

Ultrafast charge carrier dynamics in CdSe/V2O5 core/shell quantum dots.

Ultrafast transient absorption (TA) spectroscopy has been carried out to study the charge carrier dynamics of CdSe core and CdSe/V2O5 core/shell quantum dots (QDs). A significant redshift accompanied by broadening in the first excitonic peak was observed in the UV-Vis absorption spectra of the core/shell QDs as the shell thickness increases. This interesting observation is related to a quasi-type-II alignment characterized by the spatial separation of an electron into the core/shell and a hole into the core. The observed optical excitonic spectra have further been used to study the energetics of CdSe and charge separated states with the concept of Marcus theory and confirmed that electron transfer takes place in the Marcus inverted region (). Moreover, the growth kinetics of the CdSe core and CdSe/V2O5 core/shell QDs, studied with TA spectroscopy, exhibits slow electron cooling in core/shell QDs because of the de-coupling of the electronic wave functions with their hole counterpart. These exciting properties reveal a new paradigm shift from CdSe QDs to CdSe/V2O5 core/shell QDs for highly suitable applications in photovoltaics (PV) and optoelectronic devices.

A Facile Synthesis of Alkaline Electrolyte Based Graphene Sheets, Their Functionalization and Attachment of Some Drugs.

High-quality graphene is highly enviable material due to its seminal role amongst several areas in modern technology including its role as nanocarrier for site selective drug grafting and delivery applications. Here, we report a facile, cost-effective and single-step method to produce high-quality graphene through customised electrochemical exfoliation of graphite anode in alkaline electrolyte medium. The quality of graphene sheets (GS) were investigated by Raman, TEM/HRTEM, AFM, and FTIR techniques. The high quality as well as excellent Π-Π stacking nature of the honeycomb lattice of graphene was confirmed by measuring the quenching capability through photo-luminescence spectroscopy using organic dyes. A plausible mechanism for the graphite exfoliation has been given where evolution of high density of oxygen molecules exerts large force on the graphitic layers leads to exfoliation and consequent synthesis of graphene. Furthermore, to explore the application of the graphene sheets so synthesized, we carried out studies which may make them as suitable carriers for drug delivery. For this, graphene sheets were functionalized with L-cysteine and attached with the drugs Amphotericin-B (AmB) and Tamoxifen citrate (TMX). The conjugation of drugs with L-cysteine functionalized graphene has been confirmed through FTIR and Raman spectroscopic techniques. The drug loading efficiency of FGS for AmB and TMX was 75.00% and 94.31%, respectively. The present formulation of drugs (AmB and TMX) conjugated with graphene is suitable for the targeted drug delivery as it will enhance the efficacy and reduce cytotoxicity associated with drug.

Highly Luminescent Dual Mode Polymeric Nanofiber-Based Flexible Mat for White Security Paper and Encrypted Nanotaggant Applications.

Increasing counterfeiting of important data, currency, stamp papers, branded products etc., has become a major security threat which could lead to serious damage to the global economy. Consequences of such damage are compelling for researchers to develop new high-end security features to address full-proof solutions. Herein, we report a dual mode flexible highly luminescent white security paper and nanotaggants composed of nanophosphors incorporated in polymer matrix to form a nanofiber-based mat for anti-counterfeiting applications. The dual mode nanofibers are fabricated by electrospinning technique by admixing the composite of NaYF4 :Eu3+ @NaYF4 :Yb3+ , Er3+ nanophosphors in the polyvinyl alcohol solution. This flexible polymer mat derived from nanofibers appears white in daylight, while emitting strong red (NaYF4 :Eu3+ ) and green (NaYF4 :Yb3+ , Er3+ ) colors at excitation wavelengths of 254 nm and 980 nm, respectively. These luminescent nanofibers can also be encrypted as a new class of nanotaggants to protect confidential documents. These obtained results suggest that highly luminescent dual mode polymeric nanofiber-based flexible white security paper and nanotaggants could offer next-generation high-end unique security features against counterfeiting.

A Novel Approach to Synthesise a Dual-Mode Luminescent Composite Pigment for Uncloneable High-Security Codes to Combat Counterfeiting.

A strategy is demonstrated to protect valuable items, such as currency, pharmaceuticals, important documents, etc. against counterfeiting, by marking them with luminescent security codes. These luminescent security codes were printed by employing luminescent ink formulated from a cost effective dual-mode luminescent composite pigment of Gd1.7 Yb0.2 Er0.1 O3 and Zn0.98 Mn0.02 S phosphors using commercially available PVC Gold medium. In the composite, Gd1.7 Yb0.2 Er0.1 O3 and Zn0.98 Mn0.02 S account for upconversion and downconversion processes, respectively. The synthesis procedure of the composite involves the admixing of Gd1.7 Yb0.2 Er0.1 O3 nanorods and Zn0.98 Mn0.02 S phosphor, synthesised by hydrothermal and facile solid-state reaction methods, respectively. The structural, morphological, microstructural, and photoluminescent features of Gd1.7 Yb0.2 Er0.1 O3 nanorods, Zn0.98 Mn0.02 S phosphor and composite were characterised by using XRD, SEM, TEM, and photoluminescence (PL) techniques, respectively. The distribution of PL intensity of the printed pattern was examined by using confocal PL mapping microscopy. The obtained results reveal that security codes printed using ink formulated from this bi-luminescent composite pigment provide dual-stage security against counterfeiting.

Probing highly luminescent europium-doped lanthanum orthophosphate nanorods for strategic applications.

Herein we have established a strategy for the synthesis of highly luminescent and biocompatible europium-doped lanthanum orthophosphate (La0.85PO4Eu0.15(3+)) nanorods. The structure and morphogenesis of these nanorods have been probed by XRD, SEM, and TEM/HRTEM techniques. The XRD result confirms that the as-synthesized nanorods form in a monazite phase with a monoclinic crystal structure. Furthermore, the surface morphology shows that the synthesized nanorods have an average diameter of ∼90 nm and length of ∼2 µm. The HRTEM images show clear lattice fringes that support the presence of better crystal quality and enhanced photoluminescence hypersensitive red emission at 610 nm ((5)D0-(7)F2) upon 394 nm wavelength excitation. Furthermore, time-resolved spectroscopy and an MTT assay of these luminescent nanorods demonstrate a photoluminescent decay time of milliseconds with nontoxic behavior. Hence, these obtained results suggest that the as-synthesized luminescent nanorods could be potentially used in invisible security ink and high-contrast bioimaging applications.

New perspective in garnet phosphor: low temperature synthesis, nanostructures, and observation of multimodal luminescence.

Herein, we report a new concept for garnet materials in terms of the synthesis of nanocrystalline structure at low temperatures and its multimodal luminescence processes. Terbium- and ytterbium-ion-codoped yttrium gallium garnet nanophosphors have been synthesized via solution combustion technique; nearly pure phase nanophosphor samples were obtained. The synthesized nanophosphor shows efficient multimodal upconversion (UC), downshifting (DS), and quantum cutting (QC)/downconversion (DC) luminescence, which is a new paradigm in garnet material. The garnet nanophosphor shows strong green emission through DS and UC processes both. Furthermore, cooperative energy transfer (CET) has been described in detail, and a possible mechanism for the QC process is also proposed. A UV/blue photon absorbed by Tb(3+) ion splits into two near-infrared photons (wavelength range 900-1040 nm), emitted by a Yb(3+) ion pair, with an efficiency of more than 100%. The Yb(3+) concentration dependent ET from Tb(3+) to Yb(3+) has been verified using time domain analysis. An ET efficiency as high as 28% and a corresponding QC efficiency of about 128% (for 15 mol % of Yb(3+) concentration) have been attained. Such a multimode emitting nanophosphor could be very useful in display devices and for enhancing the conversion efficiency of next generation solar cells via spectral modification etc.

Graphene quantum dots derived from carbon fibers.

Graphene quantum dots (GQDs), which are edge-bound nanometer-size graphene pieces, have fascinating optical and electronic properties. These have been synthesized either by nanolithography or from starting materials such as graphene oxide (GO) by the chemical breakdown of their extended planar structure, both of which are multistep tedious processes. Here, we report that during the acid treatment and chemical exfoliation of traditional pitch-based carbon fibers, that are both cheap and commercially available, the stacked graphitic submicrometer domains of the fibers are easily broken down, leading to the creation of GQDs with different size distribution in scalable amounts. The as-produced GQDs, in the size range of 1-4 nm, show two-dimensional morphology, most of which present zigzag edge structure, and are 1-3 atomic layers thick. The photoluminescence of the GQDs can be tailored through varying the size of the GQDs by changing process parameters. Due to the luminescence stability, nanosecond lifetime, biocompatibility, low toxicity, and high water solubility, these GQDs are demonstrated to be excellent probes for high contrast bioimaging and biosensing applications.

Synthesis and Characterization of Highly Crystalline Bi-Functional Mn-Doped Zn2SiO4 Nanostructures by Low-Cost Sol-Gel Process.

Herein, we demonstrate a process for the synthesis of a highly crystalline bi-functional manganese (Mn)-doped zinc silicate (Zn2SiO4) nanostructures using a low-cost sol-gel route followed by solid state reaction method. Structural and morphological characterizations of Mn-doped Zn2SiO4 with variable doping concentration of 0.03, 0.05, 0.1, 0.2, 0.5, 1.0, and 2.0 wt% were investigated by using X-ray diffraction and high-resolution transmission electron microscopy (HR-TEM) techniques. HR-TEM-assisted elemental mapping of the as-grown sample was conducted to confirm the presence of Mn in Zn2SiO4. Photoluminescence (PL) spectra indicated that the Mn-doped Zn2SiO4 nanostructures exhibited strong green emission at 521 nm under 259 nm excitation wavelengths. It was observed that PL intensity increased with the increase of Mn-doping concentration in Zn2SiO4 nanostructures, with no change in emission peak position. Furthermore, magnetism in doped Zn2SiO4 nanostructures was probed by static DC magnetization measurement. The observed photoluminescence and magnetic properties in Mn-doped Zn2SiO4 nanostructures are discussed in terms of structural defect/lattice strain caused by Mn doping and the Jahn-Teller effect. These bi-functional properties of as-synthesized Zn2SiO4 nanostructures provide a new platform for their potential applications towards magneto-optical and spintronic and devices areas.

New insights into APCVD grown monolayer MoS2 using time-domain terahertz spectroscopy.

In modern era, wireless communications at ultrafast speed are need of the hour and search for its solution through cutting edge sciences is a new perspective. To address this issue, the data rates in order of terabits per second (TBPS) could be a key step for the realization of emerging sixth generation (6G) networks utilizing terahertz (THz) frequency regime. In this context, new class of transition metal dichalcogenides (TMDs) have been introduced as potential candidates for future generation wireless THz technology. Herein, a strategy has been adopted to synthesize high-quality monolayer of molybdenum di-sulfide (MoS2) using indigenously developed atmospheric pressure chemical vapor deposition (APCVD) set-up. Further, the time-domain transmission and sheet conductivity were studied as well as a plausible mechanism of terahertz response for monolayer MoS2 has been proposed and compared with bulk MoS2. Hence, the obtained results set a stepping stone to employ the monolayer MoS2 as potential quantum materials benefitting the next generation terahertz communication devices.

Highly luminescent-paramagnetic nanophosphor probes for in vitro high-contrast imaging of human breast cancer cells.

Highly luminescent-paramagnetic nanophosphors have a seminal role in biotechnology and biomedical research due to their potential applications in biolabeling, bioimaging, and drug delivery. Herein, the synthesis of high-quality, ultrafine, europium-doped yttrium oxide nanophosphors (Y(1.9)O(3):Eu(0.1)(3+)) using a modified sol-gel technique is reported and in vitro fluorescence imaging studies are demonstrated in human breast cancer cells. These highly luminescent nanophosphors with an average particle size of ≈6 nm provide high-contrast optical imaging and decreased light scattering. In vitro cellular uptake is shown by fluorescence microscopy, which visualizes the characteristic intense hypersensitive red emission of Eu(3+) peaking at 610 nm ((5)D(0)-(7)F(2)) upon 246 nm UV light excitation. No apparent cytotoxicity is observed. Subsequently, time-resolved emission spectroscopy and SQUID magnetometry measurements demonstrate a photoluminescence decay time in milliseconds and paramagnetic behavior, which assure applications of the nanophosphors in biomedical studies.

Optical bifunctionality of europium-complexed luminescent graphene nanosheets.

Graphene is an intriguing two-dimensional material, which could be modified for achieving tunable properties with many applications. Photoluminescence of graphene due to plasmonic emission is well-known, however, attempts to develop strong luminescent graphene have been difficult. Synthesis of a graphene-based material with a dual optical functionality, namely quenching the fluorescence of organic dyes while maintaining its own self-luminescence, is an interesting and challenging proposition. Here, we demonstrate this optical bifunctionality in a lattice-modified luminescent graphene, where europium(III) cations are complexed with graphene through oxygen functionalities. After excitation at 314 nm, a hypersensitive red emission is observed at 614 and 618 nm showing the complexation of europium(III) with graphene. We demonstrate dual functionality of this graphene by the quenching of luminescence of Rhodamine-B while displaying its own hypersensitive red emission. The decay lifetime observed through the time-resolved spectroscopy confirms its potential for applications in biosensing as well as optoelectronics.

Designing of two dimensional lanthanum cobalt hydroxide engineered high performance supercapacitor for longer stability under redox active electrolyte.

Redox active electrolyte supercapacitors differ significantly from the conventional electrolytes based storage devices but face a long term stability issue which requires a different approach while designing the systems. Here, we show the change in layered double hydroxides (LDHs) systems with rare earth elements (lanthanum) can drastically influence the stability of two dimensional LDH systems in redox electrolyte. We find that the choice of rare earth element (lanthanum) having magnetic properties and higher thermal and chemical stability has a profound effect on the stability of La-Co LDHs electrode in redox electrolyte. The fabricated hybrid device with rare earth based positive electrode and carbon as negative electrode having redox electrolyte leads to long stable high volumetric/gravimetric capacity at high discharge rate, demonstrates the importance of considering the rare earth elements while designing the LDH systems for redox active supercapacitor development.

Role of processing parameters in CVD grown crystalline monolayer MoSe2.

The quality of as-synthesized monolayers plays a significant role in atomically thin semiconducting transition metal dichalcogenides (TMDCs) to determine the electronic and optical properties. For designing optoelectronic devices, exploring the effect of processing parameters on optical properties is a prerequisite. In this view, we present the influence of processing parameters on the lattice and quasiparticle dynamics of monolayer MoSe2. The lab-built chemical vapour deposition (CVD) setup is used to synthesize monolayer MoSe2 flakes with varying shapes, including sharp triangle (ST), truncated triangle (TT), hexagon, and rough edge circle (REC). In particular, the features of as-synthesized monolayer MoSe2 flakes are examined using Raman and photoluminescence (PL) spectroscopy. Raman spectra reveal that the frequency difference between the A1g and E1 2g peaks is >45 cm-1 in all the monolayer samples. PL spectroscopy also shows that the synthesized MoSe2 flakes are monolayer in nature with a direct band gap in the range of 1.50-1.58 eV. Furthermore, the variation in the direct band gap is analyzed using the spectral weight of quasiparticles in PL emission, where the intensity ratio {I(A0)/I(A-)} and trion binding energy are found to be ∼1.1-5.0 and ∼23.1-47.5 meV in different monolayer MoSe2 samples. Hence, these observations manifest that the processing parameters make a substantial contribution in tuning the vibrational and excitonic properties.

Ultrasensitive Boron-Nitrogen-Codoped CVD Graphene-Derived NO2 Gas Sensor.

Recent trends in 2D materials like graphene are focused on heteroatom doping in a hexagonal honeycomb lattice to tailor the desired properties for various lightweight atomic thin-layer derived portable devices, particularly in the field of gas sensors. To design such gas sensors, it is important to either discover new materials with enhanced properties or tailor the properties of existing materials via doping. Herein, we exploit the concept of codoping of heteroatoms in graphene for more improvements in gas sensing properties and demonstrate a boron- and nitrogen-codoped bilayer graphene-derived gas sensor for enhanced nitrogen dioxide (NO2) gas sensing applications, which may possibly be another alternative for an efficient sensing device. A well-known method of low-pressure chemical vapor deposition (LPCVD) is employed for synthesizing the boron- and nitrogen-codoped bilayer graphene (BNGr). To validate the successful synthesis of BNGr, the Raman, XPS, and FESEM characterization techniques were performed. The Raman spectroscopy results validate the synthesis of graphene nanosheets, and moreover, the FESEM and XPS characterization confirms the codoping of nitrogen and boron in the graphene matrix. The gas sensing device was fabricated on a Si/SiO2 substrate with prepatterned gold electrodes. The proposed BNGr sensor unveils an ultrasensitive nature for NO2 at room temperature. A plausible NO2 gas sensing mechanism is explored via a comparative study of the experimental results through the density functional theory (DFT) calculations of the adsorbed gas molecules on doped heteroatom sites. Henceforth, the obtained results of NO2 sensing with the BNGr gas sensor offer new prospects for designing next-generation lightweight and ultrasensitive gas sensing devices.

Ultrasensitive Wearable Strain Sensors based on a VACNT/PDMS Thin Film for a Wide Range of Human Motion Monitoring.

The ever-growing bridge between stretchable electronic devices and wearable healthcare applications constitutes a significant challenge for discovery of novel materials for ultrasensitive wide-range healthcare monitoring. Herein, we propose a simplistic, amenable, cost-effective method for synthesis of a vertically aligned carbon nanotube (VACNT)/poly(dimethylsiloxane) (PDMS) thin-film composite structure for robust stretchable sensors with a full range of human motion and multimode mechanical stimuli detection functionalities. Notably, the sensor features the best reported response of carbon nanotube (CNT)-based sensors with extensive multiscale healthcare monitoring of subtle and vigorous ambulations ranging from 0.004 up to 30% strain deformations, coupled with an exceptionally high gauge factor of 6436.8 (at 30% strain), super-fast response time of 12 ms, recovery time of 19 ms, ultrasensitive loading sensing, and an excellent reproducibility over 10 000 cycles. The sensor evinces distinctive electromechanical performances and reliability in real time for motions like wrist pulsing, frowning, gulping, balloon inflation, finger bending, wrist bending, bending, twisting, gentle tapping, and rolling. Therefore, the VACNT/PDMS thin-film sensor reveals the ability to be a propitious candidate for e-skin and advanced wearable electronics.

Highly efficient luminescence from hybrid structures of ZnO/multi-walled carbon nanotubes for high performance display applications.

We report an interesting observation on strong enhancement in green luminescence from hybrid ZnO/multi-walled carbon nanotubes (MWCNTs). The hybrid structures were synthesized via a high temperature sintering method. The strong green emission at 510 nm has been attributed to surface defects of ZnO, originating from interactions between ZnO and the MWCNT surface, which has been confirmed by high resolution transmission electron microscopy and x-ray photoelectron spectroscopy. Furthermore, the two-dimensional (2D) layer of this hybrid material shows a high degree of homogeneity and 82% transparency. Time resolved emission spectroscopy measurement shows a photoluminescence decay time in microseconds, which is suitable for making optoelectronic devices.

Self-catalytic synthesis, structure and properties of ultra-fine luminescent ZnO nanostructures for field emission applications.

A facile method to produce high-quality ZnO nanostructures; either tetrapod (TP), nanotetraneedle (NTN) or multipod (MP) with a high degree of homogeneity for advanced field emission (FE) applications is presented. Among these nanostructures, NTN has been successfully employed to demonstrate enhanced current densities (2.6 mA cm(-2)), turn-on field (1.5 V microm(-1)) and field-enhancement factors (6930) over conventional multiwalled carbon nanotubes (MWCNTs), TP, MP and ZnO-spheroids. A comparative study of FE from various ZnO nanostructures, morphologies and site densities has lead to the conclusion that diameter of the tip is one of the vital parameters in enhancing the overall FE properties.

Synthesis and characterization of ultra-fine Y2O3:Eu3+ nanophosphors for luminescent security ink applications.

We report a simple method for the synthesis of ultra-fine Eu(3+)-doped yttria (Y(2)O(3)) nanophosphors with an average diameter of approximately 5 nm for development of a transparent colloid that could be used as a luminescent security ink. This has been achieved by suitably substituting Eu(3+) ions at the favorable C(2) symmetry sites of Y(3+) ions and quantum mechanically confining the growth of the nanophosphor using a novel acid-catalyzed sol-gel technique. This is one of the few reports that depict the development of a transparent aqueous-stable Y(2)O(3):Eu(3+) colloidal solution for strategic applications related to security codes. High resolution transmission electron microscopy images showed excellent lattice fringes that in turn support the presence of better crystal quality and enhanced photoluminescence (PL) emission from the Y(1.9)O(3)Eu(0.1)(3+) nanophosphor system. Time resolved emission spectroscopy measurement indicated a PL decay time in the range of a few milliseconds, suitable for making luminescent security ink and other advanced applications in optoelectronic devices and bio-labeling.