Recent Advances in Squaraine Dyes for Bulk-Heterojunction Organic Solar Cells

Squaraine (SQ) dyes are an important class of electron-donating (donors or p-type) semiconductors for organic solar cells (OSC) due to their facile synthetic access, broad optical absorption with high oscillator strengths, and chemical robustness. Blending them with compatible electron-acceptors (acceptors or n-type) yields OSC devices known as bulk-heterojunction (BHJ) small molecule donor organic solar cells (SMD-OSCs). Through extensive research on materials design, synthesis, characterization, and device optimization over the past ˝ve years, SMD-OSCs employing SQ-based structures have achieved remarkable increases in device power conversion e˚ciency (PCE), now approaching 8%. Although these PCEs have not yet equaled the performance of state- of-the art donor polymers and some other SMD semiconductors, SQ-based OSC progress highlights successful and generalizable strategies for small molecule solar cells that should lead to future advances. In this review, recent developments in SQ-based OSCs are discussed and analyzed.

Diketopyrrolopyrrole latent pigment-based bilayer solar cells

Two Diketopyrrolopyrrole based latent pigment donor materials were fabricated into thin film bilayer photovoltaic devices featuring PCBM as the acceptor. Thermal deprotection of the thin film, carried out at 200∘ C, returns the dye-like small molecule to the corresponding pristine pigment quantitatively. The connected evolution of electrical and morphological features of pure thin films and blends are examined. A significant decrease in extinction coefficient was noted and correlated both to intrinsic changes of the electronic structure upon cleavage and to an increase in internal scattering due to extensive crystallization. Power conversion efficiencies of 0.33% were achieved for bilayer devices, nearly doubling previous results with latent pigment DPP devices, under comparable experimental conditions.

The effect of PbS nanocrystal additives on the charge transfer state recombination in a bulk heterojunction blend

A persistent limitation of organic semiconductors is their low dielectric constant єr, which limits the performance of bulk heterojunction (BHJ) solar cells. One way to increase єr is to employ high-єr additives, such as PbS nanocrystals (QDs) to BHJ blends. In this work, we use the recombination of the interfacial charge transfer (CT) state as a means to study the effects of PbS nanocrystals on blends of a narrow bandgap copolymer: poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1- b;3,4-b′]dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT), and phenyl-C61-butyric acid methyl ester (PCBM). We show that at low dilution levels (0.25% - 0.75% by weight), there is a decrease in the relative weight of the CT recombination lifetime (longer decay component); suggesting that there is an increase in the local єr of the ternary blend.

Enhanced Photovoltaic Performance via Co-sensitization of Ruthenium (II)-Based Complex Sensitizers with Metal-Free Indoline Dye in Dye-Sensitized Solar Cells

Co-sensitization is shown to be an effective method to improve the efficiency of dye-sensitized solar cells wherein ruthenium (ii)-based complex sensitizers (N749, N719) is co-sensitized with the metal-free indoline dye (D149), where photovoltaic efficiency of 5.40% is achieved by co-sensitized N749+D149 and efficiency of 4.94% is achieved by co-sensitized N719+D149. The assembled dye-sensitized solar cells were studied by UVvis absorption measurements of dye solutions, the absorption spectra of the dye-sensitized TiO

Influence of chemical structure of branched and dendritic organosilicon luminophores on their optical and thermal properties

Synthesis and investigation of optical and thermal properties of a homologous series of highly luminescent nanostructured organosilicon luminophores (NOLs) containing different donor to acceptor ratio (D:A) are reported. Each of the NOL consists of a 1,4-bis(5-phenylthienyl-2-yl)benzene (PTPTP) acceptor unit and four, six or twelve 2,2′-bithienyl donor fragments connected to each other through two or six silicon atoms. These complex molecules show a “molecular antenna” effect with high efficiency of intramolecular energy transfer about 97-98% combined with excellent photoluminescence (PL) quantum yield of 84-91% and fast PL decay time of 0.90-0.95 ns. A significant increase of the molar extinction coefficient from 94 000 to 257 000 M

Group 14 metalloles condensed with heteroaromatic systems

There has been keen interest in group 14 metalloles as building units of conjugated organic functional materials. This short review summarizes our recent work on group 14 metalloles condensed with heteroaromatic systems, including thiophene and pyridine. These condensed metalloles show interesting properties depending on both the group 14 metallole elements and the heteroaromatic systems. High planarity of the condensed systems and interaction between the element σ*-orbital and the heteroaromatic π*-orbital enhance the conjugation in these systems leading to their potential applications as functional materials, such as carrier transporting materials and emissive materials.

Ultrafast electron and hole transfer in bulk heterojunctions of low-bandgap polymers

In modern bulk heterojunction (BHJ) organic solar cells, blends of low-bandgap polymer and [70]PCBM acceptor are used in the active layer. In this combination, the polymer absorbs photons from the red and near-IR parts of the solar spectrum, while the blue and near-UV photons are harvested by [70]PCBM. As a result, both electron transfer from polymer to [70]PCBM and hole transfer from [70]PCBM to polymer are of utmost importance in free charge generation and have to be optimized simultaneously. Here we study electron and hole transfer processes in BHJ blends of two low-bandgap polymers, BTT-DPP and PCPDTBT, by ultrafast photoinduced spectroscopy (PIA). By tracking the PIA dynamics, we observed substantially different charge separation pathways in BHJs of the two polymers with [70]PCBM. From the photoinduced anisotropy dynamics, we demonstrated that in the PCPDTBT:[70]PCBM system both electron and hole transfer processes are highly efficient, while in the BTTBPP:[ 70]PCBM electron transfer is blocked due to the unfortunate energy level alignment leaving hole transfer the only pathway to free charge generation. Calculations at the density functional theory level are used to gain more insight into our findings. The presented results highlight the importance of the energy level alignment on the charge separation process.

New chromophores based on combination of ethylenedioxythiophene and carbazole fragments: synthesis and optoelectronic properties

Two new D-π-A chromophores composed of an electron-donating carbazole unit linked through π- bridges, bearing 3,4-ethylenedioxythiophene (EDOT) moiety, with an electron withdrawing dicyanovinyl group (DCV) were successfully synthesized involving Suzuki or Heck cross-coupling and Knöevenagel reactions as the key steps. The obtained compounds absorb light over a broad spectral range, including the visible spectrum. The HOMO/LUMO energies and band gap energy values (Eg) were calculated on the basis of the experimental optical and electrochemical data: HOMO, LUMO, Eg (eV), −5.51, −3.14, 2.37 (4), −5.34, −3.14, 2.20 (7). The presence of the HC=CH unit in compound 7 resulted in the increase of the HOMO energy level, the decrease of a band gap value and red shifts of the absorption and emission bands in comparison with those of 4. Large Stokes shifts and broadband luminescence inherent to both chromophores suggest their use as materials for luminescent solar collectors (LSCs). The obtained compounds demonstrated good solubility and suitable thin-film forming properties. For this reason, they may be suitable for solution-processable photovoltaic applications.

Plausible role of nanoparticle contamination in the synthesis and properties of organic electronic materials

Traceless transition metal catalysis (Pd, Ni, Cu, etc.) is very difficult to achieve. Metal contamination in the synthesized products is unavoidable and the most important questions are: How to control metal impurities? What amount of metal impurities can be tolerated? What is the influence of metal impurities? In this brief review, the plausible origins of nanoparticle contamination are discussed in the framework of catalytic synthesis of organic electronic materials. Key factors responsible for increasing the probability of contamination are considered from the point of view of catalytic reaction mechanisms. The purity of the catalyst may greatly affect the molecular weight of a polymer, reaction yield, selectivity and several other parameters. Metal contamination in the final polymeric products may induce some changes in the electric conductivity, charge transport properties, photovoltaic performance and other important parameters.

Synthesis and luminescence of some rare earth metal complexes

In the present paper the synthesis, photoand electroluminescent properties of new rare earth metal complexes prepared and studied at the Razuvaev Institute of Organometallic Chemistry during the last decade are reviewed. The obtained compounds give luminescence in UV, visible and NIR regions. The substituted phenolates, naphtholates, mercaptobenzothiazolate, 8-oxyquinolinolate, polyfluorinated alcoholates and chalcogenophosphinates were used as ligands. The synthesis and structure of unusual three–nuclear sulfidenitride clusters of Nd and Dy are described. The new excitation mechanism of ytterbium phenolates and naphtholates, which includes the stage of reversible reduction of Yb to divalent state and oxidation of the ligands in the excitation process, is discussed.