Self-Assembled Monolayer-Based Hole-Transporting Materials for Perovskite Solar Cells.

Ever since self-assembled monolayers (SAMs) were adopted as hole-transporting layers (HTL) for perovskite solar cells (PSCs), numerous SAMs for HTL have been synthesized and reported. SAMs offer several unique advantages including relatively simple synthesis, straightforward molecular engineering, effective surface modification using small amounts of molecules, and suitability for large-area device fabrication. In this review, we discuss recent developments of SAM-based hole-transporting materials (HTMs) for PSCs. Notably, in this article, SAM-based HTMs have been categorized by similarity of synthesis to provide general information for building a SAM structure. SAMs are composed of head, linker, and anchoring groups, and the selection of anchoring groups is key to design the synthetic procedure of SAM-based HTMs. In addition, the working mechanism of SAM-based HTMs has been visualized and explained to provide inspiration for finding new head and anchoring groups that have not yet been explored. Furthermore, both photovoltaic properties and device stabilities have been discussed and summarized, expanding reader's understanding of the relationship between the structure and performance of SAMs-based PSCs.

Switchable Design of Redox-Enhanced Nonaromatic Quinones Enabled by Conjugation Recovery.

An innovative switchable design strategy for modulating the electronic structures of quinones is proposed herein, leading to remarkably enhanced intrinsic redox potentials by restoring conjugated but nonaromatic backbone architectures. Computational validation of two fundamental hypotheses confirms the recovery of backbone conjugation and optimal utilization of the inductive effect in switched quinones, which affords significantly improved redox chemistry and overall performance compared to reference quinones. Geometric and electronic analyses provide strong evidence for the restored backbone conjugation and nonaromaticity in the switched quinones, while highlighting the reinforcement of the inductive effect and suppression of the resonance effect. This strategic approach facilitates the development of an exceptional quinone, viz. 2,6-naphthoquinone, with outstanding performance parameters (338.9 mAh g-1 and 912.9 mWh g-1). Furthermore, 2,6-anthraquinone with superior cyclic stability, demonstrates comparable performance (257.4 mAh g-1 and 702.8 mWh g-1). These findings offer valuable insights into the design of organic cathode materials with favorable redox chemistry in secondary batteries.

Development of n-Type Small-Molecule Acceptors for Low Dark Current Density and Fast Response Organic Photodetectors.

Suppressing the dark current density (Jd) while maintaining sufficient charge transport is important for improving the specific detectivity (D*) and dynamic characteristics of organic photodetectors (OPDs). In this study, we synthesized three novel small-molecule acceptors (SMAs) densely surrounded by insulating alkyl side chains to minimize the Jd in OPDs. Introducing trialkylated N-annulated perylene diimide as a terminal moiety to the alkylated π-conjugated core structure was highly efficient in suppressing Jd in the devices, resulting in an extremely low Jd of 4.60 × 10-11 A cm-2 and 10-100 times improved D* values in the devices. In addition, SMAs with a geometrically aligned backbone structure exhibited better intermolecular ordering in the blended films, resulting in 3-10 times as high responsivity (R) values in the OPDs. Outstanding OPD performances with a D* of 8.09 × 1012 Jones, -3 dB cutoff frequency of 205.2 kHz, and rising response time of 16 µs were achieved under a 530 nm illumination in photoconductive mode. Geometrically aligned core-terminal SMAs densely surrounded by insulating alkyl side chains are promising for improving the static and dynamic properties of OPDs.

Quantification of polystyrene microsphere attachment probability at the oil‒water interface using a microfluidic platform.

This study investigates the effects of interparticle interactions and wettability on the particle attachment efficacy to the oil‒water interface. Three types of PS particles with different surface functional groups were examined at varying salt concentrations and the number of particles injected into the interface. Based on the microfluidic method and the surface coverage measurement, we found that the two contributing factors significantly influenced particle attachment efficiency to the interface, while the wettability factor has a major contribution. This research contributes to the understanding of physicochemical aspects of particle assembly at fluid interfaces and can offer strategies for forming tailored structures with desired interfacial properties.

Development of Alkylthiazole-Based Novel Thermoelectric Conjugated Polymers for Facile Organic Doping.

In this study, we developed two novel conjugated polymers that can easily be doped with F4TCNQ organic dopants using a sequential doping method and then studied their organic thermoelectric (OTE) properties. In particular, to promote the intermolecular ordering of OTE polymers in the presence of the F4TCNQ dopant, alkylthiazole-based conjugated building blocks with highly planar backbone structures were synthesized and copolymerized. All polymers showed strong molecular ordering and edge-on orientation in the film state, even in the presence of the F4TCNQ organic dopant. Thus, the sequential doping process barely changed the molecular ordering of the polymer films while making efficient molecular doping. In addition, the doping efficiency was improved in the more π-extended polymer backbones with thienothiophene units due to the emptier space in the polymer lamellar structure to locate ionized F4TCNQ. Moreover, the study of organic thin-film transistors (OTFTs) revealed that higher hole mobility in OTFTs was the key to increasing the electrical conductivity of OTE devices fabricated using the sequential doping method.

Fabrication of Partially Etched Polystyrene Nanoparticles.

Non-spherical polymer nanoparticles (NPs) have gained attention in various fields, but their fabrication remains challenging. In this study, we present a simple protocol for synthesizing partially etched polystyrene (PS) nanoparticles through emulsion polymerization and chemical etching. By adjusting the degree of crosslinking, we selectively dissolve the weakly crosslinked portions of the particles, resulting in partially etched PS NPs with increased surface area. These partially etched NPs are evaluated for their use as solid surfactants in Pickering emulsions, where they demonstrate significantly improved emulsion stability compared to intact spherical NPs. Our results contribute to the field of nanoparticle shape control and provide insights into developing novel materials for various applications, particularly in the area of solid surfactant usage. Additionally, the importance of conducting cellular toxicity studies using these partially etched NPs for future work is also emphasized.

Development of Benzobisoxazole-Based Novel Conjugated Polymers for Organic Thin-Film Transistors.

Benzo[1,2-d:4,5-d']bis(oxazole) (BBO) is a heterocyclic aromatic ring composed of one benzene ring and two oxazole rings, which has unique advantages on the facile synthesis without any column chromatography purification, high solubility on the common organic solvents and planar fused aromatic ring structure. However, BBO conjugated building block has rarely been used to develop conjugated polymers for organic thin film transistors (OTFTs). Three BBO-based monomers, BBO without π-spacer, BBO with non-alkylated thiophene π-spacer and BBO with alkylated thiophene π-spacer, were newly synthesized and they were copolymerized with a strong electron-donating cyclopentadithiophene conjugated building block to give three p-type BBO-based polymers. The polymer containing non-alkylated thiophene π-spacer showed the highest hole mobility of 2.2 × 10-2 cm2 V-1 s-1, which was 100 times higher than the other polymers. From the 2D grazing incidence X-ray diffraction data and simulated polymeric structures, we found that the intercalation of alkyl side chains on the polymer backbones was crucial to determine the intermolecular ordering in the film states, and the introduction of non-alkylated thiophene π-spacer to polymer backbone was the most effective to promote the intercalation of alkyl side chains in the film states and hole mobility in the devices.

Improvement of Dynamic Performance and Detectivity in Near-Infrared Colloidal Quantum Dot Photodetectors by Incorporating Conjugated Polymers.

Colloidal quantum dots (CQDs) have a unique advantage in realizing near-infrared (NIR) photodetection since their optical properties are readily tuned by the particle size, but CQD-based photodetectors (QPDs) presently show a high dark current density (Jd) and insufficient dynamic characteristics. To overcome these two problems, we synthesized and introduced two types of conjugated polymers (CPs) by replacing the p-type CQD layer in the QPDs. The low dielectric constant and insulating properties of CPs under dark conditions effectively suppressed the Jd in the QPDs. In addition, the energy-level alignment and high-hole mobility of the CPs facilitated hole transport. Therefore, both the responsivity and specific detectivity were highly enhanced in the CP-based QPDs. Notably, the dynamic characteristics of the QPDs, such as the -3 dB cut-off frequency and rising/falling response times, were significantly improved in the CP-based QPDs owing to the sizable molecular ordering and fast hole transport of the CP in the film state as well as the low trap density, well-aligned energy levels, and good interfacial contact in the CP-based devices.

Simple-Structured Low-Cost Dopant-Free Hole-Transporting Polymers for High-Stability CsPbI2Br Perovskite Solar Cells.

Among the solution-processed devices, perovskite solar cells (PSCs) exhibit the highest power conversion efficiency (PCE) of over 25%; tremendous efforts are being undertaken to improve their stability. Recently, all-inorganic CsPbI2Br-based PSCs were reported to exhibit a significantly improved device stability, with a promising PCE of up to 16.79%. In this study, we report stable all-inorganic PSCs by incorporating novel dopant-free hole-transporting materials (HTMs). The synthesis strategy of the newly synthesized polymeric HTMs was similar to that of 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene (spiro-OMeTAD), with the exception that they were designed to exhibit dopant-free characteristics. In particular, their polymeric backbone structure was significantly simpler than that of spiro-OMeTADs, and they were easily synthesized in two steps from commercially available chemicals, with an overall yield of ∼50%. The cost of synthesis at the laboratory scale was calculated to be at least 2.4 times cheaper than that of spiro-OMeTADs. The PCE of dopant-free HTM-based PSCs was 11.01%, which is 1.5 times higher than that of the dopant-free spiro-OMeTAD-based devices (7.52%) and comparable to that of the doped spiro-OMeTAD-based devices (12.22%). Notably, the stability of the device based on our dopant-free HTM to atmospheric oxygen and moisture as well as heat and light irradiation was superior to that of devices based on doped and dopant-free spiro-OMeTAD HTMs. On consideration of the synthesis cost, device efficiency, and device stability, our dopant-free HTM is highly promising for all-inorganic PSCs.

Enhanced Static and Dynamic Properties of Highly Miscible Fullerene-Free Green-Selective Organic Photodetectors.

We developed p-n junction organic photodetectors (OPDs) composed of a polymer donor and a nonfullerene acceptor (NFA) to increase both the responsivity (R) and detectivity (D*) while maintaining a narrow wavelength selectivity. The selection of the polymer donor and NFA with similar green (G) absorption is important for achieving G-wavelength selectivity in these OPDs, which differentiates them from current fullerene-based OPDs and NFA-based panchromatic absorption OPDs. In addition, mixing the polymer donor and asymmetric NFA was efficient toward increasing the miscibility and decreasing the interfacial energy difference of the blended films, resulting in the formation of a uniform and well-mixed nanomorphology in the photoconductive layer. Two-dimensional (2D) grazing incidence X-ray diffraction and Fourier-transform infrared spectroscopy revealed that the lamellar ordering of the polymer donor was enhanced in the blend film prepared with an asymmetric NFA, whereas the aggregation of a symmetric NFA in the blend films did not increase the lamellar ordering of the polymer donor. Consequently, we achieved an R value of 0.31 A/W and D* value of 2.0 × 1013 Jones with a full width at half-maximum value of 230 nm at -2 V and fast response time of 27 µs without any external bias in the asymmetric NFA-based OPDs. The enhancement in the lamellar ordering and miscibility of the blended films are crucial toward increasing the static and dynamic properties of OPDs.

High-Performance Near-Infrared Absorbing n-Type Porphyrin Acceptor for Organic Solar Cells.

While the outstanding charge transport and sunlight-harvesting properties of porphyrin molecules are highly attractive as active materials for organic photovoltaic (OPV) devices, the development of n-type porphyrin-based electron acceptors has been challenging. In this work, we developed a high-performance porphyrin-based electron acceptor for OPVs by substitution of four naphthalene diimide (NDI) units at the perimeter of a Zn-porphyrin (PZn) core using ethyne linkage. Effective π-conjugation between four NDI wings and the PZn core significantly broadened Q-band absorption to the near infrared region, thereby achieving the narrow band gap of 1.33 eV. Employing a windmill-structured tetra-NDI substituted PZn-based acceptor ( PZn-TNDI) and mid-band gap polymer donor (PTB7-Th), the bulk heterojunction OPV devices achieved a power conversion efficiency (PCE) of 8.15% with an energy loss of 0.61 eV. The PCE of our PZn-TNDI-based device was the highest among the reported OPVs using porphyrin-based acceptors. Notably, the amorphous characteristic of PZn-TNDI enabled optimization of the device performance without using any additive, which should make industrial fabrication simpler and cheaper.

Development of n-Type Porphyrin Acceptors for Panchromatic Light-Harvesting Fullerene-Free Organic Solar Cells.

The development of n-type porphyrin acceptors is challenging in organic solar cells. In this work, we synthesized a novel n-type porphyrin acceptor, PZn-TNI, via the introduction of the electron withdrawing naphthalene imide (NI) moiety at the meso position of zinc porphyrin (PZn). PZn-TNI has excellent thermal stability and unique bimodal absorption with a strong Soret band (300-600 nm) and weak Q-band (600-800 nm). The weak long-wavelength absorption of PZn-TNI was completely covered by combining the low bandgap polymer donor, PTB7-Th, which realized the well-balanced panchromatic photon-to-current conversion in the range of 300-800 nm. Notably, the one-step reaction of the NI moiety from a commercially available source leads to the cheap and simple n-type porphyrin synthesis. The substitution of four NIs in PZn ring induced sufficient n-type characteristics with proper HOMO and LUMO energy levels for efficient charge transport with PTB7-Th. Fullerene-free organic solar cells based-on PTB7-Th:PZn-TNI were investigated and showed a promising PCE of 5.07% without any additive treatment. To the best of our knowledge, this is the highest PCE in the porphyrin-based acceptors without utilization of the perylene diimide accepting unit.

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.

Performance Improvement in Low-Temperature-Processed Perovskite Solar Cells by Molecular Engineering of Porphyrin-Based Hole Transport Materials.

Porphyrin derivatives have recently emerged as hole transport layers (HTLs) because of their electron-rich characteristics. Although several successes with porphyrin-based HTLs have been recently reported, achieving excellent solar cell performance, the chances to improve this further by molecular engineering are still open. In this work, Zn porphyrin (PZn)-based HTLs were developed by conjugating fluorinated triphenylamine (FTPA) wings at the perimeter of the PZn core for low-temperature perovskite solar cells (L-PSCs). The fluorinated PZn-HTLs (PZn-2FTPA and PZn-3FTPA) exhibited superior HTL properties compared to the nonfluorinated one (PZn-TPA). Moreover, their deeper highest occupied molecular orbital energy levels were beneficial for boosting open-circuit voltages, and their enhanced face-on stacking improved the hole transport properties. The L-PSC using PZn-2FTPA achieved the highest performance of 18.85%. Thus far, this result is one of the highest reported power conversion efficiencies among the PSCs using porphyrin-based HTLs.

Interfacial Modifier Having Julolidine for the Cathode Buffer Layer in PTB-7:PC70BM Based Inverted Organic Photovoltaic Cells.

The julolidine based interfacial modifier (IM-J) for cathode buffer layer following the "donor-acceptor" design concept with julolidine substituent as an electron donating moiety was incoporated to improve the surface properties of ZnO. Simple treatment of metal oxide type cathode buffer materials with organic interfacial modifier induces the enhanced photovoltaic performance and could effectively overcome several interfacial problems in inverted organic photovoltaic cells (I-OPVs). We studied on the coverage of IM-J on ZnO surface with variation of solution concentrations to reduce charge recombination and macroscopic phase separation. At the optimum condition, ZnO/IM-J (0.05 w/v%), IM-J significantly decreased the surface tension (46.1 mN/m) and improved surface morphology (RMS roughness: 0.61 nm). As a result, compared to the unmodified ZnO based device, the ZnO/IM-J based I-OPVs showed significantly improved power conversion efficiency (PCE) from 7.41 to 8.07% due to the increased photocurrent density (Jsc) and fill factor (FF). It is concluded that IM-J is one of the promising candidates for controlling electronic property of ZnO buffer layer in inverted organic photovoltaic cells. Also, our interfacial modified system can be utilized in other optoelectronic devices.

Polystyrene-block-Poly(ionic liquid) Copolymers as Work Function Modifiers in Inverted Organic Photovoltaic Cells.

Interfacial layers play a critical role in building up the Ohmic contact between electrodes and functional layers in organic photovoltaic (OPV) solar cells. These layers are based on either inorganic oxides (ZnO and TiO2) or water-soluble organic polymers such as poly[(9,9-dioctyl-2,7-fluorene)-alt-(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)] and polyethylenimine ethoxylated (PEIE). In this work, we have developed a series of novel poly(ionic liquid) nonconjugated block copolymers for improving the performance of inverted OPV cells by using them as work function modifiers of the indium tin oxide (ITO) cathode. Four nonconjugated polyelectrolytes (n-CPEs) based on polystyrene and imidazolium poly(ionic liquid) (PSImCl) were synthesized by reversible addition-fragmentation chain transfer polymerization. The ratio of hydrophobic/hydrophilic block copolymers was varied depending on the ratio of polystyrene to the PSImCl block. The ionic density, which controls the work function of the electrode by forming an interfacial dipole between the electrode and the block copolymers, was easily tuned by simply changing the PSImCl molar ratio. The inverted OPV device with the ITO/PS29-b-PSImCl60 cathode achieved the best power conversion efficiency (PCE) of 7.55% among the synthesized block copolymers, exhibiting an even higher PCE than that of the reference OPV device with PEIE (7.30%). Furthermore, the surface properties of the block copolymers films were investigated by contact angle measurements to explore the influence of the controlled hydrophobic/hydrophilic characters on the device performances.

Artificial light-harvesting n-type porphyrin for panchromatic organic photovoltaic devices.

A near-infrared-harvesting n-type porphyrin-based acceptor for organic photovoltaics (OPVs) was developed. The n-type acceptor, PDI-PZn-PDI, was designed by connecting a zinc porphyrin (PZn) core to two perylenediimide (PDI) wings through ethyne bridges. A narrow bandgap of 1.27 eV was achieved through the extended π-conjugation and intramolecular charge transfer between the strongly electron-donating PZn core and the electron-accepting PDI wings. A bulk heterojunction (BHJ) structured photovoltaic device fabricated from PDI-PZn-PDI with PTB7-Th exhibited panchromatic photon-to-current conversion from 350 to 900 nm. A power conversion efficiency of 5.25% with a remarkably low Eloss of 0.54 eV was achieved by optimizing the nanomorphology of the BHJ films by adding pyridine and by controlling the ZnO/BHJ interfacial properties.

Fullerene-Free Organic Solar Cells with an Efficiency of 10.2% and an Energy Loss of 0.59 eV Based on a Thieno[3,4-c]Pyrrole-4,6-dione-Containing Wide Band Gap Polymer Donor.

Although the combination of wide band gap polymer donors and narrow band gap small-molecule acceptors achieved state-of-the-art performance as bulk heterojunction (BHJ) active layers for organic solar cells, there have been only several of the wide band gap polymers that actually realized high-efficiency devices over >10%. Herein, we developed high-efficiency, low-energy-loss fullerene-free organic solar cells using a weakly crystalline wide band gap polymer donor, PBDTTPD-HT, and a nonfullerene small-molecule acceptor, ITIC. The excessive intermolecular stacking of ITIC is efficiently suppressed by the miscibility with PBDTTPD-HT, which led to a well-balanced nanomorphology in the PBDTTPD-HT/ITIC BHJ active films. The favorable optical, electronic, and energetic properties of PBDTTPD-HT with respect to ITIC achieved panchromatic photon-to-current conversion with a remarkably low energy loss (0.59 eV).

Diphenyl-2-pyridylamine-Substituted Porphyrins as Hole-Transporting Materials for Perovskite Solar Cells.

The susceptibility of porphyrin derivatives to light-harvesting and charge-transport operations have enabled these materials to be employed in solar cell applications. The potential of porphyrin derivatives as hole-transporting materials (HTMs) for perovskite solar cells (PSCs) has recently been demonstrated, but knowledge of the relationships between the porphyrin structure and device performance remains insufficient. In this work, a series of novel zinc porphyrin (PZn) derivatives has been developed and employed as HTMs for low-temperature processed PSCs. Key to the design strategy is the incorporation of an electron-deficient pyridine moiety to down-shift the HOMO levels of porphyrin HTMs. The porphyrin HTMs incorporating diphenyl-2-pyridylamine (DPPA) have HOMO levels that are in good agreement with the perovskite active layers, thus facilitating hole transfers from the perovskite to the HTMs. The DPPA-containing zinc porphyrin-based PSCs gave the best performance, with efficiency levels comparable to those of PSCs using spiro-OMeTAD, a current state-of-the-art HTM. In particular, PZn-DPPA-based PSCs show superior air stability, in both doped and undoped forms, to spiro-OMeTAD based devices.

High Thermoelectric Power Factor of a Diketopyrrolopyrrole-Based Low Bandgap Polymer via Finely Tuned Doping Engineering.

We studied the thermoelectric properties of a diketopyrrolopyrrole-based semiconductor (PDPP3T) via a precisely tuned doping process using Iron (III) chloride. In particular, the doping states of PDPP3T film were linearly controlled depending on the dopant concentration. The outstanding Seebeck coefficient of PDPP3T assisted the excellent power factors (PFs) over 200 µW m-1K-2 at the broad range of doping concentration (3-8 mM) and the maximum PF reached up to 276 µW m-1K-2, which is much higher than that of poly(3-hexylthiophene), 56 µW m-1K-2. The high-mobility of PDPP3T was beneficial to enhance the electrical conductivity and the low level of total dopant volume was important to maintain high Seebeck coefficients. In addition, the low bandgap PDPP3T polymer effiectively shifted its absorption into near infra-red area and became more colorless after doping, which is great advantage to realize transparent electronic devices. Our results give importance guidance to develop thermoelectric semiconducting polymers and we suggest that the use of low bandgap and high-mobility polymers, and the accurate control of the doping levels are key factors for obtaining the high thermoelectric PF.