Cold-Trap-Mediated Broad Dynamic Photodetection in Graphene-Organic Hybrid Photonic Barristors.

One of the most popular approaches to improve the performance of organic photonic devices has been to control the electrically heterogeneous charge-transferring interfaces via chemical modifications. Despite intense research efforts, however, the rapid pace of material evolution through the chemical versatility of the organic compound allows only limited room for the fine-tuning of the interfaces exclusive to specific materials. This limitation leads to an ill-controlled charge recombination behavior that relies solely on the inherent characteristics of each material; thus, the common device architecture cannot harness its full potential. In this work, we demonstrate the use of a graphene-organic hybrid barristor-type phototriode architecture as an alternative platform to realize a linearly and highly photosensitive photodetector operating in a broad dynamic range with rapid temporal responses. With the capability of interfacial energetic modulation, our model system exhibits the dominance of swiftly saturable and slowly responding "cold" traps (TC < 3kT) in charge recombination behaviors, leading to a broad linear dynamic range of 110 dB as well as unconventional illumination-driven increments of both D* and R up to 1013 Jones and 360 mA/W, respectively, that surpass the best-reported organic photodiodes. Our findings demonstrate that the organic-graphene hybrid photonic barristor architecture can open new avenues to design high-performance photodetectors for various photonic applications in the future.

Percolation-Limited Dual Charge Transport in Vertical p-n Heterojunction Schottky Barrier Transistors.

Solution-processed, high-speed, and polarity-selective organic vertical Schottky barrier (SB) transistors and logic gates are presented. The organic layer, which is a bulk heterojunction (BHJ) composed of PBDB-T and PC71BM, is employed to simultaneously realize vertical electron and hole transports through the separate p-channel and n-channel. The gate-modulated graphene work functions enable broad modulation of SB heights at both the graphene-PBDB-T and graphene-PC71BM heterointerfaces. Interestingly, the fine-tuned energy-level alignment enables an exclusive injection of holes or electrons unlike conventional BHJ-based ambipolar transistors, leading to a clear transition between p-channel and n-channel single-carrier-like transistor characteristics. Furthermore, the improved percolation-limited dual charge transport in vertical architecture results in high charge carrier density and high-speed on-off switching characteristics, providing a high on-off current ratio exceeding 105 and an operation speed of 100 kHz. Solution-based on-substrate fabrications of low-power complementary logic gates such as NOT, NOR, and NAND are also successfully performed.

Overcoming the Photovoltage Plateau in Large Bandgap Perovskite Photovoltaics.

Development of large bandgap (1.80-1.85 eV Eg) perovskite is crucial for perovskite-perovskite tandem solar cells. However, the performance of 1.80-1.85 eV Eg perovskite solar cells (PVKSCs) are significantly lagging their counterparts in the 1.60-1.75 eV Eg range. This is because the photovoltage ( Voc) does not proportionally increase with Eg due to lower optoelectronic quality of conventional (MA,FA,Cs)Pb(I,Br)3 and results in a photovoltage plateau ( Voc limited to 80% of the theoretical limit for ∼1.8 eV Eg). Here, we incorporate phenylethylammonium (PEA) in a mixed-halide perovskite composition to solve the inherent material-level challenges in 1.80-1.85 eV Eg perovskites. The amount of PEA incorporation governs the topography and optoelectronic properties of resultant films. Detailed structural and spectroscopic characterization reveal the characteristic trends in crystalline size, orientation, and charge carrier recombination dynamics and rationalize the origin of improved material quality with higher luminescence. With careful interface optimization, the improved material characteristics were translated to devices and Voc values of 1.30-1.35 V were achieved, which correspond to 85-87% of the theoretical limit. Using an optimal amount of PEA incorporation to balance the increase in Voc and the decrease in charge collection, a highest power conversion efficiency of 12.2% was realized. Our results clearly overcome the photovoltage plateau in the 1.80-1.85 eV Eg range and represent the highest Voc achieved for mixed-halide PVKSCs. This study provides widely translatable insights, an important breakthrough, and a promising platform for next-generation perovskite tandems.

Long-Lived, Non-Geminate, Radiative Recombination of Photogenerated Charges in a Polymer/Small-Molecule Acceptor Photovoltaic Blend.

Minimization of open-circuit-voltage ( VOC) loss is required to transcend the efficiency limitations on the performance of organic photovoltaics (OPV). We study charge recombination in an OPV blend comprising a polymer donor with a small molecule nonfullerene acceptor that exhibits both high photovoltaic internal quantum efficiency and relatively high external electroluminescence quantum efficiency. Notably, this donor/acceptor blend, consisting of the donor polymer commonly referred to as PCE10 with a pseudoplanar small molecule acceptor (referred to as FIDTT-2PDI) exhibits relatively bright delayed photoluminescence on the microsecond time scale beyond that observed in the neat material. We study the photoluminescence decay kinetics of the blend in detail and conclude that this long-lived photoluminescence arises from radiative nongeminate recombination of charge carriers, which we propose occurs via a donor/acceptor CT state located close in energy to the singlet state of the polymer donor. Additionally, crystallographic and spectroscopic studies point toward low subgap disorder, which could be beneficial for low radiative and nonradiative losses. These results provide an important demonstration of photoluminescence due to nongeminate charge recombination in an efficient OPV blend, a key step in identifying new OPV materials and materials-screening criteria if OPV is to approach the theoretical limits to efficiency.

Stabilized Wide Bandgap Perovskite Solar Cells by Tin Substitution.

Wide bandgap MAPb(I1-yBry)3 perovskites show promising potential for application in tandem solar cells. However, unstable photovoltaic performance caused by phase segregation has been observed under illumination when y is above 0.2. Herein, we successfully demonstrate stabilization of the I/Br phase by partially replacing Pb2+ with Sn2+ and verify this stabilization with X-ray diffractometry and transient absorption spectroscopy. The resulting MAPb0.75Sn0.25(I1-yBry)3 perovskite solar cells show stable photovoltaic performance under continuous illumination. Among these cells, the one based on MAPb0.75Sn0.25(I0.4Br0.6)3 perovskite shows the highest efficiency of 12.59% with a bandgap of 1.73 eV, which make it a promising wide bandgap candidate for application in tandem solar cells. The engineering of internal bonding environment by partial Sn substitution is believed to be the main reason for making MAPb0.75Sn0.25(I1-yBry)3 perovskite less vulnerable to phase segregation during the photostriction under illumination. Therefore, this study establishes composition engineering of the metal site as a promising strategy to impart phase stability in hybrid perovskites under illumination.

Rational Design of Dipolar Chromophore as an Efficient Dopant-Free Hole-Transporting Material for Perovskite Solar Cells.

In this paper, an electron donor-acceptor (D-A) substituted dipolar chromophore (BTPA-TCNE) is developed to serve as an efficient dopant-free hole-transporting material (HTM) for perovskite solar cells (PVSCs). BTPA-TCNE is synthesized via a simple reaction between a triphenylamine-based Michler's base and tetracyanoethylene. This chromophore possesses a zwitterionic resonance structure in the ground state, as evidenced by X-ray crystallography and transient absorption spectroscopies. Moreover, BTPA-TCNE shows an antiparallel molecular packing (i.e., centrosymmetric dimers) in its crystalline state, which cancels out its overall molecular dipole moment to facilitate charge transport. As a result, BTPA-TCNE can be employed as an effective dopant-free HTM to realize an efficient (PCE ≈ 17.0%) PVSC in the conventional n-i-p configuration, outperforming the control device with doped spiro-OMeTAD HTM.

Atomically thin epitaxial template for organic crystal growth using graphene with controlled surface wettability.

A two-dimensional epitaxial growth template for organic semiconductors was developed using a new method for transferring clean graphene sheets onto a substrate with controlled surface wettability. The introduction of a sacrificial graphene layer between a patterned polymeric supporting layer and a monolayer graphene sheet enabled the crack-free and residue-free transfer of free-standing monolayer graphene onto arbitrary substrates. The clean graphene template clearly induced the quasi-epitaxial growth of crystalline organic semiconductors with lying-down molecular orientation while maintaining the "wetting transparency", which allowed the transmission of the interaction between organic molecules and the underlying substrate. Consequently, the growth mode and corresponding morphology of the organic semiconductors on graphene templates exhibited distinctive dependence on the substrate hydrophobicity with clear transition from lateral to vertical growth mode on hydrophilic substrates, which originated from the high surface energy of the exposed crystallographic planes of the organic semiconductors on graphene. The optical properties of the pentacene layer, especially the diffusion of the exciton, also showed a strong dependency on the corresponding morphological evolution. Furthermore, the effect of pentacene-substrate interaction was systematically investigated by gradually increasing the number of graphene layers. These results suggested that the combination of a clean graphene surface and a suitable underlying substrate could serve as an atomically thin growth template to engineer the interaction between organic molecules and aromatic graphene network, thereby paving the way for effectively and conveniently tuning the semiconductor layer morphologies in devices prepared using graphene.

Graphene barristors for de novo optoelectronics.

Graphene-based vertical Schottky-barrier transistors (SBTs), renowned as graphene barristors, have emerged as a feasible candidate to fundamentally expand the horizon of conventional transistor technology. The remote tunability of graphene's electronic properties could endorse multi-stimuli responsive functionalities for a broad range of electronic and optoelectronic applications of transistors, with the capability of incorporating nanochannel architecture with dramatically reduced footprints from the vertical integrations. In this Feature Article, we provide a comprehensive overview of the progress made in the field of SBTs over the last 10 years, starting from the operating principles, materials evolution, and processing developments. Depending on the types of stimuli such as electrical, optical, and mechanical stresses, various fields of applications from conventional digital logic circuits to sensory technologies are highlighted. Finally, more advanced applications toward beyond-Moore electronics are discussed, featuring recent advancements in neuromorphic devices based on SBTs.

Monolithic Tandem Vertical Electrochemical Transistors for Printed Multi-Valued Logic.

Organic electrochemical transistors (OECTs) have recently emerged as a feasible candidate to realize the next generation of printable electronics. Especially, their chemical versatility and the unique redox-based operating principle have provided new possibilities in high-functioning logic circuitry beyond the traditional binary Boolean logic. Here, a simple strategy to electrochemically realize monolithic multi-valued logic transistors is presented, which is one of the most promising branches of transistor technology in the forthcoming era of hyper Moore's law. A vertically stacked heterogeneous dual-channel architecture is introduced with a patterned reference electrode, which enables a facile manifestation of stable and equiprobable ternary logic states with a reduced transistor footprint. The dual-ion-penetration mechanism coupled with ultrashort vertical channel even allows a very-high accessing frequency to multiple logic states reaching over 10 MHz. Furthermore, printed arrays of ternary logic gates with full voltage swing within 1 V are demonstrated.

Multiplexed Complementary Signal Transmission for a Self-Regulating Artificial Nervous System.

Neuromorphic engineering has emerged as a promising research field that can enable efficient and sophisticated signal transmission by mimicking the biological nervous system. This paper presents an artificial nervous system capable of facile self-regulation via multiplexed complementary signals. Based on the tunable nature of the Schottky barrier of a complementary signal integration circuit, a pair of complementary signals is successfully integrated to realize efficient signal transmission. As a proof of concept, a feedback-based blood glucose level control system is constructed by incorporating a glucose/insulin sensor, a complementary signal integration circuit, an artificial synapse, and an artificial neuron circuit. Certain amounts of glucose and insulin in the initial state are detected by each sensor and reflected as positive and negative amplitudes of the multiplexed presynaptic pulses, respectively. Subsequently, the pulses are converted to postsynaptic current, which triggered the injection of glucose or insulin in a way that confined the glucose level to a desirable range. The proposed artificial nervous system demonstrates the notable potential of practical advances in complementary control engineering.

Approaching Theoretical Limits in the Performance of Printed P-Type CuI Transistors via Room Temperature Vacancy Engineering.

Development of a novel high performing inorganic p-type thin film transistor could pave the way for new transparent electronic devices. This complements the widely commercialized n-type counterparts, indium-gallium-zinc-oxide (IGZO). Of the few potential candidates, copper monoiodide (CuI) stands out. It boasts visible light transparency and high intrinsic hole mobility (>40 cm2 V-1 s-1 ), and is suitable for various low-temperature processes. However, the performance of reported CuI transistors is still below expected mobility, mainly due to the uncontrolled excess charge- and defect-scattering from thermodynamically favored formation of copper and iodine vacancies. Here, a solution-processed CuI transistor with a significantly improved mobility is reported. This enhancement is achieved through a room-temperature vacancy-engineering processing strategy on high-k dielectrics, sodium-embedded alumina. A thorough set of chemical, structural, optical, and electrical analyses elucidates the processing-dependent vacancy-modulation and its corresponding transport mechanism in CuI. This encompasses defect- and phonon-scattering, as well as the delocalization of charges in crystalline domains. As a result, the optimized CuI thin film transistors exhibit exceptionally high hole mobility of 21.6 ± 4.5 cm2 V-1 s-1 . Further, the successful operation of IGZO-CuI complementary logic gates confirms the applicability of the device.

Humanlike spontaneous motion coordination of robotic fingers through spatial multi-input spike signal multiplexing.

With advances in robotic technology, the complexity of control of robot has been increasing owing to fundamental signal bottlenecks and limited expressible logic state of the von Neumann architecture. Here, we demonstrate coordinated movement by a fully parallel-processable synaptic array with reduced control complexity. The synaptic array was fabricated by connecting eight ion-gel-based synaptic transistors to an ion gel dielectric. Parallel signal processing and multi-actuation control could be achieved by modulating the ionic movement. Through the integration of the synaptic array and a robotic hand, coordinated movement of the fingers was achieved with reduced control complexity by exploiting the advantages of parallel multiplexing and analog logic. The proposed synaptic control system provides considerable scope for the advancement of robotic control systems.

Enhancing Efficiency and Stability of Tin Halide Perovskite Light-Emitting Diodes via Engineered Alkali/Multivalent Metal Salts.

Sn-based perovskite light-emitting diodes (PeLEDs) have emerged as promising alternatives to Pb-based PeLEDs with their rapid increase in performance owing to the various research studies on inhibiting Sn oxidation. However, the absence of defect passivation strategies for Sn-based perovskite LEDs necessitates further research in this field. We performed systematic studies to investigate the design rules for defect passivation agents for Sn-based perovskites by incorporating alkali/multivalent metal salts with various cations and anions. From the computational and experimental analyses, sodium trifluoromethanesulfonate (NaTFMS) was found to be the most effective passivation agent for PEA2SnI4 films among the explored candidate agents owing to favorable reaction energetics to passivate iodide Frenkel defects. Consequently, the incorporation of NaTFMS facilitates the formation of uniform films with relatively large crystals and reduced Sn4+. The NaTFMS-containing PEA2SnI4 PeLEDs demonstrate an improved luminance of 138.9 cd/m2 and external quantum efficiency (EQE) of 0.39% with an improved half-lifetime of more than threefold. This work provides important insight into the design of defect passivation agents for Sn-based perovskites.

A general fruit acid chelation route for eco-friendly and ambient 3D printing of metals.

Recent advances in metal additive manufacturing (AM) have provided new opportunities for prompt designs of prototypes and facile personalization of products befitting the fourth industrial revolution. In this regard, its feasibility of becoming a green technology, which is not an inherent aspect of AM, is gaining more interests. A particular interest in adapting and understanding of eco-friendly ingredients can set its important groundworks. Here, we demonstrate a water-based solid-phase binding agent suitable for binder jetting 3D printing of metals. Sodium salts of common fruit acid chelators form stable metal-chelate bridges between metal particles, enabling elaborate 3D printing of metals with improved strengths. Even further reductions in the porosity between the metal particles are possible through post-treatments. A compatibility of this chelation chemistry with variety of metals is also demonstrated. The proposed mechanism for metal 3D printing can open up new avenues for consumer-level personalized 3D printing of metals.

Non-von Neumann multi-input spike signal processing enabled by an artificial synaptic multiplexer.

Multiplexing is essential for technologies that require processing of a large amount of information in real time. Here, we present an artificial synaptic multiplexing unit capable of realizing parallel multi-input control system. Ion gel was used as a dielectric layer of the artificial synaptic multiplexing unit because of its ionic property, allowing multigating for parallel input. A closed-loop control system that enables multi-input-based feedback for actuator bending control was realized by incorporating an ion gel-based artificial synaptic multiplexing unit, an actuator, and a bending angle sensor. The proposed multi-input control system could simultaneously process input and feedback signals, offering a breakthrough in industries in which the processing of vast amounts of streaming data is essential.

The Molecular Ordering and Double-Channel Carrier Generation of Nonfullerene Photovoltaics within Multi-Length-Scale Morphology.

The success of nonfullerene acceptor (NFA) solar cells lies in their unique physical properties beyond the extended absorption and suitable energy levels. The current study investigates the morphology and photophysical behavior of PBDB-T donor blending with ITIC, 4TIC, and 6TIC acceptors. Single-crystal study shows that the π-π stacking and side-chain interaction dictate molecular assembly, which can be carried to blended films, forming a multi-length-scale morphology. Spontaneous carrier generation is seen in ITIC, 4TIC, and 6TIC neat films and their blended thin films using the PBDB-T donor, providing a new avenue of zero-energy-loss carrier formation. The molecular packing associated with specific contacts and geometry is key in influencing the photophysics, as demonstrated by the charge transfer and carrier lifetime results. The 2D layer of 6TIC facilitates the exciton-to-polaron conversion, and the largest photogenerated polaron yield is obtained. The new mechanism, together with the highly efficient blending region carrier generation, has the prospect of the fundamental advantage for NFA solar cells, from molecular assembly to thin-film morphology.

Comb-type polymer-hybridized MXene nanosheets dispersible in arbitrary polar, nonpolar, and ionic solvents.

Solution-based processing of two-dimensional (2D) nanomaterials is highly desirable, especially for the low-temperature large-area fabrication of flexible multifunctional devices. MXenes, an emerging family of 2D materials composed of transition metal carbides, carbonitrides, or nitrides, provide excellent electrical and electrochemical properties through aqueous processing. Here, we further expand the horizon of MXene processing by introducing a polymeric superdispersant for MXene nanosheets. Segmented anchor-spacer structures of a comb-type polymer, polycarboxylate ether (PCE), provide polymer grafting-like steric spacings over the van der Waals range of MXene surfaces, thereby reducing the colloidal interactions by the order of 103, regardless of solvent. An unprecedented broad dispersibility window for Ti3C2Tx MXene, covering polar, nonpolar, and even ionic solvents, was achieved. Furthermore, close PCE entanglements in MXene@PCE composite films resulted in highly robust properties upon prolonged mechanical and humidity stresses.

Dilution effect for highly efficient multiple-component organic solar cells.

Although the multiple-component (MC) blend strategy has been frequently used as a very effective way to improve the performance of organic solar cells (OSCs), there is a strong need to understand the fundamental working mechanism and material selection rule for achieving optimal MC-OSCs. Here we present the 'dilution effect' as the mechanism for MC-OSCs, where two highly miscible components are molecularly intermixed. Contrary to the aggregation-induced non-radiative decay, the dilution effect enables higher luminescence quantum efficiencies and open-circuit voltages (VOC) in MC-OSCs via suppressed electron-vibration coupling. The continuously broadened bandgap together with reduced electron-vibration coupling also explains the composition-dependent VOC in ternary blends well. Moreover, we show that electrons can transfer between different acceptors, depending on the energy offset between them, which contributes to the largely unperturbed charge transport and high fill factors in MC-OSCs. The discovery of the dilution effect enables the demonstration of a high power conversion efficiency of 18.31% in an MC-OSC.

A biomimetic ocular prosthesis system: emulating autonomic pupil and corneal reflections.

The human light modulation response allows humans to perceive objects clearly by receiving the appropriate amount of light from the environment. This paper proposes a biomimetic ocular prosthesis system that mimics the human light modulation response capable of pupil and corneal reflections. First, photoinduced synaptic properties of the quantum dot embedded photonic synapse and its biosimilar signal transmission is confirmed. Subsequently, the pupillary light reflex is emulated by incorporating the quantum dot embedded photonic synapse, electrochromic device, and CMOS components. Moreover, a solenoid-based eyelid is connected to the pupillary light reflex system to emulate the corneal reflex. The proposed ocular prosthesis system represents a platform for biomimetic prosthesis that can accommodate an appropriate amount of stimulus by self-regulating the intensity of external stimuli.

Recent Advances on Multivalued Logic Gates: A Materials Perspective.

The recent advancements in multivalued logic gates represent a rapid paradigm shift in semiconductor technology toward a new era of hyper Moore's law. Particularly, the significant evolution of materials is guiding multivalued logic systems toward a breakthrough gradually, whereby they are transcending the limits of conventional binary logic systems in terms of all the essential figures of merit, i.e., power dissipation, operating speed, circuit complexity, and, of course, the level of the integration. In this review, recent advances in the field of multivalued logic gates based on emerging materials to provide a comprehensive guideline for possible future research directions are reviewed. First, an overview of the design criteria and figures of merit for multivalued logic gates is presented, and then advancements in various emerging nanostructured materials-ranging from 0D quantum dots to multidimensional heterostructures-are summarized and these materials in terms of device design criteria are assessed. The current technological challenges and prospects of multivalued logic devices are also addressed and major research trends are elucidated.