RESUMO
Non-fullerene acceptors (NFAs) for organic solar cells (OSCs) have significantly developed over the past five years with continuous improvements in efficiency now over 18%. However, a key challenge still remains in order to fully realize their commercialization potential: the need to extend device lifetime and to control degradation mechanisms. Herein, we investigate the effect of two different molecular engineering routes on the widely utilized ITIC NFA, to tune its optoelectronic properties and interactions with the donor polymer in photoactive blends. Heavier selenium (Se) atoms substitute sulfur (S) atoms in the NFA core in either outer or inner positions, and methyl chains are attached to the end groups. By investigating the effects of these structural modifications on the long-term operational stability of bulk-heterojunction OSC devices, we identify outer selenation as a powerful strategy to significantly increase device lifetime compared to ITIC. Combining outer selenation and methylation results in an impressive 95% of the initial OSC efficiency being retained after 450 h under operating conditions, with an exceptionally long projected half-lifetime of 5600 h compared to 400 h for ITIC. We find that the heavier and larger Se atoms at outer-core positions rigidify the molecular structure to form highly crystalline films with low conformational energetic disorder. It further enhances charge delocalization over the molecule, promoting strong intermolecular interactions among acceptor molecules. Upon methylation, this strong intermolecular interaction stabilizes acceptor domains in blends to be resilient to light-induced morphological changes, thereby leading to superior device stability. Our results highlight the crucial role of NFA molecular structure for OSC operational stability and provide important NFA design rules via heteroatom position and end-group control.
RESUMO
A series of acene-modified small molecules have been designed and synthesized, and their photovoltaic characteristics were studied by using the small molecules in organic photovoltaics (OPVs). Different cores were introduced to modulate the conjugation lengths of the small molecules and the bulk heterojunction (BHJ) morphologies. Three small-molecule donors were prepared, namely Ph-TTR, Na-TTR, and An-TTR, which have phenyl, naphthalene, and anthracene moieties, respectively, as conjugated cores. These donors were synthesized in a few steps and exhibited favorable BHJ morphologies, thereby giving promising power conversion efficiencies (PCEs). The donors showed excellent miscibility with the acceptor PC71 BM, and the use of the additive 1,8-diiodooctane (DIO) led to a remarkable increase in crystallinity, thereby increasing the PCEs of their OPVs. Of the three donors, Na-TTR showed the most efficient charge carrier generation and favorable molecular packing structures; hence, of the three types of devices tested, the Na-TTR:PC71 BM devices exhibited the highest PCE, specifically 6.27 %, without pre- or post-treatments. The promising PCEs achieved from these easily synthesized acene-modified small molecules suggested that acene-modified small molecules can be useful materials in OPVs.
RESUMO
To investigate the influence of donor molecule crystallinity on photovoltaic performance in all-small-molecule solar cells, two dithieno[2,3- d:2',3'- d']-benzo[1,2- b:4,5- b']dithiophene (DTBDT)-based small molecules, denoted as DTBDT-Rho and DTBDT-S-Rho and incorporating different side chains, are synthesized and characterized. The photovoltaic properties of solar cells made of these DTBDT-based donor molecules are systemically studied with the [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) fullerene acceptor and the O-IDTBR nonfullerene acceptor to study the aggregation behavior and crystallinity of the donor molecules in both blends. Morphological analyses and a charge carrier dynamics study are carried out simultaneously to derive structure-property relationships and address the requirements of all-small-molecule solar cells. This study reveals exciton decay loss driven by large-scale phase separation of the DTBDT molecules to be a crucial factor limiting photocurrent generation in the all-small-molecule solar cells incorporating O-IDTBR. In the all-small-molecule blends, DTBDT domains with dimensions greater than 100 nm limit the exciton migration to the donor-acceptor interface, whereas blends with PC71BM exhibit homogeneous phase separation with smaller domains than in the O-IDTBR blends. The significant energy losses in nonfullerene-based devices lead to decreased Jsc and fill factor values and unusual decrease in Voc values. These results indicate the modulation of phase separation to be important for improving the photovoltaic performances of all-small-molecule blends. In addition, the enhanced molecular aggregation of DTBDT-S-Rho with the alkylthio side chain leads to higher degrees of phase separation and unfavorable charge transfer, which are mainly responsible for the relatively low photocurrent when using DTBDT-S-Rho compared with that when using DTBDT-Rho. On the other hand, this enhanced molecular aggregation improves the crystallinity of DTBDT-S-Rho and results in its increased hole mobility.
RESUMO
OBJECTIVE: Anterior odontoid screw fixation is a safe and effective method for the treatment of odontoid fractures. The surgical technique is recommended for perforation of the apical cortex of the dens by the lag screw. However, overpenetration of the apical cortex may lead to potentially serious complications such as damages of adjacent vascular and neural structures. The purpose of this study was to assess the role of three-dimensional computed tomography (CT) scan to evaluate the safe margin beyond dens tip to ventral dura for anterior odontoid screw fixation. METHODS: We retrospectively analyzed the three-dimensional CT scans of the cervical spines in 55 consecutive patients at our trauma center. The patients included 38 males and 17 females aged between 22 and 73 years (mean age±standard deviation, 45.8±14.2 years). Using sagittal images of 3-dimensional CT scan, the safe margins beyond dens tip to ventral dura as well as the appropriate screw length were measured. RESULTS: The mean width of the apical dens tip was 9.6±1.1 mm. The mean lengths from the screw entry point to the apical dens tip and posterior end of dens tip were 39.2±2.6 mm and 36.6±2.4 mm. The safe margin beyond apical dens tip to ventral dura was 7.7±1.7 mm. However, the safe margin beyond the posterior end of dens tip to ventral dura was decreased to 2.1±3.2 mm, which was statistically significant (p<0.01). There were no significant differences of safe margins beyond dens tip to ventral dura with patient gender and age. CONCLUSION: Extension by several millimeters beyond the dens tip is safe, if the trajectory of anterior odontoid screw is targeted at the apical dens tip. However, if the trajectory of the screw is targeted to the posterior end of dens tip, extension beyond dens tip may lead to damage immediately adjacent to the vental dura mater.
RESUMO
A push-pull-type donor copolymer, named PP-TPD, was synthesized with the Suzuki coupling reaction using 6H-phenanthro[1,10,9,8-cdefg]carbazole (PCZ) as the donor unit and 1,3-bis(5-bromothiophen-2-yl)-5-octyl-4H-thieno[3,4-c]pyrrole-4,6(5H)-dione (TPD) as the acceptor unit. The synthesized PP-TPD was systematically investigated in terms of crystallinity and thermal, electrical, electrochemical, and optical properties. PP-TPD revealed green-selective absorption with a narrow full width at half-maximum of 138 nm. Green-selective organic photodiodes (OPDs) were constructed using PP-TPD as the green-absorbing donor and ZnO as the nonabsorbing acceptor material. The fabricated OPDs exhibited an extremely low dark current of 0.68 nA/cm2 at -5 V and a high detectivity above 1012 Jones at 550 nm. Moreover, they showed a sufficiently high 3-dB frequency and a linear dynamic range, similar to those of ideal-operating OPDs. The origin and physics background of the observed low dark current and high detectivity are discussed in detail.