Unsymmetrical Squaraines Incorporating Quinoline for Near Infrared Responsive Dye-Sensitized Solar Cells

Two new unsymmetrical squaraines (<b>WCH-SQ10</b> and <b>WCH-SQ11</b>), wherein the electron-rich 3,4-ethylenedioxy-thiophene conjugated fragment was linked unconventionally to the squaraine core and triphenyl amine donor, and carboxylic acid substituted quinoline was used as an acceptor, were prepared. <b>WCH-SQ10</b> and <b>WCH-SQ11</b> dyes in ethanol have the λ_max of 686 and 673 nm, respectively. The corresponding photovoltaic devices exhibit an attractively panchromatic response over 1000 nm, suggesting that quinoline benefits the low energetic electron injection

Diastereoisomers of Ruthenium Dyes with Unsymmetric Ligands for DSC: Fundamental Chemistry and Photovoltaic Performance

A new thiocyanic acid-free ruthenium sensitizer, CYC-B29, containing two unsymmetrical ancillary ligands, was synthesized, and its three diastereoisomers CYC-B29-CC, CYC-B29-TT, and CYC-B29-CT with significantly different optical, electronic, and electrochemical properties were carefully separated. CYC-B29-TT with the smallest size has the strongest absorption coefficient of the MLCT band, the shortest λ_max, the lowest highest occupied molecular orbital level and the highest dye loading. Therefore, dye-sensitized solar cell based on CYC-B29-TT has the highest efficiency, which is two times higher than that of CYC-B29-CC-sensitized device and 10% higher than that of N719-based cell. Time-dependent density functional theory-calculated transition bands for the three isomers are not identical, and only CYC-B29-TT has the calculated transition bands close to the experimental absorption profile. Although the calculated transition bands for CYC-B29-CC and CYC-B29-CT are not consistent with the experimental data, the ground-state vertical excitation energy with oscillator strength and electron-density difference map data combining with the dye loading predict correctly the order of the photocurrent for the three isomers sensitized devices

<i>S</i>,<i>N</i>‑Heteroacene-Based Copolymers for Highly Efficient Organic Field Effect Transistors and Organic Solar Cells: Critical Impact of Aromatic Subunits in the Ladder π‑System

Three novel donor–acceptor alternating polymers containing ladder-type pentacyclic heteroacenes (<b>PBo</b>, <b>PBi</b>, and <b>PT</b>) are synthesized, characterized, and further applied to organic field effect transistors (OFETs) and polymer solar cells. Significant aspects of quinoidal characters, electrochemical properties, optical absorption, frontier orbitals, backbone coplanarity, molecular orientation, charge carrier mobilities, morphology discrepancies, and the corresponding device performances are notably different with various heteroarenes. <b>PT</b> exhibits a stronger quinoidal mesomeric structure, linear and coplanar conformation, smooth surface morphology, and better bimodal crystalline structures, which is beneficial to extend the π-conjugation and promotes charge transport via 3-D transport pathways and in consequence improves overall device performances. Organic photovoltaics based on the <b>PT</b> polymer achieve a power conversion efficiency of 6.04% along with a high short-circuit current density (<i>J</i>_SC) of 14.68 mA cm^–2, and a high hole mobility of 0.1 cm² V^–1 s^–1 is fulfilled in an OFET, which is superior to those of its counterparts, <b>PBi</b> and <b>PBo</b>

Metal-Free Tetrathienoacene Sensitizers for High-Performance Dye-Sensitized Solar Cells

A new series of metal-free organic chromophores (TPA-TTAR-A (<b>1</b>), TPA-T-TTAR-A (<b>2</b>), TPA-TTAR-T-A (<b>3</b>), and TPA-T-TTAR-T-A (<b>4</b>)) are synthesized for application in dye-sensitized solar cells (DSSC) based on a donor-π-bridge-acceptor (D−π–A) design. Here a simple triphenylamine (TPA) moiety serves as the electron donor, a cyanoacrylic acid as the electron acceptor and anchoring group, and a novel tetrathienoacene (TTA) as the π-bridge unit. Because of the extensively conjugated TTA π-bridge, these dyes exhibit high extinction coefficients (4.5–5.2 × 10⁴ M^–1 cm^–1). By strategically inserting a thiophene spacer on the donor or acceptor side of the molecules, the electronic structures of these TTA-based dyes can be readily tuned. Furthermore, addition of a thiophene spacer has a significant influence on the dye orientation and self-assembly modality on TiO₂ surfaces. The insertion of a thiophene between the π-bridge and the cyanoacrylic acid anchoring group in TPA-TTAR-T-A (dye <b>3</b>) promotes more vertical dye orientation and denser packing on TiO₂ (molecular footprint = 79 Ų), thus enabling optimal dye loading. Using dye <b>3</b>, a DSSC power conversion efficiency (PCE) of 10.1% with <i>V</i>_oc = 0.833 V, <i>J</i>_sc = 16.5 mA/cm², and FF = 70.0% is achieved, among the highest reported to date for metal-free organic DSSC sensitizers using an I^–/I₃^– redox shuttle. Photophysical measurements on dye-grafted TiO₂ films reveal that the additional thiophene unit in dye <b>3</b> enhances the electron injection efficiency, in agreement with the high quantum efficiency

Performance Characterization of Dye-Sensitized Photovoltaics under Indoor Lighting

Indoor utilization of emerging photovoltaics is promising; however, efficiency characterization under room lighting is challenging. We report the first round-robin interlaboratory study of performance measurement for dye-sensitized photovoltaics (cells and mini-modules) and one silicon solar cell under a fluorescent dim light. Among 15 research groups, the relative deviation in power conversion efficiency (PCE) of the samples reaches an unprecedented 152%. On the basis of the comprehensive results, the gap between photometry and radiometry measurements and the response of devices to the dim illumination are identified as critical obstacles to the correct PCE. Therefore, we use an illuminometer as a prime standard with a spectroradiometer to quantify the intensity of indoor lighting and adopt the reverse-biased current–voltage (<i>I</i>–<i>V</i>) characteristics as an indicator to qualify the <i>I</i>–<i>V</i> sampling time for dye-sensitized photovoltaics. The recommendations can brighten the prospects of emerging photovoltaics for indoor applications