Dipole-field-assisted charge extraction in metal-perovskite-metal back-contact solar cells

Hybrid organic-inorganic halide perovskites are low-cost solution-processable solar cell materials with photovoltaic properties that rival those of crystalline silicon. The perovskite films are typically sandwiched between thin layers of hole and electron transport materials, which efficiently extract photogenerated charges. This affords high-energy conversion efficiencies but results in significant performance and fabrication challenges. Herein we present a simple charge transport layer-free perovskite solar cell (PSC), comprising only a perovskite layer with two interdigitated gold back-contacts. Charge extraction is achieved via self-assembled molecular monolayers (SAMs) and their associated dipole fields at the metal/perovskite interface. Photovoltages of approximately 600 mV generated by SAM-modified PSCs are equivalent to the built-in potential generated by individual dipole layers. Efficient charge extraction results in photocurrents of up to 12.1 mA/cm2 under simulated sunlight, despite a large electrode spacing.Comment: 18 pages, 5 figure

Injection Kinetics and Electronic Structure at the N719 TiO2 Interface Studied by Means of Ultrafast XUV Photoemission Spectroscopy

The method of transient XUV photoemission spectroscopy is developed to investigate the ultrafast dynamics of heterogeneous electron transfer at the interface between the N719 ruthenium dye complex and TiO2 nanoparticles. XUV light from high order harmonic generation is used to probe the electron density distribution among the ground and excited states at the interface after its exposure to a pump laser pulse of 530 nm wavelength. A spectral decomposition of the transient emission signal is used to follow the population and decay dynamics of the involved transient states individually. By comparing results obtained for the N719 TiO2 and N719 FTO interfaces, we can unambiguously reveal the kinetics of electrons injected to TiO2 from the singlet metal to ligand charge transfer MLCT excited state of the dye. With the developed approach, we characterize both the kinetic constants and the absolute binding energies of the singlet and triplet MLCT states of the dye and the state of electrons injected to the conduction band of TiO2. The energy levels of the singlet and triplet states are found to lie 0.7 eV above and 0.2 eV below the conduction band minimum, respectively. This energetic structure gives rise to a strong driving force for injection from the singlet state and a slow electron transfer from the triplet state, the latter being possible due to a partial overlap of the triplet state band of N719 and the conduction band of TiO

Dye regeneration and charge recombination in dye-sensitized solar cells with ferrocene derivatives as redox mediators

Ferrocene compounds are promising redox shuttles for application in dye-sensitized solar cells (DSCs). Chemical modification of the cyclopentadienyl rings is easily achievable affording almost unlimited variation of the redox properties. This allows fine-tuning of the driving force for dye-regeneration and optimization of the energy conversion efficiency of DSCs. Herein, six ferrocene derivatives have been chosen for investigation which cover the large redox potential range of 0.85 V, by virtue of simple alkylation and halogenation of the cyclopentadienyl ring, and enable improved matching of the energy levels of the sensitizer and the electrolyte. Although the focus of this work was to examine the effect of the redox potential on charge transfer processes, DSCs were fabricated which achieved high energy conversion efficiencies of over 5%. Charge transfer reactions were studied to reveal the dependence of the dye regeneration rate, recombination losses and recombination pathways on the reaction driving force. An increase in redox potential led to a higher efficiency due to higher open circuit potentials until a threshold is reached. At this threshold, the driving force for dye regeneration (18 kJ DE ¼ 0.19 V) becomes too small for efficient device operation, leading to rapid recombination between the oxidized dye and electrons in the TiO2 conduction band. As a result of this work guidelines can be formulated to aid the selection of redox couples for a particular sensitizer in order to maximize the utilization of incident solar energy

Improved performance of porphyrin-based dye sensitised solar cells by phosphinic acid surface treatment

Chemical surface treatment of porphyrin-sensitised titania films using bis-(4-methoxyphenyl) phosphinic acid after dye adsorption, results in large improvements in DSSC efficiencies which originate primarily from higher short circuit currents. The result was attributed to a positive shift in the TiO2 quasi-Fermi level with simultaneous retardation of charge recombination. High device performances have been achieved even using simplified electrolyte matrices devoid of the common additives, LiI and t-butylpyridine

Spectroscopic studies on photoinduced reactions of the anticancer prodrug, trans,trans,trans-[Pt(N3)2(OH)2(py)2]

The photodecomposition mechanism of trans,trans,trans-[Pt(N3)2(OH)2(py)2] (1, py = pyridine), an anticancer prodrug candidate, was probed using complementary Attenuated Total Reflection Fourier Transform Infrared (ATR-FTIR), transient electronic absorption and UV-Vis spectroscopy. Data fitting using Principal Component Analysis (PCA) and multi-curve resolution alternating least squares, suggests the formation of a trans-[Pt(N3)(py)2(OH/H2O)] intermediate and trans [Pt(py)2(OH/H2O)2] as the final product upon 420 nm irradiation of 1 in water. Rapid disappearance of the hydroxido ligand stretching vibration upon irradiation is correlated with a -10 cm-1 shift to the anti-symmetric azido vibration, suggesting a possible second intermediate. Experimental proof of subsequent dissociation of azido ligands from platinum is presented, where at least one hydroxyl radical is formed in the reduction of Pt(IV) to Pt(II). Additionally, the photoinduced reaction of 1 with 5'-guanosine monophosphate was studied, and the identity of key photoproducts was assigned with the help of ATR FTIR spectroscopy, mass spectrometry and DFT calculations. The identification of marker bands for photoproducts, e.g. trans-[Pt(N3)(py)2(5'-GMP)] and trans-[Pt(py)2(5'-GMP)2], will aid elucidation of the chemical and biological mechanism of anticancer action of 1. In general, these studies demonstrate the potential of vibrational spectroscopic techniques as promising tools for studying such metal complexes

Ability of GHTD-amide and analogs to enhance insulin activity through zinc chelation and dispersal of insulin oligomers

GHTD-amide is a tetrapeptide originally isolated from human urine that has hypoglycemic activity. Insulin occurs in secretory granules of beta cells as zinc-stabilized hexamers and must disperse to monomeric form in order to bind to its receptor. The aim of this study was to identify whether GHTD-amide and an analog called ISF402 (VHTD-amide) reduce blood glucose through enhancement of insulin activity by dispersing oligomers of insulin. Peptides containing the HTD-amide sequence and a free α-amino group were optimal at binding Zn2+ and adopting secondary structure in the presence of Zn2+. Binding was concentration dependent and resulted in a 1:1 Zn:peptide complex. In vitro the tetrapeptides dispersed hexameric insulin to dimers and monomers. GHTD-amide and ISF402 potentiated the activity of hexameric insulin when co-injected into insulin resistant Zucker rats. Injection of peptides with insulin caused reductions in blood glucose and C-peptide significantly larger than achieved with insulin alone, and serum insulin time profiles were also altered consistent with a reduced clearance or enhanced dispersal of the injected insulin. Insulin potentiation by ISF402 was reduced when lispro insulin, which does not form zinc-stabilized hexamers, was used in place of hexameric zinc insulin. In conclusion, GHTD-amide and ISF402 are zinc binding peptides that disperse hexameric insulin in vitro, and potentiate the activity of hexameric insulin more so than monomeric lispro insulin. These results suggest that dispersal of hexameric insulin through chelation of Zn2+ contributes to the hypoglycemic activity of these tetrapeptides. Crown Copyright © 2009

1,1′-[(5-Hy­droxy­methyl-1,3-phenyl­ene)bis­(methyl­ene)]dipyridin-4(1H)-one monohydrate

The asymmetric unit of the title compound, C19H18N2O3, comprises a whole organic dipyridinone mol­ecule plus a water mol­ecule of crystallization. The planes of the pyridinone rings are approximately perpendicular with the plane of the central aromatic ring [dihedral angles = 80.68 (8) and 83.65 (8)°]. The C—O bond of the hy­droxy group subtends an angle of 31.71 (10)° with the plane through the central aromatic ring. The crystal packing is mediated by the presence of several O—H⋯O hydrogen-bonding inter­actions and while the water mol­ecules form a C 2 1(4) chain parallel to the c axis of the unit cell, the pendant hy­droxy groups are engaged in O—H⋯O=C hydrogen bonds described by a C 1 1(12) graph-set motif which runs parallel to the a axis