A Centimeter‐Scale Inorganic Nanoparticle Superlattice Monolayer with Non‐Close‐Packing and its High Performance in Memory Devices

Due to the near‐field coupling effect, non‐close‐packed nanoparticle (NP) assemblies with tunable interparticle distance (d) attract great attention and show huge potential applications in various functional devices, e.g., organic nano‐floating‐gate memory (NFGM) devices. Unfortunately, the fabrication of device‐scale non‐close‐packed 2D NPs material still remains a challenge, limiting its practical applications. Here, a facile yet robust “rapid liquid–liquid interface assembly” strategy is reported to generate a non‐close‐packed AuNP superlattice monolayer (SM) on a centimeter scale for high‐performance pentacene‐based NFGM. The d and hence the surface plasmon resonance spectra of SM can be tailored by adjusting the molecular weight of tethered polymers. Precise control over the d value allows the successful fabrication of photosensitive NFGM devices with highly tunable performances from short‐term memory to nonvolatile data storage. The best performing nonvolatile memory device shows remarkable 8‐level (3‐bit) storage and a memory ratio over 10⁵ even after 10 years compared with traditional devices with a AuNP amorphous monolayer. This work provides a new opportunity to obtain large area 2D NPs materials with non‐close‐packed structure, which is significantly meaningful to microelectronic, photovoltaics devices, and biochemical sensors.     

非挥发浮栅存储器用PtAu纳米颗粒单层膜的制备

将Langmuir-Blodgett（LB）膜等化学方法应用于非挥发浮栅存储器制备工艺中．采用反相微乳液方法合成的分散良好的PtAu纳米颗粒粒径约为5m,并应用LB膜方法在存储器隧穿氧化层上制备了PtAu纳米颗粒的单层膜．采用SEM对LB膜的表面形貌进行观测,研究了表面压对成膜质量的影响,结果表明在表面压为15mN／m时可获得密度为10^11cm^-2均匀分布的PtAu纳米颗粒单层二维阵列,可应用于非挥发性金属纳米颗粒浮栅存储器,并成功拓展了LB膜等化学方法的应用范围．     

Graphene–Graphene Oxide Floating Gate Transistor Memory

A novel transparent, flexible, graphene channel floating‐gate transistor memory (FGTM) device is fabricated using a graphene oxide (GO) charge trapping layer on a plastic substrate. The GO layer, which bears ammonium groups (NH₃⁺), is prepared at the interface between the crosslinked PVP (cPVP) tunneling dielectric and the Al₂O₃ blocking dielectric layers. Important design rules are proposed for a high‐performance graphene memory device: i) precise doping of the graphene channel, and ii) chemical functionalization of the GO charge trapping layer. How to control memory characteristics by graphene doping is systematically explained, and the optimal conditions for the best performance of the memory devices are found. Note that precise control over the doping of the graphene channel maximizes the conductance difference at a zero gate voltage, which reduces the device power consumption. The proposed optimization via graphene doping can be applied to any graphene channel transistor‐type memory device. Additionally, the positively charged GO (GO–NH₃⁺) interacts electrostatically with hydroxyl groups of both UV‐treated Al₂O₃ and PVP layers, which enhances the interfacial adhesion, and thus the mechanical stability of the device during bending. The resulting graphene–graphene oxide FGTMs exhibit excellent memory characteristics, including a large memory window (11.7 V), fast switching speed (1 μs), cyclic endurance (200 cycles), stable retention (10⁵ s), and good mechanical stability (1000 cycles).     

Organic Field‐Effect Transistor Memory Devices Using Discrete Ferritin Nanoparticle‐Based Gate Dielectrics

Organic field‐effect transistor (OFET) memory devices made using highly stable iron‐storage protein nanoparticle (NP) multilayers and pentacene semiconductor materials are introduced. These transistor memory devices have nonvolatile memory properties that cause reversible shifts in the threshold voltage (V_th) as a result of charge trapping and detrapping in the protein NP (i.e., the ferritin NP with a ferrihydrite phosphate core) gate dielectric layers rather than the metallic NP layers employed in conventional OFET memory devices. The protein NP‐based OFET memory devices exhibit good programmable memory properties, namely, large memory window ΔV_th (greater than 20 V), a fast switching speed (10 μs), high ON/OFF current ratio (above 10⁴), and good electrical reliability. The memory performance of the devices is significantly enhanced by molecular‐level manipulation of the protein NP layers, and various biomaterials with heme Fe^III/Fe^II redox couples similar to a ferrihydrite phosphate core are also employed as charge storage dielectrics. Furthermore, when these protein NP multilayers are deposited onto poly(ethylene naphthalate) substrates coated with an indium tin oxide gate electrode and a 50‐nm‐thick high‐k Al₂O₃ gate dielectric layer, the approach is effectively extended to flexible protein transistor memory devices that have good electrical performance within a range of low operating voltages (<10 V) and reliable mechanical bending stability.     

A High‐Performance Optical Memory Array Based on Inhomogeneity of Organic Semiconductors

Organic optical memory devices keep attracting intensive interests for diverse optoelectronic applications including optical sensors and memories. Here, flexible nonvolatile optical memory devices are developed based on the bis[1]benzothieno[2,3‐d;2′,3′‐d′]naphtho[2,3‐b;6,7‐b′]dithiophene (BBTNDT) organic field‐effect transistors with charge trapping centers induced by the inhomogeneity (nanosprouts) of the organic thin film. The devices exhibit average mobility as high as 7.7 cm² V^?1 s^?1, photoresponsivity of 433 A W^?1, and long retention time for more than 6 h with a current ratio larger than 10⁶. Compared with the standard floating gate memory transistors, the BBTNDT devices can reduce the fabrication complexity, cost, and time. Based on the reasonable performance of the single device on a rigid substrate, the optical memory transistor is further scaled up to a 16 × 16 active matrix array on a flexible substrate with operating voltage less than 3 V, and it is used to map out 2D optical images. The findings reveal the potentials of utilizing [1]benzothieno[3,2‐b][1]benzothiophene (BTBT) derivatives as organic semiconductors for high‐performance optical memory transistors with a facile structure. A detailed study on the charge trapping mechanism in the derivatives of BTBT materials is also provided, which is closely related to the nanosprouts formed inside the organic active layer.     

High‐Performance Vertical Organic Transistors

Vertical organic thin‐film transistors (VOTFTs) are promising devices to overcome the transconductance and cut‐off frequency restrictions of horizontal organic thin‐film transistors. The basic physical mechanisms of VOTFT operation, however, are not well understood and VOTFTs often require complex patterning techniques using self‐assembly processes which impedes a future large‐area production. In this contribution, high‐performance vertical organic transistors comprising pentacene for p‐type operation and C₆₀ for n‐type operation are presented. The static current–voltage behavior as well as the fundamental scaling laws of such transistors are studied, disclosing a remarkable transistor operation with a behavior limited by injection of charge carriers. The transistors are manufactured by photolithography, in contrast to other VOTFT concepts using self‐assembled source electrodes. Fluorinated photoresist and solvent compounds allow for photolithographical patterning directly and strongly onto the organic materials, simplifying the fabrication protocol and making VOTFTs a prospective candidate for future high‐performance applications of organic transistors.     

Well‐Combined Magnetically Separable Hybrid Cobalt Ferrite/Nitrogen‐Doped Graphene as Efficient Catalyst with Superior Performance for Oxygen Reduction Reaction

Catalysts with low‐cost, high activity and stability toward oxygen reduction reaction (ORR) are extremely desirable, but its development still remains a great challenge. Here, a novel magnetically separable hybrid of multimetal oxide, cobalt ferrite (CoFe₂O₄), anchored on nitrogen‐doped reduced graphene oxide (CoFe₂O₄/NG) is prepared via a facile solvothermal method followed by calcination at 500 °C. The structure of CoFe₂O₄/NG and the interaction of both components are analyzed by several techniques. The possible formation of Co/Fe N interaction in the CoFe₂O₄/NG catalyst is found. As a result, the well‐combination of CoFe₂O₄ nanoparticles with NG and its improved crystallinity lead to a synergistic and efficient catalyst with high performance to ORR through a four‐electron‐transfer process in alkaline medium. The CoFe₂O₄/NG exhibits particularly comparable catalytic activity as commercial Pt/C catalyst, and superior stability against methanol oxidation and CO poisoning. Meanwhile, it has been proved that both nitrogen doping and the spinel structure of CoFe₂O₄ can have a significant contribution to the catalytic activity by contrast experiments. Multimetal oxide hybrid demonstrates better catalysis to ORR than a single metal oxide hybrid. All results make the low‐cost and magnetically separable CoFe₂O₄/NG a promising alternative for costly platinum‐based ORR catalyst in fuel cells and metal‐air batteries.     

Nonvolatile Perovskite‐Based Photomemory with a Multilevel Memory Behavior

Solution‐processable organic–inorganic hybrid perovskite materials with a wealth of exotic semiconducting properties have appeared as the promising front‐runners for next‐generation electronic devices. Further, regarding its well photoresponsibility, various perovskite‐based photosensing devices are prosperously developed in recent years. However, most exploited devices to date only transiently transduce the optical signals into electrical circuits while under illumination, which necessitates using additional converters to further store the output signals for recording the occurrence of light stimulation. Herein, a nonvolatile perovskite‐based floating‐gate photomemory with a multilevel memory behavior is demonstrated, for which a floating gate comprising a polymer matrix impregnated with perovskite nanoparticles is employed. Owing to the well photoresponsibility introduced by the embedded nanoparticles, the device is enabled to access multiple wavelength response and the functionalities of recording power/time‐dependent illumination under no vertical electrical field. Intriguingly, a nonvolatility of photorecording exceeding three months with a high On/Off current ratio over 10⁴ can be achieved.