Md. K. Nazeeruddin

Porphyrin-Sensitized Solar Cells with Cobalt (II/III)–Based Redox Electrolyte Exceed 12 Percent Efficiency

Simultaneous modification of the dye and redox shuttle boosts the efficiency of a dye-sensitized solar cell. The iodide/triiodide redox shuttle has limited the efficiencies accessible in dye-sensitized solar cells. Here, we report mesoscopic solar cells that incorporate a Co(II/III)tris(bipyridyl)–based redox electrolyte in conjunction with a custom synthesized donor-π-bridge-acceptor zinc porphyrin dye as sensitizer (designated YD2-o-C8). The specific molecular design of YD2-o-C8 greatly retards the rate of interfacial back electron transfer from the conduction band of the nanocrystalline titanium dioxide film to the oxidized cobalt mediator, which enables attainment of strikingly high photovoltages approaching 1 volt. Because the YD2-o-C8 porphyrin harvests sunlight across the visible spectrum, large photocurrents are generated. Cosensitization of YD2-o-C8 with another organic dye further enhances the performance of the device, leading to a measured power conversion efficiency of 12.3% under simulated air mass 1.5 global sunlight.

Mesoscopic CH3NH3PbI3/TiO2 heterojunction solar cells.

We report for the first time on a hole conductor-free mesoscopic methylammonium lead iodide (CH(3)NH(3)PbI(3)) perovskite/TiO(2) heterojunction solar cell, produced by deposition of perovskite nanoparticles from a solution of CH(3)NH(3)I and PbI(2) in γ-butyrolactone on a 400 nm thick film of TiO(2) (anatase) nanosheets exposing (001) facets. A gold film was evaporated on top of the CH(3)NH(3)PbI(3) as a back contact. Importantly, the CH(3)NH(3)PbI(3) nanoparticles assume here simultaneously the roles of both light harvester and hole conductor, rendering superfluous the use of an additional hole transporting material. The simple mesoscopic CH(3)NH(3)PbI(3)/TiO(2) heterojunction solar cell shows impressive photovoltaic performance, with short-circuit photocurrent J(sc)= 16.1 mA/cm(2), open-circuit photovoltage V(oc) = 0.631 V, and a fill factor FF = 0.57, corresponding to a light to electric power conversion efficiency (PCE) of 5.5% under standard AM 1.5 solar light of 1000 W/m(2) intensity. At a lower light intensity of 100W/m(2), a PCE of 7.3% was measured. The advent of such simple solution-processed mesoscopic heterojunction solar cells paves the way to realize low-cost, high-efficiency solar cells.

Highly Efficient Dye-Sensitized Solar Cells Based on Carbon Black Counter Electrodes

Carbon black was employed as the catalyst for triiodide reduction on fluorine-doped tin oxide glass substrates (FTO-glass) used as counter electrodes in platinum-free dye-sensitized solar cells. The fill factors were strongly dependent on the thickness of the carbon layer, and the light energy conversion efficiency also increased up to a thickness of 10 μm. The charge-transfer resistance (R ct ) of the carbon counter electrode decreased with the thickness of the carbon layer. The R ct for the thicker carbon layer is less than three times that for the platinized FTO-glass. The highest cell efficiency was 9.1% under 100 mW cm -2 light intensity (1 sun AM 1.5 light, J sc = 16.8 mA cm -2 , V oc = 789.8 mV, fill factor = 0.685).

Efficient CdSe quantum dot-sensitized solar cells prepared by an improved successive ionic layer adsorption and reaction process

In pursuit of efficient quantum dot (QD)-sensitized solar cells based on mesoporous TiO(2) photoanodes, a new procedure for preparing selenide (Se(2-)) was developed and used for depositing CdSe QDs in situ over TiO(2) mesopores by the successive ionic layer adsorption and reaction (SILAR) process in ethanol. The sizes and density of CdSe QDs over TiO(2) were controlled by the number of SILAR cycles applied. After some optimization of these QD-sensitized TiO(2) films in regenerative photoelectrochemical cells using a cobalt redox couple [Co(o-phen)(3)(2+/3+)], including addition of a final layer of CdTe, over 4% overall efficiencies were achieved at 100 W/m(2) with about 50% IPCE at its maximum. Light-harvesting properties and transient voltage decay/impedance measurements confirmed that CdTe-terminated CdSe QD cells gave better charge-collection efficiencies and kinetic parameters than corresponding CdSe QD cells. In a preliminary study, a CdSe(Te) QD-sensitized TiO(2) film was combined with an organic hole conductor, spiro-OMeTAD, and shown to exhibit a promising efficiency of 1.6% at 100 W/m(2) in inorganic/organic hybrid all-solid-state cells.

High-Performance Nanostructured Inorganic−Organic Heterojunction Solar Cells

We report all solid-state nanostructured inorganic-organic heterojunction solar cells fabricated by depositing Sb(2)S(3) and poly(3-hexylthiophene) (P3HT) on the surface of a mesoporous TiO(2) layer, where Sb(2)S(3) acts as an absorbing semiconductor and P3HT acts as both a hole conductor and light absorber. These inorganic-organic light harvesters perform remarkably well with a maximum incident-photon-to-current efficiency (IPCE) of 80% and power conversion efficiency of 5.13% under air-mass 1.5 global (AM 1.5G) illumination with the intensity of 100 mW cm(-2). These devices are highly stable under room light in air, even without encapsulation. The present findings offer novel directions for achieving high-efficiency solid-state solar cells by hybridization of inorganic-organic light harvesters and hole transporters.

A cobalt complex redox shuttle for dye-sensitized solar cells with high open-circuit potentials

Dye-sensitized solar cells are a promising alternative to traditional inorganic semiconductor-based solar cells. Here we report an open-circuit voltage of over 1,000 mV in mesoscopic dye-sensitized solar cells incorporating a molecularly engineered cobalt complex as redox mediator. Cobalt complexes have negligible absorption in the visible region of the solar spectrum, and their redox properties can be tuned in a controlled fashion by selecting suitable donor/acceptor substituents on the ligand. This approach offers an attractive alternate to the traditional I3−/I− redox shuttle used in dye-sensitized solar cells. A cobalt complex using tridendate ligands [Co(bpy-pz)2]3+/2+(PF6)3/2 as redox mediator in combination with a cyclopentadithiophene-bridged donor-acceptor dye (Y123), adsorbed on TiO2, yielded a power conversion efficiency of over 10% at 100 mW cm−2. This result indicates that the molecularly engineered cobalt redox shuttle is a legitimate alternative to the commonly used I3−/I− redox shuttle.

Cation-Induced Band-Gap Tuning in Organohalide Perovskites: Interplay of Spin-Orbit Coupling and Octahedra Tilting

Organohalide lead perovskites have revolutionized the scenario of emerging photovoltaic technologies. The prototype MAPbI3 perovskite (MA = CH3NH3(+)) has dominated the field, despite only harvesting photons above 750 nm (∼1.6 eV). Intensive research efforts are being devoted to find new perovskites with red-shifted absorption onset, along with good charge transport properties. Recently, a new perovskite based on the formamidinium cation ((NH2)2CH(+) = FA) has shown potentially superior properties in terms of band gap and charge transport compared to MAPbI3. The results have been interpreted in terms of the cation size, with the larger FA cation expectedly delivering reduced band-gaps in Pb-based perovskites. To provide a full understanding of the interplay among size, structure, and organic/inorganic interactions in determining the properties of APbI3 perovskites, in view of designing new materials and fully exploiting them for solar cells applications, we report a fully first-principles investigation on APbI3 perovskites with A = Cs(+), MA, and FA. Our results evidence that the tetragonal-to-quasi cubic structural evolution observed when moving from MA to FA is due to the interplay of size effects and enhanced hydrogen bonding between the FA cations and the inorganic matrix altering the covalent/ionic character of Pb-I bonds. Most notably, the observed cation-induced structural variability promotes markedly different electronic and optical properties in the MAPbI3 and FAPbI3 perovskites, mediated by the different spin-orbit coupling, leading to improved charge transport and red-shifted absorption in FAPbI3 and in general in pseudocubic structures. Our theoretical model constitutes the basis for the rationale design of new and more efficient organohalide perovskites for solar cells applications.

High efficiency stable inverted perovskite solar cells without current hysteresis

The inverted perovskite solar cell fabricated using a two-step method exhibited the highest FF of 0.85 and good efficiency of 18% based on CH3NH3PbI3. A small amount of H2O was added into PbI2/DMF to make a homogenous precursor solution. A high quality PbI2 film with full coverage was formed on a PEDOT:PSS surface by spin coating of the homogeneous PbI2 precursor solution. The perovskite film fabricated from the high quality PbI2 film is highly pure, smooth and very dense even without any pinhole. The champion cell achieves a remarkable fill factor (FF) of 0.85, which is the highest value reported in perovskite solar cells. The FF value is also very reproducible with less than 10% deviation for 50 cells. The cell exhibits no current hysteresis and is stable under both dark and illumination conditions in dry and inert atmospheres. The results not only provide a strategy to fabricate high efficiency inverted perovskite solar cells but also reveal how the water additive in the PbI2/DMF solution may affect the properties of PbI2 and therefore the perovskite film prepared using the two-step method and the overall photovoltaic performance of the corresponding inverted solar cell.

Panchromatic engineering for dye-sensitized solar cells

The dye-sensitized mesoscopic solar cell has been intensively investigated as a promising photovoltaic cell. Its ecological and economical fabrication processes make it attractive and credible alternative to conventional photovoltaic systems. In contrast to the latter design, the DSC approach separates tasks of light absorption and charge transport. The primary step of light absorption is performed by a sensitizer anchored to the surface of a wide band gap semiconductor. In order to reach a high conversion efficiency, the first requirement is that the sensitizer should absorb as much as possible of the incoming sunlight. Strategies for achieving panchromatic response in dye-sensitized mesoscopic solar cells are discussed.

Regenerative PbS and CdS Quantum Dot Sensitized Solar Cells with a Cobalt Complex as Hole Mediator

Metal sulfide (PbS and CdS) quantum dots (QDs) were prepared over mesoporous TiO2 films by improved successive ionic layer adsorption and reaction (SILAR) processes. The as-prepared QD-sensitized electrodes were combined with a cobalt complex redox couple [Co(o-phen)3]2+/3+ to make a regenerative liquid-type photovoltaic cell. The optimized PbS QD-sensitized solar cells exhibited promising incident photon-to-current conversion efficiency (IPCE) of over 50% and an overall conversion efficiency of 2% at 0.1 sun in a regenerative mode. The overall photovoltaic performance of the PbS QD-sensitized cells was observed to be dependent on the final turn of the SILAR process, giving a better result when the final deposition was Pb2+, not S2-. However, in the case of CdS QD-sensitized cells, S2- termination was better than that of Cd2+. The cobalt complex herein used as a regenerative redox couple was found to be more efficient in generating photocurrents from PbS QD cells than the typical hole scavenger Na2S in a three-electrode configuration. The CdS-sensitized cell with this redox mediator also showed better defined current-voltage curves and an IPCE reaching 40%.