Sandheep Ravishankar

Bio: Sandheep Ravishankar is an academic researcher from Forschungszentrum Jülich. The author has contributed to research in topics: Perovskite (structure) & Photocurrent. The author has an hindex of 11, co-authored 19 publications receiving 833 citations. Previous affiliations of Sandheep Ravishankar include James I University.

Tunable hysteresis effect for perovskite solar cells

Abstract: Perovskite solar cells (PSCs) usually suffer from a hysteresis effect in current–voltage measurements, which leads to an inaccurate estimation of the device efficiency. Although ion migration, charge trapping/detrapping, and accumulation have been proposed as a basis for the hysteresis, the origin of the hysteresis has not been apparently unraveled. Herein we reported a tunable hysteresis effect based uniquely on open-circuit voltage variations in printable mesoscopic PSCs with a simplified triple-layer TiO2/ZrO2/carbon architecture. The electrons are collected by the compact TiO2/mesoporous TiO2 (c-TiO2/mp-TiO2) bilayer, and the holes are collected by the carbon layer. By adjusting the spray deposition cycles for the c-TiO2 layer and UV-ozone treatment, we achieved hysteresis-normal, hysteresis-free, and hysteresis-inverted PSCs. Such unique trends of tunable hysteresis are analyzed by considering the polarization of the TiO2/perovskite interface, which can accumulate positive charges reversibly. Successfully tuning of the hysteresis effect clarifies the critical importance of the c-TiO2/perovskite interface in controlling the hysteretic trends observed, providing important insights towards the understanding of this rapidly developing photovoltaic technology.

Near-complete suppression of surface losses and total internal quantum efficiency in BiVO4 photoanodes

Abstract: Bismuth vanadate (BiVO4) is one of the most efficient light absorbing metal oxides for solar water splitting. BiVO4 photoanodes immersed in an electrolyte in an open circuit configuration and exposed to simulated solar illumination for prolonged time achieve superior photoelectrochemical (PEC) activity. This photocharging (PC) effect is capable of almost completely overcoming the surface and bulk limitations of BiVO4. Herein we show that alkaline conditions favor the PC effect; specifically BiVO4 photoanodes subjected to PC treatment at pH 10 achieve a record high photocurrent for undoped and uncatalyzed BiVO4 of 4.3 mA cm−2 @ 1.23 VRHE, an outstandingly low onset potential of 0.25 VRHE, and a very steep photocurrent onset. Alkaline conditions also facilitate excellent external and internal quantum efficiencies of 75 and 95% respectively (average in the 440 nm > λ > 330 nm range). Moreover, impedance spectroscopy and in situ XAS study suggest that electronic, structural and chemical properties of the bulk of these films remain unchanged during the PC treatment. However, appreciable changes in the surface-related properties take place. Ultimately, our results indicate that the improved activity of PC-BiVO4 is enhanced by surface reaction pathways of the semiconductor–liquid junction, which is directly correlated with the electrochemical environment in which it is modified.

Surface Polarization Model for the Dynamic Hysteresis of Perovskite Solar Cells.

Abstract: The dynamic hysteresis of perovskite solar cells consists of the occurrence of significant deviations of the current density–voltage curve shapes depending on the specific conditions of measurement such as starting voltage, waiting time, scan rate, and other factors. Dynamic hysteresis is a serious impediment to stabilized and reliable measurement and operation of the perovskite solar cells. In this Letter, we formulate a model for the dynamic hysteresis based on the idea that the cell accumulates a huge quantity of surface electronic charge at forward bias that is released on voltage sweeping, causing extra current over the normal response. The charge shows a retarded dynamics due to the slow relaxation of the accompanying ionic charge, that produces variable shapes depending on scan rate or poling value and time. We show that the quantitative model provides a consistent description of experimental results and allows us to determine significant parameters of the perovskite solar cell for both the transie...

Halide Perovskite Photovoltaics: Background, Status, and Future Prospects

Abstract: The photovoltaics of organic–inorganic lead halide perovskite materials have shown rapid improvements in solar cell performance, surpassing the top efficiency of semiconductor compounds such as CdTe and CIGS (copper indium gallium selenide) used in solar cells in just about a decade. Perovskite preparation via simple and inexpensive solution processes demonstrates the immense potential of this thin-film solar cell technology to become a low-cost alternative to the presently commercially available photovoltaic technologies. Significant developments in almost all aspects of perovskite solar cells and discoveries of some fascinating properties of such hybrid perovskites have been made recently. This Review describes the fundamentals, recent research progress, present status, and our views on future prospects of perovskite-based photovoltaics, with discussions focused on strategies to improve both intrinsic and extrinsic (environmental) stabilities of high-efficiency devices. Strategies and challenges regardi...

Challenges for commercializing perovskite solar cells.

Abstract: BACKGROUND Perovskite solar cells (PSCs) have attracted intensive attention because of their ever-increasing power conversion effi­ciency (PCE), low-cost materials constituents, and simple solution fabrication process. Initi­ated in 2009 with an efficiency of 3.8%, PSCs have now achieved a lab-scale power conversion efficiency of 23.3%, rivaling the performance of commercial multicrystalline silicon solar cells, as well as copper indium gallium selenide (CIGS) and cadmium telluride (CdTe) thin-film solar cells. Thousands of articles re­lated to PSCs have been published each year since 2015, highlighting PSCs as a topic of in­tense interest in photovoltaics (PV) research. With high efficiencies achieved in lab devices, stability and remaining challenges in upscal­ing the manufacture of PSCs are two critical concerns that must be addressed on the path to PSC commercialization. ADVANCES We review recent progress in PSCs and discuss the remaining challenges along the pathway to their commercialization. Device configurations of PSCs (see the figure) include mesoscopic formal (n-i-p) and inverted (p-i-n) structures, planar formal and inverted struc­tures, and the printable triple mesoscopic structures. PCEs of devices that use these structures have advanced rapidly in the case of small-area devices (~0.1 cm 2 ). PSCs are also attracting attention as top cells for the construction of tandem solar cells with existing mature PV technologies to increase efficiency beyond the Shockley-Queisser limit of single-junction devices. The stability of PSCs has attracted much well-deserved attention of late, and notable progress has been made in the past few years. PSCs have recently achieved exhibited life­times of 10,000 hours under 1 sun (1 kW/m 2 ) illumina­tion with an ultraviolet filter at a stabilized temperature of 55°C and at short-circuit conditions for a printable triple mesoscopic PSCs. This irradiation is equivalent to the total irradiation of 10 years of outdoor use in most of Europe. However, within the PSC community, standard testing protocols require further development. In addition, transpar­ency in reporting standards on stability tests needs to be improved; this can be achieved by providing both initial photovoltaic performance and normalization parameters. The upscaling of PSCs has also progressed steadily, leading to PSC mini-modules, standard-sized modules, and power systems. PV companies have set out to manufacture large-area PSC modules (see the figure), and a 110-m 2 perovskite PV system with screen-printed triple mesoscopic PSC modules was recently debuted. Studies of these increased-area modules and systems will promote the development of PSCs toward commercializa­tion. PSC research is expanding to cover fundamental topics on materials and lab-sized cells, as well as to address issues of in­dustrial-scale manufacturing and deployment. OUTLOOK The PV market has been continu­ously expanding in recent years, bringing op­portunities for new PV technologies of which PSCs are promising candidates. It is impera­tive to achieve a low cost per watt, which means that both efficiency and lifetime need improve­ment relative to current parameters. The efficiency gap between lab cells and industrial modules has seen impressive reduc­tions in crystalline silicon; PSCs must simi­larly enlarge module areas to the panel level and need to achieve lifetimes comparable to those of legacy PV technologies. Other improvements will need to include industry-scale electronic-grade films, recycling methods to address concerns regarding lead toxicity, and the adoption of standardized testing protocols to predict the operation lifetime of PSCs. Modules will need to endure light-induced degradation, potential-induced degradation, partial-shade stress, and mechanical shock. The field can benefit from lessons learned during the development of mature PV technologies as it strives to de­fine, and overcome, the hurdles to PSC com­mercial impact.

Light-induced lattice expansion leads to high-efficiency perovskite solar cells

Abstract: Light-induced structural dynamics plays a vital role in the physical properties, device performance, and stability of hybrid perovskite–based optoelectronic devices. We report that continuous light illumination leads to a uniform lattice expansion in hybrid perovskite thin films, which is critical for obtaining high-efficiency photovoltaic devices. Correlated, in situ structural and device characterizations reveal that light-induced lattice expansion benefits the performances of a mixed-cation pure-halide planar device, boosting the power conversion efficiency from 18.5 to 20.5%. The lattice expansion leads to the relaxation of local lattice strain, which lowers the energetic barriers at the perovskite-contact interfaces, thus improving the open circuit voltage and fill factor. The light-induced lattice expansion did not compromise the stability of these high-efficiency photovoltaic devices under continuous operation at full-spectrum 1-sun (100 milliwatts per square centimeter) illumination for more than 1500 hours.

Photocatalysis with Reduced TiO2: From Black TiO2 to Cocatalyst-Free Hydrogen Production.

Abstract: Black TiO2 nanomaterials have recently emerged as promising candidates for solar-driven photocatalytic hydrogen production. Despite the great efforts to synthesize highly reduced TiO2, it is apparent that intermediate degree of reduction (namely, gray titania) brings about the formation of peculiar defective catalytic sites enabling cocatalyst-free hydrogen generation. A precise understanding of the structural and electronic nature of these catalytically active sites is still elusive, as well as the fundamental structure-activity relationships that govern formation of crystal defects, increased light absorption, charge separation, and photocatalytic activity. In this Review, we discuss the basic concepts that underlie an effective design of reduced TiO2 photocatalysts for hydrogen production such as (i) defects formation in reduced TiO2, (ii) analysis of structure deformation and presence of unpaired electrons through electron paramagnetic resonance spectroscopy, (iii) insights from surface science on electronic singularities due to defects, and (iv) the key differences between black and gray titania, that is, photocatalysts that require Pt-modification and cocatalyst-free photocatalytic hydrogen generation. Finally, future directions to improve the performance of reduced TiO2 photocatalysts are outlined.

Electronic structure of hybrid halide perovskite photovoltaic absorbers

Abstract: The performance of organometallic perovskite solar cells has rapidly surpassed those of both traditional dye-sensitized and organic photovoltaics, e.g. solar cells based on CH3NH3PbI3 have recently reached 18% conversion efficiency. We analyze its electronic structure and optical properties within the quasiparticle self-consistent GW approximation (QSGW ). Quasiparticle self-consistency is essential for an accurate description of the band structure: bandgaps are much larger than what is predicted by the local density approximation (LDA) or GW based on the LDA. Several characteristics combine to make the electronic structure of this material unusual. First, there is a strong driving force for ferroelectricity, as a consequence the polar organic moiety CH3NH3. The moiety is only weakly coupled to the PbI3 cage; thus it can rotate give rise to ferroelectric domains. This in turn will result in internal junctions that may aid separation of photoexcited electron and hole pairs, and may contribute to the current-voltage hysteresis found in perovskite solar cells. Second, spin orbit modifies both valence band and conduction band dispersions in a very unusual manner: both get split at the R point into two extrema nearby. This can be interpreted in terms of a large Dresselhaus term, which vanishes at R but for small excursions about R varies linearly in k. Conduction bands (Pb 6p character) and valence bands (I 5p) are affected differently; moreover the splittings vary with the orientation of the moiety. We will show how the splittings, and their dependence on the orientation of the moiety through the ferroelectric effect, have important consequences for both electronic transport and the optical properties of this material.