High-Performance LiNbO3 Domain Wall Memory Devices with Enhanced Selectivity via Optimized Metal-Semiconductor Contact.

Lithium niobate (LiNbO3) single-crystal nanodevices featuring elevated readout domain wall currents exhibit significant potential for integrated circuits in memory computing applications. Nevertheless, challenges stem from suboptimal electrode-LiNbO3 single crystal contact characteristics, which impact the stability of high currents within these devices. In this work, we concentrate on augmenting the domain wall current by refining the fabrication processes of domain wall random access memory (DWRAM). Each LiNbO3 domain wall nanodevice was fabricated using a self-aligned process. Device performance was significantly enhanced by introducing a 10 nm interlayer between the LiNbO3 and Cu electrodes. A comparative analysis of electrical properties was conducted on devices with interlayers made of chromium (Cr) and titanium (Ti), as well as devices without interlayers. After the introduction of the Ti interlayer, the device's coercive voltage demonstrated an 82% reduction, while the current density showed a remarkable 94-fold increase. A 100 nm sized device with the Ti interlayer underwent positive down-negative up pulse testing, demonstrating a writing time of 82 ns at 8 V and an erasing time of 12 µs at -9 V. These operating speeds are significantly faster than those of devices without interlayers. Moreover, the enhanced devices exhibited symmetrical domain switching hysteresis loops with retention times exceeding 106 s. Notably, the coercive voltage (Vc) dispersion remained narrow after more than 1000 switching cycles. At an elevated temperature of 400 K, the device's on/off ratio was maintained at 105. The device's embedded selector demonstrated an ultrahigh selectivity (>106) across various reading voltages. These results underscore the viability of high-density nanoscale integration of ferroelectric domain wall memory.

Spurious-Free Shear Horizontal Wave Resonators Based on 36Y-Cut LiNbO3 Thin Film.

This article presents lithium niobate (LiNbO3) based on shear horizontal (SH0) resonators, utilizing a suspended structure, for radio frequency (RF) applications. It demonstrates the design, analysis, and fabrication of SH0 resonators based on a 36Y-cut LiNbO3 thin film. The spurious-free SH0 resonator achieves an electromechanical coupling coefficient (kt2) of 42.67% and a quality factor (Qr) of 254 at the wave-propagating orientation of 0° in the 36Y-cut plane.

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.

LiNbO3 Thin Films through a Sol-Gel/Spin-Coating Approach Using a Novel Heterobimetallic Lithium-Niobium Precursor.

Lithium niobate is a lead-free material which has attracted considerable attention due to its excellent optical, piezoelectric, and ferroelectric properties. This research is devoted to the synthesis through an innovative sol-gel/spin-coating approach of polycrystalline LiNbO3 films on Si substrates. A novel single-source hetero-bimetallic precursor containing lithium and niobium was synthesized and applied to the sol-gel synthesis. The structural, compositional, and thermal characteristics of the precursor have been tested through attenuated total reflection, X-ray photoelectron spectroscopy, thermogravimetric analysis, and differential scanning calorimetry. The LiNbO3 films have been characterized from a structural point of view with combined X-ray diffraction and Raman spectroscopy. Field-emission scanning electron microscopy, energy dispersive X-ray analysis, and X-ray photoelectron spectroscopy have been used to study the morphological and compositional properties of the deposited films.

Integration of epitaxial LiNbO3thin films with silicon technology.

Development of bulk acoustic wave filters with ultra-wide pass bands and operating at high frequencies for 5thand 6thgeneration telecommunication applications and micro-scale actuators, energy harvesters and sensors requires lead-free piezoelectric thin films with high electromechanical coupling and compatible with Si technology. In this paper, the epitaxial growth of 36°Y-X and 30°X-Y LiNbO3films by direct liquid injection chemical vapour deposition on Si substrates by using epitaxial SrTiO3layers, grown by molecular beam epitaxy, has been demonstrated. The stability of the interfaces and chemical interactions between SrTiO3, LiNbO3and Si were studied experimentally and by thermodynamical calculations. The experimental conditions for pure 36°Y-X orientation growth have been optimized. The piezoelectricity of epitaxial 36°Y-X LiNbO3/SrTiO3/Si films was confirmed by means of piezoelectric force microscopy measurements and the ferroelectric domain inversion was attained at 85 kV.cm-1as expected for the nearly stoichiometric LiNbO3. According to the theoretical calculations, 36°Y-X LiNbO3films on Si could offer an electromechanical coupling of 24.4% for thickness extension excitation of bulk acoustic waves and a comparable figure of merit of actuators and vibrational energy harvesters to that of standard PbZr1-xTixO3films.

Microfabrication of piezoelectric MEMS based on thick LiNbO3single-crystal films.

Microfabrication procedure of piezoelectric micro electro-mechanical systems based on 5µm thick LiNbO3films on SiO2/Si substrate at wafer scale including deep dry etching of thick LiNbO3films by implementing pulsed mode of Ar/SF6gas was developed. In particular, two (YXlt)/128°/90°LiNbO3-Si cantilevers with tip mass were fabricated and characterized in terms of resonance frequency (511 and 817 Hz), actuation and acceleration sensing capabilities. The quality factor of 89.5 and the electromechanical coupling of 4.8% were estimated from measured frequency dependency of electrical impedance, fitted by using Butterworth-Van Dyke model. The fabricated piezoelectric micro-electro-mechanical systems have demonstrated highly linear displacement with good sensitivity (5.28 ± 0.02µm V-1) as a function of applied voltage and high sensitivity to vibrations of 667 mV g-1indicating a suitability of the structure for actuation purposes and for acceleration or frequency sensing with high precision, respectively.

Nonclassical Nucleation and Crystallization of LiNbO3 Nanoparticles from the Aqueous Solvothermal Alkoxide Route.

The exact molecular reaction pathway and crystallization mechanisms of LiNbO3 nanoparticles under solvothermal conditions are derived through extensive time- and temperature-resolved experiments allowing to track all the transient molecular and solid species. Starting with a simple mixing of Li/Nb ethoxides, water addition is used to promote condensation after ligand exchange with different co-solvents including alcohols and glycols of variable carbon-chain length. A nonclassical nucleation scheme is first demonstrated after the identification of new octanuclear complexes with a {Li4Nb4O10} core whose solvophobic interactions mediate their aggregation, thus, resulting in a colloidal gel at room-temperature. Upon heating, a more or less frustrated aggregation-mediated crystallization process is then evidenced leading to LiNbO3 nanocrystals of adjustable mean size between 20 and 100 nm. Such a fine control can be attributed to the variable Nb-OR (R = alkoxy/glycoxy ligand) binding interactions at the surface of crystalline intermediates. Demonstration of such a nonclassical nucleation process and crystallization mechanism for LiNbO3 not only sheds light on the entire growth process of multifunctional nanomaterials with non-perovskite crystalline structures, but also opens new avenues for the identification of novel bimetallic oxoclusters involved in the formation of several mixed oxides from the aqueous alkoxide route.

Irreversible Bonding of Polydimethylsiloxane-Lithium Niobate using Oxygen Plasma Modification for Surface Acoustic Wave based Microfluidic Application: Theory and Experiment.

Acoustic microfluidic chips, fabricated by combining lithium niobate (LiNbO3 ) with polydimethylsiloxane (PDMS), practically find applications in biomedicine. However, high-strength direct bonding of LiNbO3 substrate with PDMS microchannel remains a challenge due to the large mismatching of thermal expansion coefficient at the interface and the lack of bonding theory. This paper elaborately reveals the bonding mechanisms of PDMS and LiNbO3 , demonstrating an irreversible bonding method for PDMS-LiNbO3 heterostructures using oxygen plasma modification. An in-situ monitoring strategy by using resonant devices is proposed for oxygen plasma, including quartz crystal microbalance (QCM) covered with PDMS and surface acoustic wave (SAW) fabricated by LiNbO3 . When oxygen plasma exposure occurs, surfaces are cleaned, oxygen ions are implanted, and hydroxyl groups (-OH) are formed. Upon interfaces bonding, the interface will form niobium-oxygen-silicon covalent bonds to realize an irreversible connection. A champion bonding strength is obtained of 1.1 MPa, and the PDMS-LiNbO3 acoustic microfluidic chip excels in leakage tests, withstanding pressures exceeding 60 psi, outperforming many previously reported devices. This work addresses the gap in PDMS-LiNbO3 bonding theory and advances its practical application in the acoustic microfluidic field.

Time-domain Brillouin scattering for evaluation of materials interface inclination: Application to photoacoustic imaging of crystal destruction upon non-hydrostatic compression.

Time-domain Brillouin scattering (TDBS) is a developing technique for imaging/evaluation of materials, currently used in material science and biology. Three-dimensional imaging and characterization of polycrystalline materials has been recently reported, demonstrating evaluation of inclined material boundaries. Here, the TDBS technique is applied to monitor the destruction of a lithium niobate single crystal upon non-hydrostatic compression in a diamond anvil cell. The 3D TDBS experiments reveal, among others, modifications of the single crystal plate with initially plane-parallel surfaces, caused by non-hydrostatic compression, the laterally inhomogeneous variations of the plate thickness and relative inclination of opposite surfaces. Our experimental observations, supported by theoretical interpretation, indicate that TDBS enables the evaluation of materials interface orientation/inclination locally, from single point measurements, avoiding interface profilometry. A variety of observations reported in this paper paves the way to further expansion of the TDBS imaging use to analyze fascinating processes/phenomena occurring when materials are subjected to destruction.

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.

Through-Holes Design for Ideal LiNbO3 A1 Resonators.

This paper proposes a method to realize ideal lithium niobate (LiNbO3) A1 resonators. By introducing subwavelength through-holes between the interdigital transducer (IDT) electrodes on the LiNbO3 surface, all unfavorable spurious modes of the resonators can be suppressed completely. It is convenient and valid for various IDT electrode parameters and different LiNbO3 thicknesses. Also, this method does not require additional device fabrication steps. At the same time, these through-holes can greatly reduce the suspended area of the LiNbO3 thin film, thus significantly improving the design flexibility, compactness, mechanical stability, temperature stability, and power tolerance of the resonators (and subsequent filters). It is expected to become an important means to promote the practical application of LiNbO3 A1 filters and even all Lamb waves filters.

LiNbO3 dynamic memristors for reservoir computing.

Information in conventional digital computing platforms is encoded in the steady states of transistors and processed in a quasi-static way. Memristors are a class of emerging devices that naturally embody dynamics through their internal electrophyiscal processes, enabling nonconventional computing paradigms with enhanced capability and energy efficiency, such as reservoir computing. Here, we report on a dynamic memristor based on LiNbO3. The device has nonlinear I-V characteristics and exhibits short-term memory, suitable for application in reservoir computing. By time multiplexing, a single device can serve as a reservoir with rich dynamics which used to require a large number of interconnected nodes. The collective states of five memristors after the application of trains of pulses to the respective memristors are unique for each combination of pulse patterns, which is suitable for sequence data classification, as demonstrated in a 5 × 4 digit image recognition task. This work broadens the spectrum of memristive materials for neuromorphic computing.

Detection of the minimum concentrations of α-lactose solution using high-power THz-ATR spectroscopy.

Terahertz (THz) technology has emerged as a promising tool for the qualitative and quantitative identification of markers containing major diseases, enabling early diagnosis and staged treatment of diseases. Nevertheless, the detection of water-containing biological samples is facing significant challenges due to limitations in high-power THz radiation sources and high-sensitivity detection devices. In this paper, we present a designed and constructed set of Terahertz-Attenuated Total Reflection (THz-ATR) spectrometer for high-sensitivity detection of liquid biological samples, which can dynamically maintain the signal-to-noise ratio (SNR) of THz detection signal of liquid biological samples at 40-60 dB. Our high-power THz-ATR spectroscopy can identify and quantitatively detect α-lactose aqueous solution with a minimum concentration of 0.292 mol/L. Moreover, we observed that the rate of change in the absorption peak position varied greatly between high and low concentration samples. Our high-power, high-sensitivity THz-ATR spectroscopy detection provides a rapid, accurate, and low-cost method for detecting disease markers such as blood and urine indicators. Additionally, this approach offers new perspectives for the refinement and in-depth detection of biomedical samples.

Design and Analysis of Lithium-Niobate-Based Laterally Excited Bulk Acoustic Wave Resonator with Pentagon Spiral Electrodes.

In this paper, we present a comprehensive study on the propagation and dispersion characteristics of A1 mode propagating in Z-cut LiNbO3 membrane. The A1 mode resonators with pentagon spiral electrodes utilizing Z-cut lithium niobate (LiNbO3) thin film are designed and fabricated. The proposed structure excites the A1 mode waves in both x- and y-direction by utilizing both the piezoelectric constants e24 and e15 due to applying voltage along both the x- and y-direction by arranging pentagon spiral electrode. The fabricated resonator operates at 5.43 GHz with no spurious mode and effective electromechanical coupling coefficient (Keff2) of 21.3%, when the width of electrode is 1 µm and the pitch is 5 µm. Moreover, we present a comprehensive study of the effect of different structure parameters on resonance frequency and Keff2 of XBAR. The Keff2 keeps a constant with varied thickness of LiNbO3 thin film and different electrode rotation angles, while it declines with the increase of p from 5 to 20 µm. The proposed XBAR with pentagon spiral electrodes realize high frequency response with no spurious mode and tunable Keff2, which shows promising prospects to satisfy the needs of various 5 G high-band application.

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.

Li7La3Zr2O12-co-LiNbO3 Surface Modification Improves the Interface Stability between Cathode and Sulfide Solid-State Electrolyte in All-Solid-State Batteries.

With the rapid development of energy storage and electric vehicles, thiophosphate-based all-solid-state batteries (ASSBs) are considered the most promising power source. In order to commercialize ASSBs, the interfacial problem between high-voltage cathode active materials and thiophosphate-based solid-state electrolytes needs to be solved in a simple, effective way. Surface coatings are considered the most promising approach to solving the interfacial problem because surface coatings could prevent direct physical contact between cathode active materials and thiophosphate-based solid-state electrolytes. In this work, Li7La3Zr2O12 (LLZO) and LiNbO3 (LNO) coatings for LiCoO2 (LCO) were fabricated by in-situ interfacial growth of two high-Li+ conductive oxide electrolytes on the LCO surface and tested for thiophosphate-based ASSBs. The coatings were obtained from a two-step traditional sol-gel coatings process, the inner coatings were LNO, and the surface coatings were LLZO. Electrochemical evaluations confirmed that the two-layer coatings are beneficial for ASSBs. ASSBs containing LLZO-co-LNO coatings LiCoO2 (LLZO&LNO@LCO) significantly improved long-term cycling performance and discharge capacity compared with those assembled from uncoated LCO. LLZO&LNO@LCO||Li6PS5Cl (LPSC)||Li-In delivered discharge capacities of 138.8 mAh/g, 101.8 mAh/g, 60.2 mAh/g, and 40.2 mAh/g at 0.05 C, 0.1 C, 0.2 C, and 0.5 C under room temperature, respectively, and better capacity retentions of 98% after 300 cycles at 0.05 C. The results highlighted promising low-cost and scalable cathode material coatings for ASSBs.

Changes in the Raman Spectrum of Monolayer Graphene under Compression/Stretching Strain in Graphene/Piezoelectric Crystal Structures.

Results from studying the effect of an applied electric voltage on the Raman spectrum of graphene deposited on a lithium niobate crystal substrate with a ferroelectric domain structure are presented. The use of the principal component method for data processing in combination with correlation analysis made it possible to reveal the contribution to the change in the spectra associated with the linear deformation of the substrate due to the inverse piezoelectric effect. An effect of the graphene coating peeling was found. Furthermore, bending deformations of the graphene coating associated with the presence of a relief on the substrate were found. An analysis of the change in the spectra of graphene under the application of an electric voltage made it possible to determine the height of this relief.

Quantitative analysis of aqueous biomolecular mixtures by THz spectroscopy based on high-power LiNbO3 radiation source.

The rapid and accurate identification of the types and contents of early pathological markers by THz technology are of particular importance for the prevention and treatment of major diseases. Nevertheless, these markers usually contain interference from water and other non-target molecules, resulting in low signal-to-noise ratio (SNR) and making identification and quantitative analysis difficult. Here, based on THz spectroscopy from a high-power THz source radiated by LiNbO3, we perform quantitative and real-time THz detection of mixtures (α-lactose monohydrate and 4-aminobenzoic acid) in liquids. The results demonstrate that the absorption spectra of the aqueous biomolecular mixtures exhibit an accumulation of THz features of each pure product, i.e., the amplitude of the absorption peaks is proportional to the mixing ratio, while the corresponding absorption baseline increases with decreasing concentration. Furthermore, the content of the target substance can be calculated from the linear relationship between the absorption spectra of pure and mixed samples. This technology will support the future application of THz-TDS in early disease diagnosis under complex states and environments.

High-Performance SAW Low Temperature Sensors with Double Electrode Transducers Based on 128° YX LiNbO3.

Low temperature measurement is crucial in deep space exploration. Surface acoustic wave (SAW) sensors can measure temperature wirelessly, making them ideal in extreme situations when wired sensors are not applicable. In this study, 128° YX LiNbO3 was first introduced into low temperature measurements for its little creep or hysteresis in cryogenic environments and affordable price. The finite element method was utilized to raise the design efficiency and optimize the performance of SAW sensors by comparing the performance with different interdigital transducer (IDT) structure parameters, including the height of electrodes, pairs of IDTs, reflecting grid logarithm and acoustic aperture. Once the parameters were changed, a novel design of high-performance SAW temperature sensors based on 128° YX LiNbO3 with double electrode transducers was obtained, of which the Q value could reach up to 5757.18, 4.2-times higher than originally reported. Low temperature tests were conducted, and the frequency responsiveness of SAW sensors was almost linear from -100 °C to 150 °C, which is in good agreement with the simulation results. All results demonstrate that double electrode transducers are considerably efficient for performance enhancement, especially for high-Q SAW sensors, and indicate that LiNbO3 substrate can be a potential high-performance substitute for cryogenic temperature measurements.