All-nanosheet ultrathin capacitors assembled layer-by-layer via solution-based processes.

All-nanosheet ultrathin capacitors of Ru0.95O20.2-/Ca2Nb3O10-/Ru0.95O20.2- were successfully assembled through facile room-temperature solution-based processes. As a bottom electrode, conductive Ru0.95O20.2- nanosheets were first assembled on a quartz glass substrate through a sequential adsorption process with polycations. On top of the Ru0.95O20.2- nanosheet film, Ca2Nb3O10- nanosheets were deposited by the Langmuir-Blodgett technique to serve as a dielectric layer. Deposition parameters were optimized for each process to construct a densely packed multilayer structure. The multilayer buildup process was monitored by various characterizations such as atomic force microscopy (AFM), ultraviolet-visible absorption spectra, and X-ray diffraction data, which provided compelling evidence for regular growth of Ru0.95O20.2- and Ca2Nb3O10- nanosheet films with the designed multilayer structures. Finally, an array of circular films (50 μm ϕ) of Ru0.95O20.2- nanosheets was fabricated as top electrodes on the as-deposited nanosheet films by combining the standard photolithography and sequential adsorption processes. Microscopic observations by AFM and cross-sectional transmission electron microscopy, as well as nanoscopic elemental analysis, visualized the sandwich metal-insulator-metal structure of Ru0.95O20.2-/Ca2Nb3O10-/Ru0.95O20.2- with a total thickness less than 30 nm. Electrical measurements indicate that the system really works as an ultrathin capacitor, achieving a capacitance density of ∼27.5 μF cm(-2), which is far superior to currently available commercial capacitor devices. This work demonstrates the great potential of functional oxide nanosheets as components for nanoelectronics, thus contributing to the development of next-generation high-performance electronic devices.

[1]  T. Sasaki,et al.  Titania Nanostructured Films Derived from a Titania Nanosheet/Polycation Multilayer Assembly via Heat Treatment and UV Irradiation , 2002 .

[2]  K. Fukuda,et al.  Synthesis of nanosheet crystallites of ruthenate with an alpha-NaFeO2-related structure and its electrochemical supercapacitor property. , 2010, Inorganic chemistry.

[3]  L. Schultz,et al.  Structure-related optical properties of laser-deposited BaxSr1−xTiO3 thin films grown on MgO (001) substrates , 1997 .

[4]  M. Anis-Ur-Rehman,et al.  Enhancement in dielectric and magnetic properties of Ni–Zn ferrites prepared by sol–gel method , 2013 .

[5]  Yi-Lung Cheng,et al.  Deposition cycle of atomic layer deposition HfO2 film: Effects on electrical performance and reliability , 2013 .

[6]  J. Autran,et al.  Tantalum pentoxide (Ta2O5) thin films for advanced dielectric applications , 1998 .

[7]  A. Marigo,et al.  Influence of substrate on structural properties of TiO2 thin films obtained via MOCVD , 1994 .

[8]  M. Yamamuka,et al.  (Ba, Sr)TiO3 Films Prepared by Liquid Source Chemical Vapor Deposition on Ru Electrodes , 1996 .

[9]  D. Kwong,et al.  Characterization of RuO2 electrodes on Zr silicate and ZrO2 dielectrics , 2001 .

[10]  John G. Simmons,et al.  Poole-Frenkel Effect and Schottky Effect in Metal-Insulator-Metal Systems , 1967 .

[11]  S. B. Krupanidhi,et al.  Studies on structural and electrical properties of barium strontium titanate thin films developed by metallo-organic decomposition , 1997 .

[12]  Q. X. Jia,et al.  Effects of very thin strain layers on dielectric properties of epitaxial Ba0.6Sr0.4TiO3 films , 2001 .

[13]  G. Wahl,et al.  CVD of ZrO2, Al2O3 and Y2O3 from metalorganic compounds in different reactors , 2000 .

[14]  Mark A. Rodriguez,et al.  Neo‐pentoxide Precursors for MOCVD Thin Films of TiO2 and ZrO2 , 2000 .

[15]  S. W. Kirchoefer,et al.  Influence of strain on microwave dielectric properties of (Ba,Sr)TiO3 thin films , 2000 .

[16]  Mikko Heikkilä,et al.  Atomic Layer Deposition of High‐k Oxides of the Group 4 Metals for Memory Applications , 2009 .

[17]  M. Osada,et al.  Construction of highly ordered lamellar nanostructures through Langmuir-Blodgett deposition of molecularly thin titania nanosheets tens of micrometers wide and their excellent dielectric properties. , 2009, ACS nano.

[18]  Minoru Osada,et al.  Engineered interfaces of artificial perovskite oxide superlattices via nanosheet deposition process. , 2010, ACS nano.

[19]  Winco K.C. Yung,et al.  Embedded components in printed circuit boards: a processing technology review , 2005 .

[20]  L. Lauhon,et al.  Quantitatively enhanced reliability and uniformity of high-κ dielectrics on graphene enabled by self-assembled seeding layers. , 2013, Nano letters.

[21]  R. M. Fleming,et al.  Discovery of a useful thin-film dielectric using a composition-spread approach , 1998, Nature.

[22]  Jack C. Lee,et al.  Thermal stability and electrical characteristics of ultrathin hafnium oxide gate dielectric reoxidized with rapid thermal annealing , 2000 .

[23]  C. Hwang,et al.  Study on the Step Coverage of Metallorganic Chemical Vapor Deposited TiO2 and SrTiO3 Thin Films , 2005 .

[24]  Anton J. Bauer,et al.  Structural properties of as deposited and annealed ZrO2 influenced by atomic layer deposition, substrate, and doping , 2013 .

[25]  C. Randall Scientific and Engineering Issues of the State-of-the-Art and Future Multilayer Capacitors , 2001 .

[26]  Gonen Ashkenasy,et al.  Molecular engineering of semiconductor surfaces and devices. , 2002, Accounts of chemical research.

[27]  A. Jonscher Dielectric relaxation in solids , 1983 .

[28]  M. Osada,et al.  Robust high-κ response in molecularly thin perovskite nanosheets. , 2010, ACS nano.

[29]  C. Tracy,et al.  Characterization of sputtered barium strontium titanate and strontium titanate-thin films , 1997 .

[30]  M. Osada,et al.  Controlled Polarizability of One‐Nanometer‐Thick Oxide Nanosheets for Tailored, High‐κ Nanodielectrics , 2011 .

[31]  K. Choy Chemical vapour deposition of coatings , 2003 .

[32]  Ho Jin Cho,et al.  New TIT Capacitor with ZrO2/Al2O3/ZrO2 dielectrics for 60nm and below DRAMs , 2006, 2006 European Solid-State Device Research Conference.

[33]  K. Saraswat,et al.  Thermal stability of polycrystalline silicon electrodes on ZrO2 gate dielectrics , 2002 .

[34]  Ho-Kyu Kang,et al.  Deposition of extremely thin (Ba,Sr)TiO3 thin films for ultra‐large‐scale integrated dynamic random access memory application , 1995 .

[35]  David Vanderbilt,et al.  First-principles study of structural, vibrational, and lattice dielectric properties of hafnium oxide , 2002 .

[36]  J. Aarik,et al.  Epitaxial growth of high-κ TiO[sub 2] rutile films on RuO[sub 2] electrodes , 2009 .

[37]  S. Shannigrahi,et al.  Effect of bottom electrode and resistive layer on the dielectric and ferroelectric properties of sol–gel derived BiFeO3 thin films , 2011 .

[38]  Minoru Osada,et al.  High‐κ Dielectric Nanofilms Fabricated from Titania Nanosheets , 2006 .

[39]  Hiroshi Kishi,et al.  Base-Metal Electrode-Multilayer Ceramic Capacitors: Past, Present and Future Perspectives , 2003 .

[40]  P. R. Emtage,et al.  Schottky Emission Through Thin Insulating Films , 1962 .

[41]  K. Fukuda,et al.  Conductivity of ruthenate nanosheets prepared via electrostatic self-assembly: characterization of isolated single nanosheet crystallite to mono- and multilayer electrodes. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[42]  S. Bourgeois,et al.  SEM and XPS studies of titanium dioxide thin films grown by MOCVD , 1998 .