Ferroelectric Domain Wall Delayer and Low-Dropout Regulator.

A switching-type power converter providing an accurate and stable switching output voltage against line/load variations and power supply ripple is mostly complicated in system-on-chip power management integrated circuits (PMICs) within a limited occupation area. Here we fabricated domain wall (DW) nanodevices using an X-cut LiNbO3 thin film on silicon. The domain switching event occurs after a delay time predicted by Merz's law under the applied voltage. But the output current is irrespective of the applied voltage and can be adjusted by conducting wall width as well as input resistance in the circuit. The regulating currents appear repetitively across the volatile interfacial domains between the nanodevice and electrode under intermittently applied voltages. A wall-current-limited domain switching model is developed to explain the phenomenon. The multifunctional DW nanodevices with smaller occupation areas can serve as compact low-dropout regulators in PMICs, time-domain delayers in energy-efficient neural network systems, and on-chip electrostatic discharge protection besides nonvolatile memories and selectors.

A ferroelectric fin diode for robust non-volatile memory.

Among today's nonvolatile memories, ferroelectric-based capacitors, tunnel junctions and field-effect transistors (FET) are already industrially integrated and/or intensively investigated to improve their performances. Concurrently, because of the tremendous development of artificial intelligence and big-data issues, there is an urgent need to realize high-density crossbar arrays, a prerequisite for the future of memories and emerging computing algorithms. Here, a two-terminal ferroelectric fin diode (FFD) in which a ferroelectric capacitor and a fin-like semiconductor channel are combined to share both top and bottom electrodes is designed. Such a device not only shows both digital and analog memory functionalities but is also robust and universal as it works using two very different ferroelectric materials. When compared to all current nonvolatile memories, it cumulatively demonstrates an endurance up to 1010 cycles, an ON/OFF ratio of ~102, a feature size of 30 nm, an operating energy of ~20 fJ and an operation speed of 100 ns. Beyond these superior performances, the simple two-terminal structure and their self-rectifying ratio of ~ 104 permit to consider them as new electronic building blocks for designing passive crossbar arrays which are crucial for the future in-memory computing.

Advanced Etching Techniques of LiNbO3 Nanodevices.

Single LiNbO3 (LNO) crystals are widely utilized in surface acoustic wave devices, optoelectronic devices, and novel ferroelectric memory devices due to their remarkable electro-optic and piezoelectric properties, and high saturation and remnant polarizations. However, challenges remain regarding their nanofabrication that hinder their applications. The prevailing etching techniques for LNO encompass dry etching, wet etching, and focused-ion-beam etching, each having distinct merits and demerits. Achieving higher etching rates and improved sidewall angles presents a challenge in LNO nanofabrication. Building upon the current etching researches, this study explores various etching methods using instruments capable of generating diverse plasma densities, such as dry etching in reactive ion etching (RIE) and inductively coupled plasma (ICP), proton exchange-enhanced etching, and wet chemical etching following high-temperature reduction treatment, as well as hybrid dry and wet etching. Ultimately, after employing RIE dry etching combined with wet etching, following a high-temperature reduction treatment, an etching rate of 10 nm/min and pretty 90° sidewall angles were achieved. Furthermore, high etching rates of 79 nm/min with steep sidewall angles of 83° were obtained using ICP dry etching. Additionally, using SiO2 masks, a high etching rate of 108 nm/min and an etching selectivity ratio of 0.86:1 were achieved. Distinct etching conditions yielded diverse yet exceptional results, providing multiple processing paths of etching for the versatile application of LNO.

Hybrid Dry and Wet Etching of LiNbO3 Domain-Wall Memory Devices with 90° Etching Angles and Excellent Electrical Properties.

Ferroelectric domain walls, agile nanoscale interfaces of polar order, can be selectively controlled by electric fields for their position, conformation, and function, which is ultimately the key to realizing novel low-energy memory and computing structures. LiNbO3 single-crystal domain wall memory has the advantages of high operational speed, high integration density, and virtually unlimited endurance cycles, appearing as a good solution for the next generation of highly miniaturized low-energy memories. However, the etching process poses significant challenges in the nanofabrication and high-density integration of LiNbO3 domain-wall memories. Here, we employed a hybrid etching technique to achieve smooth sidewalls with a 90° inclined angle, leading to a 24% reduction in the coercive field and a 2.5-fold increase in the linear domain wall current density with a retention time of more than 106 seconds and endurance of over 105 writing cycles. Combined with the results of X-ray diffraction patterns and X-ray photoelectric spectra, it is concluded that the excellent electrical performance is related to the formation of an oxygen-deficient LiNbO3-x layer on the sidewall surface during the wet chemical etching process, which is a conductive layer that reduces the thickness of the "dead" layer between the side electrodes and the LiNbO3 cell and rectifies the diode-like wall currents with an onset voltage reduced from 1.23 to 0.28 V. These results prove the high-density integration of ferroelectric domain-wall memories at the nanoscale and provide a new strategy applicable to the development of LiNbO3 photonic devices.

High-Power LiNbO3 Domain-Wall Nanodevices.

Wide band gap semiconductors keep on pushing the limits of power electronic devices to higher switching speeds and higher operating temperatures, including diodes and transistors on low-cost Si substrates. Alternatively, erasable conducting walls created within ferroelectric single-crystal films integrated on the Si platform have emerged as a promising gateway to adaptive nanoelectronics in sufficient output power, where the repetitive creation of highly charged domain walls (DWs) is particularly important to increase the wall current density. Here, we observe large conduction of the head-to-head DW at an optimized inclination angle of 15° within a LiNbO3 single crystal that is 3-4 orders of magnitude higher than that of the tail-to-tail DW. The wall conduction is diode-like with a linear current density of higher than 1 mA/µm and an on/off ratio of larger than 106 under the application of a repetitive switching voltage pulse in time less than 10 ns and an endurance number of higher than 105. The high-power diodes can not only perform direct data processing in high-density nonvolatile DW memories in fast operation speeds and low-energy consumption but also function as sensors in compact electromechanical systems, selectors in phase-change memory and resistive random-access memory, and half-wave/full-wave rectifiers in modern nanocircuits in dimensions approaching the thickness of the depletion layer below which the tradition p-n junction malfunctions.

Size-Controlled Polarization Retention and Wall Current in Lithium Niobate Single-Crystal Memories.

Highly conductive domain walls in insulating ferroelectric LiNbO3 (LNO) single-crystal thin films with atomic smoothness are attractive for use in high-density integration of the ferroelectric domain wall random access memory (DWRAM) because of their excellent reliability and high read currents. However, downscaling of the memory size to the nanoscale could cause poor polarization retention. Understanding the size-dependent electrical performance of a memory cell is therefore crucial. In this work, highly insulating X-cut LNO thin films were bonded to SiO2/Si wafers and lateral mesa-like cells were fabricated on the film surfaces, where contact occurred with two-sided electrodes along the polar z-axis. Under application of an in-plane electric field above a coercive field (Ec), the domain within each memory cell was switched to be antiparallel to the unswitched referencing domain at the bottom; this resulted in the formation of a conducting domain wall, which enables the nondestructive readout strategy of the DWRAM. The cell, which has a lateral length (l) above a critical size (l0) of 105 nm, is found to be a mixture of two phases across the cell area. The inner area of the cell suffers from poor polarization retention because Ec = 150 kV/cm, as demonstrated by in-plane piezoresponse force microscopy imaging. In comparison, the outer periphery domains, which have lengths of 70 nm (∼l0/2), show good retention but require a much higher Ec of 785 kV/cm. The relevant physics is discussed as phase reconstruction occurs after release of the in-plane compressive strain near the outer regions; the results show good agreement with those of one-dimensional thermodynamic calculations and phase-field simulations. The measured current-voltage curves demonstrated a sudden enhancement of the wall current across the cell when l < l0, thus implying higher readout wall currents and better retention for the DWRAM at higher storage densities.

Precise preparation of WO3@SnO2 core shell nanosheets for efficient NH3 gas sensing.

Development of high-performance ammonia (NH3) sensor is imperative for monitoring NH3 in the living environment. In this work, to obtain a high performance NH3 gas sensor, structurally well-defined WO3@SnO2 core shell nanosheets with a controllable thickness of SnO2 shell layer have been employed as sensing materials. The prepared core shell nanosheets were used to obtain a miniaturized gas sensor based on micro-electro-mechanical system (MEMS). By tuning the thickness of SnO2 layer via atomic layer deposition, a series of WO3@SnO2 core-shell nanosheets with tunable sensing properties were realized. Particularly, the sensor base on the fabricated WO3@SnO2 nanosheets with 20-nm SnO2 shell layer demonstrated superior gas sensing performance with the highest response (1.55) and selectivity toward 15 ppm NH3 at 200 °C. This remarkable enhancement of NH3 sensing ability could be ascribed to the formation of unique WO3-SnO2 core-shell heterojunction structure. The detailed mechanism was elucidated by the heterojunction-depletion model with the help of specific band alignment.

Atomic Layer Deposition of Nickel on ZnO Nanowire Arrays for High-Performance Supercapacitors.

A novel hybrid core-shell structure of ZnO nanowires (NWs)/Ni as a pseudocapacitor electrode was successfully fabricated by atomic layer deposition of a nickel shell, and its capacitive performance was systemically investigated. Transmission electron microscopy and X-ray photoelectron spectroscopy results indicated that the NiO was formed at the interface between ZnO and Ni where the Ni was oxidized by ZnO during the ALD of the Ni layer. Electrochemical measurement results revealed that the Ti/ZnO NWs/Ni (1500 cycles) electrode with a 30 nm thick Ni-NiO shell layer had the best supercapacitor properties including ultrahigh specific capacitance (∼2440 F g-1), good rate capability (80.5%) under high current charge-discharge conditions, and a relatively better cycling stability (86.7% of the initial value remained after 750 cycles at 10 A g-1). These attractive capacitive behaviors are mainly attributed to the unique core-shell structure and the combined effect of ZnO NW arrays as short charge transfer pathways for ion diffusion and electron transfer as well as conductive Ni serving as channel for the fast electron transport to Ti substrate. This high-performance Ti/ZnO NWs/Ni hybrid structure is expected to be one of a promising electrodes for high-performance supercapacitor applications.

Low-Cost and High-Productivity Three-Dimensional Nanocapacitors Based on Stand-Up ZnO Nanowires for Energy Storage.

Highly powered electrostatic capacitors based on nanostructures with a high aspect ratio are becoming critical for advanced energy storage technology because of their high burst power and energy storage capability. We report the fabrication process and the electrical characteristics of high capacitance density capacitors with three-dimensional solid-state nanocapacitors based on a ZnO nanowire template. Stand-up ZnO nanowires are grown face down on p-type Si substrates coated with a ZnO seed layer using a hydrothermal method. Stacks of AlZnO/Al2O3/AlZnO are then deposited sequentially on the ZnO nanowires using atomic layer deposition. The fabricated capacitor has a high capacitance density up to 92 fF/µm(2) at 1 kHz (around ten times that of the planar capacitor without nanowires) and an extremely low leakage current density of 3.4 × 10(-8) A/cm(2) at 2 V for a 5-nm Al2O3 dielectric. Additionally, the charge-discharge characteristics of the capacitor were investigated, indicating that the resistance-capacitance time constants were 550 ns for both the charging and discharging processes and the time constant was not dependent on the voltage. This reflects good power characteristics of the fabricated capacitors. Therefore, the current work provides an exciting strategy to fabricate low-cost and easily processable, high capacitance density capacitors for energy storage.

Surface-plasmon mediated photoluminescence enhancement of Pt-coated ZnO nanowires by inserting an atomic-layer-deposited Al2O3 spacer layer.

Surface-plasmon mediated photoluminescence emission enhancement has been investigated for ZnO nanowire (NW)/Pt nanoparticle (NP) nanostructures by inserting an Al2O3 spacer layer. The thickness of the Al2O3 spacer layer and of the Pt NPs capped on the ZnO NWs are well controlled by atomic layer deposition. It is found that the photoluminescence property of the ZnO NW/Al2O3/Pt hybrid structure is highly tunable with respect to the thickness of the inserted Al2O3 spacer layer. The highest enhancement (∼14 times) of the near band emission of ZnO NWs is obtained with an optimized Al2O3 spacer layer thickness of 10 nm leading to a ultraviolet-visible emission ratio of 271.2 compared to 18.8 for bare ZnO NWs. The enhancement of emission is influenced by a Förster-type non-radiative energy transfer process of the exciton energy from ZnO NWs to Pt NPs as well as the coupling effect between excitons of ZnO NWs and surface plasmons of Pt NPs. The highly versatile and tunable photoluminescence properties of Pt-coated ZnO NWs achieved by introducing an Al2O3 spacer layer demonstrate their potential application in highly efficient optoelectronic devices.

Alternative interpretations for decreasing voltage with increasing charge in ferroelectric capacitors.

Recent claim on the direct observation of a negative capacitance (NC) effect from a single layer epitaxial Pb(Zr0.2,Ti0.8)O3 (PZT) thin film was carefully reexamined, and alternative interpretations that can explain the experimental results without invoking the NC effect are provided. Any actual ferroelectric capacitor has an interfacial layer, and experiment always measures the sum of voltages across the interface layer and the ferroelectric layer. The main observation of decreasing ferroelectric capacitor voltage (VF) for increasing ferroelectric capacitor charge (QF), claimed to be the direct evidence for the NC effect, could be alternatively interpreted by either the sudden increase in the positive capacitance of a ferroelectric capacitor or decrease in the voltage across the interfacial layer due to resistance degradation. The experimental time-transient VF and QF could be precisely simulated by these alternative models that fundamentally assumes the reverse domain nucleation and growth. Supplementary experiments using an epitaxial BaTiO3 film supported this claim. This, however, does not necessarily mean that the realization of the NC effect within the ferroelectric layer is impractical under appropriate conditions. Rather, the circuit suggested by Khan et al. may not be useful to observe the NC effect directly.

Ultrasensitive and Broadband MoS2 Photodetector Driven by Ferroelectrics.

A few-layer MoS2 photodetector driven by poly(vinylidene fluoride-trifluoroethylene) ferroelectrics is achieved. The detectivity and responsitivity are up to 2.2 × 10(12) Jones and 2570 A W(-1), respectively, at 635 nm with ZERO gate bias. E(g) of MoS2 is tuned by the ultrahigh electrostatic field from the ferroelectric polarization. The photoresponse wavelengths of the photodetector are extended into the near-infrared (0.85-1.55 µm).

Giant Negative Electrocaloric Effect in Antiferroelectric La-Doped Pb(ZrTi)O3 Thin Films Near Room Temperature.

Antiferroelectric thin films are demonstrated as a new class of giant electrocaloric materials that exhibit a negative electrocaloric response of about -5 K near room temperature. The giant negative electrocaloric effect may open up a new paradigm for light, compact, reliable, and high-efficiency refrigeration devices.

Optical properties of epitaxial BiFeO3 thin film grown on SrRuO3-buffered SrTiO3 substrate.

The BiFeO3 (BFO) thin film was deposited by pulsed-laser deposition on SrRuO3 (SRO)-buffered (111) SrTiO3 (STO) substrate. X-ray diffraction pattern reveals a well-grown epitaxial BFO thin film. Atomic force microscopy study indicates that the BFO film is rather dense with a smooth surface. The ellipsometric spectra of the STO substrate, the SRO buffer layer, and the BFO thin film were measured, respectively, in the photon energy range 1.55 to 5.40 eV. Following the dielectric functions of STO and SRO, the ones of BFO described by the Lorentz model are received by fitting the spectra data to a five-medium optical model consisting of a semi-infinite STO substrate/SRO layer/BFO film/surface roughness/air ambient structure. The thickness and the optical constants of the BFO film are obtained. Then a direct bandgap is calculated at 2.68 eV, which is believed to be influenced by near-bandgap transitions. Compared to BFO films on other substrates, the dependence of the bandgap for the BFO thin film on in-plane compressive strain from epitaxial structure is received. Moreover, the bandgap and the transition revealed by the Lorentz model also provide a ground for the assessment of the bandgap for BFO single crystals.

Three-dimensional AlZnO/Al2O3/AlZnO nanocapacitor arrays on Si substrate for energy storage.

High density three-dimensional AZO/Al2O3/AZO nanocapacitor arrays have been fabricated for energy storage applications. Using atomic layer deposition technique, the stack of AZO/Al2O3/AZO has been grown in the porous anodic alumina template which is directly formed on the Si substrate. The fabricated capacitor shows a high capacitance density of 15.3 fF/µm2 at 100 kHz, which is nearly 2.5 times over the planar capacitor under identical conditions in theory. Further, the charge-discharge characteristics of the capacitor are characterized, indicating that the resistance-capacitance time constants are equal to 300 ns for the charging and discharging processes, and have no dependence on the voltage supply. This reflects good power characteristics of the electrostatic capacitor.

Nano-embossing technology on ferroelectric thin film Pb(Zr0.3,Ti0.7)O3 for multi-bit storage application.

In this work, we apply nano-embossing technique to form a stagger structure in ferroelectric lead zirconate titanate [Pb(Zr0.3, Ti0.7)O3 (PZT)] films and investigate the ferroelectric and electrical characterizations of the embossed and un-embossed regions, respectively, of the same films by using piezoresponse force microscopy (PFM) and Radiant Technologies Precision Material Analyzer. Attributed to the different layer thickness of the patterned ferroelectric thin film, two distinctive coercive voltages have been obtained, thereby, allowing for a single ferroelectric memory cell to contain more than one bit of data.

Rh:BaTiO3 thin films with large nonlinear optical properties.

We report the fabrication and the nonlinear optical properties of Rh-doped BaTiO3 thin films. The films were deposited on SrTiO3 (100) substrates by pulsed-laser deposition. The deposited Rh:BaTiO3 thin films were single phase and c-axis orientation investigated by x-ray diffraction. The films exhibited large nonlinear optical effects, which were determined using Z-scan technique at a wavelength of 532 nm with a laser duration of 10 ns. The real and imaginary parts of the third-order nonlinear susceptibility chi (3) were 5.71 x 10(-7) esu and 9.59 x 10(-8) esu, respectively. The value of Re chi (3) of Rh:BaTiO3 films is much larger than those of several representative nonlinear optical thin films. The results show that Rh:BaTiO3 thin films have great potential applications for nonlinear optical devices.