Improving FAPbBr3 Perovskite Crystal Quality via Additive Engineering for High Voltage Solar Cell over 1.5 V.

Lead bromide-based perovskites are promising materials as the top cells of tandem solar cells and for application in various fields requiring high voltages owing to their wide band gaps and excellent environmental resistances. However, several factors, such as the formation of bulk and surface defects, impede the performances of corresponding devices, thereby limiting the efficiencies of these devices as single-junction devices. To reduce the number of defect sites, urea is added to the formamidinium lead bromide (FAPbBr3) perovskite material to increase its grain size. Nevertheless, urea undesirably reacts with lead(II) bromide (PbBr2) in the perovskite structure, creating unfavorable impurities in the device. To solve this problem, herein, in addition to urea, we introduced formamidinium chloride (FACl) into FAPbBr3. Owing to the synergistic effect of urea and FACl, the FAPbBr3 film quality effectively improved due to suppression of the generation of impurities and stabilization of film crystallinity. Consequently, the FAPbBr3 single-junction solar cell constructed using FACl and urea as additives demonstrated a power conversion efficiency of 9.6% and an open-circuit voltage of 1.516 V with negligible hysteresis. This study provides new insights into the use of additive engineering for overcoming the energy losses caused by defects in perovskite films.

Spectrally Resolved Exciton Polarizability for Understanding Charge Generation in Organic Bulk Hetero-Junction Diodes.

Despite decades of research, the dominant charge generation mechanism in organic bulk heterojunction (BHJ) devices is not completely understood. While the local dielectric environments of the photoexcited molecules are important for exciton dissociation, conventional characterizations cannot separately measure the polarizability of electron-donor and electron-acceptor, respectively, in their blends, making it difficult to decipher the spectrally different charge generation efficiencies in organic BHJ devices. Here, by spectrally resolved electroabsorption spectroscopy, we report extraction of the excited state polarizability for individual donors and acceptors in a series of organic blend films. Regardless of the donor and acceptor, we discovered that larger exciton polarizability is linked to larger π-π coherence length and faster charge transfer across the heterojunction, which fundamentally explains the origin of the higher charge generation efficiency near 100% in the BHJ photodiodes. We also show that the molecular packing of the donor and acceptor influence each other, resulting in a synergetic enhancement in the exciton polarizability.

Single-Step Fabrication of Polymeric Composite Membrane via Centrifugal Colloidal Casting for Fuel Cell Applications.

Recent interest in polymer electrolyte membranes (PEMs) for fuel cell systems has spurred the development of infiltration technology by which to insert ionomers into mechanically robust reinforcement structures by solution casting in order to produce a cost effective and highly efficient electrolyte. However, the results of the fabrication process often continue to present challenges related to the structural complexity and self-assembly dynamics between the hydrophobic and hydrophilic parts of the constituents which in turn, necessitates additional processing steps and increases production costs. Here, a single-step process is reported for highly compact polymeric composite membranes (PCMs), fabricated using a centrifugal colloidal casting (C3) method. Combined structural analyses as well as coarse-grained molecular dynamics simulations are employed to determine the micro-/macroscopic structural characteristics of the fabricated PCMs. These findings indicate that the C3 method is capable of forming highly dense ionomer matrix-reinforcement composites consisting of microphase-separated ionomer structures with tailored crystallinity and ionic cluster sizes. An outcome that is very unlikely with the single-step coating steps in conventional methods. These structural attributes ensure PCMs with better proton conductivity, greater strain stability, and lower gas crossover properties compared to commercial pristine membranes, expanding their possible range of applicability to PEMs.

Novel Polymer-Based Organic/c-Si Monolithic Tandem Solar Cell: Enhanced Efficiency using Interlayer and Transparent Top Electrode Engineering.

Tandem solar cells which are electrically connected with various photoactive materials have the potential to solve the current challenges by exceeding the theoretically limited efficiency of single junction solar cells. Here the first monolithic organic/silicon tandem cell is reported based on a semitransparent polymer on a crystalline silicon (c-Si) substrate. Herein, experimental results are presented for four-terminal (4-T) and monolithic two-terminal (2-T) organic/c-Si tandem cells using organic cells with an inverted n-i-p structure and c-Si cells with an n-type TOPCon structure with detailed analysis. The best 4-T tandem cell efficiency is 15.22%, and 2-T results show that the top (organic) and bottom (c-Si) cells are electrically connected by an open-circuit voltage over 1.4 V. Further, a simulated efficiency of over 20% using the organic/c-Si tandem is achieved, implying the tandem efficiency can be enhanced through further improvement of electric and optical characteristics with the optimization.

Simultaneous Enhanced Efficiency and Stability of Perovskite Solar Cells Using Adhesive Fluorinated Polymer Interfacial Material.

For enhancing the performance and long-term stability of perovskite solar cell (PSC) devices, interfacial engineering between the perovskite and hole-transporting material (HTM) is important. We developed a fluorinated conjugated polymer PFPT3 and used it as an interfacial layer between the perovskite and HTM layers in normal-type PSCs. Interaction of perovskite and PFPT3 via Pb-F bonding effectively induces an interfacial dipole moment, which resulted in energy-level bending; this was favorable for charge transfer and hole extraction at the interface. The PSC device achieved an increased efficiency of 22.00% with an open-circuit voltage of 1.13 V, short-circuit current density of 24.34 mA/cm2, and fill factor of 0.80 from a reverse scan and showed an averaged power conversion efficiency of 21.59%, which was averaged from forward and reverse scans. Furthermore, the device with PFPT3 showed much improved stability under an 85% RH condition because hydrophobic PFPT3 reduced water permeation into the perovskite layer, and more importantly, the enhanced contact adhesion at the PFPT3-mediated perovskite/HTM interface suppressed surface delamination and retarded water intrusion. The fluorinated conjugated polymeric interfacial material is effective for improving not only the efficiency but also the stability of the PSC devices.

Guidelines for accreditation of endoscopy units: quality measures from the Korean Society of Coloproctology.

PURPOSE: Colonoscopy is an effective method of screening for colorectal cancer (CRC), and it can prevent CRC by detection and removal of precancerous lesions. The most important considerations when performing colonoscopy screening are the safety and satisfaction of the patient and the diagnostic accuracy. Accordingly, the Korean Society of Coloproctology (KSCP) herein proposes an optimal level of standard performance to be used in endoscopy units and by individual colonoscopists for screening colonoscopy. These guidelines establish specific criteria for assessment of safety and quality in screening colonoscopy. METHODS: The Colonoscopy Committee of the KSCP commissioned this Position Statement. Expert gastrointestinal surgeons representing the KSCP reviewed the published evidence to identify acceptable quality indicators and indicators that lacked sufficient evidence. RESULTS: The KSCP recommends an optimal standard list for quality control of screening colonoscopy in the following 6 categories: training and competency of the colonoscopist, procedural quality, facilities and equipment, performance indicators and auditable outcomes, disinfection of equipment, and sedation and recovery of the patient. CONCLUSION: The KSCP recommends that endoscopy units performing CRC screening evaluate 6 key performance measures during daily practice.

Progress in Materials, Solution Processes, and Long-Term Stability for Large-Area Organic Photovoltaics.

Organic solar cells based on bulk heterojunctions (BHJs) are attractive energy-conversion devices that can generate electricity from absorbed sunlight by dissociating excitons and collecting charge carriers. Recent breakthroughs attained by development of nonfullerene acceptors result in significant enhancement in power conversion efficiency (PCEs) exceeding 17%. However, most of researches have focused on pursuing high efficiency of small-area (<1 cm2 ) unit cells fabricated usually with spin coating. For practical application of organic photovoltaics (OPVs) from lab-scale unit cells to industrial products, it is essential to develop efficient technologies that can extend active area of devices with minimized loss of performance and ensured operational stability. In this progress report, an overview of recent advancements in materials and processing technologies is provided for transitioning from small-area laboratory-scale devices to large-area industrial scale modules. First, development of materials that satisfy requirements of high tolerability in active layer thickness and large-area adaptability is introduced. Second, morphology control using various coating techniques in a large active area is discussed. Third, the recent research progress is also underlined for understanding mechanisms of OPV degradation and studies for improving device long-term stability along with reliable evaluation procedures.

Understanding the Performance of Organic Photovoltaics under Indoor and Outdoor Conditions: Effects of Chlorination of Donor Polymers.

Understanding the effects of the chemical structures of donor polymers on the photovoltaic properties of their corresponding organic photovoltaic (OPV) devices under various light-intensity conditions is important for improving the performance of these devices. We synthesized a series of copolymers based on poly[(2,6-(4,8-bis(5-(2-thioethylhexyl)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-TS) and studied the effects of chlorine substitution of its thiophene-substituted benzodithiophene (BDT-Th) unit on its photovoltaic properties. Chlorination of the polymer resulted in a bulk heterojunction (BHJ) morphology optimized for efficient charge transport with suppressed leakage current and an increased open-circuit voltage of the OPV device; this optimization led to a remarkable enhancement of the OPV device's power conversion efficiency (PCE) not only under the condition of 1 sun illumination but also under a low light intensity mimicking indoor light; the PCE increased from 8.7% for PBDB-TS to ∼13% for the chlorinated polymers, PBDB-TS-3Cl, and PBDB-TS-4Cl under the 1 sun illumination condition and from 5.3% for PBDB-TS to 21.7% for PBDB-TS-4Cl under 500 lx fluorescence illuminance. Interestingly, although the OPV PCEs under 1 sun illumination were independent of the position of chlorine substitution onto the polymer, PBDB-TS-4Cl exhibited better performance under simulated indoor light than its derivative PBDB-TS-3Cl. Our results demonstrate that efficient light absorption and charge-carrier generation play key roles in achieving high OPV efficiency under low-light-intensity conditions.

3D Printer-Based Encapsulated Origami Electronics for Extreme System Stretchability and High Areal Coverage.

Stretchability and areal coverage of active devices are critical design considerations of stretchable or wearable photovoltaics and photodetections where high areal coverages are required. However, simultaneously maximizing both properties in conventional island-bridge structures through traditional two-dimensional manufacturing processes is difficult due to their inherent trade-offs. Here, a 3D printer-based strategy to achieve extreme system stretchability and high areal coverage through combining fused deposition modeling (FDM) and flexible conductive nanocomposites is reported. Distinguished from typical approaches of using conductive filaments for FDM which have a flexibility dilemma and conductivity trade-offs, the proposed axiomatic approach to embed a two-dimensional silver nanowire percolation network into the surfaces of flexible 3D printed structures offers sufficient conductivity and deformability as well as additional benefits of electrical junction enhancement and encapsulation of silver nanowires. Kirigami/origami-pattern-guided three-dimensional arrangements of encapsulated interconnections provide efficient control over stretchability and areal coverage. The suggested process enables a perovskite solar module with an initial areal coverage of ∼97% to be electrically and mechanically reversible with 400% system stretchability and 25 000% interconnect stretchability under the 1000 cycle test, by folding down or hiding the origami-applied interconnects under the islands. This 3D printing strategy of potentially low cost, large size capabilities, and high speed is promising for highly flexible future energy conversion applications.

High ligation of the anal fistula tract by lateral approach: A prospective cohort study on a modification of the ligation of the intersphincteric fistula tract (LIFT) technique.

BACKGROUND: Ligation of the intersphincteric fistula tract (LIFT) is a sphincter-preserving operation for anal fistulas. Although it has advantages in preserving continence after surgery, it is difficult to perform owing to the narrow field of view. We performed a modified surgical procedure based on the LIFT to overcome these drawbacks. MATERIALS AND METHODS: Twenty-eight patients who were scheduled to undergo high ligation of the anal fistula tract by the lateral approach for the treatment of transsphincteric anal fistulas were prospectively studied. Instead of making a new stab incision on the intersphincteric groove, we dissected along the fistula tract from the external opening until the intersphincteric space appeared. The fistula tract was then ligated close to the internal anal sphincter with absorbable sutures, and the distal part of the ligation was cut off. A cored-out wound was left open for drainage. RESULTS: The median follow-up was 16 months (range, 8-27 months). Of the 28 patients, 19 (68%) had simple transsphincteric fistulas and 9 (32%) had complex transsphincteric fistulas. Successful fistula closure was achieved in 21 patients (75%), with a median healing time of 4 weeks (range, 3-7 weeks). None of the patients complained of any incontinence symptoms after the procedure. Of the seven patients (25%) who failed to heal successfully, two (7%) did not heal up to 2 months after surgery and five (18%) experienced recurrence after complete healing. CONCLUSION: High ligation of the anal fistula tract by lateral approach may be a useful sphincter-sparing procedure for transsphincteric anal fistulas.

Development of Dopant-Free Donor-Acceptor-type Hole Transporting Material for Highly Efficient and Stable Perovskite Solar Cells.

In perovskite solar cells (PSCs), overlying hole transporting materials (HTMs) are important for achieving high efficiencies as well as protecting perovskite active layers from degradation factors. This study reports the synthesis of a dopant-free HTM based on a D'-A-D-A-D-A-D' (D, D': electron donor, A: electron acceptor) conjugated structure and incorporation of the HTM into a PSC. The resulting PSC exhibits a high efficiency of 17.3%, which is comparable to that of the device based on doped spiro-OMeTAD HTM, and exhibits much improved stability: without encapsulation, the PSC based on the new HTM was found to retain 80% of its initial performance over 500 h under the conditions of 60% relative humidity/1 sun light-soaking without encapsulation. The high performance is attributed to efficient hole-extraction/collection and hole transport. We demonstrate that the extended π-structure of the D'-A-D-A-D-A-D'-type HTM slows moisture intrusion and protects the perovskite layer better than smaller D-A-type molecules. The improved stability is primarily due to the hydrophobic nature of the HTM; the relatively large π-conjugated molecule forms denser films, which effectively decrease the spaces between the molecules and retard water intrusion. The dopant-free D-A-type HTM with an extended π-structure is effective not only in improving device efficiency, but also device stability.

Accelerated Degradation Due to Weakened Adhesion from Li-TFSI Additives in Perovskite Solar Cells.

Reliable integration of organometallic halide perovskite in photovoltaic devices is critically limited by its low stability in humid environments. Furthermore, additives to increase the mobility in the hole transport material (HTM) have deliquescence and hygroscopic properties, which attract water molecules and result in accelerated degradation of the perovskite devices. In this study, a double cantilever beam (DCB) test is used to investigate the effects of additives in the HTM layer on the perovskite layer through neatly delaminating the interface between the perovskite and HTM layers. Using the DCB test, the bottom surface of the HTM layers is directly observed, and it is found that the additives are accumulated at the bottom along the thickness (i.e., through-plane direction) of the films. It is also found that the additives significantly decrease the adhesion at the interface between the perovskite and HTM layers by more than 60% through hardening the HTM films. Finally, the adhesion-based degradation mechanism of perovskite devices according to the existence of additives is proposed for humid environments.

Vertically aligned nanostructured TiO2 photoelectrodes for high efficiency perovskite solar cells via a block copolymer template approach.

We fabricated perovskite solar cells with enhanced device efficiency based on vertically oriented TiO2 nanostructures using a nanoporous template of block copolymers (BCPs). The dimension and shape controllability of the nanopores of the BCP template allowed for the construction of one-dimensional (1-D) TiO2 nanorods and two-dimensional (2-D) TiO2 nanowalls. The TiO2 nanorod-based perovskite solar cells showed a more efficient charge separation and a lower charge recombination, leading to better performance compared to TiO2 nanowall-based solar cells. The best solar cells employing 1-D TiO2 nanorods showed an efficiency of 15.5% with VOC = 1.02 V, JSC = 20.0 mA cm(-2) and fill factor = 76.1%. Thus, TiO2 nanostructures fabricated from BCP nanotemplates could be applied to the preparation of electron transport layers for improving the efficiency of perovskite solar cells.

Compositional and Interfacial Modification of Cu2 ZnSn(S,Se)4 Thin-Film Solar Cells Prepared by Electrochemical Deposition.

A highly efficient Cu2 ZnSn(S,Se)4 (CZTSSe)-based thin-film solar cell (9.9%) was prepared using an electrochemical deposition method followed by thermal annealing. The Cu-Zn-Sn alloy films was grown on a Mo-coated glass substrate using a one-pot electrochemical deposition process, and the metallic precursor films was annealed under a mixed atmosphere of S and Se to form CZTSSe thin films with bandgap energies ranging from 1.0 to 1.2 eV. The compositional modification of the S/(S+Se) ratio shows a trade-off effect between the photocurrent and photovoltage, resulting in an optimum bandgap of roughly 1.14 eV. In addition, the increased S content near the p-n junction reduces the dark current and interface recombination, resulting in a further enhancement of the open-circuit voltage. As a result of the compositional and interfacial modification, the best CZTSSe-based thin-film solar cell exhibits a conversion efficiency of 9.9%, which is among the highest efficiencies reported so far for electrochemically deposited CZTSSe-based thin-film solar cells.

Effect of multi-armed triphenylamine-based hole transporting materials for high performance perovskite solar cells.

A series of hole-transporting materials (HTMs) based on [2,2]paracyclophane and triphenyl-amine (TPA) was synthesized. We studied the effect of the chemical structure of the HTM on the photovoltaic performance of perovskite solar cells by varying the number of TPA charge transporting components in the HTM. Tetra-TPA, in which four TPAs are incorporated into the [2,2]paracyclophane core, exhibited better hole transport properties than di-TPA and tri-TPA, which contain two and three TPAs, respectively. In particular, incorporation of the TPA group with a multi-armed structure effectively enhanced the conductivity of the HTM layer in the out-of-plane direction in the solar cell device. Due to the improved charge transport and appropriate molecular energy levels of tetra-TPA, the perovskite solar cell based on the tetra-TPA HTM achieved higher Jsc and FF values than the devices based on di-TPA and tri-TPA HTMs, with a high solar cell efficiency (17.9%).

Enhancement of charge transport properties of small molecule semiconductors by controlling fluorine substitution and effects on photovoltaic properties of organic solar cells and perovskite solar cells.

We prepared a series of small molecules based on 7,7'-(4,4-bis(2-ethylhexyl)-4H-silolo[3,2-b:4,5-b']dithiophene-2,6-diyl)bis(4-(5'-hexyl-[2,2'-bithiophene]-5-yl)benzo[c][1,2,5]thiadiazole) with different fluorine substitution patterns (0F-4F). Depending on symmetricity and numbers of fluorine atoms incorporated in the benzo[c][1,2,5]thiadiazole unit, they show very different optical and morphological properties in a film. 2F and 4F, which featured symmetric and even-numbered fluorine substitution patterns, display improved molecular packing structures and higher crystalline properties in a film compared with 1F and 3F and thus, 2F achieved the highest OTFT mobility, which is followed by 4F. In the bulk heterojunction solar cell fabricated with PC71BM, 2F achieves the highest photovoltaic performance with an 8.14% efficiency and 0F shows the lowest efficiency of 1.28%. Moreover, the planar-type perovskite solar cell (PSC) prepared with 2F as a dopant-free hole transport material shows a high power conversion efficiency of 14.5% due to its high charge transporting properties, which were significantly improved compared with the corresponding PSC device obtained from 0F (8.5%). From the studies, it is demonstrated that low variation in the local dipole moment and the narrow distribution of 2F conformers make intermolecular interactions favorable, which may effectively drive crystal formations in the solid state and thus, higher charge transport properties compared with 1F and 3F.

Highly Efficient Copper-Indium-Selenide Quantum Dot Solar Cells: Suppression of Carrier Recombination by Controlled ZnS Overlayers.

Copper-indium-selenide (CISe) quantum dots (QDs) are a promising alternative to the toxic cadmium- and lead-chalcogenide QDs generally used in photovoltaics due to their low toxicity, narrow band gap, and high absorption coefficient. Here, we demonstrate that the photovoltaic performance of CISe QD-sensitized solar cells (QDSCs) can be greatly enhanced simply by optimizing the thickness of ZnS overlayers on the QD-sensitized TiO2 electrodes. By roughly doubling the thickness of the overlayers compared to the conventional one, conversion efficiency is enhanced by about 40%. Impedance studies reveal that the thick ZnS overlayers do not affect the energetic characteristics of the photoanode, yet enhance the kinetic characteristics, leading to more efficient photovoltaic performance. In particular, both interfacial electron recombination with the electrolyte and nonradiative recombination associated with QDs are significantly reduced. As a result, our best cell yields a conversion efficiency of 8.10% under standard solar illumination, a record high for heavy metal-free QD solar cells to date.

A highly planar fluorinated benzothiadiazole-based conjugated polymer for high-performance organic thin-film transistors.

High-mobility and low-voltage-operated organic field-effect transistors (OFETs) are demonstrated by the design of a new fluorinated benzothiadiazole-based conjugated polymer with fluorinated high-k polymer dielectrics. A record-breaking high hole mobility of 9.0 cm(2) V(-1) s(-1) for benzothiadiazole-based semiconducting polymers is achieved by the excellent planarity of the semiconducting polymer.

High performance of low band gap polymer-based ambipolar transistor using single-layer graphene electrodes.

Bottom-contact bottom-gate organic field-effect transistors (OFETs) are fabricated using a low band gap pDTTDPP-DT polymer as a channel material and single-layer graphene (SLG) or Au source/drain electrodes. The SLG-based ambipolar OFETs significantly outperform the Au-based ambipolar OFETs, and thermal annealing effectively improves the carrier mobilities of the pDTTDPP-DT films. The difference is attributed to the following facts: (i) the thermally annealed pDTTDPP-DT chains on the SLG assume more crystalline features with an edge-on orientation as compared to the polymer chains on the Au, (ii) the morphological features of the thermally annealed pDTTDPP-DT films on the SLG electrodes are closer to the features of those on the gate dielectric layer, and (iii) the SLG electrode provides a flatter, more hydrophobic surface that is favorable for the polymer crystallization than the Au. In addition, the preferred carrier transport in each electrode-based OFET is associated with the HOMO/LUMO alignment relative to the Fermi level of the employed electrode. All of these experimental results consistently explain why the carrier mobilities of the SLG-based OFET are more than 10 times higher than those of the Au-based OTFT. This work demonstrates the strong dependence of ambipolar carrier transport on the source/drain electrode and annealing temperature.

Tailoring of energy levels in D-π-A organic dyes via fluorination of acceptor units for efficient dye-sensitized solar cells.

A molecular design is presented for tailoring the energy levels in D-π-A organic dyes through fluorination of their acceptor units, which is aimed at achieving efficient dye-sensitized solar cells (DSSCs). This is achieved by exploiting the chemical structure of common D-π-A organic dyes and incorporating one or two fluorine atoms at the ortho-positions of the cyanoacetic acid as additional acceptor units. As the number of incorporated fluorine atoms increases, the LUMO energy level of the organic dye is gradually lowered due to the electron-withdrawing effect of fluorine, which ultimately results in a gradual reduction of the HOMO-LUMO energy gap and an improvement in the spectral response. Systematic investigation of the effects of incorporating fluorine on the photovoltaic properties of DSSCs reveals an upshift in the conduction-band potential of the TiO2 electrode during impedance analysis; however, the incorporation of fluorine also results in an increased electron recombination rate, leading to a decrease in the open-circuit voltage (Voc). Despite this limitation, the conversion efficiency is gradually enhanced as the number of incorporated fluorine atoms is increased, which is attributed to the highly improved spectral response and photocurrent.