Marius Franckevičius

Ionic polarization-induced current–voltage hysteresis in CH3NH3PbX3 perovskite solar cells

CH3NH3PbX3 (MAPbX3) perovskites have attracted considerable attention as absorber materials for solar light harvesting, reaching solar to power conversion efficiencies above 20%. In spite of the rapid evolution of the efficiencies, the understanding of basic properties of these semiconductors is still ongoing. One phenomenon with so far unclear origin is the so-called hysteresis in the current–voltage characteristics of these solar cells. Here we investigate the origin of this phenomenon with a combined experimental and computational approach. Experimentally the activation energy for the hysteretic process is determined and compared with the computational results. First-principles simulations show that the timescale for MA+ rotation excludes a MA-related ferroelectric effect as possible origin for the observed hysteresis. On the other hand, the computationally determined activation energies for halide ion (vacancy) migration are in excellent agreement with the experimentally determined values, suggesting that the migration of this species causes the observed hysteretic behaviour of these solar cells.

Nanowire Perovskite Solar Cell

Organolead iodide perovskite, CH3NH3PbI3, was prepared in the form of nanowire by means of a small quantity of aprotic solvent in two-step spin-coating procedure. One-dimensional nanowire perovskite with the mean diameter of 100 nm showed faster carrier separation in the presence of hole transporting layer and higher lateral conductivity than the three-dimensional nanocuboid crystal. Reduction in dimensionality resulted in the hypsochromic shift of both absorption and fluorescence spectra, indicative of more localized exciton states in nanowires. The best performing device employing nanowire CH3NH3PbI3 delivered photocurrent density of 19.12 mA/cm(2), voltage of 1.052 V, and fill factor of 0.721, leading to a power conversion efficiency (PCE) of 14.71% at standard AM 1.5G solar illumination. A small I-V hysteresis was observed, where a PCE at forward scan was measured to be 85% of the PCE at reverse scan.

A dopant-free spirobi[cyclopenta[2,1-b:3,4-b′]dithiophene] based hole-transport material for efficient perovskite solar cells

We present the design and synthesis of a promising hole transporting material (HTM) using the 4,4′-spirobi[cyclopenta[2,1-b:3,4-b′]dithiophene] derivative (spiro-CPDT) as the core and triarylamines as terminal units. The implementation of the new HTM in CH3NH3PbI3-based perovskite solar cells exhibited an excellent overall power conversion efficiency (PCE) of 13.4% without the use of any dopants and additives which is comparable to 15.0% obtained using p-doped spiro-MeOTAD-based devices. Furthermore, the device based on the new HTM generated a slightly higher open circuit voltage (VOC) of 971 mV compared to a spiro-MeOTAD (VOC = 951 mV) based device. The present results demonstrate that spiro-CPDT could be an excellent building block to prepare dopant-free HTMs for perovskite solar cells and holds promise to replace the p-doped spiro-OMeTAD, which is important for the fabrication of cost-effective devices in the future.

A–D–A-type S,N-heteropentacene-based hole transport materials for dopant-free perovskite solar cells

This work reports the design and synthesis of acceptor–donor–acceptor (A–D–A) type low band gap hole transport materials (HTM) comprising S,N-heteropentacene central units for solid-state perovskite-based solar cells. The optical and electrochemical properties were tuned by the insertion of thiophene or ethylenedioxythiophene units in the molecular backbone. These HTMs showed strong absorption in the visible region and suitable highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies with respect to the CH3NH3PbI3 perovskite. Mesoscopic solid state perovskite solar cells prepared by solution-processing using these HTMs generated power conversion efficiencies (PCE) of 10.3–11.4% without the use of any additive or dopant. The charge transfer behavior between photoexcited perovskite and the HTMs was further investigated by photo-induced absorption spectroscopy.

High-Efficiency Perovskite Solar Cells Employing a S,N-Heteropentacene-based D–A Hole-Transport Material

We developed a new donor-π-acceptor-type hole-transport material (HTMs) incorporating S,N-heteropentacene as π-spacer, triarylamine as donor, and dicyanovinylene as acceptor. In addition to appropriate frontier molecular orbital energies, the new HTM showed high photo absorptivity in the visible region. Without the use of p-dopants, solution-processed mixed perovskite devices using the HTM achieved power conversion efficiencies of up to 16.9% and high photocurrents of up to 22.2 mA cm(-2). These results demonstrate that heteroacene can be an excellent building block to prepare alternative HTMs for perovskite solar cells and hold promise for further advancement through fine-tuning the molecular structure.

Mechanosynthesis of the hybrid perovskite CH3NH3PbI3: characterization and the corresponding solar cell efficiency

We present a facile mechanochemical route for the preparation of hybrid CH3NH3PbI3 (MAPbI3) perovskite particles with the size of several hundred nanometers for high-efficiency thin-film photovoltaic devices. Powder X-ray diffraction measurements demonstrate that mechanosynthesis is a suitable strategy to produce a highly crystalline CH3NH3PbI3 material showing no detectable amounts of the starting CH3NH3I and PbI2 reagents. Thermal stability measurements based on the thermogravimetric analysis data of mechanosynthesized perovskite particles indicated that the as-ground MAPbI3 is stable up to 300 °C with no detectable material loss at lower temperatures. The optical properties of newly synthesized perovskite particles were characterized by applying steady state absorption and fluorescence spectroscopy, which confirmed a direct band-gap of 1.48 eV. Time resolved single photon counting measurements revealed that 70% of charges undergo recombination with a 61 ns lifetime. The solar cell devices made from mechanosynthesized perovskite particles achieved a power conversion efficiency of 9.1% when applying a one step deposition method.

Twisted Intramolecular Charge Transfer States in Trinary Star-Shaped Triphenylamine-Based Compounds

Excited state dynamics of trinary star-shaped dendritic compounds with triphenylamine arms and different cores were studied by means of time-resolved fluorescence and transient absorption. Under optical excitation, nonpolar C3 symmetry molecules form polar excited states localized on one of the molecular substituents. Conformational excited state stabilization of molecules with an electron-accepting core causes a formation of twisted internal charge transfer (TICT) states in polar solvents. A low transition dipole moment from TICT state to the ground state causes very weak fluorescence of those compounds and strong dependence on the solvent polarity. The compound formed from the triphenylamine central core and identical arms also experiences excited state twisting, however, weakly sensitive to the solvent polarity.

Hindered Amine Light Stabilizers Increase the Stability of Methylammonium Lead Iodide Perovskite Against Light and Oxygen

Methylammonium lead iodide perovskite (MAPI) is a promising material for highly efficient photovoltaic devices. However, it suffers from photooxidation, which imposes strict requirements for its protection from oxygen during processing and operation. A hindered amine light stabilizer (HALS) has been found to exert a stabilization effect on methylammonium iodide (MAI) and MAPI against photooxidation. The HALS prevents the degradation of MAI by inhibiting the oxidation of iodide to iodine. Chemical modification of HALS allows its incorporation in MAPI films, which extends the resistivity of MAPI against photodegradation in ambient air from a couple of hours to several days, while causing no significant changes in key properties, such as optical absorption and charge transport. These results represent an important advance in the stabilization of MAPI against decomposition and demonstrate for the first time that antioxidants improve the stability of MAPI.

Enhanced Nonlinear Optical Response of Resonantly Coupled Silver Nanoparticle–Organic Dye Complexes

The influence of metal nanoparticles on linear and nonlinear optical properties of surrounding organic molecules has been widely investigated, whereas much less attention has been paid to the influence of molecules on properties of nanoparticles. Here, we employ transient absorption spectroscopy to address the nonlinear optical responses of the resonantly coupled silver nanoparticle–organic dye systems and demonstrate that silver nanoparticles covered with dye molecules show enhanced and spectrally different nonlinear extinction changes from pristine nanoparticles. We identify changes of the plasmon resonance band of nanoparticles induced by excitation of surrounding dye. We attribute these exciton–plasmon coupling effects to the excitation-induced refractive index modifications of the dye layer surrounding a nanoparticle and to the back-transfer of the oscillator strength borrowed by the dye from the nanoparticle.