Control-Etched Ti3C2Tx MXene Nanosheets for a Low-Voltage-Operating Flexible Memristor for Efficient Neuromorphic Computation.

Hardware neural networks with mechanical flexibility are promising next-generation computing systems for smart wearable electronics. Overcoming the challenge of developing a fully synaptic plastic network, we demonstrate a low-operating-voltage PET/ITO/p-MXene/Ag flexible memristor device by controlling the etching of aluminum metal ions in Ti3C2Tx MXene. The presence of a small fraction of Al ions in partially etched MXene (p-Ti3C2Tx) significantly suppresses the operating voltage to 1 V compared to 7 V from fully Al etched MXene (f-Ti3C2Tx)-based devices. Former devices exhibit excellent non-volatile data storage properties, with a robust ∼103 ON/OFF ratio, high endurance of ∼104 cycles, multilevel resistance states, and long data retention measured up to ∼106 s. High mechanical stability up to ∼73° bending angle and environmental robustness are confirmed with consistent switching characteristics under increasing temperature and humid conditions. Furthermore, a p-Ti3C2Tx MXene memristor is employed to mimic the biological synapse by measuring the learning-forgetting pattern for ∼104 cycles as potentiation and depression. Spike time-dependent plasticity (STDP) based on Hebb's Learning rules is also successfully demonstrated. Moreover, a remarkable accuracy of ∼95% in recognizing modified patterns from the National Institute of Standards and Technology (MNIST) data set with just 29 training epochs is achieved in simulation. Ultimately, our findings underscore the potential of MXene-based flexible memristor devices as versatile components for data storage and neuromorphic computing.

Interface Engineering Enables Multilevel Resistive Switching in Ultra-Low-Power Chemobrionic Copper Silicate.

Memristor is assuming prominence due to its exceptionally low power consumption, adaptable, and parallel signal processing capabilities that address the limitations of the von Neumann architecture to meet the growing demand for advanced technologies such as artificial intelligence, Internet of Things (IoTs), and neuromorphic computation. In this work, we demonstrate resistive switching in copper silicate-based hollow tube-forming self-organized membrane structures belonging to the category of chemobrionics or chemical gardens to demonstrate cost-effective and highly efficient memristor devices. The device architecture is configured as ITO/PEDOT:PSS/active layer (copper silicate)/PMMA/Ag, an arrangement that serves to stabilize current-voltage hysteresis and exhibit a low SET voltage ∼0.2 V with a 0.8 nJ power consumption while manifesting robust data endurance and multilevel resistive switching. The inherent self-rectifying behavior, characterized by a high rectification ratio of 60, underscores the potential utility of these devices across a spectrum of electronic applications. To emulate the functionality of biological synapses, fundamental synaptic characteristics are assessed, including paired-pulse facilitation (PPF) and potentiation and depression (P&D). We validate the potential of copper silicate chemical garden-based memristor devices for applications that require real-time synaptic processing. Importantly, the fabrication of these devices was accomplished through a comprehensive solution-based, low-temperature process conducted under ambient environmental conditions, obviating the need for specialized glovebox facilities.

Insights into synaptic functionality and resistive switching in lead iodide flexible memristor devices.

Neuromorphic platforms are gaining popularity due to their superior efficiency, low power consumption, and adaptable parallel signal processing capabilities, overcoming the limitations of traditional von Neumann architecture. We conduct an in-depth investigation into the factors influencing the resistive switching mechanism in memristor devices utilizing lead iodide (PbI2). We establish correlations between device performance and morphological features, unveiling synaptic like behaviour of device making it suitable for range of flexible neuromorphic applications. Notably, a highly reliable unipolar switching mechanism is identified, exhibiting stability even under mechanical strain (with a bending radius of approximately 4 mm) and in high humidity environment (at 75% relative humidity) without the need for encapsulation. The investigation delves into the complex interplay of charge transport, ion migration and the active interface, elucidating the factors contributing to the remarkable resistive switching observed in PbI2-based memristors. The detailed findings highlight synaptic behaviors akin to the modulation of synaptic strengths, with an impressive potentiation and depression of 2 × 104 cycles, emphasizing the role of spike time-dependent plasticity (STDP). The flexible platform demonstrates exceptional performance, achieving a simulated accuracy rate of 95.06% in recognizing modified patterns from the National Institute of Standards and Technology (MNIST) dataset with just 30 training epochs. Ultimately, this research underscores the potential of PbI2-based flexible memristor devices as versatile component for neuromorphic computing. Moreover, it demonstrate the robustness of PbI2 memristors in terms of their resistive switching capabilities, showcasing resilience both mechanically and electrically. This underscores their potential in replicating synaptic functions for advanced information processing systems.

Advances in Flexible Memristors with Hybrid Perovskites.

Hybrid organic-inorganic metal halide perovskite (HOIP)-based memristors have captured strong attention not only as an emerging candidate for next-generation high-density information storage technology but also for use in healthcare technology and the Internet of Things (IoT) because of their unique properties: low weight, flexibility, compatibility, stretchability, and low power consumption. In this Perspective, we review the recent advances of various aspects of flexible memristors focusing on the selection of the flexible substrates, materials, interfaces, several resistive switching mechanisms, and different methodologies of perovskite growth. The current state of the art of the memristor as an artificial synapse, light-induced resistive switching, and logic gates is comprehensively and systematically reviewed. Finally, we briefly discuss the stability factors of perovskites and present the conclusion with a broad outlook on the progress and challenges in the field of perovskite-based flexible memristors.

Electronic States Modulation by Coherent Optical Phonons in 2D Halide Perovskites.

Excitonic effects underpin the fascinating optoelectronic properties of 2D perovskites that are highly favorable for photovoltaics and light-emitting devices. Analogous to switching in transistors, manipulating these excitonic properties in 2D perovskites using coherent phonons could unlock new applications. Presently, a detailed understanding of this underlying mechanism remains modest. Herein, the origins of the carrier-phonon coupling in 2D perovskites using transient absorption (TA) spectroscopy are explicated. The exciton fine structure is modulated by coherent optical phonons dominated by the vibrational motion of the PbI6 octahedra via deformation potential. Originating from impulsive stimulated Raman scattering, these coherent vibrations manifest as oscillations in the TA spectrum comprising of the generation and detection processes of coherent phonons. This two-step process leads to a unique pump- and probe-energy dependence of the phonon modulation determined by the imaginary part of the refractive index and its derivative, respectively. The phonon frequency and lattice displacement of the inorganic octahedra are highly dependent on the organic cation. This study injects fresh insights into the exciton-phonon coupling of 2D perovskites relevant for emergent optoelectronics development.

Heavy Water Additive in Formamidinium: A Novel Approach to Enhance Perovskite Solar Cell Efficiency.

Heavy water or deuterium oxide (D2 O) comprises deuterium, a hydrogen isotope twice the mass of hydrogen. Contrary to the disadvantages of deuterated perovskites, such as shorter recombination lifetimes and lower/invariant efficiencies, the serendipitous effect of D2 O as a beneficial solvent additive for enhancing the power conversion efficiency (PCE) of triple-A cation (cesium (Cs)/methylammonium (MA)/formaminidium (FA)) perovskite solar cells from ≈19.2% (reference) to 20.8% (using 1 vol% D2 O) with higher stability is reported. Ultrafast optical spectroscopy confirms passivation of trap states, increased carrier recombination lifetimes, and enhanced charge carrier diffusion lengths in the deuterated samples. Fourier transform infrared spectroscopy and solid-state NMR spectroscopy validate the N-H2 group as the preferential isotope exchange site. Furthermore, the NMR results reveal the induced alteration of the FA to MA ratio due to deuteration causes a widespread alteration to several dynamic processes that influence the photophysical properties. First-principles density functional theory calculations reveal a decrease in PbI6 phonon frequencies in the deuterated perovskite lattice. This stabilizes the PbI6 structures and weakens the electron-LO phonon (Fröhlich) coupling, yielding higher electron mobility. Importantly, these findings demonstrate that selective isotope exchange potentially opens new opportunities for tuning perovskite optoelectronic properties.

Excitons in 2D perovskites for ultrafast terahertz photonic devices.

In recent years, two-dimensional (2D) Ruddlesden-Popper perovskites have emerged as promising candidates for environmentally stable solar cells, highly efficient light-emitting diodes, and resistive memory devices. The remarkable existence of self-assembled quantum well (QW) structures in solution-processed 2D perovskites offers a diverse range of optoelectronic properties, which remain largely unexplored. Here, we experimentally observe ultrafast relaxation of free carriers in 20 ps due to the quantum confinement of free carriers in a self-assembled QW structures that form excitons. Furthermore, hybridizing the 2D perovskites with metamaterials on a rigid and a flexible substrate enables modulation of terahertz fields at 50-GHz modulating speed, which is the fastest for a solution-processed semiconductor-based photonic device. Hence, an exciton-based ultrafast response of 2D perovskites opens up large avenues for a wide range of scalable dynamic photonic devices with potential applications in flexible photonics, ultrafast wavefront control, and short-range wireless terahertz communications.

Interfacial Mechanism for Efficient Resistive Switching in Ruddlesden-Popper Perovskites for Non-volatile Memories.

Ion migration, one origin of current-voltage hysteresis, is the bane of halide perovskite optoelectronics. Herein, we leverage this unwelcome trait to unlock new opportunities for resistive switching using layered Ruddlesdsen-Popper perovskites (RPPs) and explicate the underlying mechanisms. The ON/OFF ratio of RPP-based devices is strongly dependent on the layers and peaks at n̅ = 5, demonstrating the highest ON/OFF ratio of ∼104 and minimal operation voltage in 1.0 mm2 devices. Long data retention even in 60% relative humidity and stable write/erase capabilities exemplify their potential for memory applications. Impedance spectroscopy reveals a chemical reaction between migrating ions and the external contacts to modify the charge transfer barrier at the interface to control the resistive states. Our findings explore a new family of facile materials and the necessity of ionic population, migration, and their reactivity with external contacts in devices for switching and memory applications.

Hot carrier extraction in CH3NH3PbI3 unveiled by pump-push-probe spectroscopy.

Halide perovskites are promising materials for development in hot carrier (HC) solar cells, where the excess energy of above-bandgap photons is harvested before being wasted as heat to enhance device efficiency. Presently, HC separation and transfer processes at higher-energy states remain poorly understood. Here, we investigate the excited state dynamics in CH3NH3PbI3 using pump-push-probe spectroscopy. It has its intrinsic advantages for studying these dynamics over conventional transient spectroscopy, albeit complementary to one another. By exploiting the broad excited-state absorption characteristics, our findings reveal the transfer of HCs from these higher-energy states into bathophenanthroline (bphen), an energy selective organic acceptor far above perovskite's band edges. Complete HC extraction is realized only after overcoming the interfacial barrier formed at the heterojunction, estimated to be between 1.01 and 1.08 eV above bphen's lowest unoccupied molecular orbital level. The insights gained here are essential for the development of a new class of optoelectronics.

Role of Water in Suppressing Recombination Pathways in CH3NH3PbI3 Perovskite Solar Cells.

Moisture degradation of halide perovskites is the Achilles heel of perovskite solar cells. A surprising revelation in 2014 about the beneficial effects of controlled humidity in enhancing device efficiencies overthrew established paradigms on perovskite solar cell fabrication. Despite the extensive studies on water additives in perovskite solar cell processing that followed, detailed understanding of the role of water from the photophysical perspective remains lacking; specifically, the interplay between the induced morphological effects and the intrinsic recombination pathways. Through ultrafast optical spectroscopy, we show that both the monomolecular and bimolecular recombination rate constants decrease by approximately 1 order with the addition of an optimal 1% H2O by volume in CH3NH3PbI3 as compared to the reference (without the H2O additive). Correspondingly, the trap density reduces from 4.8 × 1017 cm-3 (reference) to 3.2 × 1017 cm-3 with 1% H2O. We obtained an efficiency of 12.3% for the champion inverted CH3NH3PbI3 perovskite solar cell (1% H2O additive) as compared to the 10% efficiency for the reference cell. Increasing the H2O content further is deleterious for the device. Trace amounts of H2O afford the benefits of surface trap passivation and suppression of trap-mediated recombination, whereas higher concentrations result in a preferential dissolution of methylammonium iodide during fabrication that increases the trap density (MA vacancies). Importantly, our study reveals the effects of trace H2O additives on the photophysical properties of CH3NH3PbI3 films.

Solution-Processed Lead Iodide for Ultrafast All-Optical Switching of Terahertz Photonic Devices.

Solution-processed lead iodide (PbI2 ) governs the charge transport characteristics in the hybrid metal halide perovskites. Besides being a precursor in enhancing the performance of perovskite solar cells, PbI2 alone offers remarkable optical and ultrasensitive photoresponsive properties that remain largely unexplored. Here, the photophysics and the ultrafast carrier dynamics of the solution processed PbI2 thin film is probed experimentally. A PbI2 integrated metamaterial photonic device with switchable picosecond time response at extremely low photoexcitation fluences is demonstrated. Further, findings show strongly confined terahertz field induced tailoring of sensitivity and switching time of the metamaterial resonances for different thicknesses of PbI2 thin film. The approach has two far reaching consequences: the first lead-iodide-based ultrafast photonic device and resonantly confined electromagnetic field tailored transient nonequilibrium dynamics of PbI2 which could also be applied to a broad range of semiconductors for designing on-chip, ultrafast, all-optical switchable photonic devices.

Tunable Ferroelectricity in Ruddlesden-Popper Halide Perovskites.

Ruddlesden-Popper (RP) halide perovskites are the new kids on the block for high-performance perovskite photovoltaics with excellent ambient stability. The layered nature of these perovskites offers an exciting possibility of harnessing their ferroelectric property for photovoltaics. Adjacent polar domains in a ferroelectric material allow the spatial separation of electrons and holes. Presently, the structure-function properties governing the ferroelectric behavior of RP perovskites are an open question. Herein, we realize tunable ferroelectricity in 2-phenylethylammonium (PEA) and methylammonium (MA) RP perovskite (PEA)2(MA) n̅-1Pb n̅I3 n̅+1. Second harmonic generation (SHG) confirms the noncentrosymmetric nature of these polycrystalline thin films, whereas piezoresponse force microscopy and polarization-electric field measurements validate the microscopic and macroscopic ferroelectric properties. Temperature-dependent SHG and dielectric constant measurements uncover a phase transition temperature at around 170 °C in these films. Extensive molecular dynamics simulations support the experimental results and identified the correlated reorientation of MA molecules and ion translations as the source of ferroelectricity. Current-voltage characteristics in the dark reveal the persistence of hysteresis in these devices, which has profound implications for light-harvesting and light-emitting applications. Importantly, our findings disclose a viable approach for engineering the ferroelectric properties of RP perovskites that may unlock new functionalities for perovskite optoelectronics.

Author Correction: Indirect tail states formation by thermal-induced polar fluctuations in halide perovskites.

The original version of this article incorrectly listed the present address of Bo Wu as 'Present address: Institute of Electronic Paper Displays, South China Academy of Advanced Optoelectronics, South China Normal University, Guangzhou, Guangdong Province 510006, China'. This is the author's primary affiliation. This has been corrected in both the PDF and HTML versions of the article.

Indirect tail states formation by thermal-induced polar fluctuations in halide perovskites.

Halide perovskites possess enormous potential for various optoelectronic applications. Presently, a clear understanding of the interplay between the lattice and electronic effects is still elusive. Specifically, the weakly absorbing tail states and dual emission from perovskites are not satisfactorily described by existing theories based on the Urbach tail and reabsorption effect. Herein, through temperature-dependent and time-resolved spectroscopy on metal halide perovskite single crystals with organic or inorganic A-site cations, we confirm the existence of indirect tail states below the direct transition edge to arise from a dynamical Rashba splitting effect, caused by the PbBr6 octahedral thermal polar distortions at elevated temperatures. This dynamic effect is distinct from the static Rashba splitting effect, caused by non-spherical A-site cations or surface induced lattice distortions. Our findings shed fresh perspectives on the electronic-lattice relations paramount for the design and optimization of emergent perovskites, revealing broad implications for light harvesting/photo-detection and light emission/lasing applications.

Targeting miRNAs with CRISPR/Cas9 to Improve Recombinant Protein Production of CHO Cells.

MicroRNAs with their unique ability to target hundreds of genes have been highlighted as powerful tools to improve bioprocess behavior of cells. The common approaches to stably deplete miRNAs are the use of sponge decoy transcripts or shRNA inhibitors, which requires the introduction and expression of extra genetic material. As an alternative, we implemented the CRISPR/Cas9 system in our laboratory to generate Chinese hamster ovary (CHO) cells which lack the expression of a specific miRNA for the purpose of functional studies. To implement the system, miR-27a/b was chosen as it has been shown to be upregulated during hypothermic conditions and therefore may be involved in controlling CHO cell growth and recombinant protein productivity. In this chapter, we present a protocol for targeting miRNAs in CHO cells using CRISPR/Cas9 and the analysis of the resulting phenotype, using miR-27 as an example. We showed that it is possible to target miRNAs in CHO cells and achieved ≥80% targeting efficiency. Indel analysis and TOPO-TA cloning combined with Sanger sequencing showed a range of different indels. Furthermore, it was possible to identify clones with no detectable expression of mature miR-27b. Depletion of miR-27b led to improved viability in late stages of batch and fed-batch cultures making it a potentially interesting target to improve bioprocess performance of CHO cells.

Hybrid Lead Halide Perovskites for Ultrasensitive Photoactive Switching in Terahertz Metamaterial Devices.

The recent meteoric rise in the field of photovoltaics with the discovery of highly efficient solar-cell devices is inspired by solution-processed organic-inorganic lead halide perovskites that exhibit unprecedented light-to-electricity conversion efficiencies. The stunning performance of perovskites is attributed to their strong photoresponsive properties that are thoroughly utilized in designing excellent perovskite solar cells, light-emitting diodes, infrared lasers, and ultrafast photodetectors. However, optoelectronic application of halide perovskites in realizing highly efficient subwavelength photonic devices has remained a challenge. Here, the remarkable photoconductivity of organic-inorganic lead halide perovskites is exploited to demonstrate a hybrid perovskite-metamaterial device that shows extremely low power photoswitching of the metamaterial resonances in the terahertz part of the electromagnetic spectrum. Furthermore, a signature of a coupled phonon-metamaterial resonance is observed at higher pump powers, where the Fano resonance amplitude is extremely weak. In addition, a low threshold, dynamic control of the highly confined electric field intensity is also observed in the system, which could tremendously benefit the new generation of subwavelength photonic devices as active sensors, low threshold optically controlled lasers, and active nonlinear devices with enhanced functionalities in the infrared, optical, and the terahertz parts of the electromagnetic spectrum.

Effectiveness of External Electric Field Treatment of Conjugated Polymers in Bulk-Heterojunction Solar Cells.

External electric field treatment (EFT) on P3HT:PCBM bulk heterojunction (BHJ) devices was recently found to be a viable approach for improving the power conversion efficiencies (PCEs) through modulating the blend nanomorphology. However, its effectiveness over the broad family of polymer-fullerene blends remains unclear. Herein, we investigate the effects of external EFT on various polymer-fullerene blends with distinct morphologies stemming from the difference in molecular structure of the polymers (i.e., semicrystalline vs amorphous) in a bid to establish a clear morphology-function-charge dynamics relationship to the photovoltaic performance. Our findings reveal that EFT promotes self-organization of the semicrystalline thiophene-based conjugated polymers (i.e., P3HT and P3BT) while it was ineffective for the amorphous polymers (i.e., PTB7 and PCPDTBT) even at the maximum applied E-field of 8 kV cm-1. Transient absorption spectroscopy shows an improvement in the initial charge-carrier and polaron formation from delocalized excitons in the E-field treated semicrystalline blends compared to their untreated reference samples. Interfacial trap-assisted monomolecular and trap-free bimolecular recombination at nanosecond-microsecond time scale in the E-field treated P3BT:PC60BM devices are significantly suppressed. Importantly, our findings shed new light and provide guidelines on the effectiveness of utilizing external EFT to enhance the PCEs of a larger family of conjugated polymer-based BHJ OSCs.

Modulating carrier dynamics through perovskite film engineering.

Precise morphological control in perovskite films is key to high performance photovoltaic and light emitting devices. However, a clear understanding of the interplay of morphological effects from substrate/perovskite antisolvent treatments on the charge dynamics is still severely lacking. Through detailed ultrafast optical spectroscopy, we correlate the morphology-kinetics relationship in a combination of substrate/film treated samples (i.e., plasma-cleaned vs. piranha-etched substrates and solvent (toluene)-engineered (or toluene anti-solvent treated) perovskite films). Our findings reveal that toluene-dripped treatment has a more pronounced influence on the morphology of perovskite films prepared on plasma-cleaned substrates over those on piranha-etched substrates. Surprisingly, the highly effective toluene-dripping/washing approach reported in the literature increases the surface trap densities of perovskite films. Despite the marked improvements in the surface morphology of the toluene-dripped films, there is only a slight improvement in the carrier relaxation lifetimes - likely due to the competition between the morphology improvements and the increased surface trap densities. In addition, the injection of photoexcited holes to spiro-OMeTAD from toluene-dripped films on piranha-etched substrates is inhibited, possibly due to a realignment of the energy bands. Nonetheless, piranha-etching of the substrates could possibly offer an approach to improve the balance between the electron and hole diffusion lengths in the perovskite film. Importantly, our findings would help unravel the complex relationship of substrate/film treatments on the morphology and charge kinetics in perovskite thin films.

Correlation between blend morphology and recombination dynamics in additive-added P3HT:PCBM solar cells.

The addition of a small amount of high boiling point solvent in organic donor/acceptor blends to control their morphology is a viable approach to enhance the power conversion efficiency of bulk heterojunction (BHJ) organic solar cells. Herein, through transient absorption spectroscopy (TAS) correlated with physical characterizations and device studies, we investigate the effects of a family of thiol-based additives (i.e., 1,5-pentanedithiol (PDT), 1,6-hexanedithiol (HDT) and 1,8-octanedithiol (ODT)) in P3HT:PCBM blend films in a bid to establish a morphology-function-charge dynamics relationship with their photovoltaic performances. The performance of solar cell devices (ηHDT = 2.8%, ηODT = 2.8%, ηPDT = 1.7%) is related to the additive-induced phase separation and the degree of ordering of P3HT. TAS uncovers a more efficient initial exciton and polaron generation in the additive-treated blend samples compared to the non-additive treated control sample. HDT and ODT-added blends exhibit decay dynamics and performances similar to those of the thermally annealed samples. However, the PDT-added blend exhibits a strong trap-assisted recombination in the subsequent nanosecond-microsecond timescales. We attribute this to the loss of charge carriers in the larger isolated P3HT domains due to the lack of percolation paths to the electrode. Our findings illustrate that understanding the complex interplay of the crystalline order, intermixed phases and percolation pathways is key to optimizing the performance of thermal-annealing free, additive-treated organic solar cells.