RESUMO
Direct arylation polymerization (DArP) is a synthetic method for conjugated polymers; in DArP, organometallic functionalization steps are omitted and there are no toxic byproducts. As a result, it is considered a more sustainable alternative compared to conventional methods such as Stille polymerization. To explore the possibility of DArP-based polymers as donor materials in organic solar cells (OSCs), a series of conjugated polymers based on the structure of PDCBT (poly[2,2''''-bis[[(2-butyloctyl)oxy]carbonyl][2,2':5',2'':5'',2'''-quaterthiophene]-5,5'''-diyl]) are synthesized using DArP and Stille polymerization. By controlling the monomer concentration and reaction time in DArP, DArP-5 with the highest Mn (21.9 kDa) can be obtained and its optoelectronic properties, electrochemical properties, and microscopic molecular ordering are comparable to those of Stille-based PDCBT (Stille-P). Analysis of the polymer structure indicates no structural defects such as crosslinking from undesired ß-coupling reactions in DArP-5. Upon blending with the PC71 BM acceptor molecule, an increase in the crystallite size of DArP-5 is also observed. In OSC devices with a polymer:PC71 BM bulk-heterojunction photoactive layer, DArP-5 demonstrates a comparable power conversion efficiency of 5.8% with that of Stille-P (5.5%). These results prove that DArP is suitable for synthesizing PDCBT, and DArP-based PDCBT can be used in OSCs as an alternative of Stille-based one.
RESUMO
The femtosecond transient absorption (TA) characterization of a new benzothiadiazole (BT)-based donor-acceptor conjugated copolymer, poly[(2,6-dithieno[3,2-b:2',3'-d]thiophene)-alt-(4,7-di(4-octyldodecylthiopen-2-yl)-2,1,3-benzo[c][1,2,5]thiadiazole (PBT), as well as its fluorinated derivatives, PFBT and PDFBT, is carried out. Additionally, bulk heterojunction (BHJ) films consisting of the copolymers and [6,6]-phenyl-C71 -butylic acid methyl ester (PC70 BM) are examined using TA spectroscopy. Both the singlet excited state dynamics in the copolymers and the charge transfer state dynamics in the BHJs are investigated in terms of fluorination dependency; the fluorinated copolymers exhibit less singlet exciton recombination rate than the fluorine-free copolymer, and the BHJs including the fluorinated copolymers display slower monomolecular recombination than the fluorine-free analogue. Furthermore, the excitation-intensity-dependent TA dynamics of the copolymers and BHJs is investigated, revealing that, when sufficiently high excitation intensity is used to induce annihilation processes, the fluorinated copolymers and BHJs incorporating the fluorinated copolymers show more rapid TA decay ascribable to morphological enhancement. These TA spectroscopic findings are found to correlate with the device characteristics with respect to fluorinated content in the polymer solar cells. In particular, both the short-circuit current density and fill factor of BHJ solar cells correspond closely with the fast decay parameters of the BHJ films under high excitation intensity.
Assuntos
Fontes de Energia Elétrica , Tiadiazóis/síntese química , Tiofenos/síntese química , Halogenação , Polimerização , Energia Solar , Análise Espectral/métodos , Luz SolarRESUMO
Organic photosensitizers have been investigated as effective light-sensing elements that can promote strong absorption with high field-effect mobility in organic phototransistors (OPTs). In this study, a novel organic photosensitizer is synthesized to demonstrate broad-band photoresponse with enhanced electrical performance. An unsymmetrical small molecule of a solubilizing donor (Dsol)-acceptor (A)-dye donor (Ddye) type connected with a twisted conjugation system is designed for broad-band detection (ranging from 250 to 700 nm). This molecule has high solubility, thereby facilitating the formation of uniformly dispersed nanoparticles in an insulating polymer matrix, which is deposited on top of OPT semiconductors by a simple solution process. The broad-band photodetection shown by the organic photosensitizer is realized with improved mobility close to an order of magnitude and high on/off current ratio (â¼105) of the organic semiconductor. Furthermore, p-type charge transport behavior in the channel of the OPT is enhanced through the intrinsic electron-accepting ability of the organic photosensitizer caused by the unique molecular configuration. These structural properties of organic photosensitizers contribute to an improvement in broad-band photosensing systems with new optoelectronic properties and functionalities.
RESUMO
[This corrects the article DOI: 10.1002/advs.201900245.].
RESUMO
The synthesis of a diseleno[3,2-b:2',3'-d]selenophene (DSS) composed of three fused selenophenes is reported and it is used as a building block for the preparation of a high hole mobility conjugated polymer (PDSSTV). The polymer demonstrates strong intermolecular interactions even in solution, despite steric repulsion between the large Se atom in DSS and adjacent (Cß)-H atoms which leads to a partially twisted confirmation PDSSTV. Nevertheless, 2D grazing incidence X-ray diffraction (2D-GIXD) analysis reveals that the polymer tends to align in a highly ordered edge-on orientation after thermal annealing. The polymer demonstrates promising performance in a field-effect transistor device with saturated hole mobility up to 2 cm2 V-1 s-1 obtained under relatively low gate voltages of -30 V. The ultilization of a Se-containing fused aromatic system, therefore, appears to be a promising avenue for the development of high-performance conjugated polymers.
RESUMO
Fluorine (F) substitution on conjugated polymers in polymer solar cells (PSCs) has a diverse effect on molecular properties and device performance. We present a series of three D-A type conjugated polymers (PBT, PFBT, and PDFBT) based on dithienothiophene and benzothiadiazole units with different numbers of F atoms to explain the influence of F substitution by comparing the molecular interactions of the polymers and the recombination kinetics in PSCs. The preaggregation behavior of PFBT and PDFBT in o-DCB at the UV-vis absorption spectra proves that both polymers have strong intermolecular interactions. Besides, more closely packed structures and change into face-on orientation of fluorinated polymers are observed in polymer:PC71BM blends by GIXD which is beneficial for charge transport and, ultimately, for current density in PSCs (4.3, 13.0, and 14.5 mA cm-2 for PBT, PFBT, and PDFBT, respectively). Also, the introduction of F atoms on conjugated backbones affects the recombination kinetics by suppressing bimolecular recombination, thereby improving the fill factor (0.41, 0.68, and 0.69 for PBT, PFBT, and PDFBT, respectively). Consequently, the PCE of PSCs reached 7.3% without any additional treatment (annealing, solvent additive, etc.) in the polymer containing difluorinated BT (PDFBT) that is much higher than nonfluorinated BT (PBT â¼ 1%) and monofluorinated BT (PFBT â¼ 6%).
RESUMO
The universal role of high-k fluorinated dielectrics in assisting the carrier transport in transistors for a broad range of printable semiconductors is explored. These results present general rules for how to design dielectric materials and achieve devices with a high carrier concentration, low disorder, reliable operation, and robust properties.