A microscopic mechanism of dielectric breakdown in SiO2 films: An insight from multi-scale modeling

Despite extensive experimental and theoretical studies, the atomistic mechanisms responsible for dielectric breakdown (BD) in amorphous (a)-SiO2 are still poorly understood. A number of qualitative physical models and mathematical formulations have been proposed over the years to explain experimentally observable statistical trends. However, these models do not provide clear insight into the physical origins of the BD process. Here, we investigate the physical mechanisms responsible for dielectric breakdown in a-SiO2 using a multi-scale approach where the energetic parameters derived from a microscopic mechanism are used to predict the macroscopic degradation parameters of BD, i.e., time-dependent dielectric breakdown (TDDB) statistics, and its voltage dependence. Using this modeling framework, we demonstrate that trapping of two electrons at intrinsic structural precursors in a-SiO2 is responsible for a significant reduction of the activation energy for Si-O bond breaking. This results in a lower barrier...

[1]  G. Pacchioni,et al.  Structure and ESR properties of self-trapped holes in pure silica from first-principles density functional calculations , 2007 .

[2]  B. H. Lee,et al.  Negative oxygen vacancies in HfO2 as charge traps in high-k stacks , 2006, cond-mat/0605593.

[3]  O. Pirrotta,et al.  Microscopic Modeling of HfOx RRAM Operations: From Forming to Switching , 2015, IEEE Transactions on Electron Devices.

[4]  D. Lang,et al.  Nonradiative capture and recombination by multiphonon emission in GaAs and GaP , 1977 .

[5]  P. Blaise,et al.  Reduction of Monoclinic HfO2: A Cascading Migration of Oxygen and Its Interplay with a High Electric Field , 2016 .

[6]  G. Pacchioni,et al.  CALCULATED SPECTRAL PROPERTIES OF SELF-TRAPPED HOLES IN PURE AND GE-DOPED SIO2 , 1999 .

[7]  Andre Stesmans,et al.  H-complexed oxygen vacancy in SiO2: Energy level of a negatively charged state , 1997 .

[8]  D. Griscom.  A Minireview of the Natures of Radiation-Induced Point Defects in Pure and Doped Silica Glasses and Their Visible/Near-IR Absorption Bands, with Emphasis on Self-Trapped Holes and How They Can Be Controlled , 2013 .

[9]  David L. Griscom,et al.  Defects in SiO[2] and related dielectrics : science and technology , 2000 .

[10]  Michele Parrinello,et al.  Quickstep: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach , 2005, Comput. Phys. Commun..

[11]  J. McPherson,et al.  Thermochemical description of dielectric breakdown in high dielectric constant materials , 2003 .

[12]  David L. Griscom,et al.  Trapped-electron centers in pure and doped glassy silica: A review and synthesis , 2011 .

[13]  J. W. McPherson,et al.  Time dependent dielectric breakdown physics - Models revisited , 2012, Microelectron. Reliab..

[14]  Teter,et al.  Separable dual-space Gaussian pseudopotentials. , 1996, Physical review. B, Condensed matter.

[15]  G. Bersuker,et al.  Electron-Injection-Assisted Generation of Oxygen Vacancies in Monoclinic HfO2 , 2015 .

[16]  A. Shluger,et al.  Optical signatures of intrinsic electron localization in amorphous SiO2 , 2015, Journal of physics. Condensed matter : an Institute of Physics journal.

[17]  Joost VandeVondele,et al.  Gaussian basis sets for accurate calculations on molecular systems in gas and condensed phases. , 2007, The Journal of chemical physics.

[18]  W. B. Knowlton,et al.  A Physical Model of the Temperature Dependence of the Current Through $\hbox{SiO}_{2}\hbox{/}\hbox{HfO}_{2}$ Stacks , 2011, IEEE Transactions on Electron Devices.

[19]  John Robertson,et al.  Defect densities inside the conductive filament of RRAMs , 2013 .

[20]  T. Chan,et al.  A true single-transistor oxide-nitride-oxide EEPROM device , 1987, IEEE Electron Device Letters.

[21]  D. R. Young,et al.  Identification of electron traps in thermal silicon dioxide films , 1981 .

[22]  Jordi Suñé,et al.  On the Weibull shape factor of intrinsic breakdown of dielectric films and its accurate experimental determination. Part II: experimental results and the effects of stress conditions , 2002 .

[23]  M. Kimura.  Field and temperature acceleration model for time-dependent dielectric breakdown , 1999 .

[24]  G. Bersuker,et al.  A model for gate oxide wear out based on electron capture by localized states , 2002 .

[25]  A. Shluger,et al.  A mechanism for Frenkel defect creation in amorphous SiO2 facilitated by electron injection , 2016, Nanotechnology.

[26]  L. Larcher,et al.  Microscopic Modeling of Electrical Stress-Induced Breakdown in Poly-Crystalline Hafnium Oxide Dielectrics , 2013, IEEE Transactions on Electron Devices.

[27]  Joost VandeVondele,et al.  Auxiliary Density Matrix Methods for Hartree-Fock Exchange Calculations. , 2010, Journal of chemical theory and computation.

[28]  Joseph C. Fogarty,et al.  A reactive molecular dynamics simulation of the silica-water interface. , 2010, The Journal of chemical physics.

[29]  D. Griscom.  On the natures of radiation-induced point defects in GeO 2 -SiO 2 glasses: reevaluation of a 26-year-old ESR and optical data set , 2011 .

[30]  J. Isoya,et al.  The dynamic interchange and relationship between germanium centers in α‐quartz , 1978 .

[31]  P. Sushko,et al.  Structure and spectroscopic properties of trapped holes in silica , 2007 .

[32]  A. Shluger,et al.  Nature of intrinsic and extrinsic electron trapping in SiO2 , 2014 .

[33]  L. Skuja.  Optically active oxygen-deficiency-related centers in amorphous silicon dioxide , 1998 .

[34]  Andre Stesmans,et al.  Degradation of the thermal oxide of the Si/SiO2/Al system due to vacuum ultraviolet irradiation , 1995 .

[35]  Tibor Grasser,et al.  Stochastic charge trapping in oxides: From random telegraph noise to bias temperature instabilities , 2012, Microelectron. Reliab..

[36]  Joost VandeVondele,et al.  Robust Periodic Hartree-Fock Exchange for Large-Scale Simulations Using Gaussian Basis Sets. , 2009, Journal of chemical theory and computation.

[37]  A. Shluger,et al.  Nanoscale Transformations in Metastable, Amorphous, Silicon‐Rich Silica , 2016, Advanced materials.

[38]  G. Henkelman,et al.  A climbing image nudged elastic band method for finding saddle points and minimum energy paths , 2000 .

[39]  Bin Wang,et al.  Reliability of ultrathin silicon dioxide under combined substrate hot-electron and constant voltage tunneling stress , 2000 .

[40]  J. M. Andrews,et al.  Electrochemical Charging of Thermal SiO2 Films by Injected Electron Currents , 1971 .

[41]  G. Henkelman,et al.  Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points , 2000 .

[42]  Kin Leong Pey,et al.  The radial distribution of defects in a percolation path , 2008 .

[43]  J. Sune,et al.  New physics-based analytic approach to the thin-oxide breakdown statistics , 2001, IEEE Electron Device Letters.

[44]  James Stasiak,et al.  Trap creation in silicon dioxide produced by hot electrons , 1989 .

[45]  S. Slesazeck,et al.  Defect generation and activation processes in HfO2 thin films: Contributions to stress‐induced leakage currents , 2015 .

[46]  David L. Griscom,et al.  Self-trapped holes in pure-silica glass: A history of their discovery and characterization and an example of their critical significance to industry , 2006 .

[47]  Chenming Hu,et al.  Reliability of thin SiO2 , 1994 .

[48]  G. Bersuker,et al.  Positive and Negative Oxygen Vacancies in Amorphous Silica , 2009 .

[49]  J. McPherson,et al.  UNDERLYING PHYSICS OF THE THERMOCHEMICAL E MODEL IN DESCRIBING LOW-FIELD TIME-DEPENDENT DIELECTRIC BREAKDOWN IN SIO2 THIN FILMS , 1998 .

[50]  Matthew Watkins,et al.  Identification of intrinsic electron trapping sites in bulk amorphous silica from ab initio calculations , 2013 .

[51]  D. Arnold,et al.  Impact ionization, trap creation, degradation, and breakdown in silicon dioxide films on silicon , 1993 .

[52]  Michele Parrinello,et al.  A hybrid Gaussian and plane wave density functional scheme , 1997 .

[53]  S. Holland,et al.  Hole trapping and breakdown in thin SiO2 , 1986, IEEE Electron Device Letters.

[54]  Steve Plimpton,et al.  Fast parallel algorithms for short-range molecular dynamics , 1993 .

[55]  Ih-Chin Chen,et al.  Electrical breakdown in thin gate and tunneling oxides , 1985 .

[56]  A. V. Duin,et al.  ReaxFFSiO Reactive Force Field for Silicon and Silicon Oxide Systems , 2003 .