Showing papers by "Chandran Sudakar published in 2018"

Whispering Gallery Mode Assisted Enhancement in the Power Conversion Efficiency of DSSC and QDSSC Devices Using TiO2 Microsphere Photoanodes

Abstract: Mesoporous TiO2 nanoparticles are excellent photoanodes for sensitized solar cells (SSC). However, a significant loss in the photoconversion efficiency (PCE) occurs due to the inefficient light absorption. Large Mie scattering from mesoporous micron-sized spheres could be used to enhance the absorption and hence the PCE. Here, we show that a composite comprising a TiO2 mesoporous microsphere with smooth surface (SμS-TiO2) exhibiting whispering gallery modes (WGM) and a commercial TiO2 mesoporous nanoparticle (Degussa P25) with an optimum ratio (80:20 wt %) shows significant enhancement in PCE of DSSC and QDSSC devices. SμS-TiO2 exhibits strong WGM as evidenced from the photoluminescence studies carried out using a laser with an excitation wavelength λexc = 325 nm. These microspheres sensitized with N719 dye or CdSe/CuInS2 QDs are shown to exhibit emission characteristics strongly coupled to WGM resulting in an enhanced PCE in SSC. Increases in PCE of ∼24% in DSSC devices and 80–95% in QDSSC devices of 0.2...

Whispering Gallery Mode Enabled Efficiency Enhancement: Defect and Size Controlled CdSe Quantum Dot Sensitized Whisperonic Solar Cells

Abstract: A synergetic approach of employing smooth mesoporous TiO2 microsphere (SμS-TiO2)–nanoparticulate TiO2 (np-TiO2) composite photoanode, and size and defect controlled CdSe quantum dots (QD) to achieve high efficiency (η) in a modified Gratzel solar cell, quantum dot sensitized whisperonic solar cells (QDSWSC), is reported. SμS-TiO2 exhibits whispering gallery modes (WGM) and assists in enhancing the light scattering. SμS-TiO2 and np-TiO2 provide conductive path for efficient photocurrent charge transport and sensitizer loading. The sensitizer strongly couples with the WGM and significantly enhances the photon absorption to electron conversion. The efficiency of QDSWSC is shown to strongly depend on the size and defect characteristics of CdSe QD. Detailed structural, optical, microstructural and Raman spectral studies on CdSe QD suggest that surface defects are prominent for size ~2.5 nm, while the QD with size > 4.5 nm are well crystalline with lower surface defects. QDSWSC devices exhibit an increase in η from ≈0.46% to η ≈ 2.74% with increasing CdSe QD size. The reported efficiency (2.74%) is the highest compared to other CdSe based QDSSC made using TiO2 photoanode and I−/I3− liquid electrolyte. The concept of using whispering gallery for enhanced scattering is very promising for sensitized whisperonic solar cells.

Oxygen vacancy induced photoconductivity enhancement in Bi 1-x Ca x FeO 3-δ nanoparticle ceramics: A combined experimental and theoretical study

Abstract: Based on experimental and density functional studies, we show that tailoring of oxygen vacancies (OV) leads to large scale enhancement of photoconductivity in BiFeO3 (BFO). The OV concentration is increased by substituting an aliovalent cation Ca2+ at Bi3+ sites in the BFO structure. Furthermore, the OV concentration at the disordered grain boundaries can be increased by reducing the particle size. Photoconductivity studies carried out on spark plasma sintered Bi1-xCaxFeO3-δ ceramics show four orders of enhancement for x = 0.1. Temperature dependent Nyquist plots depict a clear decrease in impedance with increasing Ca2+ concentration which signifies the role of OV. A significant reduction in photoconductivity by 2 to 4 orders and a large increase in impedance of the air-annealed (AA) nanocrystalline ceramics suggest that OV at the grain boundaries primarily control the photocurrent. In fact, activation energy for AA samples (0.5 to 1.4 eV) is larger than the as-prepared (AP) samples (0.1 to 0.5 eV). Therefore, the room temperature J-V characteristics under 1 sun illumination show 2–4 orders more current density for AP samples. Density-functional calculations reveal that, while the defect states due to bulk OV are nearly flat, degenerate, and discrete, the defect states due to surface OV are non-degenerate and interact with the surface dangling states to become dispersive. With large vacancy concentration, they form a defect band that enables a continuous transition of charge carriers leading to significant enhancement in the photoconductivity. These studies reveal the importance of tailoring the microstructural features as well as the composition-tailored properties to achieve large short circuit current in perovskite oxide based solar cells.Based on experimental and density functional studies, we show that tailoring of oxygen vacancies (OV) leads to large scale enhancement of photoconductivity in BiFeO3 (BFO). The OV concentration is increased by substituting an aliovalent cation Ca2+ at Bi3+ sites in the BFO structure. Furthermore, the OV concentration at the disordered grain boundaries can be increased by reducing the particle size. Photoconductivity studies carried out on spark plasma sintered Bi1-xCaxFeO3-δ ceramics show four orders of enhancement for x = 0.1. Temperature dependent Nyquist plots depict a clear decrease in impedance with increasing Ca2+ concentration which signifies the role of OV. A significant reduction in photoconductivity by 2 to 4 orders and a large increase in impedance of the air-annealed (AA) nanocrystalline ceramics suggest that OV at the grain boundaries primarily control the photocurrent. In fact, activation energy for AA samples (0.5 to 1.4 eV) is larger than the as-prepared (AP) samples (0.1 to 0.5 eV). There...

High temperature magnetic studies on Bi1-xCaxFe1−yTiyO3-δ nanoparticles: Observation of Hopkinson-like effect above TN

Abstract: The magnetic properties of Bi1-xCaxFe1-yTiyO3-δ (BCFO: y = 0 and BCFTO: x = y) nanoparticles are studied across a wide range of temperatures (20 K to 960 K) for different Ca (and Ti) concentrations [x (= y) = 0, 0.025, 0.05, and 0.1]. X-ray diffraction and electron microscopy revealed the gradual emergence of the orthorhombic phase (Pnma) with an increase in the Ca2+ content in BCFO, contrary to the retention of parent rhombohedral symmetry (R3c) in Ca2+-Ti4+ co-doped BCFTO. XPS indicates the presence of 3+ valence states for Bi and Fe and under-coordinated defect peaks in O 1s spectra. The ordering of oxygen vacancies in BCFO affects the FeO6 octahedral alignment, resulting in a systematic shift of Fe-O Raman modes. Oxygen vacancies formed due to Ca2+ doping in BCFO and the non-magnetic Ti4+ ion at the Fe3+ site in BCFTO disrupt the spin-cycloid propagation in BiFeO3, largely influencing the magnetic properties. These substitutional changes, in addition to the large surface area, are the sources of net magnetization in these systems. Magnetic hysteresis and field dependent zero field cooled-field cooled curves indicate the combined presence of anti-ferromagnetic and ferromagnetic components in BCFO and BCFTO nanoparticles. High temperature magnetic studies present a clear bifurcation of magnetic Neel transition centered at ∼600 K associated with the structural variation in BCFO. A strong anomaly observed at 860 ± 40 K in all the samples suggests a Hopkinson-like effect arising due to sudden loss of anisotropy by the FM component.The magnetic properties of Bi1-xCaxFe1-yTiyO3-δ (BCFO: y = 0 and BCFTO: x = y) nanoparticles are studied across a wide range of temperatures (20 K to 960 K) for different Ca (and Ti) concentrations [x (= y) = 0, 0.025, 0.05, and 0.1]. X-ray diffraction and electron microscopy revealed the gradual emergence of the orthorhombic phase (Pnma) with an increase in the Ca2+ content in BCFO, contrary to the retention of parent rhombohedral symmetry (R3c) in Ca2+-Ti4+ co-doped BCFTO. XPS indicates the presence of 3+ valence states for Bi and Fe and under-coordinated defect peaks in O 1s spectra. The ordering of oxygen vacancies in BCFO affects the FeO6 octahedral alignment, resulting in a systematic shift of Fe-O Raman modes. Oxygen vacancies formed due to Ca2+ doping in BCFO and the non-magnetic Ti4+ ion at the Fe3+ site in BCFTO disrupt the spin-cycloid propagation in BiFeO3, largely influencing the magnetic properties. These substitutional changes, in addition to the large surface area, are the sources of net m...