Maulik K. Patel

In situ investigation of the formation and metastability of formamidinium lead tri-iodide perovskite solar cells

Organic–inorganic perovskites have emerged as an important class of next generation solar cells due to their remarkably low cost, band gap, and sub-900 nm absorption onset. Here, we show a series of in situ observations inside electron microscopes and X-ray diffractometers under device-relevant synthesis conditions focused on revealing the crystallization process of the formamidinium lead-triiodide perovskite at the optimum temperature of 175 °C. Direct in situ observations of the structure and chemistry over relevant spatial, temporal, and temperature scales enabled identification of key perovskite formation and degradation mechanisms related to grain evolution and interface chemistry. The lead composition was observed to fluctuate at grain boundaries, indicating a mobile lead-containing species, a process found to be partially reversible at a key temperature of 175 °C. Using low energy electron microscopy and valence electron energy loss spectroscopy, lead is found to be bonded in the grain interior with iodine in a tetrahedral configuration. At the grain boundaries, the binding energy associated with lead is consequently shifted by nearly 2 eV and a doublet peak is resolved due presumably to a greater degree of hybridization and the potential for several different bonding configurations. At the grain boundaries there is adsorption of hydrogen and OH− ions as a result of residual water vapor trapped as a non-crystalline material during formation. Insights into the relevant formation and decomposition reactions of formamidinium lead iodide at low to high temperatures, observed metastabilities, and relationship with the photovoltaic performance were obtained and used to optimize device processing resulting in conversion efficiencies of up to 17.09% within the stability period of the devices.

Structure and band gap determination of irradiation-induced amorphous nano-channels in LiNbO3

The irradiation of lithium niobate with swift heavy ions results in the creation of amorphous nano-sized channels along the incident ion path. These nano-channels are on the order of a hundred microns in length and could be useful for photonic applications. However, there are two major challenges in these nano-channels characterization: (i) it is difficult to investigate the structural characteristics of these nano-channels due to their very long length and (ii) the analytical electron microscopic analysis of individual ion track is complicated due to electron beam sensitive nature of lithium niobate. Here, we report the first high resolution microscopic characterization of these amorphous nano-channels, widely known as ion-tracks, by direct imaging them at different depths in the material, and subsequently correlating the key characteristics with electronic energy loss of ions. Energetic Kr ions (84Kr22 with 1.98 GeV energy) are used to irradiate single crystal lithium niobate with a fluence of 2 × 1010 ...

Contrasting the material chemistry of Cu2ZnSnSe4 and Cu2ZnSnS(4-x)Sex

Earth‐abundant sustainable inorganic thin‐film solar cells, independent of precious elements, pivot on a marginal material phase space targeting specific compounds. Advanced materials characterization efforts are necessary to expose the roles of microstructure, chemistry, and interfaces. Herein, the earth‐abundant solar cell device, Cu2ZnSnS(4– x )Sex, is reported, which shows a high abundance of secondary phases compared to similarly grown Cu2ZnSnSe4.

Improved high temperature radiation damage tolerance in a three-phase ceramic with heterointerfaces

Radiation damage tolerance for a variety of ceramics at high temperatures depends on the material’s resistance to nucleation and growth of extended defects. Such processes are prevalent in ceramics employed for space, nuclear fission/fusion and nuclear waste environments. This report shows that random heterointerfaces in materials with sub-micron grains can act as highly efficient sinks for point defects compared to grain boundaries in single-phase materials. The concentration of dislocation loops in a radiation damage-prone phase (Al2O3) is significantly reduced when Al2O3 is a component of a composite system as opposed to a single-phase system. These results present a novel method for designing exceptionally radiation damage tolerant ceramics at high temperatures with a stable grain size, without requiring extensive interfacial engineering or production of nanocrystalline materials.

Radiation Damage Behavior in Multiphase Ceramics

Ceramics belong to the promising class of radiation damage resistant materials. In particular, nanocrystalline ceramics have been observed to be more tolerant to radiation damage than ceramics with larger grains . In highly radiation damage tolerant materials, the defect annihilation counteracts and mitigates radiation damage. One route to annihilate defects is the migration of point defects to grain boundaries, which act as efficient sinks for defects. Defect migration to the grain boundaries can be enhanced by shortening the distance between the grain boundary sinks and the defects, which is why the finer grain size (nano-crystalline) improves radiation damage tolerance. However, at high temperatures, which typically exist in a nuclear reactor, nano-grains in single-phase materials will grow and irradiation induces additional grain growth. Once the grains grow larger, the material will no longer be as radiation resistant.

Structural analysis of Gd 2 Ce 2 O 7

A complex cerium bearing oxide, Gd2Ce2O7 was synthesized in order to simulate Pu in a fluorite derivative oxide. X-ray diffraction (XRD) data was collected using a lab diffractometer at room temperature and analyzed by Rietveld refinement method using the xnd program. The diffraction pattern obtained from the material could be indexed as a C-type cubic bixbyite crystal structure however several peaks showed peak broadening and could not be accounted for within the single-phase bixbyite model. A full pattern refinement, assuming a possible existence of short order disordered bixbyite regions within an average disordered fluorite phase gave a good fit with the experimental data, providing an estimate for correlation length of those bixbyite regions. Transmission electron microscopy confirms the existence of these correlated domains of disordered bixbyite type phase inside a defect fluorite lattice. Understanding the extent of these domains as a function of composition and the thermal history of the samples may have a profound effect on our understanding of miscibility gaps in Re2O3-CeO2 phase diagrams. These effects could be eventually exploited to design materials with increased radiation resistance, a desired feature for oxide matrices where actinides can be safely disposed.

Structural analysis of Gd2Ce2O7

A complex cerium bearing oxide, Gd2Ce2O7 was synthesized in order to simulate Pu in a fluorite derivative oxide. X-ray diffraction (XRD) data was collected using a lab diffractometer at room temperature and analyzed by Rietveld refinement method using the xnd program. The diffraction pattern obtained from the material could be indexed as a C-type cubic bixbyite crystal structure however several peaks showed peak broadening and could not be accounted for within the single-phase bixbyite model. A full pattern refinement, assuming a possible existence of short order disordered bixbyite regions within an average disordered fluorite phase gave a good fit with the experimental data, providing an estimate for correlation length of those bixbyite regions. Transmission electron microscopy confirms the existence of these correlated domains of disordered bixbyite type phase inside a defect fluorite lattice. Understanding the extent of these domains as a function of composition and the thermal history of the samples may have a profound effect on our understanding of miscibility gaps in Re2O3-CeO2 phase diagrams. These effects could be eventually exploited to design materials with increased radiation resistance, a desired feature for oxide matrices where actinides can be safely disposed.

Structural analysis of Gd_2Ce_2O_7

A complex cerium bearing oxide, Gd2Ce2O7 was synthesized in order to simulate Pu in a fluorite derivative oxide. X-ray diffraction (XRD) data was collected using a lab diffractometer at room temperature and analyzed by Rietveld refinement method using the xnd program. The diffraction pattern obtained from the material could be indexed as a C-type cubic bixbyite crystal structure however several peaks showed peak broadening and could not be accounted for within the single-phase bixbyite model. A full pattern refinement, assuming a possible existence of short order disordered bixbyite regions within an average disordered fluorite phase gave a good fit with the experimental data, providing an estimate for correlation length of those bixbyite regions. Transmission electron microscopy confirms the existence of these correlated domains of disordered bixbyite type phase inside a defect fluorite lattice. Understanding the extent of these domains as a function of composition and the thermal history of the samples may have a profound effect on our understanding of miscibility gaps in Re2O3-CeO2 phase diagrams. These effects could be eventually exploited to design materials with increased radiation resistance, a desired feature for oxide matrices where actinides can be safely disposed.

Structural Analysis of Gd2Ce2O7

A complex cerium bearing oxide, Gd2Ce2O7 was synthesized in order to simulate Pu in a fluorite derivative oxide. X-ray diffraction (XRD) data was collected using a lab diffractometer at room temperature and analyzed by Rietveld refinement method using the xnd program. The diffraction pattern obtained from the material could be indexed as a C-type cubic bixbyite crystal structure however several peaks showed peak broadening and could not be accounted for within the single-phase bixbyite model. A full pattern refinement, assuming a possible existence of short order disordered bixbyite regions within an average disordered fluorite phase gave a good fit with the experimental data, providing an estimate for correlation length of those bixbyite regions. Transmission electron microscopy confirms the existence of these correlated domains of disordered bixbyite type phase inside a defect fluorite lattice. Understanding the extent of these domains as a function of composition and the thermal history of the samples may have a profound effect on our understanding of miscibility gaps in Re2O3-CeO2 phase diagrams. These effects could be eventually exploited to design materials with increased radiation resistance, a desired feature for oxide matrices where actinides can be safely disposed.