Despite impressive demonstrations of memristive behavior with halide perovskites, no clear pathway for material and device design exists for their applications in neuromorphic computing. Present approaches are limited to single element structures, fall behind in terms of switching reliability and scalability, and fail to map out the analog programming window of such devices. Here, we systematically design and evaluate robust pyridinium-templated one-dimensional halide perovskites as crossbar memristive materials for artificial neural networks. We compare two halide perovskite 1D inorganic lattices, namely (propyl)pyridinium and (benzyl)pyridinium lead iodide. The absence of conjugated, electron-rich substituents in PrPyr+ prevents edge-to-face type π-stacking, leading to enhanced electronic isolation of the 1D iodoplumbate chains in (PrPyr)[PbI3], and hence, superior resistive switching performance compared to (BnzPyr)[PbI3]. We report outstanding resistive switching behaviours in (PrPyr)[PbI3] on the largest flexible crossbar implementation (16 × 16) to date - on/off ratio (>105), long term retention (105 s) and high endurance (2000 cycles). Finally, we put forth a universal approach to comprehensively map the analog programming window of halide perovskite memristive devices - a critical prerequisite for weighted synaptic connections in artificial neural networks. This consequently facilitates the demonstration of accurate handwritten digit recognition from the MNIST database based on spike-timing-dependent plasticity of halide perovskite memristive synapses.
Two-dimensional (2D) halide perovskites are exquisite semiconductors with great structural tunability. They can incorporate a rich variety of organic species that not only template their layered structures but also add new functionalities to their optoelectronic characteristics. Here, we present a series of new methylammonium (CH3NH3+ or MA)-based 2D Ruddlesden-Popper perovskites templated by dimethyl carbonate (CH3OCOOCH3 or DMC) solvent molecules. We report the synthesis, detailed structural analysis, and characterization of four new compounds: MA2(DMC)PbI4 (n = 1), MA3(DMC)Pb2I7 (n = 2), MA4(DMC)Pb3I10 (n = 3), and MA3(DMC)Pb2Br7 (n = 2). Notably, these compounds represent unique structures with MA as the sole organic cation both within and between the perovskite sheets, while DMC molecules occupy a tight space between the MA cations in the interlayer. They form hydrogen-bonded [MA···DMC···MA]2+ complexes that act as spacers, preventing the perovskite sheets from condensing into each other. We report one of the shortest interlayer distances (â¼5.7-5.9 Å) in solvent-incorporated 2D halide perovskites. Furthermore, the synthesized crystals exhibit similar optical characteristics to other 2D perovskite systems, including narrow photoluminescence (PL) signals. The density functional theory (DFT) calculations confirm their direct-band-gap nature. Meanwhile, the phase stability of these systems was found to correlate with the H-bond distances and their strengths, decreasing in the order MA3(DMC)Pb2I7 > MA4(DMC)Pb3I10 > MA2(DMC)PbI4 â¼ MA3(DMC)Pb2Br7. The relatively loosely bound nature of DMC molecules enables us to design a thermochromic cell that can withstand 25 cycles of switching between two colored states. This work exemplifies the unconventional role of the noncharged solvent molecule in templating the 2D perovskite structure.
The power conversion efficiency (PCE) of the state-of-the-art large-area slot-die-coated perovskite solar cells (PSCs) is now over 19%, but issues with their stability persist owing to significant intrinsic point defects and a mass of surface imperfections introduced during the fabrication process. Herein, the utilization of a hydrophobic all-organic salt is reported to modify the top surface of large-area slot-die-coated methylammonium (MA)-free halide perovskite layers. Bearing two molecules, each of which is endowed with anchoring groups capable of exhibiting secondary interactions with the perovskite surfaces, the organic salt acts as a molecular lock by effectively binding to both anion and cation vacancies, substantially enhancing the materials' intrinsic stability against different stimuli. It not only reduces the ingression of external species such as oxygen and moisture, but also suppresses the egress of volatile organic components during the thermal stability testing. The treated PSCs demonstrate efficiency of 19.28% (active area of 58.5 cm2 ) and 17.62% (aperture area of 64 cm2 ) for the corresponding mini-module. More importantly, unencapsulated slot-die-coated mini-modules incorporating the all-organic surface modifier show ≈80% efficiency retention after 7500 h (313 days) of storage under 30% relative humidity (RH). They also remarkably retain more than 90% of the initial efficiency for over 850 h while being measured continuously.
Mixed-dimensional perovskites containing mixtures of organic cations hold great promise to deliver highly stable and efficient solar cells. However, although a plethora of relatively bulky organic cations have been reported for such purposes, a fundamental understanding of the materials' structure, composition, and phase, along with their correlated effects on the corresponding optoelectronic properties and degradation mechanism remains elusive. Herein, we systematically engineer the structures of bulky organic cations to template low-dimensional perovskites with contrasting inorganic framework dimensionality, connectivity, and coordination deformation. By combining X-ray single-crystal structural analysis with depth-profiling XPS, solid-state NMR, and femtosecond transient absorption, it is revealed that not all low-dimensional species work equally well as dopants. Instead, it was found that inorganic architectures with lesser structural distortion tend to yield less disordered energetic and defect landscapes in the resulting mixed-dimensional perovskites, augmented in materials with a longer photoluminescence (PL) lifetime, higher PL quantum yield (up to 11%), improved solar cell performance and enhanced thermal stability (T80 up to 1000 h, unencapsulated). Our study highlights the importance of designing templating organic cations that yield low-dimensional materials with much less structural distortion profiles to be used as additives in stable and efficient perovskite solar cells.
Impulsive light excitation presents a powerful tool for investigating the interdependent structural and electronic responses in layered two-dimensional (2D) halide perovskites. However, detailed understanding of the nonlinear lattice dynamics in these soft hybrid materials remains limited. Here, we explicate the intrinsic strain propagation mechanisms in 2D perovskite single crystals using transient reflection spectroscopy. Ultrafast photoexcitation leads to the generation of strain pulses via thermoelastic (TE) stress and deformation potential (DP) interaction whence their detection proceed via Brillouin scattering. Using a two-temperature model together with strain wave propagation, we discern the TE and DP contributions in strain generation. Hot carrier cooling plays a dominant role in effecting the weak modulation amplitude. Out-of-plane lattice stiffness is reduced by the weak van der Waals bond between organic layers, resulting in a slow strain propagation velocity. Our findings inject fresh insights into the basic strain properties of layered perovskites critical for manipulating their functional properties for new applications.
Defect management strategies are vital for enhancing the performance of perovskite-based optoelectronic devices, such as perovskite-based light-emitting diodes (PeLEDs). As additives can fucntion both as acrystallization modifier and/or defect passivator, a thorough study on the roles of additives is essential, especially for blue emissive Pe-LEDs, where the emission is strictly controlled by the n-domain distribution of the Ruddlesden-Popper (RP, L2An-1PbnX3n+1, where L refers to a bulky cation, while A and X are monovalent cation, and halide anion, respectively) perovskite films. Of the various additives that are available, octyl phosphonic acid (OPA) is of immense interest because of its ability to bind with uncoordinated Pb2+ ( notorious for nonradiative recombination) and therefore passivates them. Here, with the help of various spectroscopic techniques, such as X-ray photon-spectroscopy (XPS), Fourier-transform infrared spectroscopy (FTIR), and photoluminescence quantum yield (PLQY) measurements, we demonstrate the capability of OPA to bind and passivate unpaired Pb2+ defect sites. Modification to crystallization promoting higher n-domain formation is also observed from steady-state and transient absorption (TA) measurements. With OPA treatment, both the PLQY and EQE of the corresponding PeLED showed improvements up to 53% and 3.7% at peak emission wavelength of 485 nm, respectively.
Extending halide perovskites' optoelectronic properties to stimuli-responsive chromism enables switchable optoelectronics, information display, and smart window applications. Here, we demonstrate a band gap tunability (chromism) via crystal structure transformation from three-dimensional FAPbBr3 to a ⟨110⟩ oriented FAn+2PbnBr3n+2 structure using a mono-halide/cation composition (FA/Pb) tuning. Furthermore, we illustrate reversible photochromism in halide perovskite by modulating the intermediate n phase in the FAn+2PbnBr3n+2 structure, enabling greater control of the optical band gap and luminescence of a ⟨110⟩ oriented mono-halide/cation perovskite. Proton transfer reaction-mass spectroscopy carried out to precisely quantify the decomposition product reveals that the organic solvent in the film is a key contributor to the structural transformation and, therefore, the chromism in the ⟨110⟩ structure. These intermediate n phases (2 ≤ n ≤ ∞) stabilize in metastable states in the FAn+2PbnBr3n+2 system, which is accessible via strain or optical or thermal input. The structure reversibility in the ⟨110⟩ perovskite allowed us to demonstrate a class of photochromic sensors capable of self-adaptation to lighting.
Physical Unclonable Functions (PUFs) address the inherent limitations of conventional hardware security solutions in edge-computing devices. Despite impressive demonstrations with silicon circuits and crossbars of oxide memristors, realizing efficient roots of trust for resource-constrained hardware remains a significant challenge. Hybrid organic electronic materials with a rich reservoir of exotic switching physics offer an attractive, inexpensive alternative to design efficient cryptographic hardware, but have not been investigated till date. Here, we report a breakthrough security primitive exploiting the switching physics of one dimensional halide perovskite memristors as excellent sources of entropy for secure key generation and device authentication. Measurements of a prototypical 1 kb propyl pyridinium lead iodide (PrPyr[PbI3]) weak memristor PUF with a differential write-back strategy reveals near ideal uniformity, uniqueness and reliability without additional area and power overheads. Cycle-to-cycle write variability enables reconfigurability, while in-memory computing empowers a strong recurrent PUF construction to thwart machine learning attacks.
Major strides have been made in the development of materials and devices based around low-dimensional hybrid group 14 metal halide perovskites. Thus far, this work has mostly focused on compounds containing highly toxic Pb, with the analogous less toxic Sn materials being comparatively poorly evolved. In response, the study herein aims to (i) provide insight into the impact of templating cations upon the structure of n = 1 2D tin iodide perovskites (where n refers to the number of contiguous two-dimensional (2D) inorganic layers, i.e., not separated by organic cations) and (ii) examine their potential as light absorbers for photovoltaic (PV) cells. It was discovered through systematic tuning of organic dications that imidazolium rings are able to induce the formation of (110)-oriented materials, including examples of "3 × 3" corrugated Sn-I perovskites. This structural outcome is a consequence of a combination of supramolecular interactions of the two endocyclic N atoms of the imidazolium rings with the Sn-I framework, and the comparatively high tendency of Sn2+ ions to stereochemically express their 5s2 lone pairs . More importantly, the resulting materials feature very short separations between their 2D inorganic layers with iodide-iodide (I···I) contacts as small as 4.174 Å, which is among the shortest ever recorded for 2D tin iodide perovskites. These proximate inorganic distances, combined with the polarizable nature of the imidazolium moiety, eases the separation of photogenerated charge within the materials. This is evident from the measurement of excitonic activation energies as low as 83(10) meV for ImEA[SnI4]. When combined with superior light absorption capabilities relative to their lead congeners, this allowed the fabrication of lead-free solar cells with incident photon-to-current and power conversion efficiencies of up to 70% and 2.26%, respectively, which are among the highest values reported for pure n = 1 2D group 14 metal halide perovskites. In fact, these values are superior to the corresponding lead iodide material, which demonstrates that 2D Sn-based materials have significant potential as less toxic alternatives to their Pb counterparts.
Surface imperfections created during fabrication of halide perovskite (HP) films could induce formation of various defect sites that affect device performance and stability. In this work, all-organic surface modifiers consisting of alkylammonium cations and alkanoate anions are introduced on top of the HP layer to passivate interfacial vacancies and improve moisture tolerance. Passivation using alkylammonium alkanoate does not induce formation of low-dimensional perovskites species. Instead, the organic species only passivate the perovskite's surface and grain boundaries, which results in enhanced hydrophobic character of the HP films. In terms of photovoltaic application, passivation with alkylammonium alkanoate allows significant reduction in recombination losses and enhancement of open-circuit voltage. Alongside unchanged short-circuit current density, power conversion efficiencies of more than 18.5 % can be obtained from the treated sample. Furthermore, the unencapsulated device retains 85 % of its initial PCE upon treatment, whereas the standard 3D perovskite device loses 50 % of its original PCE when both are subjected to ambient environment over 1500â h.
An amendment to this paper has been published and can be accessed via a link at the top of the paper.
Published studies of layered (2D) (100)-oriented hybrid lead-bromide perovskites evidence a correlation between increased inter-octahedral (Pb-Br-Pb) distortions and the appearance of broadband white light emission. However, the impact of distortions within their constituent [PbBr6 ]4- octahedra has yet to be assessed. Herein, we report two new (100)-oriented 2D Pb-Br perovskites, whose structures display unusually high intra-octahedral distortions, whilst retaining minimal inter-octahedral distortions. Using a combination of temperature-dependent, power-dependent and time-resolved photoluminescence spectroscopic measurements, we show that increased intra-octahedral distortion induces exciton localization processes and leads to formation of multiple photoinduced emissive colour centres. Ultimately, this leads to highly Stokes-shifted, ultrabroad white light emission at room temperature.
Pure 2D lead-iodide perovskites typically demonstrate poor charge transport and compromised visible light absorption, relative to their 3D congeners. This hinders their potential use as solar absorbers. Herein, the systematic tuning of pyridinium-based templating cations is reported to introduce intermolecular interactions that provide access to a series of new 2D lead-iodide perovskites with reduced inter-octahedral distortions (largest Pb-(µ-I)-Pb bond angles of 170-179°) and very short inorganic interlayer separations (shortest Iâ â â I contacts ≤4.278-4.447â Å). These features manifest in reduced band gaps (2.35-2.46â eV) and relaxed dielectric confinement (excitonic binding energies of 130-200â meV). As a consequence, they demonstrate (more than ten-fold) improved photo- and electrical conductivities relative to conventional 2D lead-iodide perovskites, such as that templated by 2-(1-naphthyl)ethylammonium. Through computational studies, the origin of this behavior was shown to derive from a combination of short iodoplumbate layer separations and the aromaticity of the organic dications.
Metal halide perovskite solar cells, despite achieving high power conversion efficiency (PCE), need to demonstrate high stability prior to be considered for industrialization. Prolonged exposure to heat, light, and moisture is known to deteriorate the perovskite material owing to the breakdown of the crystal structure into its non-photoactive components. In this study, we show that by combining the organic ligand 1-naphthylmethylammoinium iodide (NMAI) with methylammonium (MA) to form a mixed dimensional (NMA)2(MA)n-1PbnI3n+1 perovskite the optical, crystallographic and morphological properties of the newly formed mixed dimensional perovskite films under thermal ageing can be retained. Indeed, under thermal ageing at 85 °C, the best performing (NMA)2(MA)n-1PbnI3n+1 perovskites films show a stable morphology, a low PbI2 formation rate and a significantly reduced variation of both MA-specific vibrational modes and fluorescence lifetimes as compared to the pristine MAPbI3 films. These results highlight the role of the bulky NMA+ organic cation in mixed dimensional perovskites to both inhibit the MA+ diffusion and reduce the material defects, which act as non-radiative recombination centres. As a result, the thermal stability of metal halide perovskites has been substantially improved.
Efficient perovskite light-emitting diodes are designed by employing an ordered vertical domain distribution in quasi-two-dimensional (quasi-2D) perovskites to induce better electron flow to the emitting domains. Dimethyl sulfoxide is added to the precursor solution to tune the crystallization rate and promote the formation of high-m domains near the substrate surface via the one-step deposition method. Optimized deposition conditions yielding a film with favorable energetic landscape for both carrier injection and confinement results in a 4-fold external quantum efficiency (EQE) enhancement with maximum EQE of 5.79%. Better carrier injection is further supported by a turn-on voltage value that is comparable to the band gap of the emitter material (â¼2.25 eV).
Despite their emergence as promising materials for low-cost and efficient energy power generation technology, the instability of hybrid organic-inorganic lead-halide perovskites toward moisture and heat stress remains a serious obstacle that needs to be tackled for commercialization. Here, we show improved moisture and thermal stability through the use of cesium oleate to modify the perovskite/hole transporting material interface. Passivation using cesium oleate does not induce the formation of any low-dimensional perovskites, suggesting that the organic species only passivate the perovskite's surface and grain boundaries. As a result, enhanced hydrophobic character of the perovskite film is realized upon passivation, evidenced by a large water contact angle of 107.4° and improved stability at ambient conditions (a relative humidity of â¼70%, room temperature). Concomitantly, the proposed passivation strategy leads to an increased amount of cesium concentration within the films, resulting in beneficial enhanced thermal stability of the film at 85 °C. By maintaining the three-dimensional (3D) structure of the solar absorber while concurrently passivating the interfacial defects and vacancies, improved open-circuit voltage (Voc) and unsacrificed short-circuit current density (Jsc) were obtained from the treated devices, leading to power conversion efficiencies of more than 18%. When stored in a humid environment (a relative humidity of â¼55%), devices with cesium oleate passivation maintain 88% of their initial power conversion efficiency after 720 h, degrading two times slower than those of the control. This work offers a strategy of coating 3D perovskites with a unique combination of inorganic cations and long-chain organics to provide hydrophobicity and moisture stability to the solar absorber layer while maintaining good device performances.
Catalyst deactivation is a persistent problem not only for the scientific community but also in industry. Isolated single-site heterogeneous catalysts have shown great promise to overcome these problems. Here, a versatile anchoring strategy for molecular complex immobilization on a broad range of semiconducting or insulating metal oxide ( e. g., titanium dioxide, mesoporous silica, cerium oxide, and tungsten oxide) nanoparticles to synthesize isolated single-site catalysts has been studied systematically. An oxidatively stable anchoring group, maleimide, is shown to form covalent linkages with surface hydroxyl functionalities of metal oxide nanoparticles by photoclick chemistry. The nanocomposites have been thoroughly characterized by techniques including UV-visible diffuse reflectance spectroscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, infrared spectroscopy, and X-ray absorption spectroscopy (XAS). The IR spectroscopic studies confirm the covalent linkages between the maleimide group and surface hydroxyl functionalities of the oxide nanoparticles. The hybrid nanomaterials function as highly efficient catalysts for essentially quantitative oxidations of terminal and internal alkenes and show molecular catalyst product selectivities even in more eco-friendly solvents. XAS studies verify the robustness of the catalysts after several catalytic cycles. We have applied the photoclick anchoring methodology to precisely control the deposition of a luminescent variant of our catalyst on the metal oxide nanoparticles. Overall, we demonstrate a general approach to use irradiation to anchor molecular complexes on oxide nanoparticles to create recyclable, hybrid, single-site catalysts that function with high selectivity in a broad range of solvents. We have achieved a facile, spatially and temporally controllable photoclick method that can potentially be extended to other ligands, catalysts, functional molecules, and surfaces.
