Kirill L. Gerasimov

Probing the Intrinsic Thermal and Photochemical Stability of Hybrid and Inorganic Lead Halide Perovskites

We report a careful and systematic study of thermal and photochemical degradation of a series of complex haloplumbates APbX3 (X = I, Br) with hybrid organic (A+ = CH3NH3) and inorganic (A+ = Cs+) cations under anoxic conditions (i.e., without exposure to oxygen and moisture by testing in an inert glovebox environment). We show that the most common hybrid materials (e.g., MAPbI3) are intrinsically unstable with respect to the heat- and light-induced stress and, therefore, can hardly sustain the real solar cell operation conditions. On the contrary, the cesium-based all-inorganic complex lead halides revealed far superior stability and, therefore, provide an impetus for creation of highly efficient and stable perovskite solar cells that can potentially achieve pragmatic operational benchmarks.

High Conductivity in Molecularly p‐Doped Diketopyrrolopyrrole‐Based Polymer: The Impact of a High Dopant Strength and Good Structural Order

[3]-Radialene-based dopant CN6-CP studied herein, with its reduction potential of +0.8 versus Fc/Fc+ and the lowest unoccupied molecular orbital level of -5.87 eV, is the strongest molecular p-dopant reported in the open literature, so far. The efficient p-doping of the donor-acceptor dithienyl-diketopyrrolopyrrole-based copolymer having the highest unoccupied molecular orbital level of -5.49 eV is achieved. The doped films exhibit electrical conductivities up to 70 S cm(-1) .

Hydrazinium-loaded perovskite solar cells with enhanced performance and stability

In this study, we investigated the effects of partial substitution of methylammonium (MA) with hydrazinium (HA) cations on the optical properties, film morphology, crystal structure and photovoltaic performance of the hybrid perovskites MA1−xHAxPbI3. Planar heterojunction solar cells with an optimal hydrazinium loading demonstrated an enhanced power conversion efficiency of 11.6% and improved operation stability.

Understanding the correlation and balance between the miscibility and optoelectronic properties of polymer–fullerene solar cells

Organic photovoltaics is one of the most promising technologies for sustainable green energy supply. Because of their high electron affinity and superior electron-transporting ability, fullerene-based materials are deemed as very strong electron-accepting components in organic solar cells. However, the most widely used fullerene-based acceptors, such as phenyl-C61-butyric acid methyl ester, exhibit limited microstructural stability and unsatisfactory thermal stability owing to their insufficient compatibility with organic donors. Here, we in-depth investigate the carrier dynamics along with structural evolution and analyze the acceptor loadings in optimized bulk-heterojunction (BHJ) solar cells as a function of the polymer–fullerene miscibility. The polymer–fullerene miscibility has more influential effects than the crystallinity of single components on the optimized acceptor : donor ratio in polymer–fullerene solar cells. The findings demonstrated in this work suggest that the balance between the miscibility of BHJ composites and their optoelectronic properties has to be carefully considered for future development and optimization of OPV solar cells based on BHJ composites. Miscibility is proposed in addition to crystallinity as a further design criterion for long lived and efficient solar cells.

The impact of molecular weight, air exposure and molecular doping on the charge transport properties and electronic defects in dithienyl-diketopyrrolopyrrole-thieno[3,2-b]thiophene copolymers

We performed an in-depth study of high molecular weight poly[3,6-(dithiophene-2-yl)-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-thieno[3,2-b]thiophene] P(DPP2OD-TT) synthesized through the Stille coupling polycondensation in order to understand the correlation between molecular weight, processing conditions and charge transport. We observed a rapid increase in its aggregation in solution with increasing molecular weight which strongly limits the solubility and processability for weight average molecular weights beyond 200 kg mol−1. This results in severe limitation in the charge transport properties of the polymer. We further observe the presence of bulk electronic defects in all different polymer batches that severely limit the current flow and manifest themselves in organic field effect transistors as apparent charge density dependence of the mobility. These defects are passivated by exposure to an ambient atmosphere, as confirmed by an increase in current and mobility that is no more charge density dependent. This is further confirmed by the result of chemical doping using 2,2-(perfluoronaphthalene-2,6-diylidene)dimalononitrile, F6TCNNQ, which leads to the filling of the trap states and a higher charge density independent mobility of up to 1 cm2 V−1 s−1.

Face-on orientation of fluorinated polymers conveyed by long alkyl chains: a prerequisite for high photovoltaic performances

The recently reported high power conversion efficiencies achieved in fluorinated polymer:fullerene solar cells have been accounted for by the presence of face-on oriented polymer backbones that enable charge transport towards the collecting electrodes. In this work, we demonstrate that, in contrast to the results of a number of reports, the face-on polymer orientation is due to the bulky side chains, rather than to aggregation in solution. This conclusion is supported by a comparative study of polymers having similar conjugated backbones but different number of fluorine atoms and different number and type of alkyl side chains. While the latter are primarily introduced to tune polymer solubility, the present in-depth thin-film morphology investigation shows that increasing the chain bulkiness favors formation of crystalline lamellae with face-on oriented backbones, independently of the degree of fluorination. By contrast, introduction of fluorine atoms is found to substantially enhance the π-stacking interactions that remain invariably strong upon blending of the polymer with fullerene. Our results demonstrate that, for the polymer family under investigation, fluorination and functionalization by bulky alkyl side chains are both needed for reaching power conversion efficiencies above 10%.

Thermal Annealing Effect on Active Layer Structure in All-Polymer Organic Solar Cells

The structural evolution of the components for the active layers of all-polymer solar cells was studied by DSC, X-ray diffraction and optical microscopy. It was found that polymer donor (PTQ1) and polymer acceptor (PNDIT2) form lamellar structures with layers oriented parallel and perpendicular to the substrate, respectively. All films reveal π-π stacking in the direction normal to the film. During thermal annealing the structure improvement occurs only for the donor component. In a PTQ1/ PNDIT2 blend, two components form individual lamellar phases with the texture similar to that of the pure polymers. Upon annealing, the structure of PNDIT2 was found to be disturbed whereas the structure of PTQ1 phase improves. The micro-phase separation occurring during annealing of the PTQ1/ PNDIT2 blend is accompanied by the formation of large spherulitic objects.

Impact of Solubility of Organic Semiconductors for Solution-Processable Electronics on the Structure Formation: a Real-Time Study of Morphology and Electrical Properties

The control of structure formation in the active layers of organic solar cells allows for improvement in their processability and enhancement of the efficiency of the final devices. In the present work, in situ studies of film formation from binary toluene solutions of an electron donor, poly(3-hexylthiophene) (P3HT), and an electron acceptor such as [6,6]-phenyl-C-61-butyric acid methyl ester (PCBM) or indene-C60 bisadduct (ICBA) have been conducted. These experiments were carried out using GIWAXS with simultaneous electric current measurements. The comparative analysis of the intensity of the amorphous halo, and the 100 and 020 peaks of P3HT reveals the development of the semicrystalline morphology of the donor through a partly-ordered phase. The experiments show the impact of the chemical structure of the acceptor, as well as that of the donor : acceptor ratio on the kinetics of drying and crystallization. The optimal bulk heterojunction morphology was achieved for P3HT : ICBA 1 : 1, which exhibited the highest value of current. A more efficient phase separation in non-annealed P3HT:ICBA films as compared to P3HT:PCBM was accounted for by the differences in solubility of the components in toluene. The structure formation during solvent evaporation can be subdivided into three stages, including the ordering of the polymer in solution, phase separation during precipitation, and the perfectioning of P3HT crystals in the dry film.

Omni vehicle dynamics model: Object-oriented implementation and verification

Omni wheel is defined as one having rollers along its rim. Respectively omni vehicle is one equipped by omni wheels. Dynamical computer model for the omni vehicle multibody system is implemented as a two-layer abstraction (class) in frame of the object-oriented paradigm. For this initially, dynamics of the free roller moving in field of gravity and having a unilateral contact constraint with horizontal rigid surface is modeled. The contact tracking algorithm for the roller turns out to be extremely simple and efficient. On the next layer of the model structure the omni wheel model is developed and debugged. Finally, the whole vehicle model is assembled as a container class having arrays of objects as instantiated classes really being models of omni wheels and joints. Dynamical properties of the resulting model are illustrated via numerical experiments. Their results were used to verify the multibody vehicle model under construction in compare with its ideal simplified model having known behavior.