Nilesh Mazumder

Amino-functionalized graphene quantum dots: origin of tunable heterogeneous photoluminescence

Graphene quantum dots are known to exhibit tunable photoluminescence (PL) through manipulation of edge functionality under various synthesis conditions. Here, we report observation of excitation dependent anomalous m-n type fingerprint PL transition in synthesized amino functionalized graphene quantum dots (5-7 nm). The effect of band-to-band π*-π and interstate to band n-π induced transitions led to effective multicolor emission under changeable excitation wavelength in the functionalized system. A reasonable assertion that equi-coupling of π*-π and n-π transitions activated the heterogeneous dual mode cyan emission was made upon observation of the PL spectra. Furthermore, investigation of incremented dimensional scaling through facile synthesis of amino functionalized quantum graphene flakes (20-30 nm) revealed it had negligible effect on the modulated PL pattern. Moreover, an effort was made to trace the origin of excitation dependent tunable heterogeneous photoluminescence through the framework of energy band diagram hypothesis and first principles analysis. Ab initio results suggested formation of an interband state as a manifestation of p orbital hybridization between C-N atoms at the edge sites. Therefore comprehensive theoretical and experimental analysis revealed that newly created energy levels can exist as an interband within the energy gap in functionalized graphene quantum structures yielding excitation dependent tunable PL for optoelectronic applications.

Bane to boon: tailored defect induced bright red luminescence from cuprous iodide nanophosphors for on-demand rare-earth-free energy-saving lighting applications

The long standing controversy concerning the defect band in cuprous iodide (CuI) has been addressed in this paper from a technological point of view of its solid state lighting application. Recently, solid state lighting technology using nanophosphors has been proposed as the prime candidate in the energy saving lighting paradigm. Herein, we demonstrate a novel rare-earth free and non-toxic CuI nanophosphor, which has been synthesized via a facile solvothermal route. These nanophosphors are able to show ultra-bright and stable red emission under near UV excitation. The spectral features of this easily derived nanophosphor are not less than any rare-earth or cadmium based conventional phosphor. Furthermore, it has been conclusively verified that the deep red emission is strongly related to the excess iodine induced optimized defect level engineering in the band structure. The concepts and results presented in this paper clearly establish that the CuI nanophosphor is a promising ‘green’ material for the state-of-the-art rare-earth free lighting and display applications.

Experimental and theoretical investigation of enhanced cold cathode emission by plasma-etched 3d array of nanotips derived from CuPc nanotube

In the present work, we report fabrication and field emission responses of 3D copper phthalocyanine (CuPc) nanotip arrays synthesized over nanotube walls by facile plasma treatment. Significant field emission enhancement is confirmed for a nanotip–nanotube hybrid system (turn-on field 4.2 V μm−1@10 μA cm−2) as compared to pristine CuPc nanotubes (turn-on field 6.8 V μm−1@10 μA cm−2). Root of the observed enhanced cold cathode emission performances is further probed by a finite element method based simulation protocol that computed local electric field distribution for a single tube without and with plasma etching in a manner parallel to the experimental setup. Our obtained results strongly suggest that CuPc nanotip–nanotube hybrid nanostructures are a major potential candidate as field emitters for vacuum nanoelectronics and cold cathode based emission display applications.

Local Field Enhancement-Induced Enriched Cathodoluminescence Behavior from CuI-RGO Nanophosphor Composite for Field-Emission Display Applications.

Field-emission displays (FEDs) constitute one of the major foci of the cutting edge materials research because of the increasingly escalating demand for high-resolution display panels. However, poor efficiencies of the concurrent low voltage cathodoluminescence (CL) phosphors have created a serious bottleneck in the commercialization of such devices. Herein we report a novel CuI-RGO composite nanophosphor that exhibits bright red emission under low voltage electron beam excitation. Quantitative assessment of CL spectra reveals that CuI-RGO nanocomposite phosphor leads to the 4-fold enhancement in the CL intensity as compared to the pristine CuI counterpart. Addition of RGO in the CuI matrix facilitates efficient triggering of luminescence centers that are activated by local electric field enhancement at the CuI-RGO contact points. In addition, conducting RGO also reduces the negative loading problem on the surface of the nanophosphor composite. The concept presented here opens up a novel generic route for enhancing CL intensity of the existing (nano)phosphors as well as validates the bright prospects of the CuI-RGO composite nanophosphor in this rapidly growing field.

Chalcogen doping at anionic site: A scheme towards more dispersive valence band in CuAlO2

Using first-principles calculations, we propose to enhance the dispersion of the top of valence band at high-symmetry points by selective introduction of chalcogen (Ch) impurities at oxygen site. As ab-plane hole mobility of CuAlO2 is large enough to support a band-conduction model over a polaronic one at room temperature [M. S. Lee et al. Appl. Phys. Lett. 79, 2029, (2001); J. Tate et al. Phys. Rev. B 80, 165206, (2009)], we examine its electronic and optical properties normal to c-axis. Intrinsic indirectness of energy-gap at Γ-point can be effectively removed along with substantial increase in density of states near Fermi level (EF) upon Ch addition. This can be attributed to S 2p-Cu 3d interaction just at or below EF, which should result in significantly improved carrier mobility and conductivity profile for this important p-type TCO.

Observation of bright green luminescence in an Eu2+ complexed graphene oxide composite through reduction of Eu3+

Red light harvesting with Eu3+ graphene complexes are well known in the literature. But embedding Eu2+ in a graphene oxide matrix is a difficult proposition and could be of paramount interest because of emission tunability. Herein, we report the observation of highly visible green luminescence for Eu2+ which occurs due to the transition between the 4f7 (8S7/2) ground state and the 4f6 5d excited state with nanosecond time decay through reduction of Eu3+ using a simple chemical approach. This newly formed luminescence complex may be used as a major potential candidate for application in optoelectronics and nanobiotechnology.

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.

Exploring the effect of hole localization on the charge–phonon dynamics of hole doped delafossite

For weak or moderate doping, electrical measurement is not suitable for detecting changes in the charge localization inside a semiconductor. Here, to investigate the nature of charge-phonon coupling in the presence of gradually delocalized holes within a weak doping regime (~1016 cm-3), we examine the temperature dependent Raman spectra (303-817 K) of prototype hole doped delafossite [Formula: see text] (x  =  0/0.03, y  =  0/0.01). For both [Formula: see text] and [Formula: see text] phonons, negative lineshape asymmetry and relative thermal hardening are distinctly observed upon [Formula: see text] and [Formula: see text] doping. Using Allen formalism, charge density of states at the Fermi level per spin and molecule, and charge delocalization associated to [Formula: see text] plane, are estimated to increase appreciably upon codoping compared to the [Formula: see text]-axis. We delineate the interdependence between charge-phonon coupling constant ([Formula: see text]) and anharmonic phonon lifetime ([Formula: see text]), and deduce that excitation of delocalized holes weakly coupled with phonons of larger [Formula: see text] is the governing feature of observed Fano asymmetry ([Formula: see text]) reversal.

Negative capacitance in ZnO1-xChx (Ch = S, Se, Te): Role of localized charge recombination

We demonstrate negative capacitance (NC) dispersion in Z n O by doping lesser electronegative chalcogen (Ch = S, Se, Te) elements at the oxygen (O)-site. Approximately 4.00 ± 0.15 atomic percentage of C h O × is obtained from Rietveld refinement. Using ab initio and dielectric spectroscopy, the tailoring of charge localization around dopants and consequent charge recombination are observed to have a systematic dependence on the stabilization of NC. With the increase of dopant electronegativity difference from S O × to T e O ×, the low frequency (<100 Hz) dispersion of NC gradually extends to a larger frequency under lower external bias. Universal Debye response is found to govern the NC dispersion with calculated relaxation time indicating to trap mediated charge recombination.