When Memristance Crosses the Path with Humidity Sensing—About the Importance of Protons and Its Opportunities in Valence Change Memristors

Resistive switching devices based on oxides have outstanding properties, making them a promising candidate to replace today's transistor‐based computer memories as non‐volatile valence change memories, and can even find future application in neuromorphic computing. To date, the scientific discussion is so far mainly restricted to oxygen vacancy contributions disregarding the role of protonic defects on resistive switching. In this work, the effect of moisture and protonic contributions on resistive switching by changes in the surface to bulk ratio and oxide surface exposure of the oxide SrTiO3 is studied. Here, a linear to exponential SET current density dependency, when changing the film thickness by a factor of four, is found, whereby the surface‐to‐bulk ratio of the oxide is significantly changed. This behavior is discussed in terms of differences in total concentration of oxygen vacancies and their interplay with moisture. For classic memristor applications, this study demonstrates that protonic defects need to be accounted for memristor characteristics, as they crucially influence the switching characteristics, and give new opportunities as an additional handle to actively tune the switching performance. This memristive dependency on protonic defects opens a whole plethora of new modulatable sensor characteristics like creating humidity sensors using the property of memristance.

[1]  I. Valov,et al.  Graphene‐Modified Interface Controls Transition from VCM to ECM Switching Modes in Ta/TaOx Based Memristive Devices , 2015, Advanced materials.

[2]  W. Sigle,et al.  Electrical and structural characterization of a low-angle tilt grain boundary in iron-doped strontium titanate , 2003 .

[3]  Sascha Vongehr,et al.  The Missing Memristor has Not been Found , 2015, Scientific Reports.

[4]  Fei Zhou,et al.  Demonstration of Synaptic Behaviors and Resistive Switching Characterizations by Proton Exchange Reactions in Silicon Oxide , 2016, Scientific Reports.

[5]  J. Maier,et al.  SrTiO3: a model electroceramic , 2003 .

[6]  H. Hwang,et al.  HPHA effect on reversible resistive switching of Pt/Nb-doped SrTiO3 Schottky junction for nonvolatile memory application , 2007 .

[7]  Yidong Xia,et al.  Cathode bubbles induced by moisture electrolysis in TiO2−x-based resistive switching cells , 2016 .

[8]  J. Maier,et al.  On the proton conductivity in pure and gadolinium doped nanocrystalline cerium oxide. , 2011, Physical chemistry chemical physics : PCCP.

[9]  D. Stewart,et al.  The missing memristor found , 2008, Nature.

[10]  Shinbuhm Lee,et al.  Memristive switching in Cu/Si/Pt cells and its improvement in vacuum environment , 2016 .

[11]  Nagarajan Raghavan,et al.  Performance and reliability trade-offs for high-κ RRAM , 2014, Microelectron. Reliab..

[12]  Zhi Liu,et al.  Observation of Oxygen Vacancy Filling under Water Vapor in Ceramic Proton Conductors in Situ with Ambient Pressure XPS , 2013 .

[13]  Rainer Waser,et al.  Impact of the electroforming process on the device stability of epitaxial Fe-doped SrTiO3 resistive switching cells , 2009 .

[14]  R. Waser,et al.  Electro-degradation and resistive switching of Fe-doped SrTiO3 single crystal , 2013 .

[15]  Y. Larring,et al.  Hydrogen ion conduction in iron-substituted strontium titanate, SrTi1−xFexO3−x/2 (0≤x≤0.8) , 2001 .

[16]  Ru Huang,et al.  Engineering incremental resistive switching in TaOx based memristors for brain-inspired computing. , 2016, Nanoscale.

[17]  S. Haile,et al.  Defect Chemistry of Yttrium-Doped Barium Zirconate: A Thermodynamic Analysis of Water Uptake , 2008 .

[18]  Wei Yang Lu,et al.  Nanoscale memristor device as synapse in neuromorphic systems. , 2010, Nano letters.

[19]  Enrico Traversa,et al.  Ceramic sensors for humidity detection: the state-of-the-art and future developments , 1995 .

[20]  N. Keller,et al.  Strontium titanate (100) surfaces monitoring by high temperature in situ ellipsometry , 2016 .

[21]  J. Maier,et al.  Stoichiometry Variation in Materials with Three Mobile Carriers—Thermodynamics and Transport Kinetics Exemplified for Protons, Oxygen Vacancies, and Holes , 2015 .

[22]  Manfred Martin,et al.  On the conduction pathway for protons in nanocrystalline yttria-stabilized zirconia. , 2009, Physical chemistry chemical physics : PCCP.

[23]  S. G. Ansari,et al.  The effect of humidity on an SnO2 thick-film planar resistor , 1994 .

[24]  Zhenghao Chen,et al.  In-doped SrTiO3 ceramic thin films , 2002 .

[25]  A. Walsh,et al.  Strontium migration assisted by oxygen vacancies in SrTiO3 from classical and quantum mechanical simulations , 2011 .

[26]  R. Waser Charge transport in perovskite-type titanates: Space charge effects in ceramics and films , 1994 .

[27]  Wei Zheng,et al.  Humidity sensing properties of BaTiO3 nanofiber prepared via electrospinning , 2010 .

[28]  R. Dittmann,et al.  Coexistence of Filamentary and Homogeneous Resistive Switching in Fe‐Doped SrTiO3 Thin‐Film Memristive Devices , 2010, Advanced materials.

[29]  Yoshio Nishi,et al.  Role of Hydrogen Ions in TiO2-Based Memory Devices , 2011 .

[30]  Noboru Yamazoe,et al.  Ceramic humidity sensors , 1983 .

[31]  J. Maier,et al.  Peculiar nonmonotonic water incorporation in oxides detected by local in situ optical absorption spectroscopy. , 2007, Angewandte Chemie.

[32]  Markus Kubicek,et al.  Memristor Kinetics and Diffusion Characteristics for Mixed Anionic‐Electronic SrTiO3‐δ Bits: The Memristor‐Based Cottrell Analysis Connecting Material to Device Performance , 2014 .

[33]  Rainer Waser,et al.  On the SET/RESET current asymmetry in electrochemical metallization memory cells , 2014 .

[34]  J.-H. Oh,et al.  Humidity sensing behavior of thick films of strontium-doped lead-zirconium-titanate , 2004 .

[35]  R. Cervera,et al.  Nanograined Sc-doped BaZrO3 as a proton conducting solid electrolyte for intermediate temperature solid oxide fuel cells (IT-SOFCs) , 2014 .

[36]  Myoung-Jae Lee,et al.  Anomalous effect due to oxygen vacancy accumulation below the electrode in bipolar resistance switching Pt/Nb:SrTiO3 cells , 2014 .

[37]  L.O. Chua,et al.  Memristive devices and systems , 1976, Proceedings of the IEEE.

[38]  R. Cowley The phase transition of strontium titanate , 1996, Philosophical Transactions of the Royal Society of London. Series A: Mathematical, Physical and Engineering Sciences.

[39]  Rotraut Merkle,et al.  How is oxygen incorporated into oxides? A comprehensive kinetic study of a simple solid-state reaction with SrTiO3 as a model material. , 2008, Angewandte Chemie.

[40]  Michael W. Austin,et al.  Development of multi-functional sensors in thick-film and thin-film technology , 2000 .

[41]  Dmitri B. Strukov,et al.  Donor‐Induced Performance Tuning of Amorphous SrTiO3 Memristive Nanodevices: Multistate Resistive Switching and Mechanical Tunability , 2015 .

[42]  R. Waser Diffusion of Hydrogen Defects in BaTiO3 Ceramics and SrTiO3 Single Crystals , 1986 .

[43]  Yuchao Yang,et al.  Probing nanoscale oxygen ion motion in memristive systems , 2017, Nature Communications.

[44]  J. Bain,et al.  Mobility of oxygen vacancy in SrTiO3 and its implications for oxygen-migration-based resistance switching , 2011 .

[45]  R. Dittmann,et al.  Redox‐Based Resistive Switching Memories – Nanoionic Mechanisms, Prospects, and Challenges , 2009, Advanced materials.

[46]  Lei Bi,et al.  Towards the Next Generation of Solid Oxide Fuel Cells Operating Below 600 °C with Chemically Stable Proton‐Conducting Electrolytes , 2012, Advanced materials.

[47]  R. Dittmann,et al.  Impact of Defect Distribution on Resistive Switching Characteristics of Sr2TiO4 Thin Films , 2010, Advanced materials.

[48]  G. L. Sharma,et al.  Electrical conduction in (Ba, Sr)TiO3 thin film MIS capacitor under humid conditions , 2001 .

[49]  D. Kwon,et al.  Role of oxygen vacancies in resistive switching in Pt/Nb-doped SrTiO3 , 2014 .

[50]  Yidong Xia,et al.  Polarity-dependent effect of humidity on the resistive switching characteristics of nonpolar devices , 2016 .

[51]  Markus Kubicek,et al.  How Does Moisture Affect the Physical Property of Memristance for Anionic–Electronic Resistive Switching Memories? , 2015 .

[52]  J. Kilner,et al.  Possible proton conduction in Ce0.9Gd0.1O2−δ nanoceramics , 2009 .

[53]  Dmitri B Strukov,et al.  Flexible three-dimensional artificial synapse networks with correlated learning and trainable memory capability , 2017, Nature Communications.

[54]  Yuriy V. Pershin,et al.  Memory effects in complex materials and nanoscale systems , 2010, 1011.3053.

[55]  A. Gutiérrez–Llorente,et al.  Thin films of oxygen-deficient perovskite phases by pulsed-laser ablation of strontium titanate , 2007 .

[56]  R. Dittmann,et al.  Origin of the Ultra‐nonlinear Switching Kinetics in Oxide‐Based Resistive Switches , 2011 .

[57]  Markus Kubicek,et al.  Uncovering Two Competing Switching Mechanisms for Epitaxial and Ultrathin Strontium Titanate-Based Resistive Switching Bits. , 2015, ACS nano.

[58]  Y. Zhao,et al.  Resistive switching effect in SrTiO3−δ∕Nb-doped SrTiO3 heterojunction , 2007 .

[59]  Masakazu Aono,et al.  Humidity effects on the redox reactions and ionic transport in a Cu/Ta2O5/Pt atomic switch structure , 2016 .

[60]  R. Muccillo,et al.  Properties and applications of perovskite proton conductors , 2010 .

[61]  K. Kreuer First published online as a Review in Advance on April 9, 2003 PROTON-CONDUCTING OXIDES , 2022 .

[62]  L. P. Eksperiandova,et al.  Recent trends of ceramic humidity sensors development: A review , 2016 .

[63]  Chi-En Lu,et al.  Humidity Sensors: A Review of Materials and Mechanisms , 2005 .

[64]  C. Boothroyd,et al.  Direct Measurement and Interpretation of Electrostatic Potentials at 24° [001] Tilt Boundaries in Undoped and Niobium‐Doped Strontium Titanate Bicrystals , 2005 .

[65]  T. Tseng,et al.  Electrical Properties of Porous Titania Ceramic Humidity Sensors , 1989 .

[66]  Xue-Bing Yin,et al.  Synaptic Metaplasticity Realized in Oxide Memristive Devices , 2016, Advanced materials.

[67]  P. Jacobs,et al.  Point defect energies for strontium titanate: A pair-potentials study , 1999 .