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Small-molecule acceptor (SMA)-based organic solar cells (OSCs) have achieved high power conversion efficiencies (PCEs), while their long-term stabilities remain to be improved to meet the requirements for real applications. Herein, we demonstrate the use of donor-acceptor alternating copolymer-type compatibilizers (DACCs) in high-performance SMA-based OSCs, enhancing their PCE, thermal stability, and mechanical robustness simultaneously. Detailed experimental and computational studies reveal that the addition of DACCs to polymer donor (PD)-SMA blends effectively reduces PD-SMA interfacial tensions and stabilizes the interfaces, preventing the coalescence of the phase-separated domains. As a result, desired morphologies with exceptional thermal stability and mechanical robustness are obtained for the PD-SMA blends. The addition of 20 wt % DACCs affords OSCs with a PCE of 17.1% and a cohesive fracture energy (Gc) of 0.89 J m-2, higher than those (PCE = 13.6% and Gc = 0.35 J m-2) for the control OSCs without DACCs. Moreover, at an elevated temperature of 120 °C, the OSCs with 20 wt % DACC exhibit excellent morphological stability, retaining over 95% of the initial PCE after 300 h. In contrast, the control OSCs without the DACC rapidly degraded to below 60% of the initial PCE after 144 h.
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The advent of special types of polymeric semiconductors, known as "polymer blends," presents new opportunities for the development of next-generation electronics based on these semiconductors' versatile functionalities in device applications. Although these polymer blends contain semiconducting polymers (SPs) mixed with a considerably high content of insulating polymers, few of these blends unexpectedly yield much higher charge carrier mobilities than those of pure SPs. However, the origin of such an enhancement has remained unclear owing to a lack of cases exhibiting definite improvements in charge carrier mobility, and the limited knowledge concerning the underlying mechanism thereof. In this study, the morphological changes and internal nanostructures of polymer blends based on various SP types with different intermolecular interactions in an insulating polystyrene matrix are investigated. Through this investigation, the physical confinement of donor-acceptor type SP chains in a continuous nanoscale network structure surrounded by polystyrenes is shown to induce structural ordering with more straight edge-on stacked SP chains. Hereby, high-performance and transparent organic field-effect transistors with a hole mobility of ≈5.4 cm2 V-1 s-1 and an average transmittance exceeding 72% in the visible range are achieved.
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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.
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A low-band gap semiconducting polymer with an acceptor-donor-acceptor architecture is newly designed and synthesized by incorporating a π-extended thiazole-vinylene-thiazole unit. The resulting thiazole-containing diketopyrrolopyrrole copolymer exhibits well-balanced ambipolar characteristics with hole mobility of up to 0.11 cm2 V-1 s-1 and electron mobility of up to 0.30 cm2 V-1 s-1 , which are suitable for applications in polymer electronics.
Assuntos
Semicondutores , Tiazóis , Elétrons , PolímerosRESUMO
The need for optoelectronic and chemical compatibility between the layers in colloidal quantum dot (CQD) photovoltaic devices remains a bottleneck in further increasing performance. Conjugated polymers are promising candidates as new hole-transport layer (HTL) materials in CQD solar cells (CQD-SCs) owing to the highly tunable optoelectronic properties and compatible chemistries. A diketopyrrolopyrrole-based polymer with benzothiadiazole derivatives (PD2FCT-29DPP) as an HTL in these devices is reported. The energy level, molecular orientation, and hole mobility of this HTL are manipulated through molecular engineering. By levering the polymer's optical absorption spectrum complementary to that of the CQD active layer, EQE across the visible and near-infrared regions is maximized. As a result, a PD2FCT-29DPP-based device exhibits a fill factor of 70% and approximately 35% efficiency enhancement compared to a PTB7-based device.
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New blue (DBA-SAB) and deep-blue (TDBA-SAF) thermally activated delayed fluorescence (TADF) emitters are synthesized for blue-emitting organic-light emitting diodes (OLEDs) by incorporating spiro-biacridine and spiro-acridine fluorene donor units with an oxygen-bridged boron acceptor unit, respectively. The molecules show blue and deep-blue emission because of the deep highest occupied molecular energy levels of the donor units. Besides, both emitters exhibit narrow emission spectra with the full-width at half maximum (FWHM) of less than 65 nm due to the rigid donor and acceptor units. In addition, the long molecular structure along the transition dipole moment direction results in a high horizontal emitting dipole ratio over 80%. By combining the effects, the OLED utilizing DBA-SAB as the emitter exhibits a maximum external quantum efficiency (EQE) of 25.7% and 1931 Commission Internationale de l'éclairage (CIE) coordinates of (0.144, 0.212). Even a higher efficiency deep blue TADF OLED with a maximum EQE of 28.2% and CIE coordinates of (0.142, 0.090) is realized using TDBA-SAF as the emitter.
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Organic light-emitting diodes with thermally activated delayed fluorescence emitter have been developed with highly twisted donor-acceptor configurations and color-pure blue emitters. Synthesized 4-(4-(4,6-diphenylpyrimidin-2-yl)phenyl)-10H-spiro[acridine-9,9'-fluorene] (4,6-PhPMAF) doped device with spiroacridine as a donor unit and diphenylpyrimidine as acceptor exhibits the device characteristics such as the luminescence, external quantum efficiencies, current efficiencies, and power efficiencies corresponding to 213 cd/m2, 2.95%, 3.27 cd/A, and 2.94 lm/W with Commission International de l'Eclairage (CIE) coordinates of (0.15, 0.11) in 4,6-PhPMAF-doped DPEPO emitter. The reported 10-(4-(2,6-diphenylpyrimidin-4-yl)phenyl)-10H-spiro[acridine-9,9'-fluorene] (2,6-PhPMAF) doped device exhibit high device performance with 1,445 cd/m2, 12.38%, 19.6 cd/A, and 15.4 lm/W, which might be originated from increased internal quantum efficiency by up-converted triplet excitons to the singlet state with relatively smaller ΔE ST of 0.17 eV and higher reverse intersystem crossing rate (k RISC) of 1.0 ×108/s in 2,6-PhPMAF than 0.27 eV and 3.9 ×107/s in 4,6-PhPMAF. Despite low performance of 4,6-PhPMAF doped device, synthesized 4,6-PhPMAF has better color purity as a deep-blue emission with y axis (0.11) than reported 2,6-PhPMAF with y axis (0.19) in CIE coordinate. The synthesized 4,6-PhPMAF has higher thermal stability of any transition up to 300°C and decomposition temperature with only 5% weight loss in 400°C than reported 2,6-PhPMAF. The maximum photoluminescence emission of 4,6-PhPMAF in various solvents appeared at 438 nm, which has blue shift about 20 nm than that of 2,6-PhPMAF, which contributes deep-blue emission in synthesized 4,6-PhPMAF.
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Understanding the effects of the chemical structures of donor polymers on the photovoltaic properties of their corresponding organic photovoltaic (OPV) devices under various light-intensity conditions is important for improving the performance of these devices. We synthesized a series of copolymers based on poly[(2,6-(4,8-bis(5-(2-thioethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene))-alt-(5,5-(1',3'-di-2-thienyl-5',7'-bis(2-ethylhexyl)benzo[1',2'-c:4',5'-c']dithiophene-4,8-dione))] (PBDB-TS) and studied the effects of chlorine substitution of its thiophene-substituted benzodithiophene (BDT-Th) unit on its photovoltaic properties. Chlorination of the polymer resulted in a bulk heterojunction (BHJ) morphology optimized for efficient charge transport with suppressed leakage current and an increased open-circuit voltage of the OPV device; this optimization led to a remarkable enhancement of the OPV device's power conversion efficiency (PCE) not only under the condition of 1 sun illumination but also under a low light intensity mimicking indoor light; the PCE increased from 8.7% for PBDB-TS to â¼13% for the chlorinated polymers, PBDB-TS-3Cl, and PBDB-TS-4Cl under the 1 sun illumination condition and from 5.3% for PBDB-TS to 21.7% for PBDB-TS-4Cl under 500 lx fluorescence illuminance. Interestingly, although the OPV PCEs under 1 sun illumination were independent of the position of chlorine substitution onto the polymer, PBDB-TS-4Cl exhibited better performance under simulated indoor light than its derivative PBDB-TS-3Cl. Our results demonstrate that efficient light absorption and charge-carrier generation play key roles in achieving high OPV efficiency under low-light-intensity conditions.
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In contrast to the red and green regions, conventional fluorescent emitters continue to serve as blue emitters in commercialized organic light-emitting diodes. Many researchers have studied anthracene moieties as blue emitters, given their appropriate energy levels and good emission properties. We herein report two new deep blue-emitting anthracene derivatives that include p-xylene as moieties connecting the anthracene cores to side groups. We enhanced the efficiency by maximizing triplet-triplet fusion (TTF) without sacrificing emission color. The large steric hindrance imposed by the methyl groups of p-xylene creates a perpendicular geometry between p-xylene and the neighboring aromatic rings. Any extension of π-conjugation is thus disrupted, and the isolated core anthracene moiety emits a deep blue color with a high photoluminescence quantum yield. Moreover, the extensive steric hindrance suppresses vibration and rotation because the molecules are rigid. The high horizontal dipole ratio attributable to the large aspect ratio increases the outcoupling efficiency of the emitted light. Furthermore, the charge mobility and triplet harvesting ability are enhanced by decreasing the bulkiness of the side groups. Molecular dynamics simulation revealed that the bulkiness of the side group significantly impacted molecular density, which in turn affected the charge transport and TTF. We used two molecules, 2PPIAn (containing a phenyl side group) and 4PPIAn (containing a terphenyl side group), to form nondoped emission layers that exhibited maximum external quantum efficiencies of 8.9 and 7.1% with Commission Internationale de L'Eclairage coordinates of (0.150, 0.060) and (0.152, 0.085), respectively.
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Organic flash memories that employ solution-processed polymer semiconductors preferentially require internal stability of their active channel layers. In this paper, a series of new donor-acceptor copolymers based on cyclopentadithiophene (CDT) and diketopyrrolopyrrole (DPP) are synthesized to obtain high performance and operational stability of nonvolatile floating-gate memory transistors with various additional donor units including thiophene, thiophene-vinylene-thiophene (CDT-DPP-TVT), selenophene, and selenophene-vinylene-selenophene. Detailed analyses on the photophysical, two-dimensional grazing incident X-ray diffraction, and bias stress stability are discussed, which reveal that the CDT-DPP-TVT exhibits excellent bias stress stability over 105 s. To utilize the robust nature of CDT-DPP-TVT, floating-gate transistors are fabricated by embedding Au nanoparticles between Cytop layers as a charge storage site. The resulting memory devices reveal bistable current states with high on/off current ratio larger than 104 and each state can be distinguished for more than 1 year, indicating a long retention time. Moreover, repetitive writing-reading-erasing-reading test clearly supports the reproducible memory operation with reversible and reliable electrical responses. All these results suggest that the internal stability of CDT-DPP-TVT makes this copolymer a promising material for application in reliable organic flash memory.
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We report two newly synthesized naphthalene diimide (NDI)-based conjugated polymers, poly[(E)-2,7-bis(2-decyltetradecyl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone-vinylene-thiophene-vinylene] (PNDI-VTV) and poly[(E)-2,7-bis(2-decyltetradecyl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone-vinylene-selenophene-vinylene] (PNDI-VSV) with different donor units as electron-transporting organic semiconductors for organic field-effect transistors (OFETs). Furthermore, we study the effect of vinylene position on electron transport in the NDI polymers by using two similar polymers but with thiophene-vinylene-thiophene (PNDI-TVT) instead of vinylene-thiophene-vinylene or selenophene-vinylene-selenophene (PNDI-SVS) instead of vinylene-selenophene-vinylene. By incorporating vinylene between thiophene (or selenophene) units, the resulting NDI-based polymers PNDI-VTV and PNDI-VSV show larger backbone planarity than PNDI-TVT and PNDI-SVS. The polymers with a shorter acceptor monomer unit (PNDI-VTV and PNDI-VSV) show a strong face-on orientation, whereas those with a longer monomer unit (PNDI-TVT and SVS) exhibit a mixed face-on and edge-on orientation by two-dimensional grazing incidence X-ray diffraction. Optimized PNDI-VTV and PNDI-VSV OFETs exhibit electron mobilities of 0.043 and 0.7 cm2/(V·s), which is quite lower than those of PNDI-TVT and PNDI-SVS. In addition, the activation energies for electron transport of PNDI-VTV and PNDI-VSV were larger than those of PNDI-TVT and PNDI-SVS. Overall, this research provides the insight that the molecular alignment on the substrate can be controlled by the sequence of rigid acceptor monomer molecules for improving the electron transport of NDI polymers.
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A new small-molecule donor with a dithieno[2,3-d:2',3'-d']-benzo[1,2-b:4,5-b']-dithiophene (DTBDT) core and both alkyl and alkylthio substituents is designed and synthesized to improve the miscibility between DTBDT-based small molecules and [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM). The alkyl substituent on the 4-position and the alkylthio substituent on the 5-position of the substituted thiophene are expected to improve intermolecular interactions and prevent severe aggregation of the small molecules. The new small molecule, DTBDT-S-C8-TTR, exhibits a homogenous blend morphology with small domains and edge-on-oriented crystalline structures in blends with PC71BM, and give a maximum power conversion efficiency (PCE) of 8.43%. To recover the crystallinity of the DTBDT-S-C8-TTR small molecules weakened after being blended with PC71BM, a solvent vapor annealing (SVA) treatment is performed. The SVA-treated blend films reveal well-developed crystalline domains with interconnected fibrillar structures. This blend morphology allows efficient charge carrier transport in blends and leads to increased PCEs. The maximum PCE of 9.18% achieved using DTBDT-S-C8-TTR suggests that substituting both alkylthio and alkyl groups into DTBDT can yield small-molecule-based organic photovoltaics (OPVs) displaying improved photovoltaic performances.
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Herein, we explore the strategy of realizing a red-selective thin-film organic photodiode (OPD) by synthesizing a new copolymer with a highly selective red-absorption feature. PCZ-Th-DPP, with phenanthrocarbazole (PCZ) and diketopyrrolopyrrole (DPP) as donor and acceptor units, respectively, was strategically designed/synthesized based on a time-dependent density functional theory calculation, which predicted the significant suppression of the band II absorption of PCZ-Th-DPP due to the extremely efficient intramolecular charge transfer. We demonstrate that the synthesized PCZ-Th-DPP exhibits not only a high absorption coefficient within the red-selective band I region, as theoretically predicted, but also a preferential face-on intermolecular structure in the thin-film state, which is beneficial for vertical charge extraction as an outcome of a glancing incidence X-ray diffraction study. By employing PCZ-Th-DPP as a photoactive layer of Schottky OPD, to fully match its absorption characteristic to the spectral response of the red-selective OPD, we demonstrate a genuine red-selective specific detectivity in the order of 1012 Jones while maintaining a thin active layer thickness of â¼300 nm. This work demonstrates the possibility of realizing a full color image sensor with a synthetic approach to the constituting active layers without optical manipulation.
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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.
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A universal method that enables utilization of conventional photolithography for processing a variety of polymer semiconductors is developed. The method relies on imparting chemical and physical orthogonality to a polymer film via formation of a semi-interpenetrating diphasic polymer network with a bridged polysilsesquioxane structure, which is termed an orthogonal polymer semiconductor gel. The synthesized gel films remain tolerant to various chemical and physical etching processes involved in photolithography, thereby facilitating fabrication of high-resolution patterns of polymer semiconductors. This method is utilized for fabricating tandem electronics, including pn-complementary inverter logic devices and pixelated polymer light-emitting diodes, which require deposition of multiple polymer semiconductors through solution processes. This novel and universal method is expected to significantly influence the development of advanced polymer electronics requiring sub-micrometer tandem structures.
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Deep-blue emitting Iridium (Ir) complexes with horizontally oriented emitting dipoles are newly designed and synthesized through engineering of the ancillary ligand, where 2',6'-difluoro-4-(trimethylsilyl)-2,3'-bipyridine (dfpysipy) is used as the main ligand. Introduction of a trimethylsilyl group at the pyridine and a nitrogen at the difluoropyrido group increases the bandgap of the emitter, resulting in deep-blue emission. Addition of a methyl group (mpic) to a picolinate (pic) ancillary ligand or replacement of an acetate structure of pic with a perfluoromethyl-triazole structure (fptz) increases the horizontal component of the emitting dipoles in sequence of mpic (86%) > fptz (77%) > pic (74%). The organic light-emitting diode (OLED) using the Ir complex with the mpic ancillary ligand shows the highest external quantum efficiency (31.9%) among the reported blue OLEDs with a y-coordinate value lower than 0.2 in the 1931 Commission Internationale de L'Eclairage (CIE) chromaticity diagram.
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Phenazasiline, a sp3 hybridized silicon-bridged diphenylamine, is a promising donor moiety for deep-blue TADF emitters because of its deep highest occupied molecular orbital, high triplet level of 3.1 eV, and orthogonal connection with acceptor moieties. Herein, we report highly efficient deep-blue TADF emitters composed of phenazasiline donor and triazine acceptor combined with methyl-substituted phenylene linkers. As a series of methyl-substituted linker-based TADF emitters, we also synthesized spiroacridine donor-based sky-blue TADF emitters to study the effect of methyl-substituted linkers on the photophysical properties of TADF emitters. Deeper blue emissions of TADF emitters were obtained by substituting either one or two methyl groups at the phenylene linker of TADF molecules, and a small singlet-triplet gap below 0.2 eV was maintained for efficient reverse intersystem crossing. Organic light-emitting diodes (OLEDs) with spiroacridine-based TADF emitters, TTSA and TXSA, showed external quantum efficiencies (EQEs) of 27.9 and 20.7% with sky-blue emission of Commision Internationale de L'Eclairage (CIE) color coordinates of (0.158, 0.283) and (0.154, 0.251), respectively. With phenazasiline-based TADF emitters, TTAZ and TXAZ, highly efficient deep-blue OLEDs were realized with EQEs of 23.7 and 16% with improved CIE coordinates of (0.148, 0.158) and (0.148, 0.131), respectively.
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The effects of the molecular structure of thiazole-based polymers on the active layer morphologies and performances of electronic and photovoltaic devices were studied. Thus, thiazole-based conjugated polymers with a novel thiazole-vinylene-thiazole (TzVTz) structure were designed and synthesized. The TzVTz structure was introduced to extend the π conjugation and coplanarity of the polymer chains. By combining alkylthienyl-substituted benzo[1,2-b:4,5-b']dithiophene (BDT) or dithieno[2,3-d:2',3'-d']benzo[1,2-b:4,5-b']dithiophene (DTBDT) electron-donating units and a TzVTz electron-accepting unit, enhanced intermolecular interactions and charge transport were obtained in the novel polymers BDT-TzVTz and DTBDT-TzVTz. With a view to using the polymers in transistor and photovoltaic applications, the molecular self-assembly in and their nanoscale morphologies of the active layers were controlled by thermal annealing to enhance the molecular packing and by introducing a diphenyl ether solvent additive to improve the miscibility between polymer donors and [6,6]phenyl-C71-butyric acid methyl ester (PC71 BM) acceptors, respectively. The morphological characterization of the photoactive layers showed that a higher degree of π-electron delocalization and more favorable molecular packing in DTBDT-TzVTz compared with in BDT-TzVTz leads to distinctly higher performances in transistor and photovoltaic devices. The superior performance of a photovoltaic device incorporating DTBDT-TzVTz was achieved through the superior miscibility of DTBDT-TzVTz with PC71 BM and the improved crystallinity of DTBDT-TzVTz in the nanofibrillar structure.
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The development of highly efficient blue organic light-emitting diodes (OLEDs) with good stability is currently the most important issue in OLED displays and lighting. This paper reports an efficient blue fluorescent OLED based on a deep-blue-emitting phosphorescent sensitizer [(dfpysipy)2Ir(mpic)] and a conventional fluorescent emitter (TBPe). Efficient triplet harvesting by the fluorescent emitter occurs in the OLED because of sensitization even though the difference in the emission energy between the phosphorescent and fluorescent emissions was only 0.05 eV. These results clearly demonstrate the potential for realizing highly efficient blue fluorescent OLEDs using phosphorescent sensitizers without requiring ultraviolet-emitting phosphorescent dye.
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To utilize the potential of small-molecule-based organic solar cells, proper designs of the photoactive materials which result in reasonable performance in a halogen-free solvent system and thickness tolerance over a range are required. One of the best approaches to achieve these requirements is via the molecular engineering of small-molecule electron donors. Here, we have modified a previously reported dithienobenzodithiophene (DTBDT)-based small molecule (SM1) via the dimerization approach, that is, the insertion of an additional DTBDT into the main backbone of the small molecule (SM2). An SM1-based photoactive film showed severe pinhole formation throughout the film when processed with a halogen-free o-xylene solvent. On the other hand, the modified small-molecule SM2 formed an excellent pinhole-free film when processed with the o-xylene solvent. Because of the dimerization of the DTBDT in the SM2 core, highly crystalline films with compact lamellae and an enhanced donor/acceptor interdigitation were formed, and all of these factors led to a high efficiency of 8.64% with chloroform and 8.37% with the o-xylene solvent systems. To the best of our knowledge, this study represents one of the best results with the SM donor and fullerene derivative acceptor materials that have shown the device performance with halogen-free solvents.