High Detectivity Near Infrared Organic Photodetectors Using an Asymmetric Non-Fullerene Acceptor for Optimal Nanomorphology and Suppressed Dark Current.

Recently, the development of non-fullerene acceptors (NFAs) for near-infrared (NIR) organic photodetectors (OPDs) has attracted great interest due to their excellent NIR light absorption properties. Herein, we developed NFAs by substituting an electron-donating moiety (branched alkoxy thiophene (BAT)) asymmetrically (YOR1) and symmetrically (YOR2) for the Y6 framework. YOR1 exhibited nanoscale phase separation in a film blended with PTB7-Th. Moreover, substituting the BAT unit effectively extended the absorption wavelengths of YOR1 over 1000 nm by efficient intramolecular charge transfer and extension of the conjugation length. Consequently, YOR1-OPD exhibited significantly reduced dark current and improved responsivity by simultaneously satisfying optimal nanomorphology and significant suppression of charge recombination, resulting in 1.98 × 1013 and 3.38 × 1012 Jones specific detectivity at 950 and 1000 nm, respectively. Moreover, we successfully demonstrated the application of YOR1-OPD in highly sensitive photoplethysmography sensors using NIR light. This study suggests a strategic approach for boosting the overall performance of NIR OPDs targeting a 1000 nm light signal using an all-in-one (optimal morphology, suppressed dark current, and extended NIR absorption wavelength) NFA.

Corroboration of the Toms effect from a frictional drag reducing self-polishing copolymer.

A novel frictional drag reducing self-polishing copolymer (FDR-SPC) was first developed by the authors. The FDR-SPC is a special derivative of an SPC that was designed to achieve skin frictional drag reduction in turbulent water flow by releasing polyethylene glycol (PEG) into water through a hydrolysis reaction. Thus, the FDR-SPC coating acts as a continuous medium accommodating countless, molecular-level polymer injectors. However, direct evidence of such PEG release has not yet been demonstrated. Here, we report the results of in situ PEG concentration measurement based on the planar laser-induced fluorescence (PLIF) method. Polyethylene glycol methacrylate (PEGMA) was probed by the fluorescent functional material dansyl, and the fluorescence intensity from dansyl-PEG was then measured to quantify the concentration in the flow. The near-wall concentration of dansyl-PEG is observed to range from 1 to 2 ppm depending on the flow speed, which corroborates the existence of a drag reducing function for the FDR-SPC. In the concurrent measurement of skin friction, the present FDR-SPC specimen exhibited a skin friction reduction ratio of 9.49% at the freestream flow speed [Formula: see text]. In the comparative experiment of dansyl-PEGMA solution injection, the skin friction was found to decrease by 11.9%, which is in reasonable accordance with that for the FDR-SPC.

Surface Polarization Doping in Diketopyrrolopyrrole-Based Conjugated Copolymers Using Cross-Linkable Terpolymer Dielectric Layers Containing Fluorinated Functional Units.

It is essential to tune the electrical properties of inorganic semiconductors via a doping process in the fabrication of cutting-edge electronic devices; however, the doping in organic field-effect transistors (OFETs) is limited by the uncontrollable dopant diffusion and low doping efficiencies. This study proposes the use of a fluorinated functional group in a polymer dielectric layer as an effective p-type doping strategy for ambipolar diketopyrrolopyrrole (DPP)-based donor-acceptor (D-A)-type semiconducting copolymer films used in OFETs, without generating structural perturbations. To experimentally verify the surface polarization doping effect of the fluorinated group, two terpolymers─poly(pentafluorostyrene-co-3-azidopropyl-methacrylate-co-propargyl-methacrylate) (5F-SAPMA), wherein fluorinated units are included, and poly(phenyl-methacrylate-co-3-azidopropyl-methacrylate-co-propargyl-methacrylate) (PhAPMA), without fluorinated units─are designed and synthesized for use in OFETs. The synthesized 5F-SAPMA and PhAPMA films were cross-linked through the click reaction between the alkyne and azide units in the terpolymers at 150 °C to provide chemical, thermal, and mechanical stabilities and solvent resistance. The electrical characterization of the OFETs with the newly synthesized terpolymer dielectrics reveals that the surface polarization induced by the fluorinated groups of the 5F-SAPMA dielectrics leads to the generation of additional hole charges and helps minimize the broadening of the extended tail states in the vicinity of the valence band (highest occupied molecular orbital (HOMO) level). This not only enables a transition from the ambipolar to p-type dominant characteristics but also helps increase the hole mobility from 0.023 to 0.305 cm2/(V·s).

Recent progress of ultra-narrow-bandgap polymer donors for NIR-absorbing organic solar cells.

Solution-processed near-infrared (NIR)-absorbing organic solar cells (OSCs) have been explored worldwide because of their potential as donor:acceptor bulk heterojunction (BHJ) blends. In addition, NIR-absorbing OSCs have attracted attention as high specialty equipment in next-generation optoelectronic devices, such as semitransparent solar cells and NIR photodetectors, owing to their feasibility for real-time commercial application in industry. With the introduction of NIR-absorbing non-fullerene acceptors (NFAs), the value of OSCs has been increasing while organic donor materials capable of absorbing light in the NIR region have not been actively studied yet compared to NIR-absorbing acceptor materials. Therefore, we present an overall understanding of NIR donors.

Highly Efficient and Photostable Ternary Organic Solar Cells Enabled by the Combination of Non-Fullerene and Fullerene Acceptors with Thienopyrrolodione-based Polymer Donors.

Two polymer donors, PFBDT-8ttTPD and PClBDT-8ttTPD, consisting of halogenated thiophene-substituted benzo[1,2-b:4,5-b']dithiophene and alkyl-substituted thieno[3,2-b]thiophene linked thieno[3,4-c]pyrrole-4,6(5H)-dione, were designed and synthesized for the evaluation of photovoltaic performances. The fabricated IT-4F-based organic solar cells (OSCs) exhibited maximum power conversion efficiency (PCE) values of 12.81 and 11.12% for PFBDT-8ttTPD and PClBDT-8ttTPD, respectively. Furthermore, PFBDT-8ttTPD:Y6 showed significantly improved PCE (15.05%) due to the extended light harvesting in the broad solar spectrum, whereas the PClBDT-8ttTPD:Y6 displayed relatively low PCE (10.02%). A ternary system incorporating PC71BM as the third component into bulk-heterojuction composites (PFBDT-8ttPTD:non-fullerene) was investigated with the aim of utilizing the advantages of PC71BM. As a result, PFBDT-8ttTPD:IT-4F:PC71BM exhibited an improved PCE (13.67%) compared to that of the corresponding binary OSC. In particular, ternary OSC of PFBDT-8ttTPD:Y6:PC71BM showed outstanding photovoltaic performance (PCE = 16.43%) as well as photostability, retaining approximately 80% of the initial PCE after 500 h under continuous illumination. The introduction of a small amount of PC71BM resulted in favorable and dense molecular packing with improved crystallinity as well as enhanced charge carrier mobility for efficient OSC.

Novel Conjugated Polymers Containing 3-(2-Octyldodecyl)thieno[3,2-b]thiophene as a π-Bridge for Organic Photovoltaic Applications.

3-(2-Octyldodecyl)thieno[3,2-b]thiophen was successfully synthesized as a new π-bridge with a long branched side alkyl chain. Two donor-π-bridge-acceptor type copolymers were designed and synthesized by combining this π-bridge structure, a fluorinated benzothiadiazole acceptor unit, and a thiophene or thienothiophene donor unit, (PT-ODTTBT or PTT-ODTTBT respectively) through Stille polymerization. Inverted OPV devices with a structure of ITO/ZnO/polymer:PC71BM/MoO3/Ag were fabricated by spin-coating in ambient atmosphere or N2 within a glovebox to evaluate the photovoltaic performance of the synthesized polymers (effective active area: 0.09 cm2). The PTT-ODTTBT:PC71BM-based structure exhibited the highest organic photovoltaic (OPV) device performance, with a maximum power conversion efficiency (PCE) of 7.05 (6.88 ± 0.12)%, a high short-circuit current (Jsc) of 13.96 mA/cm2, and a fill factor (FF) of 66.94 (66.47 ± 0.63)%; whereas the PT-ODTTBT:PC71BM-based device achieved overall lower device performance. According to GIWAXS analysis, both neat and blend films of PTT-ODTTBT exhibited well-organized lamellar stacking, leading to a higher charge carrier mobility than that of PT-ODTTBT. Compared to PT-ODTTBT containing a thiophene donor unit, PTT-ODTTBT containing a thienothiophene donor unit exhibited higher crystallinity, preferential face-on orientation, and a bicontinuous interpenetrating network in the film, which are responsible for the improved OPV performance in terms of high Jsc, FF, and PCE.

Synthesis of ITIC Derivatives with Extended π-Conjugation as Non-Fullerene Acceptors for Organic Solar Cells.

The realization of printed organic solar cells (OSCs) as a commercial technology is dependent on the development of high-performance photovoltaic materials suitable for large-scale device manufacture. In this study, the design, synthesis, and characterization of a series of A-D-A'-D-A-type molecular acceptors based on indacenodithienothiophene (IDTT) and thiophene-flanked 2,1,3-benzothiadiazole (DTBT) are reported. The synthesized molecular acceptors showed broader absorption ranges and narrower band gap energies than those of well-known 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno [2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']dithiophene (ITIC)-based molecular acceptors. Furthermore, the synthesized acceptors could tune the frontier molecular orbital energy levels, dipole moments, and their crystallinities by introducing fluorine (F) atoms and cyano (CN) groups on DTBT as a core A' unit. The cyano-substituted DTBT-based molecular acceptor (CNDTBT-IDTT-FINCN) showed a strong molar absorptivity and dipole moment, high hole/electron charge mobilities, and a favorable face-on orientation using films blended with poly[(2,6-(4,8-bis(5-(2-ethylhexyl)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-T). An inverted organic photovoltaic (OPV) device using CNDTBT-IDTT-FINCN exhibits a power conversion efficiency (PCE) of 9.13% when using PBDB-T as a donor material in small cells (0.12 cm2). Sub-module devices with an active area of 55.45 cm2 are fabricated using bar-coating and exhibit PCEs of up to 7.50%. This demonstration of a high-efficiency large-area device makes CNDTBT-IDTT-FINCN a suitable and promising candidate for printed OPV devices.

Synthesis and Characterization of Self-Polishing Polyurethane Copolymers.

Synthesizing copolymers from Zn acrylate monomers is an effective strategy employed in the self-polishing materials industry. In this study, we designed and synthesized polyurethane-based self-polishing copolymers with improved surface adhesion properties. The synthesized polyurethane copolymers were characterized using Fourier transform infrared spectroscopy and inductively coupled plasma optical emission spectrometry. The properties of Zn-based polyurethane copolymers were compared with those of Zn-free polyurethane as reference. The erosion rates of the Zn-based polyurethane SPC films were determined by measuring changes in the film thickness after dynamic immersion tests. In comparison to Zn-free polyurethane, the Zn-based polyurethane self-polishing copolymers demonstrated effective self-polishing and surface adhesion properties.

Synthesis of Novel Polyacrylates Containing Cyclotetrasiloxane for Fouling-Release Coating Applications.

An acrylate monomer containing cyclotetrasiloxane (CTS) were designed and synthesized for anti-fouling coating applications. New acryl-based copolymers consisting of styrene and CTS, poly(styrene-co-CTS)s, were synthesized by changing molar ratios via free radical polymerization. The properties of poly(styrene-co-CTS)s were compared with those of poly(styrene) (PS) as a reference. The content of CTS in the copolymer increased its hydrophobicity also decreased whereas its surface decreased. Protein adsorption studies were conducted to evaluate their fouling-release properties.

Visible-Light-Responsive High-Detectivity Organic Photodetectors with a 1 µm Thick Active Layer.

Organic photodetectors (OPDs) are attracting attention for use in flexible and portable electronic applications such as image sensors, remote sensing, optical communications, and medical sensors because of their strong photon responsivity in thin films over a broad range of wavelengths. In particular, the efficient photon-to-current conversion of OPDs under visible light allows their use in indirect X-ray detectors using scintillators to convert X-rays to visible light. The polymer poly(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2- b:4,5- b']dithiophene- co-5-(2-hexyldecyl)-1,3-bis(6-octylthieno[3,2- b]thiophen-2-yl)-4 H-thieno[3,4- c]pyrrole-4,6(5 H)-dione) (PBDTT-8ttTPD) shows strong absorption bands in the region of 500-650 nm, as well as high hole mobility, which provides excellent photoresponsivity and photon-to-current conversion efficiency. A p-n junction photodetector was fabricated by blending PBDTT-8ttTPD and [6,6]-phenyl C71 butyric acid methyl ester (PC71BM) and varying the thickness of the active layer (260-1100 nm). The PBDTT-8ttTPD:PC71BM-based OPDs show promising photodetecting properties having a low dark current of 3.72 × 10-9 A cm-2 and high responsivity of 0.39 A W-1 because of the well-controlled morphology, high molar absorption coefficient, and excellent carrier mobility of the PBDTT-8ttTPD:PC71BM layer. Consequently, the specific detectivity of the PBDTT-8ttTPD-based OPD devices was 1.13 × 1013 Jones at -2 V on irradiation with a light-emitting diode (530 nm wavelength) with a power density of 55.6 µW cm-2.

Shellac Films as a Natural Dielectric Layer for Enhanced Electron Transport in Polymer Field-Effect Transistors.

Shellac, a natural polymer resin obtained from the secretions of lac bugs, was evaluated as a dielectric layer in organic field-effect transistors (OFETs) on the basis of donor (D)-acceptor (A)-type conjugated semiconducting copolymers. The measured dielectric constant and breakdown field of the shellac layer were ∼3.4 and 3.0 MV/cm, respectively, comparable with those of a poly(4-vinylphenol) (PVP) film, a commonly used dielectric material. Bottom-gate/top-contact OFETs were fabricated with shellac or PVP as the dielectric layer and one of three different D-A-type semiconducting copolymers as the active layer: poly(cyclopentadithiophene- alt-benzothiadiazole) with p-type characteristics, poly(naphthalene-bis(dicarboximide)- alt-bithiophene) [P(NDI2OD-T2)] with n-type characteristics, and poly(dithienyl-diketopyrrolopyrrole- alt-thienothiophene) [P(DPP2T-TT)] with ambipolar characteristics. The electrical characteristics of the fabricated OFETs were then measured. For all active layers, OFETs with a shellac film as the dielectric layer exhibited a better mobility than those with PVP. For example, the mobility of the OFET with a shellac dielectric and n-type P(NDI2OD-T2) active layer was approximately 2 orders of magnitude greater than that of the corresponding OFET with a PVP insulating layer. When P(DPP2T-TT) served as the active layer, the OFET with shellac as the dielectric exhibited ambipolar characteristics, whereas the corresponding OFET with the PVP dielectric operated only in hole-accumulation mode. The total density of states was analyzed using technology computer-aided design simulations. The results revealed that compared with the OFETs with PVP as the dielectric, the OFETs with shellac as the dielectric had a lower trap-site density at the polymer semiconductor/dielectric interface and much fewer acceptor-like trap sites acting as electron traps. These results demonstrate that shellac is a suitable dielectric material for D-A-type semiconducting copolymer-based OFETs, and the use of shellac as a dielectric layer facilitates electron transport at the interface with D-A-type copolymer channels.

Synthesis and Properties of Fluorinated Styrene Copolymers as Antibiofouling Coatings.

A series of polystyrene (PS) copolymers containing 2,3,4,5,6-pentafluorostyrene units with different monomer ratios were prepared for antifouling applications. PS, poly(styrene-co-pentafluorostyrene) (poly(S-co-FS)), and poly(pentafluorostyrene) (PFS) were synthesized by free-radical polymerization and characterized by 1H NMR, Fourier-transform infrared spectroscopy, and gel permeation chromatography. The surface energy of the polymer films decreased with increasing content of fluorinated styrene. Protein adsorption experiments were carried out on the synthesized polymer films using fluorescein isothiocyanate-labeled bovine serum albumin as a fluorescent protein. The photo-luminescence intensity of the protein-adsorbed polymer films decreased dramatically as the content of hydrophobic fluorinated styrene increased, suggesting that poly(S-co-FS) copolymers and PFS could be used as potential antibiofouling coatings.

Synthesis of a Zr-Based Metal-Organic Framework with Spirobifluorenetetrabenzoic Acid for the Effective Removal of Nerve Agent Simulants.

A new microporous Zr(IV)-based metal-organic framework (MOF) containing 4,4',4″,4‴-(9,9'-spirobi[fluorene]-2,2',7,7'-tetrayl)tetrabenzoic acid (Spirof-MOF) was synthesized, characterized, and size-controlled for the adsorption and decomposition of a nerve agent simulant, dimethyl 4-nitrophenylphosphate (DMNP). Spirof-MOF showed a hydrolysis half-life (t1/2) of 7.5 min to DMNP, which was confirmed by using in situ 31P NMR spectroscopy. Additionally, size-controlled Spirof-MOFb (∼1 µm) exhibited a half-life of 1.8 min and 99% removal within 18 min for DMNP. The results show that Spirof-MOF is a new active material in removing nerve agent simulants by adsorption and hydrolytic decomposition.