A Fluorination Strategy and Low-Acidity Anchoring Group in Self-Assembled Molecules for Efficient and Stable Inverted Perovskite Solar Cells.

Herein, we synthesized two donor-acceptor (D-A) type small organic molecules with self-assembly properties, namely MPA-BT-BA and MPA-2FBT-BA, both containing a low acidity anchoring group, benzoic acid. After systematically investigation, it is found that, with the fluorination, the MPA-2FBT-BA demonstrates a lower highest occupied molecular orbital (HOMO) energy level, higher hole mobility, higher hydrophobicity and stronger interaction with the perovskite layer than that of MPA-BT-BA. As a result, the device based-on MPA-2FBT-BA displays a better crystallization and morphology of perovskite layer with larger grain size and less non-radiative recombination. Consequently, the device using MPA-2FBT-BA as hole transport material achieved the power conversion efficiency (PCE) of 20.32 % and remarkable stability. After being kept in an N2 glove box for 116 days, the unsealed PSCs' device retained 93 % of its initial PCE. Even exposed to air with a relative humidity range of 30±5 % for 43 days, its PCE remained above 91 % of its initial condition. This study highlights the vital importance of the fluorination strategy combined with a low acidity anchoring group in SAMs, offering a pathway to achieve efficient and stable PSCs.

One-Pot Synthesis of All-Inorganic CsPbClBr2 Blue Perovskite Quantum Dots via Stoichiometric Precursor.

The synthesis of perovskite-based blue light-emitting particles is valuable for several applications as the excellent optical properties and performances of the constituting materials associated with multi-exciton generation can be exploited. However, the preparation of perovskite precursors requires high temperatures, resulting in a complex manufacturing process. This paper proposes a one-pot method to synthesize CsPbClBr2 blue light-emitting quantum dots (QDs). In the case of nonstoichiometric precursor synthesis, the CsPbClBr2 QDs coexisted with additional products. The solvent for synthesizing mixed perovskite nanoparticles (containing chloride) was selected by mixing dimethylformamide (DMF) and/or dimethyl sulfoxide (DMSO) in different ratios. When only DMF was used with the stoichiometric CsBr and PbX2 (X = Cl, Br) ratio, the quantum yield was 70.55%, and superior optical properties were achieved. Moreover, no discoloration was observed for 400 h, and a high photoluminescence intensity was maintained. When deionized water was added to form a double layer with hexane, the luminescence was maintained for 15 days. In other words, the perovskite did not easily decompose even when in contact with water, which suppressed the release of Pb2+, which are heavy metal atoms in the structure. Overall, the proposed one-pot method for all-inorganic-based perovskite QDs provides a platform for synthesizing superior blue light-emitting materials.

Improved light harvesting and improved efficiency by insertion of an optical spacer (ZnO) in solution-processed small-molecule solar cells.

We demonstrate that the power conversion efficiency can be significantly improved in solution-processed small-molecule solar cells by tuning the thickness of the active layer and inserting an optical spacer (ZnO) between the active layer and the Al electrode. The enhancement in light absorption in the cell was measured with UV-vis absorption spectroscopy and by measurements of the photoinduced carriers generation rate. The ZnO layer used to improve the light-harvesting increases the charge collection efficiency, serves as a blocking layer for holes, and reduces the recombination rate. The combined optical and electrical improvements raise the power conversion efficiency of solution-processed small-molecule solar cells to 8.9%, that is, comparable to that of polymer counterparts.

Surface defect mitigation via alkyl-ligand-controlled purification for stable and high-luminescence perovskite quantum dots.

Perovskite quantum dots (PQDs) have received considerable attention as fluorescent materials due to their excellent optical properties. However, because PQDs contain ionic bonds, they have the disadvantage of being vulnerable to environmental conditions, so improving their stability is essential. Indeed, recent research has focused on improving both the stability and luminescence of PQDs by mixing them with methyl acetate (MeOAc) to suppress surface defects via purification. MeOAc reacts with the surface ligands of PQDs, resulting in ligand-controlled purification. However, while the ligands are limited for the PQD synthesis, the effect of ligand alkyl-chain length has not been reported. Therefore, we report herein a strategy for obtaining stable PQDs with tunable performances by using amine ligands of various chain lengths. The amine ligand is selected because it is very effective in interacting with the halide vacancies present on the surface of the perovskite crystal structure. The results indicate that MeOAc becomes less effective as the chain length of the ligand is increased, and more effective as the chain length is decreased. Consequently, PQDs treated with MeOAc and a short-chain ligand afford a quantum yield (QY) of 79.2% and are highly stable when exposed to thermal and ambient conditions. Therefore, we suggest a facile approach to suppressing the degradation of PQDs during the fabrication process.

Layer-by-layer all-transfer-based organic solar cells.

For the first time, we describe a novel cost- and time-effective vacuum-free process to fabricate bulk-heterojunction (BHJ) organic photovoltaics (OPVs) via layer-by-layer selective stamping transfer of all layers. By controlling the surface properties of polyurethane acrylate (PUA) stamping molds with ultraviolet (UV)-ozone (UVO) exposure, poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT/PSS), BHJ layer, and metal cathode were uniformly transferred layer by layer onto each of the bottom layers. Among several interfaces between each layer, we found that the interface between the active layer and metal cathode is a critical factor in obtaining conventional device-like efficiency. To enhance the interfacial connectivity between the BHJ layer and metal cathode and increase electron extraction from the BHJ layer, a titanium oxide (TiOx) interlayer was introduced. Cell performance was optimized by controlling the concentration of TiOx solution. The poly(3-hexylthiophene-2,5-diyl)/[6,6]-phenyl-C61-butyric acid methyl ester (P3HT/PC60BM) BHJ device fabricated by transferring PEDOT/PSS, TiOx/active layer, and Al cathode showed 2.01% power conversion efficiency. This efficiency is not comparable to those of conventional OPVs, but our approach shows the possibility of fabricating OPVs via the layer-by-layer transfer method for the first time.

In Situ Interfacial-Assembly Perovskite Quantum Dot via Marangoni and Capillary Convection Manipulation for Robust Luminescence.

In solid substrates, colloidal solutions produce irregular deposits on the surface by Marangoni flow and capillary flow during evaporation. Reportedly, perovskite quantum dots (PQDs) as a colloidal solution have irregular surfaces based on a similar principle as the coffee ring effect in QD systems when droplets evaporate from the substrate. Given that this issue is due to the direction of Marangoni and capillary flows, the substrate is tilted to change the direction of the flows. The appropriate angle is determined by controlling the angle of the substrate so that the two flows circulate similarly; this method is called "assembly-coating". Herein, we compare the PL intensity before and after the thermal evaporation of the thin films prepared by conventional and assembly-coating. Moreover, by characterizing the diode device (hole-only space charge limited current) for each coating process, the charge carrier characteristics are investigated in detail. Therefore, we suggest a facile strategy to obtain a uniform surface and thermal evaporative stability using colloidal solutions. This strategy is effective in designing surface uniformity and light-emitting layers for colloidal solution deposition and assembly.

Stamping transfer of a quantum dot interlayer for organic photovoltaic cells.

An organophilic cadmium selenide (CdSe) quantum dot (QD) interlayer was prepared on the active layer in organic solar cells by a stamping transfer method. The mother substrate composed of a UV-cured film on a polycarbonate film with strong solvent resistance makes it possible to spin-coat QDs on it and dry transfer onto an active layer without damaging the active layer. The QD interlayers have been optimized by controlling the concentration of the QD solution. The coverage of QD particles on the active layer was verified by TEM analysis and fluorescence images. After insertion of the QD interlayer between the active layer and metal cathode, the photovoltaic performances of the organic solar cell were clearly enhanced. By ultraviolet photoelectron spectroscopy of CdSe QDs, it can be anticipated that the CdSe QD interlayer reduces charge recombination by blocking the holes moving to the cathode from the active layer and facilitating efficient collection of the electrons from the active layer to the cathode.

Sequential processing: control of nanomorphology in bulk heterojunction solar cells.

Bulk heterojunction organic photovoltaic devices based on poly[N-9''-hepta-decanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole) (PCDTBT)/[6,6]-phenyl C(70) butyric acid methyl ester (PC(70)BM) can be successfully fabricated by a sequential solution deposition process. When the top layer is deposited from an appropriate cosolvent, the PC(70)BM penetrates a predeposited bottom layer of PCDTBT during the spin-casting process, resulting in an interdiffused structure with a layer-evolved bulk heterojunction (LE-BHJ) nanomorphology. The PCDTBT:PC(70)BM LE-BHJ solar cells prepared with an optimized cosolvent ratio have comparable power conversion efficiency to the conventional BHJ solar cells. The nanomorphology of the optimized PCDTBT:PC(70)BM LE-BHJ mixture was found to have better vertical connectivity than the conventional BHJ material.

Fully Inorganic CsSnI3-Based Solar Cells with >6% Efficiency and Enhanced Stability Enabled by Mixed Electron Transport Layer.

Fully inorganic black orthorhombic (B-γ) CsSnI3 has become a promising candidate for perovskite solar cell (PSC) thanks to its low toxicity and decently high theoretical power conversion efficiency (PCE). However, so far, the reported PCE of the B-γ CsSnI3 PSC is still not comparable with its lead-based or organotin-based counterparts. Herein, a mixed electron transport layer (ETL) composed of ZnO nanoparticles (NPs) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) is incorporated into inverted B-γ CsSnI3 PSCs. The mixed ETL exhibits the merits of both ZnO and PCBM. The highest PCE of 6.08% was recorded for the PSC with mixed ZnO-PCBM ETL, which is 34.2% higher than that of the device with plain PCBM ETL (PCE of 4.53%) and 28.8% superior to that of plain ZnO ETL-based device (PCE of 4.72%). Meanwhile, the mixed ZnO-PCBM ETL-based PSC retained 71% of its initial PCE under inert conditions at room temperature after 60 days of storage and maintained 67% PCE after 20 days of storage under ambient air at 30% relative humidity and room temperature.

Versatile Pendant Polymer for Selective Charge Carrier Transport via Controlling the Supramolecular Self-Assembly.

Polyvinyl carbazole (P0)-based pendant polymers were synthesized by modifying carbazole motifs with pyrene derivatives (P1 and P4) to manipulate the bandgap and frontier orbital energy levels. To establish the electronic properties of pendant polymers according to structural differences, the polymers were utilized as additional hole transport layers in planar-type perovskite solar cells and organic photovoltaic cells. When P4 with thiophene-pyrene pendant was used as hole transport layer, all device parameters, except open-circuit voltage, were significantly improved in comparison with P0 and P1 (conjugated with t-butyl pyrene derivatives). Since P4 had more electrically conductive thiophene units than benzene units with fewer alkyl groups, the supramolecular assembly of P4 was found to be more favorable in electronic devices. Furthermore, devices with P4 demonstrated lower dark current than others, which could potentially be useful for charge carrier transport and sensitive photo detecting devices.

Versatile Pendant Polymer for Selective Charge Carrier Transport via Controlling the Supramolecular Self-Assembly.

Invited for this month's cover is the group of Jin Kuen Park and Dong Hwan Wang at two different universities in South Korea. The image shows how the supramolecular interaction between pendant polymers can play a role in controlling the electronic properties in perovskite-based electronics such as solar cells and photodetectors. The Full Paper itself is available at 10.1002/cssc.202101785.

A Facile and Effective Ozone Exposure Method for Wettability and Energy-Level Tuning of Hole-Transporting Layers in Lead-Free Tin Perovskite Solar Cells.

Lead-free perovskite solar cells (PSCs) have attracted interest among scientists searching for eco-friendly energy harvesting devices. Herein, the effects of ozone exposure on poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) in lead-free tin halide PSCs as a facile and low-cost process for improving device performance are analyzed. Two types of tin-based PSCs and one typical lead-based PSC were fabricated. The ozone exposure on PEDOT:PSS increases the short-circuit current density (JSC) and the fill factor (FF) of PSCs in all cases with perovskite grain enlargement and hole-mobility enhancement of the devices, respectively. For open-circuit voltage (VOC), the outcome depends on the band gap and the energy levels of the perovskite films. While ozone exposure treatment is favorable for PEA0.15FA0.85SnI3-based tin PSCs, VOC decreases with ozone exposure in the case of Ge:EDA0.01FA0.98SnI3-based tin PSCs because of a misalignment of the energy levels. Regardless, the efficiency of PEA0.15FA0.85SnI3-based tin PSCs increases from 8.7 to 10.1% when measured inside a glovebox upon ozone exposure of PEDOT:PSS. The efficiency of Ge:EDA0.01FA0.98SnI3-based tin PSCs increases from 6.8 to 8.1%, and the devices retain an efficiency of 5.0% even after 50 days in air.

High-Valent Iodoplumbate-Rich Perovskite Precursor Solution via Solar Illumination for Reproducible Power Conversion Efficiency.

The power conversion efficiency (PCE) of solution-processed organic-inorganic hybrid perovskite solar cells has been drastically improved. Despite this considerable progress, systematic research on precursor solution chemistry and its effects on photovoltaic parameters has been limited thus far. Herein, we report on the tracking of changes in chemical species in a precursor solution under solar illumination and investigate the correlation between the equilibrium change and the corresponding perovskite film formation. The illuminated perovskite precursors display a higher density of high-valent iodoplumbate, where the resulting perovskite film exhibits reduced defect density with uniform film formation. Conclusively, the perovskite solar cells prepared by the photoaged precursor solution demonstrate not only improved average PCE but also enhanced reproducibility with a narrow PCE distribution. This discovery shows robust control of perovskite precursor solutions from a simple treatment and suggests that the resulting uniform film may be applicable to various halide perovskite-based devices.

Photovoltaic devices with an active layer from a stamping transfer technique: single layer versus double layer.

In this study, organic photovoltaic devices with single or double-layered active film were prepared from a stamping transfer technique. A P3HT/PCBM single-layered active layer and a ratio-controlled P3HT/PCBM double-layered active can be successfully fabricated with the help of ultraviolet curable polycarbonate films via a stamping transfer technique. The maximum conversion efficiency values 2.85 for a single active layer transferred device and 3.24% for an optimized double active layer transferred device. Even though transferred double layers should have a sharp interface boundary, an intermixed zone with a concentration gradient was generated by the interpenetration of a donor-rich layer and an acceptor-rich layer in a thermal annealing process. The generation of the intermixed zone is confirmed by Auger electron spectroscopy. The enhanced conversion efficiency levels are attributed to the increased efficiency of the carrier transporting process, which is due to the fact that the concentration gradient is combined with the efficient charge generation from the bulk heterojunction layers.

Roles of interlayers in efficient organic photovoltaic devices.

This review discusses interfacial layers in organic photovoltaic devices. The first part of the review focuses on the hole extraction layer, which is located between a positive electrode and an organic photoactive material. Strategies to improve hole extraction from the photoactive layer include incorporation of several different types of hole extraction layers, such as conductive polymeric materials, self-assembled molecules and metal oxides, as well as surface treatment of the positive electrodes and the conductive polymeric layers. In the second part, we review recent research on interlayers that are located between a negative electrode and a photoactive layer to efficiently extract electrons from the active layer. These materials include titanium oxides, metal fluorides and other organic layers.

Acidity Suppression of Hole Transport Layer via Solution Reaction of Neutral PEDOT:PSS for Stable Perovskite Photovoltaics.

Poly(3,4-ethylenedioxythiophene): poly(4-styrenesulfonate) (PEDOT:PSS) is typically used for hole transport layers (HTLs), as it exhibits attractive mechanical, electrical properties, and easy processability. However, the intrinsically acidic property can degrade the crystallinity of perovskites, limiting the stability and efficiency of perovskite solar cells (PSCs). In this study, inverted CH3NH3PbI3 photovoltaic cells were fabricated with acidity suppressed HTL. We adjusted PEDOT:PSS via a solution reaction of acidic and neutral PEDOT:PSS. And we compared the various pH-controlled HTLs for PSCs devices. The smoothness of the pH-controlled PEDOT:PSS layer was similar to that of acidic PEDOT:PSS-based devices. These layers induced favorable crystallinity of perovskite compared with acidic PEDOT:PSS layers. Furthermore, the enhanced stability of pH optimized PEDOT:PSS-based devices, including the prevention of degradation by a strong acid, allowed the device to retain its power conversion efficiency (PCE) value by maintaining 80% of PCE for approximately 150 h. As a result, the pH-controlled HTL layer fabricated through the solution reaction maintained the surface morphology of the perovskite layer and contributed to the stable operation of PSCs.

Light-Emitting Transistors with High Color Purity Using Perovskite Quantum Dot Emitters.

The class of organic-inorganic lead halides with perovskite crystal structures has recently emerged as promising materials for a variety of practical optoelectronic applications. In particular, hybrid halide perovskite quantum dots possess excellent intrinsic optoelectronic properties such as high color purity (full width at half-maximum of 24.59 nm) and photoluminescence quantum yields (92.7%). In this work, we demonstrate the use of perovskite quantum dot materials as an emissive layer of hybrid light-emitting transistors. To investigate the working mechanism of perovskite quantum dots in light-emitting transistors, we investigated the electrical and optical characteristics under both p-channel and n-channel operation. Using these materials, we have achieved perovskite quantum dot light-emitting transistors with high electron mobilities of up to 12.06 cm2·V-1 s-1, high brightness of up to 1.41 × 104 cd m-2, and enhanced external quantum efficiencies of up to 1.79% operating at a source-drain potential of 40 V.

Selective Soxhlets extraction to enhance solubility of newly-synthesized poly(indoloindole-selenophene vinylene selenophene) donor for photovoltaic applications.

An electron-rich fused indoloindole-based poly(indoloindole-selenophene vinylene selenophene) was synthesized and characterized. Soxhlet can be obtained by continuously purifying the product with a specific solvent and obtaining a pure polymer with a high concentration. Molecular weight is affected by the vapor pressure of marginal solvent, and the polymer was fractionated using tetrahydrofuran, chloroform, and chlorobenzene. Solubility is closely related to the morphology of bulk heterojunction and device parameters. In the solution process of fabricating the organic solar cell, securement of solubility has a great effect on the performance of the device, because morphology and orientation of a photo-active layer which significantly affect charge transport in the device. Since tetrahydrofuran (THF) Soxhlet solvents have high vapor pressure and appropriate solubility parameters, THF induced the best solubility of P-IDI-SVS materials for organic solvents. And through additive optimization, the performance of the device based on P-IDI-SVS from THF-Soxhlet extraction was enhanced. This is expected to be a meaningful study because the effect on solubility of Soxhlet solvent suggests factors to be considered in the solution process in organic solar cell research. In addition, surface modified bulk heterojunction was observed using atomic force microscopy, photoluminescence, time-correlated single photon counting and Raman spectroscopy analysis.

Tuning the energy level of TAPC: crystal structure and photophysical and electrochemical properties of 4,4'-(cyclohexane-1,1-diyl)bis[N,N-bis(4-methoxyphenyl)aniline].

The energy level of a hole-transporting material (HTM) in organic electronics, such as organic light-emitting diodes (OLEDs) and perovskite solar cells (PSCs), is important for device efficiency. In this regard, we prepared 4,4'-(cyclohexane-1,1-diyl)bis[N,N-bis(4-methoxyphenyl)aniline] (TAPC-OMe), C46H46N2O4, to tune the energy level of 4,4'-(cyclohexane-1,1-diyl)bis[N,N-bis(4-methylphenyl)aniline] (TAPC), which is a well-known HTM commonly used in OLED applications. A systematic characterization of TAPC-OMe, including 1H and 13C NMR, elemental analysis, UV-Vis absorption, fluorescence emission, density functional theory (DFT) calculations and single-crystal X-ray diffraction, was performed. TAPC-OMe crystallized in the triclinic space group P-1, with two molecules in the asymmetric unit. The dihedral angles between the central amine triangular planes and those of the phenyl groups varied from 26.56 (9) to 60.34 (8)° due to the steric hindrance of the central cyclohexyl ring. This arrangement might be induced by weak hydrogen bonds and C-H...π(Ph) interactions in the extended structure. The emission maxima of TAPC-OMe showed a significant bathochomic shift compared to that of TAPC. A strong dependency of the oxidation potentials on the nature of the electron-donating ability of substituents was confirmed by comparing oxidation potentials with known Hammett parameters (σ).