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

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

Effect of Electron-Withdrawing Chlorine Substituent on Morphological and Photovoltaic Properties of All Chlorinated D-A-Type Quinoxaline-Based Polymers.

The choice of the chlorine (Cl) atom as an electron-withdrawing substituent in conjugated polymers leads to a higher potential in the commercialization of polymer solar cells than its fluorine counterpart because of the versatility and cost-effectiveness of the chlorination process. In addition, the population and location of Cl substituents can significantly influence the photovoltaic characteristics of polymers. In this study, three chlorinated quinoxaline-based polymers were invented to examine the numerical and positioning effects of the Cl atom on their photovoltaic characteristics. The number of Cl substituents in the reference polymer, PBCl-Qx, was adjusted to three: two Cl atoms in the benzodithiophene-type D unit and one Cl atom in the quinoxaline-type A unit. Subsequently, two more Cl atoms were selectively introduced at the 4- and 5-positions of the alkylated thiophene moieties at the 2,3-positions of the quinoxaline moiety in PBCl-Qx to obtain the additional polymers PBCl-Qx4Cl and PBCl-Qx5Cl, respectively. The conventional PBCl-Qx4Cl device exhibited a better power conversion efficiency (PCE) of 12.95% as compared to those of PBCl-Qx (12.44%) and PBCl-Qx5Cl (11.82%) devices. The highest PCE of the device with PBCl-Qx4Cl was ascribed to an enhancement in the open-circuit voltage and fill factor induced by the deeper energy level of the highest occupied molecular orbital and the favorable morphological features in its blended film with Y6.

The role of charge recombination to triplet excitons in organic solar cells.

The use of non-fullerene acceptors (NFAs) in organic solar cells has led to power conversion efficiencies as high as 18%1. However, organic solar cells are still less efficient than inorganic solar cells, which typically have power conversion efficiencies of more than 20%2. A key reason for this difference is that organic solar cells have low open-circuit voltages relative to their optical bandgaps3, owing to non-radiative recombination4. For organic solar cells to compete with inorganic solar cells in terms of efficiency, non-radiative loss pathways must be identified and suppressed. Here we show that in most organic solar cells that use NFAs, the majority of charge recombination under open-circuit conditions proceeds via the formation of non-emissive NFA triplet excitons; in the benchmark PM6:Y6 blend5, this fraction reaches 90%, reducing the open-circuit voltage by 60 mV. We prevent recombination via this non-radiative channel by engineering substantial hybridization between the NFA triplet excitons and the spin-triplet charge-transfer excitons. Modelling suggests that the rate of back charge transfer from spin-triplet charge-transfer excitons to molecular triplet excitons may be reduced by an order of magnitude, enabling re-dissociation of the spin-triplet charge-transfer exciton. We demonstrate NFA systems in which the formation of triplet excitons is suppressed. This work thus provides a design pathway for organic solar cells with power conversion efficiencies of 20% or more.

Effective Dark Current Suppression for High-Detectivity Organic Near-Infrared Photodetectors Using a Non-Fullerene Acceptor.

Near-infrared organic photodetectors (NIR OPDs) have attracted considerable attention because of their inherent advantages such as a tailorable light absorption property, low-cost fabrication, compatibility with flexible substrates, and room-temperature operation. In particular, the development of NIR detection between 900 and 950 nm is crucial for noise-free communication in ambient environments. In this work, we demonstrate high-detectivity NIR OPDs at 900-950 nm by employing a non-fullerene acceptor (ITIC) used with an NIR-absorbing conjugated polymer (PNIR) for bulk heterojunction (BHJ), which significantly suppressed dark current. Systemic characterizations including electrical, structural, and morphological analyses revealed that ITIC effectively reduces charge recombination during the operation of the OPDs under NIR illumination, resulting in a dark current reduction and high detectivity of over 3.2 × 1011 Jones at 900-950 nm. The results presented here demonstrate that utilizing a non-fullerene acceptor for BHJ-type NIR OPDs is evidently a strategic approach for the simultaneous achievement of the low dark current and high-detectivity of NIR OPDs.

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

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

Composite Interlayer Consisting of Alcohol-Soluble Polyfluorene and Carbon Nanotubes for Efficient Polymer Solar Cells.

We report the synthesis of composite interlayers using alcohol-soluble polyfluorene (ASP)-wrapped single-walled carbon nanotubes (SWNTs) and their application as electron-transport layers for efficient organic solar cells. The ASP enables the individual dispersion of SWNTs in solution. The ASP-wrapped SWNT solutions are stable for 54 days without any aggregation or precipitation, indicating their very high dispersion stability. Using the ASP-wrapped SWNTs as a cathode interlayer on zinc oxide nanoparticles (ZnO NPs), a power conversion efficiency of 9.45% is obtained in PTB7-th:PC71BM-based organic solar cells, which is mainly attributed to the improvement in the short circuit current. Performance enhancements of 18 and 17% are achieved compared to those of pure ZnO NPs and ASP on ZnO NPs, respectively. In addition, the composite interlayer is applied to non-fullerene-based photovoltaics with PM6:Y6, resulting in a power conversion efficiency of up to 14.37%. The type of SWNT (e.g., in terms of diameter range and length) is not critical to the improvement in the charge-transport properties. A low density of SWNTs in the film (∼1 SWNTs/µm2 for ASP-wrapped SWNTs) has a significant influence on the charge transport in solar cells. The improvement in the performance of the solar cell is attributed to the increased internal quantum efficiency, balanced mobility between electrons and holes, and minimized charge recombination.

Solution-Processed Semitransparent Organic Photovoltaics: From Molecular Design to Device Performance.

Recent research efforts on solution-processed semitransparent organic solar cells (OSCs) are presented. Essential properties of organic donor:acceptor bulk heterojunction blends and electrode materials, required for the combination of simultaneous high power conversion efficiency (PCE) and average visible transmittance of photovoltaic devices, are presented from the materials science and device engineering points of view. Aspects of optical perception, charge generation-recombination, and extraction processes relevant for semitransparent OSCs are also discussed in detail. Furthermore, the theoretical limits of PCE for fully transparent OSCs, compared to the performance of the best reported semitransparent OSCs, and options for further optimization are discussed.

Morphological and Optical Engineering for High-Performance Polymer Solar Cells.

We demonstrate morphological and optical engineering by using processing additives and optical spacers for polymer solar cells. Among various processing additives, introduction of diphenyl ether (DPE) into the active layer results in the smoothest surface roughness with uniform and well-distributed donor/acceptor domains, and the device with DPE shows the highest device efficiency of 10.22% due to enhanced charge collection efficiency and minimized recombination loss. Additional ZnO optical spacers on the active layer controls the distribution of the electric field in the whole device and enhances the light absorption within the active layer, thereby improving device efficiency up to 10.81%.

Capillary Printing of Highly Aligned Silver Nanowire Transparent Electrodes for High-Performance Optoelectronic Devices.

Percolation networks of silver nanowires (AgNWs) are commonly used as transparent conductive electrodes (TCEs) for a variety of optoelectronic applications, but there have been no attempts to precisely control the percolation networks of AgNWs that critically affect the performances of TCEs. Here, we introduce a capillary printing technique to precisely control the NW alignment and the percolation behavior of AgNW networks. Notably, partially aligned AgNW networks exhibit a greatly lower percolation threshold, which leads to the substantial improvement of optical transmittance (96.7%) at a similar sheet resistance (19.5 Ω sq(-1)) as compared to random AgNW networks (92.9%, 20 Ω sq(-1)). Polymer light-emitting diodes (PLEDs) using aligned AgNW electrodes show a 30% enhanced maximum luminance (33068 cd m(-2)) compared to that with random AgNWs and a high luminance efficiency (14.25 cd A(-1)), which is the highest value reported so far using indium-free transparent electrodes for fluorescent PLEDs. In addition, polymer solar cells (PSCs) using aligned AgNW electrodes exhibit a power conversion efficiency (PCE) of 8.57%, the highest value ever reported to date for PSCs using AgNW electrodes.

Small-bandgap polymer solar cells with unprecedented short-circuit current density and high fill factor.

Small-bandgap polymer solar cells (PSCs) with a thick bulk heterojunction film of 340 nm exhibit high power conversion efficiencies of 9.40% resulting from high short-circuit current density (JSC ) of 20.07 mA cm(-2) and fill factor of 0.70. This remarkable efficiency is attributed to maximized light absorption by the thick active layer and minimized recombination by the optimized lateral and vertical morphology through the processing additive.

An organic surface modifier to produce a high work function transparent electrode for high performance polymer solar cells.

Modification of an ITO electrode with small-molecule organic surface modifier, 4-chloro-benzoic acid (CBA), via a simple spin-coating method produces a high-work-function electrode with high transparency and a hydrophobic surface. As an alternative to PEDOT:PSS, CBA modification achieves efficiency enhancement up to 8.5%, which is attributed to enhanced light absorption within the active layer and smooth hole transport from the active layer to the anode.

Optimal top electrodes for inverted polymer solar cells.

Although polymer solar cells (PSCs) have received a tremendous amount of attention in recent years, a number of criteria must be met in order for them to be suitable as practical and commercially feasible power sources, including high performance, good air stability and inexpensive manufacturing. In this contribution, we determine the optimal top electrode for practical PSC fabrication by investigating the influence of the electrode material on the optical properties and performance of PSC devices. The optical properties of eight metals were considered, out of which three metal electrodes (aluminum (Al), silver (Ag), gold (Au)) with the best optical properties were used to prepare inverted PSC devices comprising a blended polymer thieno[3,4-b]thiophene/benzodithiophene (PTB7) and [6,6]-phenyl C71-butyric acid methyl ester (PC71BM). Among the photovoltaic parameters, the short circuit current density (JSC) was most strongly affected by the optical properties of the top electrode. In the results of the experiment, the J(SC) of the Al and Ag electrode devices was found to be approximately 13% (13.4 → 15.1 mA cm(-2)) higher than the Au electrode device due to the significant parasitic absorption of light by Au at wavelengths below 600 nm. In contrast, Al and Ag electrodes have high reflectance throughout the visible spectrum, which leads to high J(SC). Ag electrodes have relatively good stability to ambient exposure, maintaining over 96% of the original efficiency after 170 hours; this stability is comparable to Au. These data lead to the conclusion that Ag is the optimal top electrode material for use in inverted devices.

Size tailoring of aqueous germanium nanoparticle dispersions.

We demonstrate a practical route to synthesize Ge nanoparticles (NPs) in multi-gram quantities via the laser pyrolysis of GeH4 gas. The size of the as-produced Ge NPs can be precisely controlled in the range of 19.0 to 65.9 nm via a subsequent etching procedure using a dilute H2O2 solution. Stable water dispersions of Ge NPs yield particles with a Ge/GeO2 core-shell structure, however, the oxide shell can easily be removed and passivated by treatment with HCl. The feed materials used in this process are readily available and lead to non-toxic, water-based dispersions of Ge NPs. The scalability and convenience of this procedure make it attractive as a method to obtain Ge NP dispersions for use in applications such as optoelectronic devices and biosensors.

Synthesis of PCDTBT-based fluorinated polymers for high open-circuit voltage in organic photovoltaics: towards an understanding of relationships between polymer energy levels engineering and ideal morphology control.

The introduction of fluorine (F) atoms onto conjugated polymer backbone has verified to be an effective way to enhance the overall performance of polymer-based bulk-heterojunction (BHJ) solar cells, but the underlying working principles are not yet fully uncovered. As our attempt to further understand the impact of F, herein we have reported two novel fluorinated analogues of PCDTBT, namely, PCDTFBT (1F) and PCDT2FBT (2F), through inclusion of either one or two F atoms into the benzothiadiazole (BT) unit of the polymer backbone and the characterization of their physical properties, especially their performance in solar cells. Together with a profound effect of fluorination on the optical property, nature of charge transport, and molecular organization, F atoms are effective in lowering both the HOMO and LUMO levels of the polymers without a large change in the energy bandgaps. PCDTFBT-based BHJ solar cell shows a power conversion efficiency (PCE) of 3.96 % with high open-circuit voltage (VOC) of 0.95 V, mainly due to the deep HOMO level (-5.54 eV). To the best of our knowledge, the resulting VOC is comparable to the record VOC values in single junction devices. Furthermore, to our delight, the best PCDTFBT-based device, prepared using 2 % v/v diphenyl ether (DPE) additive, reaches the PCE of 4.29 %. On the other hand, doubly-fluorinated polymer PCDT2FBT shows the only moderate PCE of 2.07 % with a decrease in VOC (0.88 V), in spite of the further lowering of the HOMO level (-5.67 eV) with raising the number of F atoms. Thus, our results highlight that an improvement in efficiency by tuning the energy levels of the polymers by means of molecular design can be expected only if their truly optimized morphologies with fullerene in BHJ systems are materialized.

Vapor coating method using small-molecule organic surface modifiers to replace N-type metal oxide layers in inverted polymer solar cells.

We investigate a simple fabrication method for vapor coating small-molecule organic interlayers as replacements for metal oxide films. The interfacial layers, which serve both as both surface modifiers to reduce the substrate work function and electron selective layers, maximize light absorption within the active layer while improving electron transport and compatibility between the active layer and cathode, leading to a ∼22% enhancement in power conversion efficiency and similar air stability compared to devices using a ZnO layer.

Amine-based polar solvent treatment for highly efficient inverted polymer solar cells.

The interfacial dipolar polarization in inverted structure polymer solar cells, which arises spontaneously from the absorption of ethanolamine end groups, such as amine and hydroxyl groups on ripple-structure zinc oxide (ZnO-R), lowers the contact barrier for electron transport and extraction and leads to enhanced electron mobility, suppression of bimolecular recombination, reduction of the contact resistance and series resistance, and remarkable enhancement of the power conversion efficiency.

Redox-active charge carriers of conducting polymers as a tuner of conductivity and its potential window.

Electric conductivity of conducting polymers has been steadily enhanced towards a level worthy of being called its alias, "synthetic metal". PEDOT:PSS (poly(3,4-ethylenedioxythiophene) doped with poly(styrene sulfonate)), as a representative conducting polymer, recently reached around 3,000 S cm(-1), the value to open the possibility to replace transparent conductive oxides. The leading strategy to drive the conductivity increase is solvent annealing in which aqueous solution of PEDOT:PSS is treated with an assistant solvent such as DMSO (dimethyl sulfoxide). In addition to the conductivity enhancement, we found that the potential range in which PEDOT:PSS is conductive is tuned wider into a negative potential direction by the DMSO-annealing. Also, the increase in a redox-active fraction of charge carriers is proposed to be responsible for the enhancement of conductivity in the solvent annealing process.

Multipositional silica-coated silver nanoparticles for high-performance polymer solar cells.

We demonstrate high-performance polymer solar cells using the plasmonic effect of multipositional silica-coated silver nanoparticles. The location of the nanoparticles is critical for increasing light absorption and scattering via enhanced electric field distribution. The device incorporating nanoparticles between the hole transport layer and the active layer achieves a power conversion efficiency of 8.92% with an external quantum efficiency of 81.5%. These device efficiencies are the highest values reported to date for plasmonic polymer solar cells using metal nanoparticles.

Highly efficient polymer light-emitting diodes using graphene oxide as a hole transport layer.

We present an investigation of polymer light-emitting diodes (PLEDs) with a solution-processable graphene oxide (GO) interlayer. The GO layer with a wide band gap blocks electron transport from an emissive polymer to an ITO anode while reducing the exciton quenching between the GO and the active layer in place of poly(styrenesulfonate)-doped poly(3,4-ethylenedioxythiophene) (PEDOT:PSS). This GO interlayer maximizes hole-electron recombinations within the emissive layer, finally enhancing device performance and efficiency levels in PLEDs. It was found that the thickness of the GO layer is an important factor in device performance. PLEDs with a 4.3 nm thick GO interlayer are superior to both those with PEDOT:PSS layers as well as those with rGO, showing maximum luminance of 39 000 Cd/m(2), maximum luminous efficiencies of 19.1 Cd/A (at 6.8 V), and maximum power efficiency as high as 11.0 lm/W (at 4.4 V). This indicates that PLEDs with a GO layer show a 220% increase in their luminous efficiency and 280% increase in their power conversion efficiency compared to PLEDs with PEDOT:PSS.

Multifunctional conjugated polymers with main-chain donors and side-chain acceptors for dye sensitized solar cells (DSSCs) and organic photovoltaic cells (OPVs).

A novel multifunctional conjugated polymer (RCP-1) composed of an electron-donating backbone (carbazole) and an electron-accepting side chain (cyanoacetic acid) connected through conjugated vinylene and terthiophene has been synthesized and tested as a photosensitizer in two major molecule-based solar cells, namely dye sensitized solar cells (DSSCs) and organic photovoltaic cells (OPVs). Promising initial results on overall power conversion efficiencies of 4.11% and 1.04% are obtained from the basic structure of DSSCs and OPVs based on RCP-1, respectively. The well-defined donor (D)-acceptor (A) structure of RCP-1 has made it possible, for the first time, to reach over 4% of power conversion efficiency in DSSCs with an organic polymer sensitizer and good operation stability.