Exploring the Reconfigurable Memory Effect in Electroforming-Free YMnO3-Based Resistive Switches: Towards a Tunable Frequency Response.

Memristors, since their inception, have demonstrated remarkable characteristics, notably the exceptional reconfigurability of their memory. This study delves into electroforming-free YMnO3 (YMO)-based resistive switches, emphasizing the reconfigurable memory effect in multiferroic YMO thin films with metallically conducting electrodes and their pivotal role in achieving adaptable frequency responses in impedance circuits consisting of reconfigurable YMO-based resistive switches and no reconfigurable passive elements, e.g., inductors and capacitors. The multiferroic YMO possesses a network of charged domain walls which can be reconfigured by a time-dependent voltage applied between the metallically conducting electrodes. Through experimental demonstrations, this study scrutinizes the impedance response not only for individual switch devices but also for impedance circuitry based on YMO resistive switches in both low- and high-resistance states, interfacing with capacitors and inductors in parallel and series configurations. Scrutinized Nyquist plots visually capture the intricate dynamics of impedance circuitry, revealing the potential of electroforming-free YMO resistive switches in finely tuning frequency responses within impedance circuits. This adaptability, rooted in the unique properties of YMO, signifies a paradigm shift heralding the advent of advanced and flexible electronic technologies.

A Novel Approach to Monitor the Concentration of Phosphate Buffers in the Range of 1 M to 0.1 M Using a Silicon-Based Impedance Sensor.

We present a novel and easy approach using a silicon-based impedance chip to determine the concentration of the given aqueous buffer solution. An accurate determination of the post-dilution concentration of the buffers is necessary for ensuring optimal buffer capacity, pH stability, and to assess solution reproducibility. In this study, we focused on phosphate buffer as the test liquid to achieve precise post-dilution concentration determinations. The impedance chip consisting of a top gold ring electrode, where a test volume of 20 µL to 30 µL of phosphate buffer was introduced for impedance measurements within the frequency range of 40 Hz to 1 MHz. For impedance investigation, we used phosphate buffers with three different pH values, and the impedance was measured after diluting the phosphate buffers to a concentration of 1.00 M, 0.75 M, 0.50 M, 0.25 M, 0.10 M, 0.05 M, and 0.01 M. In order to analyze the distinctive changes in the measured impedance, an equivalent circuit was proposed and modeled. From the impedance modeling, we report that the circuit parameter RAu/Si showed exponential dependence on the concentration of phosphate buffer and no dependence on the pH values of the phosphate buffer and on the added volume inside the ring electrode. The proposed silicon-based impedance chip is quick and uses reduced liquid volume for post-dilution concentration measurements of buffers and has perspective applications in the pharmaceutical and biological domains for regulating, monitoring, and quality control of the buffers.

Review on Resistive Switching Devices Based on Multiferroic BiFeO3.

This review provides a comprehensive examination of the state-of-the-art research on resistive switching (RS) in BiFeO3 (BFO)-based memristive devices. By exploring possible fabrication techniques for preparing the functional BFO layers in memristive devices, the constructed lattice systems and corresponding crystal types responsible for RS behaviors in BFO-based memristive devices are analyzed. The physical mechanisms underlying RS in BFO-based memristive devices, i.e., ferroelectricity and valence change memory, are thoroughly reviewed, and the impact of various effects such as the doping effect, especially in the BFO layer, is evaluated. Finally, this review provides the applications of BFO devices and discusses the valid criteria for evaluating the energy consumption in RS and potential optimization techniques for memristive devices.

Embedding an Amphiphilic 4-Hydroxy Thiazole Dye in Langmuir Matrices: Studying Miscibilities with Arylic and Alkylic Matrix Amphiphiles via Langmuir Isotherms and Photo-induced Force Microscopy.

We present here a fundamental study on the miscibility between a prototype amphiphilic dye and alkylic and arylic Langmuir monolayers. Embedding dyes in such matrices is crucial for utilizing dyes in any photo-energy conversion process if the involved dyes form aggregates that provide thermal deactivation channels. Because miscibility in Langmuir matrices depends on the blending ratio between the dye and matrix and on the Langmuir film density, as characterized via the surface pressure and the mean molecular area, we employ Langmuir miscibility studies to identify ideal miscibility parameters for each matrix. Atomic force microscopy (AFM) results support miscibility between the dye and both matrix materials at low surface pressures, where smooth and homogeneous films are obtained. AFM and photo-induced force microscopy (PiFM) reveal phase separation if the Langmuir monolayers are deposited at surface pressures above 8 mN/m at which reorientation of the chromophores has been reported. The nanoscale chemical fingerprint mapping enabled by PiFM enables assigning segregated spots to small stearic acid (SA)-enriched domains that have not been detected via AFM, thus demonstrating the value of the IR-spectroscopic contrast provided by PiFM. In this work, we have presented a so far unexploited matrix material (terphenylene carboxylic acid; TPCA) and found it equally suitable for embedding dyes as the standard amphiphile SA. In contrast to SA, TPCA is composed of rigid and electrically conducting π-electron systems, hence, being predestined for aligning dyes in Langmuir matrices and for application in optoelectronic systems.

Synaptic Plasticity in Memristive Artificial Synapses and Their Robustness Against Noisy Inputs.

Emerging brain-inspired neuromorphic computing paradigms require devices that can emulate the complete functionality of biological synapses upon different neuronal activities in order to process big data flows in an efficient and cognitive manner while being robust against any noisy input. The memristive device has been proposed as a promising candidate for emulating artificial synapses due to their complex multilevel and dynamical plastic behaviors. In this work, we exploit ultrastable analog BiFeO3 (BFO)-based memristive devices for experimentally demonstrating that BFO artificial synapses support various long-term plastic functions, i.e., spike timing-dependent plasticity (STDP), cycle number-dependent plasticity (CNDP), and spiking rate-dependent plasticity (SRDP). The study on the impact of electrical stimuli in terms of pulse width and amplitude on STDP behaviors shows that their learning windows possess a wide range of timescale configurability, which can be a function of applied waveform. Moreover, beyond SRDP, the systematical and comparative study on generalized frequency-dependent plasticity (FDP) is carried out, which reveals for the first time that the ratio modulation between pulse width and pulse interval time within one spike cycle can result in both synaptic potentiation and depression effect within the same firing frequency. The impact of intrinsic neuronal noise on the STDP function of a single BFO artificial synapse can be neglected because thermal noise is two orders of magnitude smaller than the writing voltage and because the cycle-to-cycle variation of the current-voltage characteristics of a single BFO artificial synapses is small. However, extrinsic voltage fluctuations, e.g., in neural networks, cause a noisy input into the artificial synapses of the neural network. Here, the impact of extrinsic neuronal noise on the STDP function of a single BFO artificial synapse is analyzed in order to understand the robustness of plastic behavior in memristive artificial synapses against extrinsic noisy input.

Detecting Bacterial Cell Viability in Few µL Solutions from Impedance Measurements on Silicon-Based Biochips.

Using two different types of impedance biochips (PS5 and BS5) with ring top electrodes, a distinct change of measured impedance has been detected after adding 1-5 µL (with dead or live Gram-positive Lysinibacillus sphaericus JG-A12 cells to 20 µL DI water inside the ring top electrode. We relate observed change of measured impedance to change of membrane potential of L. sphaericus JG-A12 cells. In contrast to impedance measurements, optical density (OD) measurements cannot be used to distinguish between dead and live cells. Dead L. sphaericus JG-A12 cells have been obtained by adding 0.02 mg/mL of the antibiotics tetracycline and 0.1 mg/mL chloramphenicol to a batch with OD0.5 and by incubation for 24 h, 30 °C, 120 rpm in the dark. For impedance measurements, we have used batches with a cell density of 25.5 × 108 cells/mL (OD8.5) and 270.0 × 108 cells/mL (OD90.0). The impedance biochip PS5 can be used to detect the more resistive and less capacitive live L. sphaericus JG-A12 cells. Also, the impedance biochip BS5 can be used to detect the less resistive and more capacitive dead L. sphaericus JG-A12 cells. An outlook on the application of the impedance biochips for high-throughput drug screening, e.g., against multi-drug-resistant Gram-positive bacteria, is given.

Electrochemical growth mechanism of nanoporous platinum layers.

Porous platinum is a frequently used catalyst material in electrosynthesis and a robust broadband absorber in thermoelectrics. Pore size distribution and localization determine its properties by a large extent. However, the pore formation mechanism during the growth of the material remains unclear. In this work we elucidate the mechanism underlying electrochemical growth of nanoporous platinum layers and its control by ionic concentration and current density during electrolysis. The electrode kinetics and reduction steps of PtCl4 on platinum electrodes are investigated by cyclic voltammetry and impedance measurements. Cyclic voltammograms show three reduction steps: two steps relate to the platinum cation reduction, and one step relates to the hydrogen reduction. Hydrogen is not involved in the reduction of PtCl4, however it enables the formation of nanopores in the layers. These findings contribute to the understanding of electrochemical growth of nanoporous platinum layers in isopropanol with thickness of 100 nm to 500 nm.

Towards Bacteria Counting in DI Water of Several Microliters or Growing Suspension Using Impedance Biochips.

We counted bacterial cells of E. coli strain K12 in several-microliter DI water or in several-microliter PBS in the low optical density (OD) range (OD = 0.05-1.08) in contact with the surface of Si-based impedance biochips with ring electrodes by impedance measurements. The multiparameter fit of the impedance data allowed calibration of the impedance data with the concentration cb of the E. coli cells in the range of cb = 0.06 to 1.26 × 109 cells/mL. The results showed that for E. coli in DI water and in PBS, the modelled impedance parameters depend linearly on the concentration of cells in the range of cb = 0.06 to 1.26 × 109 cells/mL, whereas the OD, which was independently measured with a spectrophotometer, was only linearly dependent on the concentration of the E. coli cells in the range of cb = 0.06 to 0.50 × 109 cells/mL.

Increased static dielectric constant in ZnMnO and ZnCoO thin films with bound magnetic polarons.

A novel small signal equivalent circuit model is proposed in the inversion regime of metal/(ZnO, ZnMnO, and ZnCoO) semiconductor/Si3N4 insulator/p-Si semiconductor (MSIS) structures to describe the distinctive nonlinear frequency dependent capacitance (C-F) and conductance (G-F) behaviour in the frequency range from 50 Hz to 1 MHz. We modelled the fully depleted ZnO thin films to extract the static dielectric constant (εr) of ZnO, ZnMnO, and ZnCoO. The extracted enhancement of static dielectric constant in magnetic n-type conducting ZnCoO (εr ≥ 13.0) and ZnMnO (εr ≥ 25.8) in comparison to unmagnetic ZnO (εr = 8.3-9.3) is related to the electrical polarizability of donor-type bound magnetic polarons (BMP) in the several hundred GHz range (120 GHz for CdMnTe). The formation of donor-BMP is enabled in n-type conducting, magnetic ZnO by the s-d exchange interaction between the electron spin of positively charged oxygen vacancies [Formula: see text] in the BMP center and the electron spins of substitutional Mn2+ and Co2+ ions in ZnMnO and ZnCoO, respectively. The BMP radius scales with the Bohr radius which is proportional to the static dielectric constant. Here we show how BMP overlap can be realized in magnetic n-ZnO by increasing its static dielectric constant and guide researchers in the field of transparent spintronics towards ferromagnetism in magnetic, n-ZnO.

Charged domains in ferroelectric, polycrystalline yttrium manganite thin films resolved with scanning electron microscopy.

We have investigated ferroelectric charged domains in polycrystalline hexagonal yttrium manganite thin films (Y1Mn1O3, Y0.95Mn1.05O3, Y1Mn0.99Ti0.01O3, and Y0.94Mn1.05Ti0.01O3) by scanning electron microscopy (SEM) in secondary electron emission mode with a small acceleration voltage. Using SEM at an acceleration voltage of 1.0 kV otherwise homogenous surface charging effects are reduced, polarization charges can be observed and polarization directions (±Pz) of the ferroelectric domains in the polycrystalline thin films can be identified. Thin films of different chemical composition have been deposited by pulsed laser deposition on Pt/SiO2/Si structures under otherwise same growth conditions. Using SEM it has been shown that different charged domain density networks are existing in polycrystalline yttrium manganite thin films.

Disturbing-Free Determination of Yeast Concentration in DI Water and in Glucose Using Impedance Biochips.

Deionized water and glucose without yeast and with yeast (Saccharomyces cerevisiae) of optical density OD600 that ranges from 4 to 16 has been put in the ring electrode region of six different types of impedance biochips and impedance has been measured in dependence on the added volume (20, 21, 22, 23, 24, 25 µL). The measured impedance of two out of the six types of biochips is strongly sensitive to the addition of both liquid without yeast and liquid with yeast and modelled impedance reveals a linear relationship between the impedance model parameters and yeast concentration. The presented biochips allow for continuous impedance measurements without interrupting the cultivation of the yeast. A multiparameter fit of the impedance model parameters allows for determining the concentration of yeast (cy) in the range from cy = 3.3 × 107 to cy = 17 × 107 cells/mL. This work shows that independent on the liquid, i.e., DI water or glucose, the impedance model parameters of the two most sensitive types of biochips with liquid without yeast and with liquid with yeast are clearly distinguishable for the two most sensitive types of biochips.

P-N Junction-Based Si Biochips with Ring Electrodes for Novel Biosensing Applications.

In this work, we report on the impedance of p-n junction-based Si biochips with gold ring top electrodes and unstructured platinum bottom electrodes which allows for counting target biomaterial in a liquid-filled ring top electrode region. The systematic experiments on p-n junction-based Si biochips fabricated by two different sets of implantation parameters (i.e. biochips PS5 and BS5) are studied, and the comparable significant change of impedance characteristics in the biochips in dependence on the number of bacteria suspension, i.e., Lysinibacillus sphaericus JG-A12, in Deionized water with an optical density at 600 nm from OD600 = 4-16 in the electrode ring region is demonstrated. Furthermore, with the help of the newly developed two-phase electrode structure, the modeled capacitance and resistance parameters of the electrical equivalent circuit describing the p-n junction-based biochips depend linearly on the number of bacteria in the ring top electrode region, which successfully proves the potential performance of p-n junction-based Si biochips in observing the bacterial suspension. The proposed p-n junction-based biochips reveal perspective applications in medicine and biology for diagnosis, monitoring, management, and treatment of diseases.

Plasma-Induced Nonvolatile Resistive Switching with Extremely Low SET Voltage in TiOxFy with AgF Nanoparticles.

Low power consumption is crucial for the application of resistive random access memory. In this work, we present the bipolar resistive switching in an Ag/TiOxFy/Ti/Pt stack with extremely low switch-on voltage of 0.07 V. Operating current as low as 10 nA was also obtained by conductive atomic force microscopy. The highly defective TiOxFy layer was fabricated by plasma treatment using helium, oxygen, and carbon tetrafluoride orderly. During the electroforming process, AgF nanoparticles were formed due to the diffusion of Ag+ which reacted with the adsorbed F- in the TiOxFy layer. These nanoparticles are of great importance to resistive switching performance because they are believed to be conductive phases and become part of the conducting path when the sample is switched to a low-resistance state.

Bipolar resistive switching in YMnO3/Nb:SrTiO3 pn-heterojunctions.

Resistively switching oxides are promising materials for use in electronic applications such as nonvolatile memories, logic gates, and artificial synapses. This work presents the bipolar resistive switching (BRS) in YMnO3/Nb:SrTiO3 pn-heterojunctions. A thermally driven electroforming process is required prior to the observed BRS. Results indicate that the BRS in YMnO3/Nb:SrTiO3 originates from the combined effects of charge trapping and detrapping processes along with the electro-migration of charged point defects in the depletion layer of the pn-heterojunction. It is shown that the built-in voltage of the pn-heterojunctions can be tuned by the oxygen partial pressure during growth of the YMnO3 thin film and impacts the working parameters of the resistively switching cell. This study provides a guideline for material engineering of bipolar resistive switches based on pn-heterojunctions.

Engineering interface-type resistive switching in BiFeO3 thin film switches by Ti implantation of bottom electrodes.

BiFeO3 based MIM structures with Ti-implanted Pt bottom electrodes and Au top electrodes have been fabricated on Sapphire substrates. The resulting metal-insulator-metal (MIM) structures show bipolar resistive switching without an electroforming process. It is evidenced that during the BiFeO3 thin film growth Ti diffuses into the BiFeO3 layer. The diffused Ti effectively traps and releases oxygen vacancies and consequently stabilizes the resistive switching in BiFeO3 MIM structures. Therefore, using Ti implantation of the bottom electrode, the retention performance can be greatly improved with increasing Ti fluence. For the used raster-scanned Ti implantation the lateral Ti distribution is not homogeneous enough and endurance slightly degrades with Ti fluence. The local resistive switching investigated by current sensing atomic force microscopy suggests the capability of down-scaling the resistive switching cell to one BiFeO3 grain size by local Ti implantation of the bottom electrode.

Single pairing spike-timing dependent plasticity in BiFeO3 memristors with a time window of 25 ms to 125 µs.

Memristive devices are popular among neuromorphic engineers for their ability to emulate forms of spike-driven synaptic plasticity by applying specific voltage and current waveforms at their two terminals. In this paper, we investigate spike-timing dependent plasticity (STDP) with a single pairing of one presynaptic voltage spike and one post-synaptic voltage spike in a BiFeO3 memristive device. In most memristive materials the learning window is primarily a function of the material characteristics and not of the applied waveform. In contrast, we show that the analog resistive switching of the developed artificial synapses allows to adjust the learning time constant of the STDP function from 25 ms to 125 µs via the duration of applied voltage spikes. Also, as the induced weight change may degrade, we investigate the remanence of the resistance change for several hours after analog resistive switching, thus emulating the processes expected in biological synapses. As the power consumption is a major constraint in neuromorphic circuits, we show methods to reduce the consumed energy per setting pulse to only 4.5 pJ in the developed artificial synapses.

Plasticity in memristive devices for spiking neural networks.

Memristive devices present a new device technology allowing for the realization of compact non-volatile memories. Some of them are already in the process of industrialization. Additionally, they exhibit complex multilevel and plastic behaviors, which make them good candidates for the implementation of artificial synapses in neuromorphic engineering. However, memristive effects rely on diverse physical mechanisms, and their plastic behaviors differ strongly from one technology to another. Here, we present measurements performed on different memristive devices and the opportunities that they provide. We show that they can be used to implement different learning rules whose properties emerge directly from device physics: real time or accelerated operation, deterministic or stochastic behavior, long term or short term plasticity. We then discuss how such devices might be integrated into a complete architecture. These results highlight that there is no unique way to exploit memristive devices in neuromorphic systems. Understanding and embracing device physics is the key for their optimal use.

Bipolar electric-field enhanced trapping and detrapping of mobile donors in BiFeO3 memristors.

Pulsed laser deposited Au-BFO-Pt/Ti/Sapphire MIM structures offer excellent bipolar resistive switching performance, including electroforming free, long retention time at 358 K, and highly stable endurance. Here we develop a model on modifiable Schottky barrier heights and elucidate the physical origin underlying resistive switching in BiFeO3 memristors containing mobile oxygen vacancies. Increased switching speed is possible by applying a large amplitude writing pulse as the resistive switching is tunable by both the amplitude and length of the writing pulse. The local resistive switching has been investigated by conductive atomic force microscopy and exhibits the capability of down-scaling the resistive switching cell to the grain size.

Forming-free resistive switching in multiferroic BiFeO3 thin films with enhanced nanoscale shunts.

A controlled shunting of polycrystalline oxide thin films on the nanometer length scale opens the door to significantly modify their transport properties. In this paper, the low energy Ar(+) irradiation induced shunting effect of forming-free, non-volatile resistive switching in polycrystalline BiFeO3 thin film capacitor-like structures with macroscopic bottom and top contacts was investigated. Oxygen atoms at the BiFeO3 surface are preferentially sputtered by Ar(+) ion irradiation and oxygen vacancies and a metallic Bi phase are formed at the surface of the BiFeO3 thin film before deposition of the top contacts. A phenomenological model is that of nanoscale shunt resistors formed in parallel to the actual BiFeO3 thin film capacitor-like structure. This model fits the noticeable increase of the retention stability and current density after irradiation. The formation of stable and conductive shunts is further evidenced by conductive atomic force microscopy measurements.

Key concepts behind forming-free resistive switching incorporated with rectifying transport properties.

This work reports the effect of Ti diffusion on the bipolar resistive switching in Au/BiFeO3/Pt/Ti capacitor-like structures. Polycrystalline BiFeO3 thin films are deposited by pulsed laser deposition at different temperatures on Pt/Ti/SiO2/Si substrates. From the energy filtered transmission electron microscopy and Rutherford backscattering spectrometry it is observed that Ti diffusion occurs if the deposition temperature is above 600°C. The current-voltage (I-V) curves indicate that resistive switching can only be achieved in Au/BiFeO3/Pt/Ti capacitor-like structures where this Ti diffusion occurs. The effect of Ti diffusion is confirmed by the BiFeO3 thin films deposited on Pt/sapphire and Pt/Ti/sapphire substrates. The resistive switching needs no electroforming process, and is incorporated with rectifying properties which is potentially useful to suppress the sneak current in a crossbar architecture. Those specific features open a promising alternative concept for nonvolatile memory devices as well as for other memristive devices like synapses in neuromorphic circuits.