Tomas Edvinsson

Determination of Thermal Expansion Coefficients and Locating the Temperature-Induced Phase Transition in Methylammonium Lead Perovskites Using X-ray Diffraction

Lead halogen perovskites, and particularly methylammonium lead iodine, CH3NH3PbI3, have recently attracted considerable interest as alternative solar cell materials, and record solar cell efficiencies have now surpassed 20%. Concerns have, however, been raised about the thermal stability of methylammonium lead iodine, and a phase transformation from a tetragonal to a cubic phase has been reported at elevated temperature. Here, this phase transition has been investigated in detail using temperature-dependent X-ray diffraction measurements. The phase transformation is pinpointed to 54 °C, which is well within the normal operating range of a typical solar cell. The cell parameters were extracted as a function of the temperature, from which the thermal expansion coefficient was calculated. The latter was found to be rather high (αv = 1.57 × 10(-4) K(-1)) for both the tetragonal and cubic phases. This is 6 times higher than the thermal expansion coefficient for soda lime glass and CIGS and 11 times larger than that of CdTe. This could potentially be of importance for the mechanical stability of perovskite solar cells in the temperature cycling experienced under normal day-night operation. The experimental knowledge of the thermal expansion coefficients and precise determination of the cell parameters can potentially also be valuable while conducting density functional theory simulations on these systems in order to deliver more accurate band structure calculations.

Design of an Organic Chromophore for P-Type Dye-Sensitized Solar Cells

A successful model for the design of efficient dyes for p-type dye-sensitized solar cells (DSSCs) is presented. As an example, a novel and efficient organic dye containing a triphenylamine chromophore has been synthesized and successfully applied in a p-type DSSC. The highest incident photon-to-current conversion efficiency (IPCE) of 18% in the visible region has been obtained, which is the highest value so far in p-type DSSCs. This is remarkably high, considering that only 600 nm thin NiO mesoporous films were used as p-type DSSC electrodes.

A monolithic device for solar water splitting based on series interconnected thin film absorbers reaching over 10% solar-to-hydrogen efficiency

Efficient production of hydrogen from solar energy is anticipated to be an important component in a future sustainable post-carbon energy system. Here we demonstrate that series interconnected absorbers in a PV-electrolysis configuration based on the compound semiconductor CIGS, CuInxGa1−xSe2, are a highly interesting concept for solar water splitting applications. The band gap energy of CIGS can be adjusted to a value close to optimum for efficient absorption of the solar spectrum, but is too low to drive overall water splitting. Therefore we connect three cells in series, into a monolithic device, which provides sufficient driving force for the full reaction. Integrated with a catalyst this forms a stable PV/photo-electrochemical device, which when immersed in water reaches over 10% solar-to-hydrogen efficiency for unassisted water splitting. The results show that series interconnected device concepts, which enable use of a substantial part of the solar spectrum, provide a simple route towards highly efficient water splitting and could be used also for other solar absorbers with similar electro-optical properties. We discuss how the efficiency could be increased for this particular device, as well as the general applicability of the concepts used in this work. We also briefly discuss advantages and disadvantages of photo-electrochemical cells in relation to PV-electrolysis with respect to our results.

Resonance Raman and Excitation Energy Dependent Charge Transfer Mechanism in Halide-Substituted Hybrid Perovskite Solar Cells

Organo-metal halide perovskites (OMHPs) are materials with attractive properties for optoelectronics. They made a recent introduction in the photovoltaics world by methylammonium (MA) lead triiodide and show remarkably improved charge separation capabilities when chloride and bromide are added. Here we show how halide substitution in OMHPs with the nominal composition CH3NH3PbI2X, where X is I, Br, or Cl, influences the morphology, charge quantum yield, and local interaction with the organic MA cation. X-ray diffraction and photoluminescence data demonstrate that halide substitution affects the local structure in the OMHPs with separate MAPbI3 and MAPbCl3 phases. Raman spectroscopies as well as theoretical vibration calculations reveal that this at the same time delocalizes the charge to the MA cation, which can liberate the vibrational movement of the MA cation, leading to a more adaptive organic phase. The resonance Raman effect together with quantum chemical calculations is utilized to analyze the change in charge transfer mechanism upon electronic excitation and gives important clues for the mechanism of the much improved photovoltage and photocurrent also seen in the solar cell performance for the materials when chloride compounds are included in the preparation.

Sustainable solar hydrogen production: from photoelectrochemical cells to PV-electrolyzers and back again

Sustainable hydrogen production could, in principle, be accomplished along several different routes, where some of the most promising approaches involve utilization of solar energy. Photoelectroche ...

Absorption and Fluorescence Spectroscopy of Growing ZnO Quantum Dots : Size and Band Gap Correlation and Evidence of Mobile Trap States

ZnO nanoparticles constitute a convenient model system for fundamental studies with many possible technical applications in, for example, sensors and the field of catalysis and optoelectronics. A large set of ZnO quantum dots in the size range 2.5-7 nm have been synthesized and analyzed in detail. Time resolved in situ UV-vis absorption measurements were used to monitor the growth of these particles in solution by correlating the optical band gap to particle size given from X-ray diffraction (XRD) measurements. The particles formed were isotropic in shape, but small initial deviations gave indications of a transition from thermodynamic to kinetically controlled growth for particles around 4 nm in diameter. On the basis of this, the behavior and mechanisms for the particle growth are discussed. The fluorescence dependence on particle size was investigated by combining fluorescence and UV-vis measurements on growing particles. This revealed that the positions of the fluorescence trap states are mobile toward the conduction- and valence band. A broadening of the trap states was also found, and a surface dependent mechanism of the trap state shift and broadening is proposed.

Chemical engineering of methylammonium lead iodide/bromide perovskites: tuning of opto-electronic properties and photovoltaic performance

Hybrid (organic-inorganic) lead trihalide perovskites have attracted much attention in recent years due to their exceptionally promising potential for application in solar cells. Here a controlled ...

Frustrated Lewis pair-mediated recrystallization of CH3NH3PbI3 for improved optoelectronic quality and high voltage planar perovskite solar cells

Films of the hybrid lead halide perovskite CH3NH3PbI3 were found to react with pyridine vapor at room temperature leading to complete bleaching of the film. In dry air or nitrogen atmosphere recrystallization takes place, leading to perovskite films with markedly improved optical and photovoltaic properties. The physical and chemical origin of the reversible bleaching and recrystallization mechanism was investigated using a variety of experimental techniques and quantum chemical calculations. The strong Lewis base pyridine attacks the CH3NH3PbI3. The mechanism can be understood from a frustrated Lewis pair formation with a partial electron donation of the lone-pair on nitrogen together with competitive bonding to other species as revealed by Raman spectroscopy and DFT calculations. The bleached phase consists of methylammonium iodide crystals and an amorphous phase of PbI2(pyridine)2. After spontaneous recrystallization the CH3NH3PbI3 thin films have remarkably improved photoluminescence, and solar cell performance increased from 9.5% for as-deposited films to more than 18% power conversion efficiency for recrystallized films in solar cells with planar geometry under AM1.5G illumination. Hysteresis was negligible and open-circuit potential was remarkably high, 1.15 V. The results show that complete recrystallization can be achieved with a simple room temperature pyridine vapor treatment of CH3NH3PbI3 films leading to high quality crystallinity films with drastically improved photovoltaic performance.

Optical quantum confinement in low dimensional hematite

Hematite is considered to be a promising material for various applications, including for example photo-electrochemical cells for solar hydrogen production. Due to limitations in the charge transport properties hematite needs to be in the form of low-dimensional particles or thin films in several of these applications. This may however affect the optical properties, introducing additional complications for efficient design of photo-active devices. In this paper the optical absorption is analyzed in detail as a function of film thickness for 35 thin films of hematite ranging between 2 and 70 nm. Hematite was deposited by atomic layer deposition on FTO-substrates using Fe(CO)5 and O2 as precursors. It was found that for film thicknesses below 20 nm the optical properties are severely affected as a consequence of quantum confinement. One of the more marked effects is a blue shift of up to 0.3 eV for thinner films of both the indirect and direct transitions, as well as a 0.2 eV shift of the absorption maximum. The data show a difference in quantum confinement for the indirect and the direct transitions, where the probability for the indirect transition decreases markedly and essentially disappears for the thinnest films. Raman measurements showed no peak shift or change in relative intensity for vibrations for the thinnest films indicating that the decrease in indirect transition probability could not be assigned to depression of any specific phonon but instead seems to be a consequence of isotropic phonon confinement. The onset of the indirect transition is found at 1.75 eV for the thickest films and shifted to 2.0 eV for the thinner films. Two direct transitions are found at 2.15 eV and 2.45 eV, which are blue shifted 0.3 and 0.45 eV respectively, when decreasing the film thickness from 20 to 4 nm. Low dimensional hematite, with dimensions small enough for efficient charge transport, thus has a substantially lower absorption in the visible region than expected from bulk values. This knowledge of the intrinsic optical behavior of low dimensional hematite will be of importance in the design of efficient photo-active devices.

Vapor phase conversion of PbI2 to CH3NH3PbI3: spectroscopic evidence for formation of an intermediate phase

The formation of CH3NH3PbI3 (MAPbI3) from its precursors is probably the most significant step in the control of the quality of this semiconductor perovskite material, which is highly promising for photovoltaic applications. Here we investigated the transformation of spin coated PbI2 films to MAPbI3 using a reaction with MAI in vapor phase, referred to as vapor assisted solution process (VASP). The presence of a mesoporous TiO2 scaffold on the substrate was found to speed up reaction and led to complete conversion of PbI2, while reaction on glass substrates was slower, with some PbI2 remaining even after prolonged reaction time. Based on data from UV-visible spectroscopy, Raman spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy, the formation of an X-ray amorphous intermediate phase is proposed, which is identified by an increasing absorption from 650 to 500 nm in the absorption spectrum. This feature disappears upon long reaction times for films on planar substrates, but persists for films on mesoporous TiO2. Poor solar cell performance of planar VASP prepared devices was ascribed to PbI2 remaining in the film, forming a barrier between the perovskite layer and the compact TiO2/FTO contact. Good performance, with efficiencies up to 13.3%, was obtained for VASP prepared devices on mesoporous TiO2.