Background Since at least 400 C.E., when the Mayans first used layered clays to make dyes, people have been harnessing the properties of layered materials. This gradually developed into scientific research, leading to the elucidation of the laminar structure of layered materials, detailed understanding of their properties, and eventually experiments to exfoliate or delaminate them into individual, atomically thin nanosheets. This culminated in the discovery of graphene, resulting in a new explosion of interest in two-dimensional materials. Layered materials consist of two-dimensional platelets weakly stacked to form three-dimensional structures. The archetypal example is graphite, which consists of stacked graphene monolayers. However, there are many others: from MoS 2 and layered clays to more exotic examples such as MoO 3 , GaTe, and Bi 2 Se 3 . These materials display a wide range of electronic, optical, mechanical, and electrochemical properties. Over the past decade, a number of methods have been developed to exfoliate layered materials in order to produce monolayer nanosheets. Such exfoliation creates extremely high-aspect-ratio nanosheets with enormous surface area, which are ideal for applications that require surface activity. More importantly, however, the two-dimensional confinement of electrons upon exfoliation leads to unprecedented optical and electrical properties. Liquid exfoliation of layered crystals allows the production of suspensions of two-dimensional nanosheets, which can be formed into a range of structures. (A) MoS 2 powder. (B) WS 2 dispersed in surfactant solution. (C) An exfoliated MoS 2 nanosheet. (D) A hybrid material consisting of WS 2 nanosheets embedded in a network of carbon nanotubes. Advances An important advance has been the discovery that layered crystals can be exfoliated in liquids. There are a number of methods to do this that involve oxidation, ion intercalation/exchange, or surface passivation by solvents. However, all result in liquid dispersions containing large quantities of nanosheets. This brings considerable advantages: Liquid exfoliation allows the formation of thin films and composites, is potentially scaleable, and may facilitate processing by using standard technologies such as reel-to-reel manufacturing. Although much work has focused on liquid exfoliation of graphene, such processes have also been demonstrated for a host of other materials, including MoS 2 and related structures, layered oxides, and clays. The resultant liquid dispersions have been formed into films, hybrids, and composites for a range of applications. Outlook There is little doubt that the main advances are in the future. Multifunctional composites based on metal and polymer matrices will be developed that will result in enhanced mechanical, electrical, and barrier properties. Applications in energy generation and storage will abound, with layered materials appearing as electrodes or active elements in devices such as displays, solar cells, and batteries. Particularly important will be the use of MoS 2 for water splitting and metal oxides as hydrogen evolution catalysts. In addition, two-dimensional materials will find important roles in printed electronics as dielectrics, optoelectronic devices, and transistors. To achieve this, much needs to be done. Production rates need to be increased dramatically, the degree of exfoliation improved, and methods to control nanosheet properties developed. The range of layered materials that can be exfoliated must be expanded, even as methods for chemical modification must be developed. Success in these areas will lead to a family of materials that will dominate nanomaterials science in the 21st century.

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Liquid Exfoliation of Layered Materials

Long viewed as a topic in classical physics, ferroelectricity can be described by a quantum mechanical ab initio theory. Thin-film nanoscale device structures integrated onto Si chips have made inroads into the semiconductor industry. Recent prototype applications include ultrafast switching, cheap room-temperature magnetic-field detectors, piezoelectric nanotubes for microfluidic systems, electrocaloric coolers for computers, phased-array radar, and three-dimensional trenched capacitors for dynamic random access memories. Terabit-per-square-inch ferroelectric arrays of lead zirconate titanate have been reported on Pt nanowire interconnects and nanorings with 5-nanometer diameters. Finally, electron emission from ferroelectrics yields cheap, high-power microwave devices and miniature x-ray and neutron sources.

http://science.sciencemag.org/content/sci/315/5814/954.full.pdf

Applications of Modern Ferroelectrics

A SIGNIFICANT fraction of the computer memory industry is at present involved in the manufacture of non-volatile memory devices1—that is, devices which retain information when power is interrupted. For such applications (and also for volatile memories), the use of capacitors constructed from ferroelectric thin films has stimulated much interest1. In such structures, information is stored in the polarization state of the ferroelectric material itself, which should in principle lead to lower power requirements, faster access time and potentially lower cost1. But the use of ferroelectrics is not without problems; the memories constructed to date have generally suffered from poor retention of stored information and degradation of performance ('fatigue') with use1–3. Here we describe the preparation and characterization of thin-film capacitors using ferroelectric materials from a large family of layered perovskite oxides, exemplified by SrBi2Ta2O9, SrBi2NbTaO9 and SrBi4Ta4O15. The structural flexibility of these materials allows their properties to be tailored so that many of the problems associated with previous ferroelectric memories are avoided. In particular, our capacitors do not show significant fatigue after 1012 switching cycles, and they exhibit good retention characteristics and low leakage currents even with films less than 100 nm thick.

Fatigue-free ferroelectric capacitors with platinum electrodes

Non-volatile memory devices are so named because they retain information when power is interrupted; thus they are important computer components. In this context, there has been considerable recent interest1,2 in developing non-volatile memories that use ferroelectric thin films—‘ferroelectric random access memories’, or FRAMs—in which information is stored in the polarization state of the ferroelectric material. To realize a practical FRAM, the thin films should satisfy the following criteria: compatibility with existing dynamic random access memory technologies, large remnant polarization (Pr) and reliable polarization-cycling characteristics. Early work focused on lead zirconate titanate (PZT) but, when films of this material were grown on metal electrodes, they generally suffered from a reduction of Pr (‘fatigue’) with polarity switching. Strontium bismuth tantalate (SBT) and related oxides have been proposed to overcome the fatigue problem3, but such materials have other shortcomings, such as a high deposition temperature. Here we show that lanthanum-substituted bismuth titanate thin films provide a promising alternative for FRAM applications. The films are fatigue-free on metal electrodes, they can be deposited at temperatures of ∼650 °C and their values of Pr are larger than those of the SBT films.

Lanthanum-substituted bismuth titanate for use in non-volatile memories

Wide-band-gap oxides such as SrTiO3 are shown to be critical tests of theories of Schottky barrier heights based on metal-induced gap states and charge neutrality levels. This theory is reviewed and used to calculate the Schottky barrier heights and band offsets for many important high dielectric constant oxides on Pt and Si. Good agreement with experiment is found for barrier heights. The band offsets for electrons on Si are found to be small for many key oxides such as SrTiO3 and Ta2O5 which limit their utility as gate oxides in future silicon field effect transistors. The calculations are extended to screen other proposed oxides such as BaZrO3. ZrO2, HfO2, La2O3, Y2O3, HfSiO4, and ZrSiO4. Predictions are also given for barrier heights of the ferroelectric oxides Pb1−xZrxTiO3 and SrBi2Ta2O9 which are used in nonvolatile memories.

Band offsets of wide-band-gap oxides and implications for future electronic devices

A theoretical model of fatigue in ferroelectric thin‐film memories based upon impact ionization (e.g., Ti+4 to Ti+3 conversion in PbZr1−xTixO3), resulting in dendritic growth of oxygen‐deficient filaments, is presented. The predictions of spontaneous polarization versus switching cycles Ps(N) are compared with both Monte Carlo simulations for a two‐dimensional Ising model and with experimental data on small‐grain (40 nm) sol‐gel PZT films. Excellent agreement between theory and experiment is obtained. In addition to modeling the Ps(N) curves, the theory developed explains the observed linear proportionality between switching time ts(N) and polarization Ps(N) during fatigue; other models of aging do not account for this. Earlier theories of switching are also extended to include finite grain sizes, surface nucleation, triangular drive pulses, and dipolar forces. Good agreement with sol‐gel PZT switching data is obtained.

Fatigue and switching in ferroelectric memories: Theory and experiment

The purpose of this work is to develop and characterize an optimized sol-gel PZT process to be used in ferroelectric memories. A review of the sol-gel process is given, including discussions on hydrolysis under acidic and basic conditions. Application of the sol-gel process to thin films is then discussed. Topics such as removal of solvents, stresses in the thin film and how this relates to cracking are mentioned. A review of different synthesis methods of sol-gel PZT is then conducted in order to help determine a device worthy sol-gel PZT process. Methods of controlling the pore size by hydrolysis and different heat treatments at various stages during the drying and annealing cycles are then used. The quality of thin film PZT on Pt is characterized by using dispersive X-ray and X-ray diffraction analyses. Electrical results yield Pr ranging from 7.9-21.9 μC/cm2Ec ranging from 29.1 -92.3 kV/cm and switching times as fast as 56 ns, using a capacitor area of 1 × 104 μm2. However, these results depend on the...

Process optimization and characterization of device worthy sol-gel based PZT for ferroelectric memories

Self-patterned SrBi2Ta2O9 thin films were successfully fabricated from photo-sensitive solutions by means of UV irradiation through photo masks. After conventional baking and wet etching the films were annealed. The photo-sensitive SrBi2Ta2O9 solutions give high resolution negative-pattern of the mask image down to 1 μm line width by deep UV irradiation at 900 mJ/cm2. The capacitor characteristics of the 210 nm thick films fabricated on the Pt/Ti/SiO2/Si substrates by this process showed 2Pr values of 17 μC/cm2, 2Ec of 89 kV/cm, and leakage current densities of 5×10−9 A/cm2 at 5 V. The films showed no fatigue after 1×1011 switching cycles.

Characterization of self-patterned SrBi2Ta2O9 thin films from photo-sensitive solutions

Thin films of Ba07Sr03TiO3 have been fabricated using Enhanced Metal Organic Decomposition (EMOD) process on Si/SiO2/Ti/Pt substrates The C-V characteristics of these films reveal a relation of log(1/Cm) ∝ VA where Cm is the measured capacitance at a frequency of 10 KHz and VA is the applied voltage This voltage variable capacitance is characterized by an inverse quadratic distance proportinal charge distribution at the boundary layer between metal and paraelectric material Above a threshold voltage of 3–5 V the leakage current density exhibits a modified Schottky emission, which states that log (JL) ∝ V 1/4 Below this threshold voltage, the origin of the leakage current which is operative in normal circuit applications has been discussed and identified from its temperature variation

J. D. Cuchiaro

Papers

Fatigue-free ferroelectric capacitors with platinum electrodes

Fatigue and switching in ferroelectric memories: Theory and experiment

Process optimization and characterization of device worthy sol-gel based PZT for ferroelectric memories

Characterization of self-patterned SrBi2Ta2O9 thin films from photo-sensitive solutions

Analysis of C-V and I-V data of BST thin films