Prashant V. Kamat

Transformation of the Excited State and Photovoltaic Efficiency of CH3NH3PbI3 Perovskite upon Controlled Exposure to Humidified Air

Humidity has been an important factor, in both negative and positive ways, in the development of perovskite solar cells and will prove critical in the push to commercialize this exciting new photovoltaic technology. The interaction between CH(3)NH(3)PbI(3) and H(2)O vapor is investigated by characterizing the ground-state and excited-state optical absorption properties and probing morphology and crystal structure. These undertakings reveal that H(2)O exposure does not simply cause CH(3)NH(3)PbI(3) to revert to PbI(2). It is shown that, in the dark, H(2)O is able to complex with the perovskite, forming a hydrate product similar to (CH(3)NH(3))(4)PbI(6)·2H(2)O. This causes a decrease in absorption across the visible region of the spectrum and a distinct change in the crystal structure of the material. Femtosecond transient absorption spectroscopic measurements show the effect that humidity has on the ultrafast excited state dynamics of CH(3)NH(3)PbI(3). More importantly, the deleterious effects of humidity on complete solar cells, specifically on photovoltaic efficiency and stability, are explored in the light of these spectroscopic understandings.

TiO2-Graphene Nanocomposites. UV-Assisted Photocatalytic Reduction of Graphene Oxide

Graphene oxide suspended in ethanol undergoes reduction as it accepts electrons from UV-irradiated TiO(2) suspensions. The reduction is accompanied by changes in the absorption of the graphene oxide, as the color of the suspension shifts from brown to black. The direct interaction between TiO(2) particles and graphene sheets hinders the collapse of exfoliated sheets of graphene. Solid films cast on a borosilicate glass gap separated by gold-sputtered terminations show an order of magnitude decrease in lateral resistance following reduction with the TiO(2) photocatalyst. The photocatalytic methodology not only provides an on-demand UV-assisted reduction technique but also opens up new ways to obtain photoactive graphene-semiconductor composites.

Quantum dot solar cells. Tuning photoresponse through size and shape control of CdSe-TiO2 architecture.

Different-sized CdSe quantum dots have been assembled on TiO2 films composed of particle and nanotube morphologies using a bifunctional linker molecule. Upon band-gap excitation, CdSe quantum dots inject electrons into TiO2 nanoparticles and nanotubes, thus enabling the generation of photocurrent in a photoelectrochemical solar cell. The results presented in this study highlight two major findings: (i) ability to tune the photoelectrochemical response and photoconversion efficiency via size control of CdSe quantum dots and (ii) improvement in the photoconversion efficiency by facilitating the charge transport through TiO2 nanotube architecture. The maximum IPCE (photon-to-charge carrier generation efficiency) obtained with 3 nm diameter CdSe nanoparticles was 35% for particulate TiO2 and 45% for tubular TiO2 morphology. The maximum IPCE observed at the excitonic band increases with decreasing particle size, whereas the shift in the conduction band to more negative potentials increases the driving force and favors fast electron injection. The maximum power-conversion efficiency </=1% obtained with CdSe-TiO2 nanotube film highlights the usefulness of tubular morphology in facilitating charge transport in nanostructure-based solar cells. Ways to further improve power-conversion efficiency and maximize light-harvesting capability through the construction of a rainbow solar cell are discussed.

Anchoring Semiconductor and Metal Nanoparticles on a Two-Dimensional Catalyst Mat. Storing and Shuttling Electrons with Reduced Graphene Oxide

Using reduced graphene oxide (RGO) as a two-dimensional support, we have succeeded in selective anchoring of semiconductor and metal nanoparticles at separate sites. Photogenerated electrons from UV-irradiated TiO(2) are transported across RGO to reduce silver ions into silver nanoparticles at a location distinct from the TiO(2) anchored site. The ability of RGO to store and shuttle electrons, as visualized via a stepwise electron transfer process, demonstrates its capability to serve as a catalyst nanomat and transfer electrons on demand to adsorbed species. These findings pave the way for the development of next generation catalyst systems and can spur advancements in graphene-based composites for chemical and biological sensors.

An Inorganic Hole Conductor for Organo-Lead Halide Perovskite Solar Cells. Improved Hole Conductivity with Copper Iodide

Organo-lead halide perovskite solar cells have emerged as one of the most promising candidates for the next generation of solar cells. To date, these perovskite thin film solar cells have exclusively employed organic hole conducting polymers which are often expensive and have low hole mobility. In a quest to explore new inorganic hole conducting materials for these perovskite-based thin film photovoltaics, we have identified copper iodide as a possible alternative. Using copper iodide, we have succeeded in achieving a promising power conversion efficiency of 6.0% with excellent photocurrent stability. The open-circuit voltage, compared to the best spiro-OMeTAD devices, remains low and is attributed to higher recombination in CuI devices as determined by impedance spectroscopy. However, impedance spectroscopy revealed that CuI exhibits 2 orders of magnitude higher electrical conductivity than spiro-OMeTAD which allows for significantly higher fill factors. Reducing the recombination in these devices could render CuI as a cost-effective competitor to spiro-OMeTAD in perovskite solar cells.

Mn-Doped Quantum Dot Sensitized Solar Cells: A Strategy to Boost Efficiency over 5%

To make Quantum Dot Sensitized Solar Cells (QDSC) competitive, it is necessary to achieve power conversion efficiencies comparable to other emerging solar cell technologies. By employing Mn(2+) doping of CdS, we have now succeeded in significantly improving QDSC performance. QDSC constructed with Mn-doped-CdS/CdSe deposited on mesoscopic TiO(2) film as photoanode, Cu(2)S/Graphene Oxide composite electrode, and sulfide/polysulfide electrolyte deliver power conversion efficiency of 5.4%.

Beyond Photovoltaics: Semiconductor Nanoarchitectures for Liquid-Junction Solar Cells

3.1. Fundamental Characterization 6672 3.2. Photocurrent Action Spectroscopy 6673 3.3. Optical Characterization 6673 3.4. Characterization of Electron Transfer 6673 4. Electron Transport in Metal Oxide Films 6674 4.1. Mechanism of Photoinduced Carrier Transport 6674 4.2. Characterization of Diffusion Length 6675 4.3. One-Dimensional (1-D) Transport Architectures 6675 4.4. Electrolyte Interactions 6676 5. Recent Trends in Liquid-Junction Solar Cells 6676 5.1. Dye Sensitized Solar Cells 6677 5.2. Quantum Dot Sensitized Solar Cells 6678 5.3. Carbon Nanostructure Based Photochemical Solar Cells 6679

Graphene−Semiconductor Nanocomposites: Excited-State Interactions between ZnO Nanoparticles and Graphene Oxide†

Graphene oxide sheets suspended in ethanol interact with excited ZnO nanoparticles and undergo photocatalytic reduction. The luminescence quenching of the green emission of ZnO serves as a probe to monitor the electron transfer from excited ZnO to graphene oxide. Anchoring of ZnO nanoparticles on 2-D carbon nanostructures provides a new way to design semiconductor-carbon nanocomposites for catalytic applications.

Quantum Dot Sensitized Solar Cells. A Tale of Two Semiconductor Nanocrystals: CdSe and CdTe

CdSe and CdTe nanocrystals are linked to nanostructured TiO2 films using 3-mercaptopropionic acid as a linker molecule for establishing the mechanistic aspects of interfacial charge transfer processes. Both these quantum dots are energetically capable of sensitizing TiO2 films and generating photocurrents in quantum dot solar cells. These two semiconductor nanocrystals exhibit markedly different external quantum efficiencies ( approximately 70% for CdSe and approximately 0.1% for CdTe at 555 nm). Although CdTe with a more favorable conduction band energy (E(CB) = -1.0 V vs NHE) is capable of injecting electrons into TiO2 faster than CdSe (E(CB) = -0.6 V vs NHE), hole scavenging by a sulfide redox couple remains a major bottleneck. The sulfide ions dissolved in aqueous solutions are capable of scavenging photogenerated holes in photoirradiated CdSe system but not in CdTe. The anodic corrosion and exchange of Te with S dominate the charge transfer at the CdTe interface. Factors that dictate the efficiency and photostability of CdSe and CdTe quantum dots are discussed.

Enhanced Rates of Photocatalytic Degradation of an Azo Dye Using SnO2/TiO2 Coupled Semiconductor Thin Films.

We present here for the first time the results from electrochemically assisted photocatalytic experiments using coupled TiO{sub 2}/SnO{sub 2} semiconductor thin films in the degradation of textile dye effluent. We show that by using such a system the oxidative efficiency of photocatalytic semiconductor systems in degrading a commercial azo dye such as Acid Orange 7 (AO7) can be improved. The results presented here on the decolorization of the azo dye AO7 represents a major step forward in the development of new advanced oxidation processes for the treatment of such industrial waste. The improved charge separation as a result of coupling two semiconductor systems with different energy levels and the applied anodic bias is responsible for the enhancement in the rate of photocatalytic degradation. 20 refs., 6 figs.