Low-Temperature Cross-Linkable Hole Transport Materials for Solution-Processed Quantum Dot and Organic Light-Emitting Diodes with High Efficiency and Color Purity.

Cross-linkable hole transport materials (HTMs) are ideal for improving the performance of solution-processed quantum dot light-emitting diodes (QLEDs) and phosphorescent light-emitting diodes (OLEDs). However, previously developed cross-linkable HTMs possessed poor hole transport properties, high cross-linking temperatures, and long curing times. To achieve efficient cross-linkable HTMs with high mobility, low cross-linking temperature, and short curing time, we designed and synthesized a series of low-temperature cross-linkable HTMs comprising dibenzofuran (DBF) and 4-divinyltriphenylamine (TPA) segments for highly efficient solution-processed QLEDs and OLEDs. The introduction of divinyl-functionalized TPA in various positions of the DBF core remarkably affected their chemical, physical, and electrochemical properties. In particular, cross-linked 4-(dibenzo[b,d]furan-3-yl)-N,N-bis(4-vinylphenyl)aniline (3-CDTPA) exhibited a deep highest occupied molecular orbital energy level (5.50 eV), high hole mobility (2.44 × 10-4 cm2 V-1 s-1), low cross-linking temperature (150 °C), and short curing time (30 min). Furthermore, a green QLED with 3-CDTPA as the hole transport layer (HTL) exhibited a notable maximum external quantum efficiency (EQEmax) of 18.59% with a remarkable maximum current efficiency (CEmax) of 78.48 cd A-1. In addition, solution-processed green OLEDs with 3-CDTPA showed excellent device performance with an EQEmax of 15.61%, a CEmax of 52.51 cd A-1, and outstanding CIE(x, y) color coordinates of (0.29, 0.61). This is one of the highest reported EQEs and CEs with high color purity for green solution-processed QLEDs and OLEDs using a divinyl-functionalized cross-linked HTM as the HTL. We believe that this study provides a new strategy for designing and synthesizing practical cross-linakable HTMs with enhanced performance for highly efficient solution-processed QLEDs and OLEDs.

Efficient and Stable Fiber Dye-Sensitized Solar Cells Based on Solid-State Li-TFSI Electrolytes with 4-Oxo-TEMPO Derivatives.

Fiber-shaped dye-sensitized solar cells (FDSSCs) with flexibility, weavablity, and wearability have attracted intense scientific interest and development in recent years due to their low cost, simple fabrication, and environmentally friendly operation. Since the Grätzel group used the organic radical 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) as the redox system in dye-sensitized solar cells (DSSCs) in 2008, TEMPO has been utilized as an electrolyte to further improve power conversion efficiency (PCE) of solar cells. Hence, the TEMPO with high catalyst oxidant characteristics was developed as a hybrid solid-state electrolyte having high conductivity and stability structure by being integrated with a lithium bis(trifluoromethanesulfonyl)imide (Li-TFSI) film for FDSSCs. The optimized 4-Oxo TEMPO (OX) based solid-state FDSSC (SS-FDSSC) showed the PCE of up to 6%, which was improved by 34.2% compared to that of the reference device with 4.47%. The OX-enhanced SS-FDSSCs reduced a series resistance (Rs) resulting in effective electron extraction with improved short-circuit current density (JSC), while increasing a shunt resistance (Rsh) to prevent the recombination of photo-excited electrons. The result is an improvement in a fill factor (FF) and consequently a higher value for the PCE.

Improved device efficiency and lifetime of perovskite light-emitting diodes by size-controlled polyvinylpyrrolidone-capped gold nanoparticles with dipole formation.

Herein, an unprecedented report is presented on the incorporation of size-dependent gold nanoparticles (AuNPs) with polyvinylpyrrolidone (PVP) capping into a conventional hole transport layer, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). The hole transport layer blocks ion-diffusion/migration in methylammonium-lead-bromide (MAPbBr3)-based perovskite light-emitting diodes (PeLEDs) as a modified interlayer. The PVP-capped 90 nm AuNP device exhibited a seven-fold increase in efficiency (1.5%) as compared to the device without AuNPs (0.22%), where the device lifetime was also improved by 17-fold. This advancement is ascribed to the far-field scattering of AuNPs, modified work function and carrier trapping/detrapping. The improvement in device lifetime is attributed to PVP-capping of AuNPs which prevents indium diffusion into the perovskite layer and surface ion migration into PEDOT:PSS through the formation of induced electric dipole. The results also indicate that using large AuNPs (> 90 nm) reduces exciton recombination because of the trapping of excess charge carriers due to the large surface area.

Improved Light Harvesting of Fiber-Shaped Dye-Sensitized Solar Cells by Using a Bacteriophage Doping Method.

Fiber-shaped solar cells (FSCs) with flexibility, wearability, and wearability have emerged as a topic of intensive interest and development in recent years. Although the development of this material is still in its early stages, bacteriophage-metallic nanostructures, which exhibit prominent localized surface plasmon resonance (LSPR) properties, are one such material that has been utilized to further improve the power conversion efficiency (PCE) of solar cells. This study confirmed that fiber-shaped dye-sensitized solar cells (FDSSCs) enhanced by silver nanoparticles-embedded M13 bacteriophage (Ag@M13) can be developed as solar cell devices with better PCE than the solar cells without them. The PCE of FDSSCs was improved by adding the Ag@M13 into an iodine species (I-/I3-) based electrolyte, which is used for redox couple reactions. The optimized Ag@M13 enhanced FDSSC showed a PCE of up to 5.80%, which was improved by 16.7% compared to that of the reference device with 4.97%.

Simple one-pot synthesis and high-resolution patterning of perovskite quantum dots using a photocurable ligand.

In this study, we report a UV-light-curable azide ligand (AzL) for the micro-patterning of PeQDs. AzL can be attached to the surface of the PeQDs during their synthesis without additional ligand exchange. Using the AzL-grafted CsPbBr3 PeQDs, high-color-purity 240 × 240 µm2 square-shaped patterns were successfully fabricated using UV light irradiation, which corresponds to a resolution of >50 pixels per inch.

All-Polymer Solar Cells Approaching 12% Efficiency with a New π-Conjugated Polymer Donor Enabled by a Nonhalogenated Solvent Process.

High efficiency and nonhalogenated solvent processing are important issues for commercial application of all-polymer solar cells (all-PSCs). In this regard, we increased the photovoltaic performance of all-PSCs to a benchmark power conversion efficiency (PCE) of 11.66% by manipulating the pre-aggregation of a new π-conjugated polymer donor (Nap-SiBTz) using toluene as a solvent. This use of Nap-SiBTz enhanced the absorption coefficient (λmax = 9.30 × 104 cm-1), increased charge carrier mobility, suppressed trap-assisted recombination, improved bulk heterojunction morphology, and resulted in high PCEs of all-PSCs with an active layer thickness of 200 nm. To overcome severe charge recombination and energy losses, a 1-phenylnapthalene additive was used to achieve a well-ordered microstructure and molecular packing that inherently improved the device performances. The resulting encapsulation-free devices exhibited good ambient and thermal stabilities. The results of this study augur well for the future of the roll-to-roll production of all-PSCs.

Highly efficient, heat dissipating, stretchable organic light-emitting diodes based on a MoO3/Au/MoO3 electrode with encapsulation.

Stretchable organic light-emitting diodes are ubiquitous in the rapidly developing wearable display technology. However, low efficiency and poor mechanical stability inhibit their commercial applications owing to the restrictions generated by strain. Here, we demonstrate the exceptional performance of a transparent (molybdenum-trioxide/gold/molybdenum-trioxide) electrode for buckled, twistable, and geometrically stretchable organic light-emitting diodes under 2-dimensional random area strain with invariant color coordinates. The devices are fabricated on a thin optical-adhesive/elastomer with a small mechanical bending strain and water-proofed by optical-adhesive encapsulation in a sandwiched structure. The heat dissipation mechanism of the thin optical-adhesive substrate, thin elastomer-based devices or silicon dioxide nanoparticles reduces triplet-triplet annihilation, providing consistent performance at high exciton density, compared with thick elastomer and a glass substrate. The performance is enhanced by the nanoparticles in the optical-adhesive for light out-coupling and improved heat dissipation. A high current efficiency of ~82.4 cd/A and an external quantum efficiency of ~22.3% are achieved with minimum efficiency roll-off.

Fractional structured molybdenum oxide catalyst as counter electrodes of all-solid-state fiber dye-sensitized solar cells.

A novel hierarchical solution-processed fractional structured molybdenum oxide (MoO3) catalyst is fabricated from tricarbonyltris (propionitrile) molybdenum and used as the counter electrode of all-solid-state fiber-shaped dye-sensitized solar cells (S-FDSSC). The Tafel plot results and electrical impedance spectroscopy suggest that the use of the fractional structured MoO3 catalyst enhances the efficiency of the reduction of I3- to 3I- at the counter electrode/electrolyte interface. Because of the improvements of the short-current circuit and fill factor, the power conversion efficiency of the MoO3-modified S-FDSSC improves by 60% compared with that of the reference S-FDSSC. In addition, because of the robust fractional structure of MoO3, the MoO3-modified S-FDSSC maintains 90% and 95% of efficiency after 350-fold bending and the incident light angle dependency test, respectively. At 65% humidity and at 65 °C, the power conversion efficiency of the MoO3-modified device decreases by <20% after 350 h of storage, while that of the reference device drops by more than 70%.

Printable Free-Standing Hybrid Graphene/Dry-Spun Carbon Nanotube Films as Multifunctional Electrodes for Highly Stable Perovskite Solar Cells.

Perovskite solar cells (PSCs) have attracted immense attention owing to their outstanding power conversion efficiency (PCE). However, their counter electrodes are commonly produced by evaporating metals, such as Ag and Au, under high vacuum conditions, which make the PSCs costly, thereby limiting their large-scale production. In this study, a free-standing hybrid graphene/carbon nanotube film was carefully designed to replace noble metal PSC counter electrodes to reduce the cost and increase the stability of PSCs. A highly conductive and stable hybrid carbon thin film can be easily transferred to the various desired substrates by a simple rolling process. The PSCs with hybrid graphene/carbon nanotube films showed a high PCE of 15.36%. Moreover, the devices exhibited excellent stability and could retain 86% of their initial PCE after storage for 500 h in a high-moisture atmosphere (RH 50%). The outstanding stability of PCEs can be attributed to the efficient moisture blocking by the multilayered graphene/carbon nanotube present in the hybrid film. The thin, flexible, and easy-to-synthesize free-standing hybrid graphene/CNT film with high conductivity showed great potential for realizing the low-cost production of highly stable PSCs.

Enhancement of Photoluminescence Quantum Yield and Stability in CsPbBr3 Perovskite Quantum Dots by Trivalent Doping.

We determine the influence of substitutional defects on perovskite quantum dots through experimental and theoretical investigations. Substitutional defects were introduced by trivalent dopants (In, Sb, and Bi) in CsPbBr3 by ligand-assisted reprecipitation. We show that the photoluminescence (PL) emission peak shifts toward shorter wavelengths when doping concentrations are increased. Trivalent metal-doped CsPbBr3 enhanced the PL quantum yield (~10%) and air stability (over 10 days). Our findings provide new insights into the influence of substitutional defects on substituted CsPbBr3 that underpin their physical properties.

Clean interface without any intermixed state between ultra-thin P3 polymer and CH3NH3PbI3 hybrid perovskite thin film.

Hole transport layers (HTL) are crucial materials to improve the power conversion efficiency in organohalide hybrid perovskite-based solar-cell applications. Two important physical properties are required in HTL materials: good hole mobility and air-protection. After HTL solution-based deposition, an intermixed chemical state at the interface between HTL and hybrid perovskite is key to confirming the physical property of HTL. We performed high-resolution x-ray photoelectron spectroscopy to investigate the chemical states at the interface between an ultra-thin P3 polymer and CH3NH3PbI3 hybrid perovskite thin film. At the interface, we found no apparent intermixed chemical state. Furthermore, we confirmed that the P3 HTL with the ultra-thin layer (7 nm) protected the hybrid perovskite material against air-exposure for 2 weeks.

Replacement of n-type layers with a non-toxic APTES interfacial layer to improve the performance of amorphous Si thin-film solar cells.

Hydrogenated amorphous Si (a-Si:H) thin-film solar cells (TFSCs) generally contain p/n-type Si layers, which are fabricated using toxic gases. The substitution of these p/n-type layers with non-toxic materials while improving the device performance is a major challenge in the field of TFSCs. Herein, we report the fabrication of a-Si:H TFSCs with the n-type Si layer replaced with a self-assembled monolayer (3-aminopropyl) triethoxysilane (APTES). The X-ray photoelectron spectroscopy results showed that the amine groups from APTES attached with the hydroxyl groups (-OH) on the intrinsic Si (i-Si) surface to form a positive interfacial dipole towards i-Si. This interfacial dipole facilitated the decrease in electron extraction barrier by lowering the work function of the cathode. Consequently, the TFSC with APTES showed a higher fill factor (0.61) and power conversion efficiency (7.68%) than the reference device (without APTES). This performance enhancement of the TFSC with APTES can be attributed to its superior built-in potential and the reduction in the Schottky barrier of the cathode. In addition, the TFSCs with APTES showed lower leakage currents under dark conditions, and hence better charge separation and stability than the reference device. This indicates that APTES is a potential alternative to n-type Si layers, and hence can be used for the fabrication of non-toxic air-stable a-Si:H TFSCs with enhanced performance.

Efficient Approach for Improving the Performance of Nonhalogenated Green Solvent-Processed Polymer Solar Cells via Ternary-Blend Strategy.

The ternary-blend approach has the potential to enhance the power conversion efficiencies (PCEs) of polymer solar cells (PSCs) by providing complementary absorption and efficient charge generation. Unfortunately, most PSCs are processed with toxic halogenated solvents, which are harmful to human health and the environment. Herein, we report the addition of a nonfullerene electron acceptor 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) to a binary blend (poly[4,8-bis(2-(4-(2-ethylhexyloxy)3-fluorophenyl)-5-thienyl)benzo[1,2- b:4,5- b']dithiophene- alt-1,3-bis(4-octylthien-2-yl)-5-(2-ethylhexyl)thieno[3,4- c]pyrrole-4,6-dione] (P1):[6,6]-phenyl-C71-butyric acid methyl ester (PC71BM), PCE = 8.07%) to produce an efficient nonhalogenated green solvent-processed ternary PSC system with a high PCE of 10.11%. The estimated wetting coefficient value (0.086) for the ternary blend suggests that ITIC could be located at the P1:PC71BM interface, resulting in efficient charge generation and charge transport. In addition, the improved current density, sustained open-circuit voltage and PCE of the optimized ternary PSCs were highly correlated with their better external quantum efficiency response and flat-band potential value obtained from the Mott-Schottky analysis. In addition, the ternary PSCs also showed excellent ambient stability over 720 h. Therefore, our results demonstrate the combination of fullerene and nonfullerene acceptors in ternary blend as an efficient approach to improve the performance of eco-friendly solvent-processed PSCs with long-term stability.

An Efficient Amphiphilic-Type Triphenylamine-Based Organic Hole Transport Material for High-Performance and Ambient-Stable Dopant-Free Perovskite and Organic Solar Cells.

A new set of simply structured triphenylamine-based small molecules are synthesized and evaluated as dopant-free hole transporting materials (HTMs) for high-performance perovskite solar cells (PSCs) and bulk heterojunction inverted organic solar cells (BHJ IOSCs). Surprisingly, the new amphiphilic-type HTM-1 (with internal hydrophilic groups and peripheral hydrophobic alkyl tails) showed better compatibility and performance than the actual target molecule, that is, HTM-2 in PSCs and BHJ IOSCs. Importantly, the HTM-1-based dopant-free PSCs and BHJ IOSCs exhibited high power conversion efficiencies (PCEs) of 11.45 % and 8.34 %, respectively. These performances are superior and comparable to those of standard HTMs Spiro-OMeTAD (2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene) and PEDOT:PSS (poly(3,4-ethylenedioxythiophene)/polystyrene sulfonate) in PSCs and BHJ IOSCs, respectively. The enhanced device performance of the HTM-1-based PSCs is ascribed to its strong affinity towards the perovskite, properly aligned energy levels with respect to the perovskite valence band, and excellent hole transporting behavior. In addition, the well-organized energy levels of the HTMs showed excellent compatibility in BHJ IOSCs. The new amphiphilic-type HTM-based photovoltaic devices also showed long-term air stability over 700 h. These promising results offer new and unexpected prospects for engineering the interface between the photoactive material and HTMs in PSCs and BHJ IOSCs.

Optical Transmittance Enhancement of Flexible Copper Film Electrodes with a Wetting Layer for Organic Solar Cells.

The development of highly efficient flexible transparent electrodes (FTEs) supported on polymer substrates is of great importance to the realization of portable and bendable photovoltaic devices. Highly conductive, low-cost Cu has attracted attention as a promising alternative for replacing expensive indium tin oxide (ITO) and Ag. However, highly efficient, Cu-based FTEs are currently unavailable because of the absence of an efficient means of attaining an atomically thin, completely continuous Cu film that simultaneously exhibits enhanced optical transmittance and electrical conductivity. Here, strong two-dimensional (2D) epitaxy of Cu on ZnO is reported by applying an atomically thin (around 1 nm) oxygen-doped Cu wetting layer. Analyses of transmission electron microscopy images and X-ray diffraction patterns, combined with first-principles density functional theory calculations, reveal that the reduction in the surface and interface free energies of the wetting layers with a trace amount (1-2 atom %) of oxygen are largely responsible for the two-dimensional epitaxial growth of the Cu on ZnO. The ultrathin 2D Cu layer, embedded between ZnO films, exhibits a highly desirable optical transmittance of over 85% in a wavelength range of 400-800 nm and a sheet resistance of 11 Ω sq-1. The validity of this innovative approach is verified with a Cu-based FTE that contributes to the light-to-electron conversion efficiency of a flexible organic solar cell that incorporates the transparent electrode (7.7%), which far surpasses that of a solar cell with conventional ITO (6.4%).

Accomplishment of Multifunctional π-Conjugated Polymers by Regulating the Degree of Side-Chain Fluorination for Efficient Dopant-Free Ambient-Stable Perovskite Solar Cells and Organic Solar Cells.

We present an efficient approach to develop a series of multifunctional π-conjugated polymers (P1-P3) by controlling the degree of fluorination (0F, 2F, and 4F) on the side chain linked to the benzodithiophene unit of the π-conjugated polymer. The most promising changes were noticed in optical, electrochemical, and morphological properties upon varying the degree of fluorine atoms on the side chain. The properly aligned energy levels with respect to the perovskite and PCBM prompted us to use them in perovskite solar cells (PSCs) as hole-transporting materials (HTMs) and in bulk heterojunction organic solar cells (BHJ OSCs) as photoactive donors. Interestingly, P2 (2F) and P3 (4F) showed an enhanced power conversion efficiency (PCE) of 14.94%, 10.35% compared to P1 (0F) (9.80%) in dopant-free PSCs. Similarly, P2 (2F) and P3 (4F) also showed improved PCE of 7.93% and 7.43%, respectively, compared to P1 (0F) (PCE of 4.35%) in BHJ OSCs. The high photvoltaic performance of the P2 and P3 based photovotaic devices over P1 are well correlated with their energy level alignment, charge transporting, morphological and packing properties, and hole transfer yields. In addition, the P1-P3 based dopant-free PSCs and BHJ OSCs showed an excellent ambient stability up to 30 days without a significant drop in their initial performance.

Triazine-based Polyelectrolyte as an Efficient Cathode Interfacial Material for Polymer Solar Cells.

A novel polyelectrolyte containing triazine (TAZ) and benzodithiophene (BDT) scaffolds with polar phosphine oxide (P═O) and quaternary ammonium ions as pendant groups, respectively, in the polymer backbone (PBTAZPOBr) was synthesized to use it as a cathode interfacial layer (CIL) for polymer solar cell (PSC) application. Owing to the high electron affinity of the TAZ unit and P═O group, PBTAZPOBr could behave as an effective electron transport material. Due to the polar quaternary ammonium and P═O groups, the interfacial dipole moment created by PBTAZPOBr substantially reduced the work function of the metal cathode to afford better energy alignment in the device, thus enabling electron extraction and reducing recombination of excitons at the photoactive layer/cathode interface. Consequently, the PSC devices based on the poly[4,8-bis(2-ethylhexyloxyl)benzo[1,2-b:4,5-b']dithiophene-2,6-diyl-alt-ethylhexyl-3-fluorothithieno[3,4-b]thiophene-2-carboxylate-4,6-diyl]:[6,6]-phenyl-C71-butyric acid methyl ester (PTB7:PC71BM) system with PBTAZPOBr as CIL displayed simultaneously enhanced open-circuit voltage, short-circuit current density, and fill factor, whereas the power conversion efficiency increased from 5.42% to 8.04% compared to that of the pristine Al device. The outstanding performance of PBTAZPOBr is attributed not only to the polar pendant groups of BDT unit but also to the TAZ unit linked with the P═O group of PBTAZPOBr, demonstrating that functionalized TAZ building blocks are very promising cathode interfacial materials (CIMs). The design strategy proposed in this work will be helpful to develop more efficient CIMs for high performance PSCs in the future.

High-Performance Long-Term-Stable Dopant-Free Perovskite Solar Cells and Additive-Free Organic Solar Cells by Employing Newly Designed Multirole π-Conjugated Polymers.

Perovskite solar cells (PSCs) and organic solar cells (OSCs) are promising renewable light-harvesting technologies with high performance, but the utilization of hazardous dopants and high boiling additives is harmful to all forms of life and the environment. Herein, new multirole π-conjugated polymers (P1-P3) are developed via a rational design approach through theoretical hindsight, further successfully subjecting them into dopant-free PSCs as hole-transporting materials and additive-free OSCs as photoactive donors, respectively. Especially, P3-based PSCs and OSCs not only show high power conversion efficiencies of 17.28% and 8.26%, but also display an excellent ambient stability up to 30 d (for PSCs only), owing to their inherent superior optoelectronic properties in their pristine form. Overall, the rational approach promises to support the development of environmentally and economically sustainable PSCs and OSCs.