Reversible Switching Research Articles

Temperature-Induced Reversible Photoluminescence Switching and Ultraviolet-Pumped Light-Emitting Diode Applications of a Perovskite (C6H10N2)2MnCl6·2H2O Crystal.

Zero-dimensional (0D) organic-inorganic hybrid halides present many fascinating photophysical properties for promising optoelectronic applications such as light-emitting diodes (LEDs), X-ray imaging, photodetectors, and anticounterfeiting. Herein, a centimeter-sized single crystal (C6H10N2)2MnCl6·2H2O with a 0D perovskite structure was obtained via a solvent evaporation method. A bright red emission at 618 nm with a larger Stokes shift of more than 300 nm and a long fluorescence lifetime of 6.21 ms were measured. Notably, a reversible PL switching from red emission to nonluminescence has been presented in the cycles of heating-cooling processes from RT to 100 °C. Furthermore, the temperature-induced luminescence shows a quick recovery after 20 conversion cycles, exhibiting excellent stability and temperature sensing. According to the structural and theoretical analyses, the temperature-induced luminescence is primarily due to hydrogen-bonding interactions between (MnCl6)4- and H2O molecules. Particularly, a temperature anticounterfeiting application has been designed based on its reversible temperature-dependent PL switching. Importantly, the ultraviolet-pumped LEDs fabricated by (C6H10N2)2MnCl6·2H2O single crystals are perfectly achieved. Anyway, this work clearly demonstrates that 0D Mn-based perovskite with temperature-dependent PL switching greatly extends its potential applications in electro-optical display, temperature sensing, and anticounterfeiting devices.

Halogen Substitution Regulates High Temperature Dielectric Switch in Lead-Free Chiral Hybrid Perovskites.

Hybrid metal halides (HMHs) based phase transition materials have received widespread attention due to their excellent performance and potential applications in energy harvesting, optoelectronics, ferroics, and actuators. Nevertheless, effectively regulating the properties of phase transitions is still a thorny problem. In this work, two chiral lead-free HMHs (R-3FP)2 SbCl5 (1; 3FP=3-fluoropyrrolidinium) and (R-3FP)2 SbBr5 (2) were synthesized. By replacing the halide ions in the inorganic skeleton, the phase transition temperature of 2 changes with an increase of about 20 K, compared with 1. Meanwhile, both compounds display reversible dielectric switching properties. Through crystal structure analysis and Hirshfeld surface analysis, their phase transitions are ascribed to the disorder of the cations and deformation of the inorganic chains.

A novel 650 V snapback-free PMOS-RC-SJBT with low switching and reverse recovery losses

A novel 650 V Snapback-free Reverse-conducting Super-junction (SJ) insulated gate bipolar transistor (RC-SJBT) with low switching and reverse recovery loss is proposed and investigated in paper. In where, SJ pillar acts as the drift region, meanwhile PMOS and Schottky are combined on the cathode side. Under the action of SJ pillar, the snapback is effectively suppressed and − trade-off of IGBT is also improved. The PMOS and Schottky combined structure enhances on-state carriers of IGBT meanwhile reduces hole injection efficiency during reverse recovery of freewheel diode, thus the reverse recovery switching loss () of PMOS-RC-SJBT is reduced without sacrificing IGBT’s performance. Investigated by the TCAD tools, the total switching loss of PMOS-RC-SJBT is reduced by 51.2% from Con. RC-IGBT and 40.6% than the latest commercial RC-IGBT IKWH30N65WR6 of Infineon. Besides that, is increased by 35.3% than RC-SJBT. Additionally, the snapback-free P-collector width is reduced from 340 µm of Con.RC-IGBT to 40 µm of PMOS-RC-SJBT, where the current uniformity is substantially improved.

Near-Infrared, Organic Chiroptic Switch with High Dissymmetry Factors.

Here we unveil a chiral molecular redox switch derived from PDI-based twistacenes─chPDI[2] that has the remarkable attributes of high-intensity and a broadband chiral response. This material exhibits facile, stable, and reversible multistate chiroptical switching behavior over a broad active wavelength range close to 700 nm, encompassing ultraviolet, visible, and near-infrared regions. Upon reduction, chPDI[2] exhibits a substantial increase in the amplitude of its circular dichroic response, with an outstanding |ΔΔε| > 300 M-1 cm-1 and a high dissymmetry factor of 3 × 10-2 at 960 nm. DFT calculations suggest that the long wavelength CD signal for doubly reduced chPDI[2] originates from excitation of the PDI backbone to the π* orbital of the bridging alkene. Importantly, the dimer's molecular contortion facilitates ionic diffusion, enabling chiral switching in solid state films. The high dissymmetry factors and near-infrared response establish chPDI[2] as a unique chiroptic switch.

Dynamic reversible mechanism of phenol-carbamate bonds and their potential for the development of thermo-healing, recyclable and high-performance epoxy thermosets

In this paper, a series of small monomers were synthesized to explore the dynamic reversible properties of phenol-carbamate bonds (PCBs), and the bimolecular exchange mechanism of PCBs was verified. Based on this mechanism, a novel thermo-healing recyclable epoxy resin with high mechanical performance and shape memory function was successfully developed. Meanwhile, the number of reversible phenol-carbamate bonds in this system was increased by molecular structure design, which increased the chance of reversible cleavage and recombination of the dynamic covalent bonds. Compared with our previous work, the thermo-healing efficiency of the epoxy thermosets was greatly increased, and the target polymer achieved an excellent balance between high thermo-healing efficiency and good mechanical performance. Further post-treatment experiments show that the cured epoxy resin can also be well recycled by solvent degradation or hot-pressing process. What's more, a novel carbon fiber (CF) reinforced polymer composite material was synthesized by taking that prepared epoxy thermoset as a matrix, which greatly improve the mechanical properties of epoxy resin, and the CF cloths can be recycled when the epoxy resin is removed by chemical degradation. In addition, due to the existence of reversible crystallizable switching segments in the epoxy resin system, when the temperature is above its Tg, it can be triggered by thermal energy, so that the film can rapidly recover from the temporary shape to the permanent shape. This study also provides a new direction for the development of novel multifunctional intelligent polymers.

Highly efficient and tunable dual-state emission from diarylmaleimide derivatives in both solution and solid states for sensing and lighting

Dual-state emission (DSE) materials have attracted widespread attention for their strong luminescence in both solution and solid states. However, it is still a challenge to obtain tunable DSE materials. Through tailoring the terminal groups, a series of diphenylmaleimide derivatives DPM1-DPM7 with twisted structure are designed and synthesized. These compounds not only achieve a wide range adjustment of emission color from blue to red, but also exhibit effective DSE performance. Their quantum yields in solution range from 58.2 % to 88.2 %, while the ones in solid exceed 80 %, with a maximum of nearly 100 % for three derivatives. In addition, DPM6 with tert-butoxycarbonylamino terminal group obtains three different crystals with yellow, orange and red emission. DPM6 crystals realize the reversible switching of three colors under the stimulation of solvent vapor, which can be used to identify chloroform and dichloromethane. DSE-active DPMs can be utilized to detect selectively Fe3+ ions in solution, and also has an important application in the field of solid-state lighting, realizing white light with ultra-high luminous efficiency up to 320 lm/W.

Optical switching beyond a million cycles of low-loss phase change material Sb2Se3

The development of the next generation of optical phase change technologies for integrated photonic and free-space platforms relies on the availability of materials that can be switched repeatedly over large volumes and with low optical losses. In recent years, the antimony-based chalcogenide phase-change material Sb2Se3 has been identified as particularly promising for a number of applications owing to good optical transparency in the near-infrared part of the spectrum and a high refractive index close to silicon. The crystallization temperature of Sb2Se3 of around 460 K allows switching to be achieved at moderate energies using optical or electrical control signals while providing sufficient data retention time for non-volatile storage. Here, we investigate the parameter space for optical switching of films of Sb2Se3 for a range of film thicknesses relevant to optical applications. By identifying optimal switching conditions, we demonstrate endurance of up to 107 cycles at reversible switching rates of 20 kHz. Our work demonstrates that the combination of intrinsic film parameters with pumping conditions is particularly critical for achieving high endurance in optical phase change applications.

Dynamic Spectral Modulation Enabled by Conductive Polymer-Integrated Plasmonic Nanodisk-Hole Arrays.

The electrically driven optical performance modulation of the plasmonic nanostructure by conductive polymers provides a prospective technology for miniaturized and integrated active optoelectronic devices. These features of wafer-scale and flexible preparation, a wide spectrum adjustment range, and excellent electric cycling stability are critical to the practical applications of dynamic plasmonic components. Herein, we have demonstrated a large-scale and flexible active plasmonic nanostructure constructed by electrochemically synthesizing nanometric-thickness conductive polymer onto spatially mismatched Au nanodisk-hole (AuND-H) array on the poly(ethylene terephthalate) (PET) substrate, offering low-power electrically driven switching of reflective light in a wide wavelength range of 550-850 nm. The composite structure of the polymer/AuND-H array supports multiple plasmonic resonance modes with strong near-field enhancement and confinement, which provides an excellent dynamic spectral modulation platform. As a result, the PPy/AuND-H array achieves 18.4% reversible switching of spectral intensity at 780 nm and speedy response time, as well as maintains a stable dynamic modulation range at two-potential cycling between -0.6 and 0.1 V after 200 modulation cycles. Compared to the case of the PPy/AuND-H array, the PANI/AuND-H array obtains a more extensive intensity modulation of 25.1% at 750 nm, which is attributed to the significant differences in the extinction coefficient between the oxidized and reduced states of PANI, but its modulation range degrades apparently after 20 cycles driven at applied voltages between -0.1 and 0.8 V. Additionally, the cycling stability could be further improved by reducing the modulation voltage range. Our proposed electromodulated composite structure provides a promising technological proposal for dynamically plasmonic reconfigurable devices.

Dual-Stimulus-Driven Dynamically Controllable [3]Rotaxane with Tunable Organic Room-Temperature Phosphorescence.

A dual-stimulus-driven stiff-stilbene-based dynamic [3]rotaxane has been facilely developed using the threading-stoppering strategy and exhibits reversible shuttling motions and bidirectional rotations upon encountering acid-base and distinct light stimulations, respectively. Herein, the two dibenzo-24-crown-8 macrocycles can undergo reversible switching motion between two different stations along the axle suffered from acid-base stimulation, and simultaneously, the two rotaxanes can also perform cis-trans rotations upon irradiation with distinct light. In other words, the constructed rotaxanes can conduct two modes of regular motions without interference. Interestingly, reciprocating switching motion of the rings along the axle enabled the rotaxanes to exhibit controllable and reversible photoisomerization speed, conversion yield, and quantum yield. Crucially, these rotaxanes also manifest adjustable solid-state organic room-temperature phosphorescence (RTP) and photoluminescence stimulated by dual factors (acid-base and diverse light), which are further applied in information encryption and anticounterfeiting. The presented study provides an instructive way for precisely boosting photoisomerization performances and the fabrication of dual-stimuli-induced molecular machines with functions of two-mode mechanical motions and controllable pure organic RTP switches.

Moisture modulated refractive index difference of engineered pore interface for indoor temperature and humidity regulation

Regulation of indoor environments like temperature and humidity consumes enormous energy and brings environmental crises. Therefore, the development of energy-free approaches is critical as it simultaneously improves living comfort and decreases the carbon footprint. Here we report a moisture-modulated strategy to access switchable thermal regulation by tuning solar radiative scattering through manipulation of the refractive index difference (Δn) of a porous surface. This approach is based on a double-layered film containing an upper porous polymer layer and a lower photothermal layer. Via moisture absorption and evaporation, the film performs a reversible thermal switching between solar heating and radiative cooling, allowing efficient space temperature manipulation in the range from + 12.0 to − 8.0 °C. Besides, the moisture-modulated characteristic also offers an opportunity for solar dehumidification by automatically absorbing ambient moisture while mitigating temperature rise. This work bridges a thermal nexus between moisture with solar radiation, while providing a guideline for energy-free indoor environment manipulation.

Halide Perovskites-Based Diffusive Memristors for Artificial Mechano-Nociceptive System.

Numerous efforts for emulating organ systems comprised of multiple functional units have driven substantial advancements in bio-realistic electronics and systems. The resistance change behavior observed in diffusive memristors shares similarities with the potential change in biological neurons. Here, the diffusive threshold switching phenomenon in Ag-incorporated organometallic halide perovskites is utilized to demonstrate the functions of afferent neurons. Halide perovskites-based diffusive memristors show a low threshold voltage of ≈0.2V with little variation, attributed to the facile migration of Ag ions uniformly dispersed within the halide matrix. Based on the reversible and reliable volatile threshold switching, the memristors successfully demonstrate fundamental nociceptive functions including threshold firing, relaxation, and sensitization. Furthermore, to replicate the biological mechano-nociceptive phenomenon at a system level, an artificial mechano-nociceptive system is built by integrating a diffusive memristor with a force-sensing resistor. The presented system is capable of detecting and discerning the detrimental impact caused by a heavy steel ball, effectively exhibiting the corresponding sensitization response. By further extending the single nociceptive system into a 5 × 5 array, successful stereoscopic nociception of uneven impulses is achieved in the artificial skin system through array-scale sensitization. These results represent significant progress in the field of bio-inspired electronics and systems.

Magneto-responsive wettability-switchable surfaces for in-situ large distance droplets capturing-releasing-bouncing

In this paper, superhydrophobic magnetically responsive micro-plate arrays (SMMAs) with reverse switching wettability were studied for in-situ capturing, releasing, and directional bouncing of droplets over a large distance. A novel method for producing superhydrophobic pattern on one side surface of the micro-plates by laser texturing at 90 degree bending state, created water contact angle of 151°, a rolling angle of < 10°, and a maximum surface adhesion force of 35.5 μN. Reversible switching between droplets (volume 5–40 μL) capturing with high adhesion force (high surface energy) and droplet releasing with low adhesion force were achieved spontaneously. The instantaneous response of the SMMAs to magnetic field provided a guarantee for the directional bouncing of droplets in long distance. Droplets transportation up to 40 μL, directional bouncing of 5 μL droplets with a vertical bounce height of 4.5 mm and a horizontal bounce distance of 24.7 mm have been achieved. This work provides a novel approach for flexible droplets manipulation and multifunctional operation of droplets for non-contact, remote-driven and non-destructive reagent transfer applications.

Enhancing the Resistive Memory Window through Band Gap Tuning in Solid Solution (Cr1-xVx)2O3.

Memories based on the insulator-to-metal transition in correlated insulators are promising to overcome the limitations of alternative nonvolatile memory technologies. However, associated performances have been demonstrated so far only on narrow-gap compounds, such as (V0.95Cr0.05)2O3, exhibiting a tight memory window. In the present study, V-substituted Cr2O3 compounds (Cr1-xVx)2O3 have been synthesized and widely investigated in thin films, single crystals, and polycrystalline powders, for the whole range of chemical composition (0 < x < 1). Physicochemical, structural, and optical properties of the annealed magnetron-sputtered thin films are in very good agreement with those of polycrystalline powders. Indeed, all compounds exhibit the same crystalline structure with a cell parameter evolution consistent with a solid solution over the whole range of x values, as demonstrated by X-ray diffraction and Raman scattering. Moreover, the optical band gap of V-substituted Cr2O3 compounds decreases from 3 eV for Cr2O3 to 0 eV for V2O3. In the same way, resistivity is decreased by almost 5 orders of magnitude as the V content x is varying from 0 to 1, similarly in thin films and single crystals. Finally, a reversible resistive switching has been observed for thin films of three selected V contents (x = 0.30, 0.70, and 0.95). Resistive switching performed on MIM devices based on a 50 nm thick (Cr0.30V0.70)2O3 thin film shows a high endurance of 1000 resistive switching cycles and a memory window ROFF/RON higher by 3 orders of magnitude, as compared to (Cr0.05V0.95)2O3. This comprehensive study demonstrates that a large range of memory windows can be reached by tuning the band gap while varying the V content in the (Cr1-xVx)2O3 solid solution. It thus confirms the potential of correlated insulators for memory applications.

A Homochiral Fulgide Organic Ferroelectric Crystal with Photoinduced Molecular Orbital Breaking

AbstractThermally triggered spatial symmetry breaking in traditional ferroelectrics has been extensively studied for manipulation of the ferroelectricity. However, photoinduced molecular orbital breaking, which is promising for optical control of ferroelectric polarization, has been rarely explored. Herein, for the first time, we synthesized a homochiral fulgide organic ferroelectric crystal (E)‐(R)‐3‐methyl‐3‐cyclohexylidene‐4‐(diphenylmethylene)dihydro‐2,5‐furandione (1), which exhibits both ferroelectricity and photoisomerization. Significantly, 1 shows a photoinduced reversible change in its molecular orbitals from the 3 π molecular orbitals in the open‐ring isomer to 2 π and 1 σ molecular orbitals in the closed‐ring isomer, which enables reversible ferroelectric domain switching by optical manipulation. To our knowledge, this is the first report revealing the manipulation of ferroelectric polarization in homochiral ferroelectric crystal by photoinduced breaking of molecular orbitals. This finding sheds light on the exploration of molecular orbital breaking in ferroelectrics for optical manipulation of ferroelectricity.

Asymmetric reversible structural switching of a diene coordination polymer promoted by UV-visible light

Asymmetric reversible structural switching of a diene coordination polymer promoted by UV-visible light

A Homochiral Fulgide Organic Ferroelectric Crystal with Photoinduced Molecular Orbital Breaking.

Thermally triggered spatial symmetry breaking in traditional ferroelectrics has been extensively studied for the manipulation of ferroelectricity. However, photoinduced molecular orbital breaking, which is promising for the optical control of ferroelectric polarization, was rarely explored. Herein, for the first time, we synthesized a homochiral fulgide organic ferroelectric crystal (E)-(R)-3-methyl-3-cyclohexylidene-4-(diphenylmethylene)dihydro-2,5-furandione (1), which exhibits both ferroelectricity and photoisomerization. Significantly, 1 shows the photoinduced reversible change of molecular orbitals from the 3 π molecular orbitals in open-ring isomer to 2 π and 1 σ molecular orbitals in closed-ring isomer, which enables the reversible ferroelectric domain switching by optical manipulation. To our knowledge, this is the first report revealing the manipulation of ferroelectric polarization in homochiral ferroelectric crystal by photoinduced breaking of molecular orbitals. This finding sheds light on the exploration of molecular orbital breaking in ferroelectrics for optical manipulation of ferroelectricity.

Multi‐Level Optical Switching by Amorphization in Single‐ and Multi‐Phase Change Material Structures

AbstractThe optical properties of phase‐change materials (PCMs) can be tuned to multiple levels by controlling the transition between their amorphous and crystalline phases. In multi‐material PCM structures, the number of discrete reflectance levels can be increased according to the number of PCM layers. However, the effect of increasing the number of layers on quenching and reversibility has not been thoroughly studied. In this work, the phase‐change physics and thermal conditions required for reversible switching of single and multi‐material PCM switches are discussed based on thermo‐optical phase‐change models and laser switching experiments. By using nanosecond laser pulses, 16 different reflectance levels in Ge2Sb2Te5 are demonstrated via amorphization. Furthermore, a multi‐material switch based on Ge2Sb2Te5 and GeTe with four discrete reflectance levels is experimentally proven with a reversible multi‐level response. The results and design principles presented herein will impact active photonics applications that rely on dynamic multi‐level operation, such as optical computing, beam steering, and next‐generation display technologies.

Bifunctional photo- and ionochromic hybrids of indolyl(thienyl) diarylethenes and rhodamine

Bifunctional hybrids of a new type containing photochromic indolyl(thienyl) diarylethenes with a pyrroldione bridge directly linked by a dimethylene spacer to an ionochromic rhodamine moiety were synthesized. The synthesized hybrids in toluene exhibit absorption at 450–455 nm and fluorescence at 560 nm. Irradiation with UV light leads to the formation of ring-closed non-fluorescent diarylethene isomeric fragments. Under visible light (or gradually in the dark conditions), reverse isomerization to the initial forms occurs. The spectral and kinetic characteristics of the processes have been studied. In the presence of H+ cation, a striking naked eye effect is observed due to the opening of the rhodamine-spirolactam ring and appearance of a characteristic pink-crimson coloration at 561 nm along with intense long-wavelength emission at 586 nm. This process is completely reversible upon exposure to triethylamine. The mechanism of this transformation was confirmed by additional 1H and 13C NMR experiments. The M06-2X/Def2-TZVP method and AIM analysis were successfully used to explain observed light-induced isomerizations as well as proton-induced transformations. Thus, reversible switching of the fluorescent properties of hybrid molecules can be operated by light irradiation and proton.

Synthesis and Photochromic Properties of Diaryl [5]Helicene Derivatives.

Photoinduced tuning of aromaticity and correlative molecular properties has attracted enormous interest in recent years both for modulating photochromism properties and designing novel photochromic materials. Here, we report the synthesis and photochemical characterization of diaryl[5]helicene-based diarylethene molecular switches. 3,4-Bis(2,4-dimethyl-5-phenylthiophen-3-yl)dibenzo[c,g]phenanthrene derivative 1 a showed no photochromic reaction, whereas 3,4-bis(2-methyl-5-phenylthiophen-3-yl)dibenzo[c,g]phenanthrene derivative 2 a and 3,4-bis(5-methyl-2-phenylthiazol-4-yl)dibenzo[c,g]phenanthrene derivative 3 a exhibited reversible photochromism in different aprotic solvents with specific light irradiation. Meanwhile, the diarylethene compounds 2 a and 3 a underwent turn-off mode fluorescence photoswitching together with photoisomerization upon light irradiation. Remarkably, the photoinduced changes in the aromaticity of [5]helicene as a central ethene bridge along with the relative smaller activation energy and higher frequency factor facilitated the thermal bleaching rates of diarylethene switches 2 and 3 in solution. This research provides new insight for designing aromatic diarylethene photoswitches for reversible fluorescence switching, photoinduced changes in aromaticity and further fast thermal back reactions.

Crystal structure and magnetization reversal in single-layered Ruddlesden–Popper CaEuFeO4 ceramics

Magnetization reversal widely exists in ferrimagnets, which provides an opportunity to develop novel low-power-consumption memory in the future. In the present work, dense CaEuFeO4 ceramics with the single-layered Ruddlesden–Popper structure were prepared by a standard solid-state reaction process. The orthorhombic phase was determined to have the space group Bmab at room temperature. The antiferromagnetic state was observed below the Néel temperature of 338 K, and temperature-induced magnetization reversal was observed below the compensation temperature in the field cooling protocol. Moreover, field-induced magnetization reversal or bipolar magnetic switching between different fields was also observed at low temperatures. The intriguing temperature- and field-induced magnetization reversal is induced by the competition between the canted Fe3+ moment and the antiparallel Eu3+ moment induced by the Eu–Fe exchange interaction.