Alexander Kovalenko

Coordination Chemistry Dictates the Structural Defects in Lead Halide Perovskites.

We show the influence of species present in precursor solution during formation of lead halide perovskite materials on the structural defects of the films. The coordination of lead by competing solvent molecules and iodide ions dictate the type of complexes present in the films. Depending on the processing conditions all PbIS5 (+) , PbI2 S4, PbI3 S3 (-) , PbI4 S2 (2-) , PbI5 S2 (3-) , PbI6 (4-) and 1D (Pb2 I4 )n chains are observed by absorption measurements. Different parameters are studied such as polarity of the solvent, concentration of iodide ions, concentration of solvent molecules and temperature. It is concluded that strongly coordinating solvents will preferentially form species with a low number of iodide ions and less coordinative solvents generate high concentration of PbI6 (-) . We furthermore propose that all these plumbate ions may act as structural defects determining electronic properties of the photovoltaic films.

Role of vertical segregation in semitransparent organic photovoltaics.

In this work, the efficiency of semitransparent organic photovoltaic (OPV) devices for low intensity applications is investigated as a function of the processing conditions. It is observed that a thermal treatment of the organic layer induces fullerene migration toward the active layer/air interface. This physical process gives rise to different vertical segregation profiles of donor and acceptor molecules. Once the back contact is deposited, the amount of fullerene covering the surface will determine the contact selectivity and leakage current of the device. Control of this leakage current may not be essential for devices fabricated for high illumination condition applications. However, devices to be used under low illumination conditions may be highly influenced by the presence of this parasitic dark current which flows in the opposite direction to photogenerated current. At the proximity of the contacts, the vertical segregation profile is inferred from optical and electrical measurements. In particular, external quantum efficiency (EQE) measurements carried out from a relatively opaque back contact provide local information on the materials spatially close to the light source. Alternatively, capacitance-voltage measurements enable calculation of the percentage of fullerene molecules covering the cathode contact. Overall, a versatile method that can be used in regular and inverted configuration is presented that explains the different behavior observed for devices to be used under low illumination conditions.

Adamantane substitutions: a path to high-performing, soluble, versatile and sustainable organic semiconducting materials

Novel ethyladamantyl solubilization side groups were found to induce π–π interactions between the conjugated cores through adamantyl–adamantyl stacking in soluble diketopyrrolopyrrole (DPP) derivatives. The closeness of the DPP cores amplifies charge transfer in the material, as far as the π–π interaction is a dominant charge-hopping pathway. As a result, tenfold enhancement of hole mobilities exceeding those obtained for insoluble derivatives was reached. Moreover, due to high crystallinity and co-planarity of the conjugated cores, electron transfer was preserved with a mobility of 0.2 cm2 V−1 s−1 for dithiophene-DPP. At the same time, the material remained soluble, which is a significant advantage for purification and processing. This approach can be universally applied for many types of semiconducting organic materials containing the imide motif, where solubilization is achieved by side-group substitution.

Thiophene-free diphenyl-amino-stilbene-diketo-pyrrolo-pyrrole derivatives as donors for organic bulk heterojunction solar cells

An extended study on a group of four soluble diphenyl-amino-stilbene based diphenyl-diketopyrrolo- pyrrole molecules has been carried out. Using the materials in thin-film transistors it was shown that the above-mentioned compounds can be successfully used as donors in organic photovoltaic devices. Influence of the molecular symmetry and solubilizing chain on the morphology and solar cell performance are described. It was shown that a shorter and non-branched ethyl acetate chain leads to higher charge carrier mobility, short circuit current, and better fill factor. After the basic optimization, a power conversion efficiency of about 1.5 % was reached. This, to the best of our knowledge, is the highest reported efficiency of thiophene-free small-molecule diketo-pyrrolopyrroles.

Morphology versus Vertical Phase Segregation in Solvent Annealed Small Molecule Bulk Heterojunction Organic Solar Cells

The deep study of solvent annealed small molecules bulk heterojunction organic solar cells based on DPP(TBFu)2 : PC60BM blend is carried out. To reveal the reason of the solvent annealing advantage over the thermal one, capacitance-voltage measurements were applied. It was found that controlling the vertical phase segregation in the solar cells a high fullerene population in the vicinity of the cathode could be achieved. This results in increase of the shunt resistance of the cell, thus improving the light harvesting efficiency.

Interface inductive currents and carrier injection in hybrid perovskite single crystals

Interfaces between the absorbing perovskite and transporting layers are gaining attention as the key locus that governs solar cell operation and long term performance. The interplay of ionic and electronic processes, along with the asymmetrical architecture of any solar cell, makes the interpretation of electrical measurements always inconclusive. A strategy to progress in relating electric responses, operating mechanisms, and device architecture relies upon simplifying the probing structure. Macroscopic CH3NH3PbBr3 single crystals with symmetrical contacts are tested by means of long-time current transient and impedance spectroscopy. It is observed that interfaces govern carrier injection to (and extraction from) perovskite layers through an inductive (negative capacitance) mechanism with a response time in the range of ∼ 1 – 100 s under dark conditions and inert atmosphere. Current transient exhibits a slow recovering after the occurrence of an undershoot, signaling a complex carrier dynamics which invo...

Reducing Recombination Processes in the Inverted-Solution-Processed Small-Molecule Solar Cells by the Inserted Fullerene Cathode

Inverted architecture organic solar cells are potentially attractive, due to their long-term stability. However, this type of architecture is poorly applied in small-molecule solar cells, due to lower power conversion efficiencies (PCEs), usually caused by low fill factors. Here, the initially low fill factor of the inverted architecture small-molecule solar cells based on a DPP(TBFu)2:PC60BM blend is augmented by the inserted fullerene layer at the cathode, thus resulting in the efficient charge extraction and, up to now, highest PCE for DPP(TBFu)2 material and one of the highest for small-molecule DPP derivatives. Highly reproducible devices with PCE up to 5.29% were fabricated, which is notably higher than previously reported results.

Study on mutual interactions and electronic structures of hyaluronan with Lysine, 6-Aminocaproic acid and Arginine.

Interactions between polyelectrolytes and oppositely charged surfactants have been in a great interest for several decades, yet the conventional surfactants may cause a problem in medical applications. Interactivity between polysaccharide hyaluronan (HA) and amino acids Lysine, 6-Aminocaproic acid (6-AcA), and Arginine as an alternative system is reported. The interactions were investigated by means of rheology and electric conductance and the electronic structures were explored by the density functional theory (DFT). Lysine exhibits the strongest interaction of all, which was manifested, e.g. by nearly 6-time drop of the initial viscosity comparing with only 1.3-time lower value in the case of 6-AcA. Arginine interaction with HA was surprisingly weaker in terms of viscosity than that of Lysine due to a lower and delocalized charge density on its guanidine group. According to the DFT calculations, the binding of Lysine to HA was found to be more flexible, while Arginine creates more rigid structure with HA.

Effect of the Side Chains and Anode Material on Thermal Stability and Performance of Bulk-Heterojunction Solar Cells Using DPP(TBFu)2 Derivatives as Donor Materials

An optimized fabrication of bulk-heterojunction solar cells (BHJ SCs) based on previously reported diketopyrrolopyrrole donor, ethyl-hexylated DPP(TBFu)2, as well as two new DPP(TBFu)2 derivatives with ethyl-hexyl acetate and diethyl acetal solubilizing side-chains and PC60BM as an acceptor is demonstrated. Slow gradual annealing of the solar cell causing the effective donor-acceptor reorganization, and as a result higher power conversion efficiency (PCE), is described. By replacing a hole transporting layer PEDOT:PSS with MoO3 we obtained higher PCE values as well as higher thermal stability of the anode contact interface. DPP(TBFu)2 derivative containing ethyl-hexyl acetate solubilizing side-chains possessed the best as-cast self-assembly and high crystallinity. However, the presence of ethyl-hexyl acetate and diethyl acetal electrophilic side-chains stabilizes HOMO energy of isolated DPP(TBFu)2 donors with respect to the ethyl-hexylated one, according to cyclic voltammetry.

Physical properties investigation of reduced graphene oxide thin films prepared by material inkjet printing

The article is focused on the study of the optical properties of inkjet-printed graphene oxide (GO) layers by spectroscopic ellipsometry. Due to its unique optical and electrical properties, GO can be used as, for example, a transparent and flexible electrode material in organic and printed electronics. Spectroscopic ellipsometry was used to characterize the optical response of the GO layer and its reduced form (rGO, obtainable, for example, by reduction of prepared layers by either annealing, UV radiation, or chemical reduction) in the visible range. The thicknesses of the layers were determined by a mechanical profilometer and used as an input parameter for optical modeling. Ellipsometric spectra were analyzed according to the dispersion model and the influence of the reduction of GO on optical constants is discussed. Thus, detailed analysis of the ellipsometric data provides a unique tool for qualitative and also quantitative description of the optical properties of GO thin films for electronic applications.