Non-halogenated Solvents Research Articles

Efficient and Fully Non-Halogen Solution Processed Cs2AgBiBr6 Perovskite Solar Cell

For traditional hole transport material (HTM) 2,2′,7,7′-tetrakis(N,N′-di-pmethoxyphenylamino)9,9′-spirbiuorene(Spiro-OMeTAD) used in Cs2AgBiBr6 perovskite solar cell (PSC), the strong dependence of its performance on the hygroscopic and volatility additives, together with the mismatched energy level with Cs2AgBiBr6 and gold electrodes, are considered to be the two key factors restricting the improvement of performance. Considering this, we reported a series of dopant-free D-π-D type HTMs comprising of FNP as donor unit and Cz-Mp dimer linked benzene as π-bridge, termed o-PCz, m-PCz, and p-PCz by adjusting the linkage position of π-bridge moieties. HTM p-PCz with planar rigid structure, exhibits higher hole mobility and better film morphology compared with o-PCz and m-PCz. Notably, o-PCz, m-PCz, and p-PCz all show good dissolvability in non-halogenated solvent tetrahydrofuran (THF), making it possible to fabricate Cs2AgBiBr6 PSCs with full non-halogenated solution process. As a result, the dopant-free p-PCz based Cs2AgBiBr6 PSC device achieved an efficiency of 2.44% with enhanced ambient and thermal stability. Hence, the successful development of dopant-free p-PCz would make a great contribution for efficient and stable lead-free Cs2AgBiBr6 PSCs with full non-halogenated solution process.

Fully Non-Fused Ring Electron Acceptors Enable Effective Additive-Free Organic Solar Cells with Enhanced Exciton Diffusion Length.

Low-cost photovoltaic materials and additive-free, non-halogenated solvent processing of photoactive layers are crucial for the large-scale commercial application of organic solar cells (OSCs). However, high-efficiency OSCs that possess all these advantages remain scarce due to the lack of insight into the structure-property relationship. In this work, three fully non-fused ring electron acceptors (NFREAs), DTB21, DTB22, and DTB23, are reported by utilizing a simplified 1,4-di(thiophen-2-yl)benzene (DTB) core with varied alkoxy chain lengths on the thiophene bridge. The material-only costs of these acceptors are only 11-13$ per gram. Importantly, DTB22 has an exciton diffusion length (LD) of up to 25.5nm. The DTB21 and DTB23 exhibit decreased LDs of 20.1 and 23.1nm, respectively. After blending with the polymer donor PBQx-TF, the PBQx-TF:DTB22 film exhibits the fastest hole transfer and the longest carrier recombination lifetime among these OSCs. Consequently, the optimal PBQx-TF:DTB22-based OSC achieves an excellent PCE of 17.00%, which is among the highest values for fully NFREAs. In contrast, the PBQx-TF:DTB21- and PBQx-TF:DTB23-based OSCs show relatively lower PCEs of 15.13% and 15.63%, respectively. Notably, all these OSCs are fabricated using toluene as the solvent, without any additives. Additionally, the DTB22-based OSC also demonstrates good stability, retaining 95% of its initial efficiency after 500 h without encapsulation in a glovebox.

Nonhalogenated Solvent-Processed Efficient Ternary All-Polymer Solar Cells Enabled by the Introduction of a Naphthyloxy Group into the Side Chain of Polymer Donors.

Conjugated polymer donors are crucial for enhancing the power conversion efficiencies (PCEs) in all-polymer solar cells (All-PSCs) in nonhalogenated solvents. In this work, three wide-band-gap polymer donors (Sil-D1, Ph-Sil-D1, and Nap-Sil-D1) based on dithienobenzothiadiazole (DTBT) and benzodithiophene (BDT) donor moieties optimized by side chain engineering were designed and synthesized. Alkyl (Sil-D1), phenyloxy (Ph-Sil-D1), and naphthyloxy (Nap-Sil-D1) alkyl siloxane side chain units were incorporated into these polymer donors, respectively. Notably, the Nap-Sil-D1 polymer donor had a greater conjugation length, π-electron delocalization, and improved dipole moment. The deepest highest occupied molecular orbital level of Nap-Sil-D1, with a high absorption coefficient, showed better aggregation properties. In addition, reduced bimolecular recombination and trap-state density generated a high charge transfer to cause a significant enhancement of open-circuit voltage, current density, and fill factor values of 0.94 V, 25.5 mA/cm2, and 70.4%, respectively, for the Nap-Sil-D1-blended All-PSC ternary device (PM6:Nap-Sil-D1:PY-IT), with the highest PCE of 16.8% in the o-xylene solvent, compared to other polymers (Sil-D1 and Ph-Sil-D1) with PCEs of 15.5 and 16.2%. As a result, this optimized device architecture was found to be the most promising as a nonhalogenated solvent processed in additive-free ternary All-PSCs with good stability.

Triazine derivative as volatile solid additive for non‐halogenated solvent and thermal annealing‐free processed organic solar cells with over 18% efficiency

AbstractVolatile solid additive (VSA) has been demonstrated to be an effective strategy to optimize the morphology of the active layer for high‐performance organic solar cells (OSCs). Most of the reported OSCs with VSA are processed by chloroform (CF) and relies on thermal annealing (TA) posttreatment. However, the CF solvent problems of low boiling point, toxicity, and environmental‐unfriendly as well as increasing cost from TA restricted the large‐scale production. Here, a simple‐structured and low‐cost triazine derivative 2,4,6‐trichloro‐1,3,5‐triazine (TCT) as a VSA was introduced into PM6:BTP‐eC9‐based OSCs. Employing the TCT additive, the nonhalogenated solvent (o‐xylene) processed OSCs without TA treatment and delivered higher power conversion efficiencies (PCEs) in comparison to the TA‐treated counterpart. Benefiting from the intermolecular interactions between TCT and the active layer materials, the TCT‐treated blend films exhibited optimized morphology and enhanced crystallinity. As a result, the PM6:BTP‐eC9 OSCs achieved a champion PCE of 18.18% and fill factor (78.5%), which is among one of the most advanced nonhalogenated solvent‐processed and annealing‐free OSCs. Meanwhile, the TCT‐treated blend films also demonstrated the better photo‐stability compared to the control device. This work provides a guideline of triazine derivatives as VSA for high‐performance OSCs with TA‐free and nonhalogenated solvent‐processing treatment.

Polymer Based on Asymmetrically Halogenated Benzotriazole Enables High Performance Organic Solar Cells Prepared in Nonhalogenated Solvent.

Halogenation on the A unit of the D-π-A-type polymer donor has been proven as an effective strategy to improve the performance of organic solar cells (OSCs). Compared with fluorination, chlorination usually increases the open-circuit voltage because of the downward shift of energy levels, but decreases the charge transport ability due to the large steric hindrance of the chlorine atom. We reported herein a method to balance the energy loss and charge transport through asymmetric halogenation on the benzotriazole (BTA) unit of the polymer. The designed PE3-FCl based on the BTA unit containing fluorine and chlorine atoms rendered the highest power conversion efficiency (PCE) of 17.83% when eC9-2Cl-γ and o-xylene were used as the electron acceptor and solvent, respectively. The performance is obviously higher than that of the polymer PE3 containing a difluorinated BTA unit (16.65%) and polymer PE3-2Cl with dichlorinated BTA (14.65%) due to the manipulated morphology by preaggregation, improved and more balanced charge carrier transport, and reduced recombination loss. Notably, this PCE is a breakthrough for the BTA-based polymers processed by nonhalogenated solvent. This work gives deep insight into the asymmetric halogenation of polymer donors for high-performance green solvent-processed OSCs.

Inner Side Chain Modification of Small Molecule Acceptors Enables Lower Energy Loss and High Efficiency of Organic Solar Cells Processed with Non-halogenated Solvents.

Organic solar cells (OSCs) processed with non-halogenated solvents usually suffer from excessive self-aggregation of small molecule acceptors (SMAs), severe phase separation and higher energy loss (Eloss), leading to reduced open-circuit voltage (Voc) and power conversion efficiency (PCE). Here, we designed and synthesized two SMAs L8-PhF and L8-PhMe by introducing different substituents (fluorine for L8-PhF and methyl for L8-PhMe) on the phenyl end group of inner side chains of L8-Ph, and investigated the effect of the substituents on the intermolecular interaction of SMAs, Eloss and performance of OSCs processed with non-halogenated solvents. It is found that compared with L8-PhF, which possesses strong intermolecular interactions but downgraded molecular packing order, L8-PhMe exhibits more effective non-covalent interactions, which improves the tightness and order of molecular packing. When blending the SMAs with PM6, the OSCs based on L8-PhMe shows reduced non-radiative energy loss, and enhanced Voc than the devices based on the other two SMAs. Consequently, the L8-PhMe based device processed with o-xylene and using 2PACz as the hole transport layer shows an outstanding PCE of 19.27%. This study highlights that the Eloss of OSCs processed with non-halogenated solvents could be decreased through regulating the intermolecular interactions of SMAs by inner side chain modification.

Extraction of poly(3-hydroxybutirate) from Priestia megaterium using non-halogenated solvents: A comparative performance analysis

Solvent extraction using chloroform is the most common industrial process for poly(3-hydroxybutyrate) (P(3HB)) recovery from dried biomass, and still a major barrier to expanding the commercial application of this biodegradable biopolymer. Consequently, there is great interest in alternative non-halogenated solvents for this process and some relevant related results are available in the literature for P(3HB) recovery from Gram-negative bacteria. This work evaluated the potential of a set of non-halogenated solvents for the extraction of P(3HB) from Priestia megaterium, a Gram-positive bacterium of great potential for P(3HB) production. Ethyl acetate (EtAc), methyl ethyl ketone (MEK), dimethyl carbonate (DMC), dimethyl sulfoxide (DMSO), N,N-dimethylacetamide (NNDA), 2-heptanone (2-Hp), propylene carbonate (PC), and isoamyl propionate (IAP) were tested. Preliminary solubilization tests using commercial P(3HB) showed that EtAc, MEK, DMC and IAP had lower P(3HB) solubilization capacity (below 0.08 g/L for EtAc, MEK, and DMC; 1.3–2.5 g/L for IAP) than DMSO (65–70 g/L) and PC, 2-Hp and NNDA (>100 g/L). Then, only DMSO, PC, 2-Hp, and NNDA were evaluated in recovery tests with intracellular P(3HB). DMSO was not selective for P(3HB), causing digestion of cell wall components. PC, 2-Hp, and NNDA outperformed chloroform, but NNDA stood out for its remarkably higher recovery (98.5 %, 30 min, 140 ºC).

Photostability of Phenoxazine Derivatives.

Phenoxazine is a commonly used molecular building block, for example in optoelectronic applications and pharmaceuticals. However, it is highly susceptible to rapid photodegradation, especially in halogenated solvents. In the present study, we identify the degradation products in both halogenated and non-halogenated solvents by UV/Vis absorption, NMR spectroscopy and mass spectrometry. We also propose a substitution strategy aimed at effectively suppressing the high photoreactivity. Kinetic studies show that the quantum yield of photodegradationϕdiffers by a factor of more than 1000 between trisubstituted derivatives and N-substituted phenoxazine.

P19-72 Comparative risk profile of Dichloromethane (DCM) and non-halogenated solvent alternatives in pharmaceutical manufacturing processes

P19-72 Comparative risk profile of Dichloromethane (DCM) and non-halogenated solvent alternatives in pharmaceutical manufacturing processes

Composite side chain induced ordered preaggregation in liquid state for high-performance non-halogen solvent processed organic solar cells

Eco-friendly organic solar cells (OSCs) have become a promising choice for commercialization, particularly emphasizing the importance of using non-halogenated solvents. However, non-halogenated OSCs with high-performance remain limited due to the uncontrollable preaggregation behaviors of photovoltaic materials in these solvents. Here, composite side chain engineering was shown to enhance photovoltaic performance of non-halogenated solvents processed OSCs by developing two small molecular acceptors, C10ch-F and C10ch-Cl, and to study the preaggregation behavior in toluene. Through a combination of in situ absorption analyses and molecular dynamics simulations, we demonstrated that the cyclohexyl moiety at the tail of the linear chain acted as a fixative, effectively mitigating the entanglement of the amorphous long chains and prolonging the kinetics of film formation process, resulting in reinforced molecular packing with a preferential face-on orientation. With effective charge generation, transport, and collection, C10ch-Cl-based device from Tol showed an impressive PCE of 18.4 % and 19.2 % in the binary and ternary systems. Moreover, the PCE remained at 80 % of its initial value after 790 h of continuous illumination, indicating excellent photostability. The uncovered preaggregation and realized excellent performance obtained through the composite side chain strategy may allow for further synthetic advances, potentially leading to significantly improved eco-friendly OSCs.

Aggregation Regulation of Acceptor via Thiophene‐Substituted Alkyl Chains Enables High‐Performance Toluene‐Processed Organic Solar Cells without Additive and Post‐Treatment

AbstractDue to the mismatched aggregation behavior and limited compatibility between the donor and acceptor, it is a challenge for the active layer of organic solar cells (OSCs) to spontaneously realize well‐developed morphology in nonhalogenated solvents. In this contribution, an aggregation regulation strategy for acceptors with strong aggregation is developed via thiophene‐substituted alkyl chain engineering to fabricate high‐performance nonhalogenated solvent‐processed OSCs without an additive or post‐treatment. With the replacement of alkyl chains with steric conjugated thiophene‐substituted alkyl chains, the resulting acceptor (namely BTP‐2T, BTP‐T, and BTP‐T‐BO) shows reduced aggregation to match the polymer donor D18‐Cl using toluene as a processing solvent, enabling ordered molecular arrangement and uniform phase separation morphology. Especially, the combined modification of the asymmetric thiophene‐substituted inner chain and branched outer side chains for BTP‐T‐BO enables the formation of a superior nanoscale bi‐continuous interpenetrating network along with ordered and compact molecular packing in the D18‐Cl:BTP‐T‐BO blend. As a result, an excellent PCE of 18.05% is achieved in the D18‐Cl:BTP‐T‐BO‐based device using toluene as the processing solvent without any extra treatment, which is the highest value for nonhalogenated solvent‐processed OSCs without any extra treatment.

Inner/Outer Side Chain Engineering of Non-Fullerene Acceptors for Efficient Large-Area Organic Solar Modules Based on Non-Halogenated Solution Processing in Air.

Achieving efficient and large-area organic solar modules via non-halogenated solution processing is vital for the commercialization yet challenging. The primary hurdle is the conservation of the ideal film-formation kinetics and bulk-heterojunction (BHJ) morphology of large-area organic solar cells (OSCs). A cutting-edge non-fullerene acceptor (NFA), Y6, shows efficient power conversion efficiencies (PCEs) when processed with toxic halogenated solvents, but exhibits poor solubility in non-halogenated solvents, resulting in suboptimal morphology. Therefore, in this study, the impact of modifying the inner and outer side-chains of Y6 on OSC performance is investigated. The study reveals that blending a polymer donor, PM6, with one of the modified NFAs, namely N-HD, achieved an impressive PCE of 18.3% on a small-area OSC. This modified NFA displays improved solubility in o-xylene at room temperature, which facilitated the formation of a favorable BHJ morphology. A large-area (55 cm2) sub-module delivered an impressive PCE of 12.2% based on N-HD using o-xylene under ambient conditions. These findings underscore the significant impact of the modified Y6 derivatives on structural arrangements and film processing over a large-area module at room temperature. Consequently, these results are poised to deepen the comprehension of the scaling challenges encountered in OSCs and may contribute to their commercialization.

Precisely Controlling Polymer Acceptors with Weak Intramolecular Charge Transfer Effect and Superior Coplanarity for Efficient Indoor All-Polymer Solar Cells with over 27% Efficiency.

Indoor photovoltaics (IPVs) are garnering increasing attention from both the academic and industrial communities due to the pressing demand of the ecosystem of Internet-of-Things. All-polymer solar cells (all-PSCs), emerging as a sub-type of organic photovoltaics, with the merits of great film-forming properties, remarkable morphological and light stability, hold great promise to simultaneously achieve high efficiency and long-term operation in IPV's application. However, the dearth of polymer acceptors with medium-bandgap has impeded the rapid development of indoor all-PSCs. Herein, a highly efficient medium-bandgap polymer acceptor (PYFO-V) is reported through the synergistic effects of side chain engineering and linkage modulation and applied for indoor all-PSCs operation. As a result, the PM6:PYFO-V-based indoor all-PSC yields the highest efficiency of 27.1% under LED light condition, marking the highest value for reported binary indoor all-PSCs to date. More importantly, the blade-coated devices using non-halogenated solvent (o-xylene) maintain an efficiency of over 23%, demonstrating the potential for industry-scale fabrication. This work not only highlights the importance of fine-tuning intramolecular charge transfer effect and intrachain coplanarity in developing high-performance medium-bandgap polymer acceptors but also provides a highly efficient strategy for indoor all-PSC application.

Iodine(III)-Mediated Ring-Contraction Reactions Using Halogenated and Non-halogenated Solvents

AbstractThe transformation of a six-membered ring into the corresponding five-membered product is an important synthetic approach used in medicinal chemistry and industrial technologies. However, the yield of the product obtained through a simple one-step reaction is lower in some reported solvent systems. Here, we present the ring contraction of 1,2-dihydronaphthalene derivatives into the corresponding indanes­ using an environmentally friendly reagent hydroxy(tosyloxy)iodobenzene (HTIB). This transformation is achieved in both non-halogenated and halogenated solvents. We show that the halogenated solvent system not only increased the yield of the anticipated product but also reduced the formation of by-products. This study delivers an important development regarding the effectiveness of hypervalent iodine reagents in halogenated and non-halogenated solvents for ring-contraction reactions.

Non-halogenated solvent processed new Spiro-type hole transport material for efficient perovskite solar cells

Perovskite solar cells (PSCs) are the fastest developing solar cells and pull in a part of attention due to the prevalent advantages such as solution process, light weight, flexibility, and low cost. In common, Spiro-OMeTAD is the most used hole transport material (HTM) in PSCs. Thanks to its good merits, such as forming smooth surface films, matching energy levels with perovskites, and high tolerance with dopants. Therefore, Spiro-P was designed and synthesized by using an end group strategy (Propargyloxy). Additionally, the thermal, optical, and electrochemical properties of the new HTM and device performance were investigated. As a result, the Spiro-P HTM based device showed high power conversion efficiency (PCE) of 22.36% with an open circuit voltage (Voc ) of 1.102 V, a short-circuit density (Jsc ) of 26.20 mA/cm2 and a fill factor (FF) of 77.43%. This investigation shows that the new synthesized Spiro-P is a potential HTM to achieve good performance in the field of PSCs.

Correlating Aggregation Ability of Polymer Donors with Film Formation Kinetics for Organic Solar Cells with Improved Efficiency and Processability.

Film formation kinetics significantly impact molecular processability and power conversion efficiency (PCE) of organic solar cells. Here, two ternary random copolymerization polymers are reported, D18─N-p and D18─N-m, to modulate the aggregation ability of D18 by introducing trifluoromethyl-substituted pyridine unit at para- and meta-positions, respectively. The introduction of pyridine unit significantly reduces material aggregation ability and adjusts the interactions with acceptor L8-BO, thereby leading to largely changed film formation kinetics with earlier phase separation and longer film formation times, which enlarge fiber sizes in blend films and improve carrier generation and transport. As a result, D18─N-p with moderate aggregation ability delivers a high PCE of 18.82% with L8-BO, which is further improved to 19.45% via interface engineering. Despite the slightly inferior small area device performances, D18─N-m shows improved solubility, which inspires to adjust the ratio of meta-trifluoromethyl pyridine carefully and obtain a polymer donor D18─N-m-10 with good solubility in nonhalogenated solvent o-xylene. High PCEs of 13.07% and 12.43% in 1 cm2 device and 43 cm2 module fabricated with slot-die coating method are achieved based on D18─N-m-10:L8-BO blends. This work emphasizes film formation kinetics optimization in device fabrication via aggregation ability modulation of polymer donors for efficient devices.

Non-halogenated Solvent-Processed Organic Solar Cells with Approaching 20 % Efficiency and Improved Photostability.

The development of high-efficiency organic solar cells (OSCs) processed from non-halogenated solvents is crucially important for their scale-up industry production. However, owing to the difficulty of regulating molecular aggregation, there is a huge efficiency gap between non-halogenated and halogenated solvent processed OSCs. Herein, we fabricate o-xylene processed OSCs with approaching 20 % efficiency by incorporating a trimeric guest acceptor named Tri-V into the PM6:L8-BO-X host blend. The incorporation of Tri-V effectively restricts the excessive aggregation of L8-BO-X, regulates the molecular packing and optimizes the phase-separation morphology, which leads to mitigated trap density states, reduced energy loss and suppressed charge recombination. Consequently, the PM6:L8-BO-X:Tri-V-based device achieves an efficiency of 19.82 %, representing the highest efficiency for non-halogenated solvent-processed OSCs reported to date. Noticeably, with the addition of Tri-V, the ternary device shows an improved photostability than binary PM6:L8-BO-X-based device, and maintains 80 % of the initial efficiency after continuous illumination for 1380 h. This work provides a feasible approach for fabricating high-efficiency, stable, eco-friendly OSCs, and sheds new light on the large-scale industrial production of OSCs.

Low‐Temperature Processed Efficient and Reproducible Blade‐Coating Organic Photovoltaic Devices with γ‐Position Branched Inner Side Chains‐Containing Nonfullerene Acceptor

Recent advancements in blade‐coating organic photovoltaic (OPV) devices utilizing eco‐friendly nonhalogenated solvents have demonstrated high power conversion efficiencies (PCEs) when processed at high substrate temperatures. However, this method poses challenges in device reproducibility and stability. Herein, a BTP‐eC9‐γ nonfullerene acceptor (analogous to BTP‐eC9) with γ‐position‐branched inner side chains within the BTP‐eC9‐based structural motif is developed. This pin‐sized extension in the branching position enhances the solubility of BTP‐eC9‐γ in nonhalogenated toluene solvent. This improvement not only mitigates excessive aggregation in the film state but also facilitates device fabrication at lower substrate temperatures. Optimized at a substrate temperature of 40 °C, the BTP‐eC9‐γ‐based blade‐coating devices with toluene achieve remarkable PCEs of 16.43% (0.04 cm2) and 14.95% (1.0 cm2). Furthermore, these devices retain their high film uniformity at 40 °C, which contributes to superior device reproducibility. This is attributed to the minimized alteration in the evolution kinetics of fluid flow. These findings signify a promising direction for the industrial production of blade‐coating OPV devices.

Heterogeneous Nucleating Agent for High-Boiling-Point Nonhalogenated Solvent-Processed Organic Solar Cells and Modules.

High-boiling-point nonhalogenated solvents are superior solvents to produce large-area organic solar cells (OSCs) in industry because of their wide processing window and low toxicity; while, these solvents with slow evaporation kinetics will lead excessive aggregation of state-of-the-art small molecule acceptors (e.g. L8-BO), delivering serious efficiency losses. Here, a heterogeneous nucleating agent strategy is developed by grafting oligo (ethylene glycol) side-chains on L8-BO (BTO-BO). The formation energy of the obtained BTO-BO; while, changing from liquid in a solvent to a crystalline phase, is lower than that of L8-BO irrespective of the solvent type. When BTO-BO is added as the third component into the active layer (e.g. PM6:L8-BO), it easily assembles to form numerous seed crystals, which serve as nucleation sites to trigger heterogeneous nucleation and increase nucleation density of L8-BO through strong hydrogen bonding interactions even in high-boiling-point nonhalogenated solvents. Therefore, it can effectively suppress excessive aggregation during growth, achieving ideal phase-separation active layer with small domain sizes and high crystallinity. The resultant toluene-processed OSCs exhibit a record power conversion efficiency (PCE) of 19.42% (certificated 19.12%) with excellent operational stability. The strategy also has superior advantages in large-scale devices, showing a 15.03-cm2 module with a record PCE of 16.35% (certificated 15.97%).

Nonhalogenated Solvent Processable and High-Density Photopatternable Polymer Semiconductors Enabled by Incorporating Hydroxyl Groups in the Side Chains.

Polymer semiconductors hold tremendous potential for applications in flexible devices, which is however hindered by the fact that they are usually processed by halogenated solvents rather than environmentally more friendly solvents. An effective strategy to boost the solubility of high-performance polymer semiconductors in nonhalogenated solvents such as tetrahydrofuran (THF) by appending hydroxyl groups in the side chains is herein presented. The results show that hydroxyl groups, which can be easily incorporated into the side chains, can significantly improve the solubility of typical p- and n-types as well as ambipolar polymer semiconductors in THF. Meanwhile, the thin films of these polymer semiconductors from the respective THF solutions show high charge mobilities. With THF as the processing and developing solvents these polymer semiconductors with hydroxyl groups in the side chains can be well photopatterned in the presence of the photo-crosslinker, and the charge mobilities of the patterned thin films are mostly maintained by comparing with those of the respective pristine thin films. Notably, THF is successfully utilized as the processing and developing solvent to achieve high-density photopatterning with ≈82000 device arrays cm-2 for polymer semiconductors in which hydroxyl groups are appended in the side chains.