Dye-sensitized solar cells based on titanium dioxide (TiO(2)) are promising low-cost alternatives to conventional solid-state photovoltaic devices based on materials such as Si, CdTe and ...CuIn(1-x)Ga(x)Se(2) (refs 1, 2). Despite offering relatively high conversion efficiencies for solar energy, typical dye-sensitized solar cells suffer from durability problems that result from their use of organic liquid electrolytes containing the iodide/tri-iodide redox couple, which causes serious problems such as electrode corrosion and electrolyte leakage. Replacements for iodine-based liquid electrolytes have been extensively studied, but the efficiencies of the resulting devices remain low. Here we show that the solution-processable p-type direct bandgap semiconductor CsSnI(3) can be used for hole conduction in lieu of a liquid electrolyte. The resulting solid-state dye-sensitized solar cells consist of CsSnI(2.95)F(0.05) doped with SnF(2), nanoporous TiO(2) and the dye N719, and show conversion efficiencies of up to 10.2 per cent (8.51 per cent with a mask). With a bandgap of 1.3 electronvolts, CsSnI(3) enhances visible light absorption on the red side of the spectrum to outperform the typical dye-sensitized solar cells in this spectral region.
Perovskite-based solar cells have recently been catapulted to the cutting edge of thin-film photovoltaic research and development because of their promise for high-power conversion efficiencies and ...ease of fabrication. Two types of generic perovskites compounds have been used in cell fabrication: either Pb- or Sn-based. Here, we describe the performance of perovskite solar cells based on alloyed perovskite solid solutions of methylammonium tin iodide and its lead analogue (CH3NH3Sn1–x Pb x I3). We exploit the fact that, the energy band gaps of the mixed Pb/Sn compounds do not follow a linear trend (the Vegard’s law) in between these two extremes of 1.55 and 1.35 eV, respectively, but have narrower bandgap (<1.3 eV), thus extending the light absorption into the near-infrared (∼1,050 nm). A series of solution-processed solid-state photovoltaic devices using a mixture of organic spiro-OMeTAD/lithium bis(trifluoromethylsulfonyl)imide/pyridinium additives as hole transport layer were fabricated and studied as a function of Sn to Pb ratio. Our results show that CH3NH3Sn0.5Pb0.5I3 has the broadest light absorption and highest short-circuit photocurrent density ∼20 mA cm–2 (obtained under simulated full sunlight of 100 mW cm–2).
Lead-free solution-processed solid-state photovoltaic devices based on methylammonium tin iodide (CH3 NH3 SnI3 ) perovskite semiconductor as the light harvester are reported. Featuring an optical ...bandgap of 1.3 eV, the CH3 NH3 SnI3 perovskite material can be incorporated into devices with the organic hole-transport layer spiro-OMeTAD and show an absorption onset at 950 nm, which is significantly redshifted compared with the benchmark CH3 NH3 PbI3 counterpart (1.55 eV). Bandgap engineering was implemented by chemical substitution in the form of CH3 NH3 SnI3-x Brx solid solutions, which can be controllably tuned to cover much of the visible spectrum, thus enabling the realization of lead-free solar cells with an initial power conversion efficiency of 5.73% under simulated full sunlight. Further efficiency enhancements are expected following optimization and a better fundamental understanding of the internal electron dynamics and corresponding interfacial engineering. The reported CH3 NH3 SnI3-x Brx perovskite solar cells represent a step towards the realization of low-cost, environmentally friendly solid-state solar cells.
Organo-lead halide perovskite solar cells have gained enormous significance and have now achieved power conversion efficiencies of ∼20%. However, the potential toxicity of lead in these systems ...raises environmental concerns for widespread deployment. Here we investigate solvent effects on the crystallization of the lead-free methylammonium tin triiodide (CH3NH3SnI3) perovskite films in a solution growth process. Highly uniform, pinhole-free perovskite films are obtained from a dimethyl sulfoxide (DMSO) solution via a transitional SnI2·3DMSO intermediate phase. This high-quality perovskite film enables the realization of heterojunction depleted solar cells based on mesoporous TiO2 layer but in the absence of any hole-transporting material with an unprecedented photocurrent up to 21 mA cm–2. Charge extraction and transient photovoltage decay measurements reveal high carrier densities in the CH3NH3SnI3 perovskite device which are one order of magnitude larger than CH3NH3PbI3-based devices but with comparable recombination lifetimes in both devices. The relatively high background dark carrier density of the Sn-based perovskite is responsible for the lower photovoltaic efficiency in comparison to the Pb-based analogues. These results provide important progress toward achieving improved perovskite morphology control in realizing solution-processed highly efficient lead-free perovskite solar cells.
A series of In2O3 thin films, ranging from X-ray diffraction amorphous to highly crystalline, were grown on amorphous silica substrates using pulsed laser deposition by varying the film growth ...temperature. The amorphous-to-crystalline transition and the structure of amorphous In2O3 were investigated by grazing angle X-ray diffraction (GIXRD), Hall transport measurement, high resolution transmission electron microscopy (HRTEM), electron diffraction, extended X-ray absorption fine structure (EXAFS), and ab initio molecular dynamics (MD) liquid-quench simulation. On the basis of excellent agreement between the EXAFS and MD results, a model of the amorphous oxide structure as a network of InO x polyhedra was constructed. Mechanisms for the transport properties observed in the crystalline, amorphous-to-crystalline, and amorphous deposition regions are presented, highlighting a unique structure–property relationship.
A new and highly regioselective direct C–H arylation polymerization (DARP) methodology enables the reproducible and sustainable synthesis of high-performance π-conjugated photovoltaic copolymers. ...Unlike traditional Stille polycondensation methods for producing photovoltaic copolymers, this DARP protocol eliminates the need for environmentally harmful, toxic organotin compounds. This DARP protocol employs low loadings of commercially available catalyst components, Pd2(dba)3·CHCl3 (0.5 mol%) and P(2-MeOPh)3 (2 mol%), sterically tuned carboxylic acid additives, and an environmentally friendly solvent, 2-methyltetrahydrofuran. Using this DARP protocol, several representative copolymers are synthesized in excellent yields and high molecular masses. The DARP-derived copolymers are benchmarked versus Stille-derived counterparts by close comparison of optical, NMR spectroscopic, and electrochemical properties, all of which indicate great chemical similarity and no significant detectable structural defects in the DARP copolymers. The DARP- and Stille-derived copolymer and fullerene blend microstructural properties and morphologies are characterized with AFM, TEM, and XRD and are found to be virtually indistinguishable. Likewise, the charge generation, recombination, and transport characteristics of the fullerene blend films are found to be identical. For the first time, polymer solar cells fabricated using DARP-derived copolymers exhibit solar cell performances rivalling or exceeding those achieved with Stille-derived materials. For the DARP copolymer PBDTT-FTTE, the power conversion efficiency of 8.4% is a record for a DARP copolymer.
A new series of metal-free organic chromophores (TPA-TTAR-A (1), TPA-T-TTAR-A (2), TPA-TTAR-T-A (3), and TPA-T-TTAR-T-A (4)) are synthesized for application in dye-sensitized solar cells (DSSC) based ...on a donor-π-bridge-acceptor (D−π–A) design. Here a simple triphenylamine (TPA) moiety serves as the electron donor, a cyanoacrylic acid as the electron acceptor and anchoring group, and a novel tetrathienoacene (TTA) as the π-bridge unit. Because of the extensively conjugated TTA π-bridge, these dyes exhibit high extinction coefficients (4.5–5.2 × 104 M–1 cm–1). By strategically inserting a thiophene spacer on the donor or acceptor side of the molecules, the electronic structures of these TTA-based dyes can be readily tuned. Furthermore, addition of a thiophene spacer has a significant influence on the dye orientation and self-assembly modality on TiO2 surfaces. The insertion of a thiophene between the π-bridge and the cyanoacrylic acid anchoring group in TPA-TTAR-T-A (dye 3) promotes more vertical dye orientation and denser packing on TiO2 (molecular footprint = 79 Å2), thus enabling optimal dye loading. Using dye 3, a DSSC power conversion efficiency (PCE) of 10.1% with V oc = 0.833 V, J sc = 16.5 mA/cm2, and FF = 70.0% is achieved, among the highest reported to date for metal-free organic DSSC sensitizers using an I–/I3 – redox shuttle. Photophysical measurements on dye-grafted TiO2 films reveal that the additional thiophene unit in dye 3 enhances the electron injection efficiency, in agreement with the high quantum efficiency.
The influence of the number-average molecular weight (M n) on the blend film morphology and photovoltaic performance of all-polymer solar cells (APSCs) fabricated with the donor polymer ...poly5-(2-hexyldodecyl)-1,3-thieno3,4-cpyrrole-4,6-dione-alt-5,5-(2,5-bis(3-dodecylthiophen-2-yl)thiophene) (PTPD3T) and acceptor polymer poly{N,N′-bis(2-octyldodecyl)naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl-alt-5,5′-(2,2′-bithiophene)} (P(NDI2OD-T2); N2200) is systematically investigated. The M n effect analysis of both PTPD3T and N2200 is enabled by implementing a polymerization strategy which produces conjugated polymers with tunable M ns. Experimental and coarse-grain modeling results reveal that systematic M n variation greatly influences both intrachain and interchain interactions and ultimately the degree of phase separation and morphology evolution. Specifically, increasing M n for both polymers shrinks blend film domain sizes and enhances donor–acceptor polymer–polymer interfacial areas, affording increased short-circuit current densities (J sc). However, the greater disorder and intermixed feature proliferation accompanying increasing M n promotes charge carrier recombination, reducing cell fill factors (FF). The optimized photoactive layers exhibit well-balanced exciton dissociation and charge transport characteristics, ultimately providing solar cells with a 2-fold PCE enhancement versus devices with nonoptimal M ns. Overall, it is shown that proper and precise tuning of both donor and acceptor polymer M ns is critical for optimizing APSC performance. In contrast to reports where maximum power conversion efficiencies (PCEs) are achieved for the highest M ns, the present two-dimensional M n optimization matrix strategy locates a PCE “sweet spot” at intermediate M ns of both donor and acceptor polymers. This study provides synthetic methodologies to predictably access conjugated polymers with desired M n and highlights the importance of optimizing M n for both polymer components to realize the full potential of APSC performance.
To minimize interfacial power losses, thin (5-80 nm) layers of NiO, a p-type oxide semiconductor, are inserted between the active organic layer, poly(3-hexylthiophene) (P3HT) + 6,6-phenyl-C₆₁ butyric ...acid methyl ester (PCBM), and the ITO (tin-doped indium oxide) anode of bulk-heterojunction ITO/P3HT:PCBM/LiF/Al solar cells. The interfacial NiO layer is deposited by pulsed laser deposition directly onto cleaned ITO, and the active layer is subsequently deposited by spin-coating. Insertion of the NiO layer affords cell power conversion efficiencies as high as 5.2% and enhances the fill factor to 69% and the open-circuit voltage (Voc) to 638 mV versus an ITO/P3HT:PCBM/LiF/Al control device. The value of such hole-transporting/electron-blocking interfacial layers is clearly demonstrated and should be applicable to other organic photovoltaics.
Depositing a pinhole-free perovskite film is of paramount importance to achieve high performance perovskite solar cells, especially in a heterojunction device format that is free of hole transport ...material (HTM). Here, we report that high-quality pinhole-free CH3NH3PbI3 perovskite film can be controllably deposited via a facile low-temperature (<150 °C) gas–solid crystallization process. The crystallite formation process was compared with respect to the conventional solution approach, in which the needle-shaped solvation intermediates (CH3NH3PbI3·DMF and CH3NH3PbI3·H2O) have been recognized as the main cause for the incomplete coverage of the resultant film. By avoiding these intermediates, the films crystallized at the gas–solid interface offer several beneficial features for device performance including high surface coverage, small surface roughness, as well as controllable grain size. Highly efficient HTM-free perovskite solar cells were constructed with these pinhole-free CH3NH3PbI3 films, exhibiting significant enhancement of the light harvesting in the long wavelength regime with respect to the conventional solution processed one. Overall, the gas–solid method yields devices with an impressive power conversion efficiency of 10.6% with high reproducibility displaying a negligible deviation of 0.1% for a total of 30 cells.
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