Development of hafnium based high-k materials—A review

Abstract The move to implement metal oxide based gate dielectrics in a metal-oxide-semiconductor field effect transistor is considered one of the most dramatic advances in materials science since the invention of silicon based transistors. Metal oxides are superior to SiO 2 in terms of their higher dielectric constants that enable the required continuous down-scaling of the electrical thickness of the dielectric layer while providing a physically thicker layer to suppress the quantum mechanical tunneling through the dielectric layer. Over the last decade, hafnium based materials have emerged as the designated dielectrics for future generation of nano-electronics with a gate length less than 45 nm, though there exists no consensus on the exact composition of these materials, as evolving device architectures dictate different considerations when optimizing a gate dielectric material. In addition, the implementation of a non-silicon based gate dielectric means a paradigm shift from diffusion based thermal processes to atomic layer deposition processes. In this report, we review how HfO 2 emerges from all likely candidates to become the new gold standard in the microelectronics industry, its different phases, reported electrical properties, and materials processing techniques. Then we use specific examples to discuss the evolution in designing hafnium based materials, from binary to complex oxides and to non-oxide forms as gate dielectric, metal gates and diffusion barriers. To address the impact of these hafnium based materials, their interfaces with silicon as well as a variety of semiconductors are discussed. Finally, the integration issues are highlighted, including carrier scattering, interface state passivation, phonon engineering, and nano-scale patterning, which are essential to realize future generations of devices using hafnium-based high- k materials.

[1]  M. Perego,et al.  Conduction band offset of HfO2 on GaAs , 2007 .

[2]  P. Chalker,et al.  Growth of Hafnium Dioxide Thin Films by Liquid‐Injection MOCVD Using Alkylamide and Hydroxylamide Precursors , 2003 .

[3]  B. E. White,et al.  Impact of Deposition and Annealing Temperature on Material and Electrical Characteristics of ALD HfO2 , 2004 .

[4]  S. Pearton,et al.  Influence of ion mixing on the energy dependence of the ion-assisted chemical etch rate in reactive plasmas , 2006 .

[5]  Two-step interfacial reaction of HfO2 high-k gate dielectric thin films on Si , 2004 .

[6]  M. Blanchin,et al.  Structure and dielectric properties of HfO2 films prepared by a sol–gel route , 2008 .

[7]  M. D. Rogers,et al.  The crystal structure of ZrO2 and HfO2 , 1959 .

[8]  John Robertson,et al.  Interfaces and defects of high-K oxides on silicon , 2005 .

[9]  D. Kwong,et al.  Electrical properties and thermal stability of CVD HfOxNy gate dielectric with poly-Si gate electrode , 2003, IEEE Electron Device Letters.

[10]  C. F. Cline,et al.  Verification of Existence of Cubic Zirconia at High Temperature , 1962 .

[11]  H. Wong,et al.  Atomic and electronic structure of amorphous and crystalline hafnium oxide: X-ray photoelectron spectroscopy and density functional calculations , 2007 .

[12]  Lauri Niinistö,et al.  Advanced electronic and optoelectronic materials by Atomic Layer Deposition: An overview with special emphasis on recent progress in processing of high-k dielectrics and other oxide materials , 2004 .

[13]  A. Kahn,et al.  Band offsets at heterojunctions between SrTiO3 and BaTiO3 and Si(100) , 2004 .

[14]  T. Ma,et al.  High-temperature phase stability of hafnium aluminate films for alternative gate dielectrics , 2004 .

[15]  Ru Huang,et al.  Program/erase injection current characteristics of a low-voltage low-power NROM using high-K materials as the tunnel dielectric , 2006 .

[16]  Ming-Ta Hsieh,et al.  MOSFET transistors fabricated with high permitivity TiO/sub 2/ dielectrics , 1997 .

[17]  R. Opila,et al.  Low‐temperature deposition of zirconium and hafnium boride films by thermal decomposition of the metal borohydrides (M[BH4]4) , 1988 .

[18]  M. Fischetti,et al.  Electron mobility in silicon and germanium inversion layers: The role of remote phonon scattering , 2007 .

[19]  M. Li,et al.  Electrical conduction and band offsets in Si/HfxTi1−xO2/metal structures , 2004 .

[20]  L. Vasanelli,et al.  Physical characterization of hafnium oxide thin films and their application as gas sensing devices , 1998 .

[21]  C. Ye,et al.  Structure and electrical properties of HfO2 high-k films prepared by pulsed laser deposition on Si (100) , 2008 .

[22]  Y. J. Lee,et al.  MBE-grown high κ gate dielectrics of HfO2 and (Hf-Al)O2 for Si and III-V semiconductors nano-electronics , 2005 .

[23]  Jane P. Chang,et al.  Material and electrical properties of HfxRuy and HfxRuyNz metals as gate electrodes for p-metal oxide semiconductor field effect transistor devices , 2008 .

[24]  E. Fortunato,et al.  Influence of the oxygen/argon ratio on the properties of sputtered hafnium oxide , 2005 .

[25]  C. Wiemer,et al.  La2Hf2O7 high-κ gate dielectric grown directly on Si(001) by molecular-beam epitaxy , 2004 .

[26]  K. Yokota,et al.  Effects of oxygen ion beam application on crystalline structures of TiO2 films deposited on Si wafers by an ion beam assisted deposition , 2006 .

[27]  R. Ruh,et al.  Crystal structure of monoclinic hafnia and comparison with monoclinic zirconia Locality: synthetic , 1970 .

[28]  C. Ong,et al.  Reaction of SiO2 with hafnium oxide in low oxygen pressure , 2003 .

[29]  Temperature dependence of La2Hf2O7 thin films growth on Si(0 0 1) substrates by pulsed laser deposition , 2008 .

[30]  T. Nabatame,et al.  Effect of Al2O3 capping layer on suppression of interfacial SiO2 growth in HfO2/ultrathin SiO2/Si(001) structure , 2003 .

[31]  H. Kumigashira,et al.  Chemistry and band offsets of HfO2 thin films on Si revealed by photoelectron spectroscopy and x-ray absorption spectroscopy , 2004 .

[32]  K. Trueblood,et al.  The crystal structure of baddeleyite (monoclinic ZrO2) , 1959 .

[33]  Soon-Gil Yoon,et al.  Structural and electrical characterizations of ultrathin HfO2 gate dielectrics treated by nitrogen-plasma atmosphere , 2006 .

[34]  S. Honda,et al.  Surface, structural and optical properties of sol-gel derived HfO2 films , 2000 .

[35]  K. Onishi,et al.  Improvement of surface carrier mobility of HfO/sub 2/ MOSFETs by high-temperature forming gas annealing , 2003 .

[36]  R. Casali,et al.  Ab initio localized basis set study of structural parameters and elastic properties of HfO2 polymorphs , 2005, Journal of physics. Condensed matter : an Institute of Physics journal.

[37]  Production of a hafnium silicate dielectric layer for use as a gate oxide by solid-state reaction , 2002, cond-mat/0202328.

[38]  Max C. Lemme,et al.  Navigation aids in the search for future high-k dielectrics: Physical and electrical trends , 2007 .

[39]  Athanasios Dimoulas,et al.  Complex admittance analysis for La2Hf2O7/SiO2 high-κ dielectric stacks , 2004 .

[40]  R. Ruh,et al.  Nonstoichiometry of ZrO2 and Its Relation to Tetragonal‐Cubic Inversion in ZrO2 , 1967 .

[41]  Antonio J. R. da Silva,et al.  Comparative study of defect energetics in HfO2 and SiO2 , 2004 .

[42]  A. Shluger,et al.  Modeling HfO2/SiO2/Si interface , 2007 .

[43]  R. Ruh,et al.  Proposed Phase Relations in the HfO2‐Rich Portion of the System Hf‐HfO2 , 1973 .

[44]  Jane P. Chang,et al.  First-principles exploration of alternative gate dielectrics: Electronic structure of ZrO2/Si and ZrSiO4/Si interfaces , 2004 .

[45]  Luhua Lu,et al.  Room-temperature weak ferromagnetism of amorphous HfAlOx thin films deposited by pulsed laser deposition , 2006 .

[46]  Epitaxial La2Hf2O7 thin films on Si(001) substrates grown by pulsed laser deposition for high-k gate dielectrics , 2008 .

[47]  Xingzhong Zhao,et al.  Influence of N2 flow ratio on the properties of hafnium nitride thin films prepared by DC magnetron sputtering , 2007 .

[48]  David-Wei Zhang,et al.  Surface reaction mechanism of atomic layer deposition of HfO2 on Ge(1 0 0)-2 × 1: A density functional theory study , 2006 .

[49]  Jane P. Chang,et al.  Plasma etching selectivity of ZrO2 to Si in BCl3/Cl2 plasmas , 2003 .

[50]  Hua Chun Zeng,et al.  A catalyst-free approach for sol–gel synthesis of highly mixed ZrO2–SiO2 oxides , 1999 .

[51]  Y. J. Lee,et al.  Structural and electrical characteristics of atomic layer deposited high κ HfO2 on GaN , 2007 .

[52]  R. Wallace,et al.  Hafnium and zirconium silicates for advanced gate dielectrics , 2000 .

[53]  C. Wiemer,et al.  Evolution of crystallographic ordering in Hf1-xAlxOy high-κ dielectric deposited by atomic layer deposition , 2003 .

[54]  E. Eisenbraun,et al.  Metallorganic Chemical Vapor Deposition of Hafnium Silicate Thin Films Using a Dual Source Dimethyl-alkylamido Approach , 2006 .

[55]  Jane P. Chang,et al.  Plasma enhanced atomic layer deposition of HfO2 and ZrO2 high-k thin films , 2005 .

[56]  Olivier Joubert,et al.  Etching mechanisms of HfO2, SiO2, and poly-Si substrates in BCl3 plasmas , 2007 .

[57]  Jane P. Chang,et al.  Plasma etching of Hf-based high-k thin films. Part I. Effect of complex ions and radicals on the surface reactions , 2009 .

[58]  A. Demkov Thermodynamic stability and band alignment at a metal-high- k dielectric interface , 2006 .

[59]  Angus I. Kingon,et al.  High temperature stability in lanthanum and zirconia-based gate dielectrics , 2001 .

[60]  M. Ritala,et al.  Growth of SrTiO3 and BaTiO3 Thin Films by Atomic Layer Deposition , 1999 .

[61]  S. Bent,et al.  Achieving area-selective atomic layer deposition on patterned substrates by selective surface modification , 2005 .

[62]  C. Lynch,et al.  Monoclinic‐Tetragonal Transition of Zirconia , 1961 .

[63]  M. Wuttig,et al.  Towards understanding the superior properties of transition metal oxynitrides prepared by reactive DC magnetron sputtering , 2006 .

[64]  M. Bazant,et al.  Lifetime of high- k gate dielectrics and analogy with strength of quasibrittle structures , 2009 .

[65]  W. Maeng,et al.  Thermal and plasma enhanced atomic layer deposition ruthenium and electrical characterization as a metal electrode , 2008 .

[66]  Study of the effect of substrate bias on the electrical properties of sputtered HfO2 thin film deposited on silicon substrate , 2007 .

[67]  R. Waser,et al.  Mononuclear precursor for MOCVD of HfO2 thin films. , 2004, Chemical communications.

[68]  R. Manory,et al.  Growth and structure control of HfO2−x films with cubic and tetragonal structures obtained by ion beam assisted deposition , 2002 .

[69]  A. Ogura,et al.  HfO2 growth by low-pressure chemical vapor deposition using the Hf(N(C2H5)2)4/O2 gas system , 2001 .

[70]  Lawrence H. Bennett,et al.  Binary alloy phase diagrams , 1986 .

[71]  M. Ritala,et al.  Development of crystallinity and morphology in hafnium dioxide thin films grown by atomic layer epitaxy , 1994 .

[72]  H. Hwang,et al.  Electrical and physical properties of HfO2 deposited via ALD using Hf(OtBu)4 and ozone atop Al2O3 , 2004 .

[73]  Martin M. Frank,et al.  Hafnium oxide gate dielectrics on sulfur-passivated germanium , 2006 .

[74]  Control of silicidation in HfO2∕Si(100) interfaces , 2005 .

[75]  Christian Mitterer,et al.  Borides in Thin Film Technology , 1997 .

[76]  S. Santucci,et al.  Synthesis and characterization of hafnium oxide and hafnium aluminate ultra-thin films by a sol–gel spin coating process for microelectronic applications , 2007 .

[77]  A. Pasquarello,et al.  Band alignments and defect levels in Si–HfO2 gate stacks: Oxygen vacancy and Fermi-level pinning , 2008 .

[78]  Jane P. Chang,et al.  Ion-enhanced chemical etching of HfO2 for integration in metal–oxide–semiconductor field effect transistors , 2003 .

[79]  J. Robertson,et al.  Bonding and interface states of Si:HfO2 and Si:ZrO2 interfaces , 2006 .

[80]  Lin‐gun Liu New high pressure phases of ZrO2 and HfO2 , 1980 .

[81]  Jong-Wan Park,et al.  Characteristics of lanthanum hafnium oxide deposited by electron cyclotron resonance atomic layer deposition , 2008 .

[82]  V. M. Donnelly,et al.  Etching of high-k dielectric Zr1−xAlxOy films in chlorine-containing plasmas , 2001 .

[83]  R. K. Nahar,et al.  Study of electrical and microstructure properties of high dielectric hafnium oxide thin film for MOS devices , 2007 .

[84]  Supratik Guha,et al.  Compatibility Challenges for High-ĸ Materials Integration into CMOS Technology , 2002 .

[85]  L. Zhang,et al.  Effect of postdeposition annealing on the thermal stability and structural characteristics of sputtered HfO2 films on Si(100) , 2005 .

[86]  Investigation of high-quality ultra-thin LaAlO3 films as high-k gate dielectrics , 2003 .

[87]  V. Narayanan,et al.  Oxygen vacancies in high dielectric constant oxide-semiconductor films. , 2007, Physical review letters.

[88]  J. Kavalieros,et al.  High-/spl kappa//metal-gate stack and its MOSFET characteristics , 2004, IEEE Electron Device Letters.

[89]  A. Kingon,et al.  Crystallization in SiO_2–metal Oxide Alloys , 2002 .

[90]  Bulk Properties of MOCVD-Deposited HfO2 Layers for High k Dielectric Applications , 2004 .

[91]  M. Jeong,et al.  Characterization and process effects of HfO2 thin films grown by metal-organic molecular beam epitaxy , 2005 .

[92]  Observation of spin-dependent transport and large magnetoresistance in La0.7Sr0.3MnO3/SrTiO3/La0.7Sr0.3MnO3 ramp-edge junctions , 1998 .

[93]  C. Musgrave,et al.  Atomic layer deposition of hafnium oxide: A detailed reaction mechanism from first principles , 2002 .

[94]  G. Lucovsky,et al.  Band offset measurements of the GaN (0001)/HfO2 interface , 2003 .

[95]  Eduard A. Cartier,et al.  Materials characterization of ZrO2–SiO2 and HfO2–SiO2 binary oxides deposited by chemical solution deposition , 2001 .

[96]  Je-Hun Lee,et al.  Thermal stability and structural characteristics of HfO2 films on Si (100) grown by atomic-layer deposition , 2002 .

[97]  C. O. Chui,et al.  HfO2 gate dielectric on (NH4)2S passivated (100) GaAs grown by atomic layer deposition , 2008 .

[98]  M. White,et al.  Interfacial oxide determination and chemical/electrical structures of HfO2/SiOx/Si gate dielectrics , 2004 .

[99]  M. White,et al.  Modeling of MOSFET Gate leakage for High k Gate Dielectrics , 2006, 2005 International Semiconductor Device Research Symposium.

[100]  S. Lee,et al.  High-performance InP/In/sub 0.53/Ga/sub 0.47/As/InP double HBTs on GaAs substrates , 2002, IEEE Electron Device Letters.

[101]  P. Ehrhart,et al.  Guanidinate-stabilized monomeric hafnium amide complexes as promising precursors for MOCVD of HfO2. , 2006, Inorganic chemistry.

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

[103]  Ju H. Choi,et al.  Effects of post-deposition annealing on the material characteristics of ultrathin HfO2 films on silicon , 2005 .

[104]  V. Fiorentini,et al.  Theoretical evaluation of zirconia and hafnia as gate oxides for si microelectronics. , 2002, Physical review letters.

[105]  Krishna C. Saraswat,et al.  Interfacial characteristics of HfO2 grown on nitrided Ge (100) substrates by atomic-layer deposition , 2004 .

[106]  Masamichi Suzuki,et al.  LaAlO3 gate dielectric with ultrathin equivalent oxide thickness and ultralow leakage current directly deposited on Si substrate , 2008 .

[107]  Jack C. Lee,et al.  Inversion-type indium phosphide metal-oxide-semiconductor field-effect transistors with equivalent oxide thickness of 12 Å using stacked HfAlOx HfO2 gate dielectric , 2008 .

[108]  V. Afanas’ev,et al.  HfO2-based insulating stacks on 4H–SiC(0001) , 2003 .

[109]  S. Pokrant,et al.  Crystal structure and band gap determination of HfO2 thin films , 2007 .

[110]  Richard Wise,et al.  Plasma-etching processes for ULSI semiconductor circuits , 1999, IBM J. Res. Dev..

[111]  Lin Li,et al.  Phase Diagram Prediction of the Al2O3-SiO2-La2O3 System , 2009 .

[112]  Tingting Li,et al.  The interface reaction of high-k La2Hf2O7/Si thin film grown by pulsed laser deposition , 2009 .

[113]  Guido Groeseneken,et al.  Electrical and reliability characterization of metal-gate/HfO2/Ge FET's with Si passivation , 2007 .

[114]  R. Waser,et al.  LI-MOCVD of HfO2 thin films using engineered amide based Hf precursors , 2007 .

[115]  Jane P. Chang,et al.  Characteristics of Hf-silicate thin films synthesized by plasma enhanced atomic layer deposition , 2008 .

[116]  Zi-kui Liu,et al.  Thermodynamic modeling of the Hf–Si–O system , 2006, 0708.4239.

[117]  G. Lo,et al.  Wide $V_{\rm fb}$ and $V_{\rm th}$ Tunability for Metal-Gated MOS Devices With HfLaO Gate Dielectrics , 2007, IEEE Electron Device Letters.

[118]  Jinke Tang,et al.  4f-5d hybridization in a high k dielectric , 2006 .

[119]  John Robertson,et al.  Fermi level pinning by defects in HfO2-metal gate stacks , 2007 .

[120]  H. Koinuma,et al.  Combinatorial solid-state chemistry of inorganic materials , 2004, Nature materials.

[121]  Olivier Joubert,et al.  The Cutting Edge of Plasma Etching , 2008, Science.

[122]  Y. Nishi,et al.  Synchrotron radiation photoemission spectroscopic study of band offsets and interface self-cleaning by atomic layer deposited HfO2 on In0.53Ga0.47As and In0.52Al0.48As , 2008 .

[123]  Nitrogen incorporation engineering and electrical properties of high-k gate dielectric (HfO2 and Al2O3) films on Si (100) substrate , 2004 .

[124]  J. Robertson High dielectric constant oxides , 2004 .

[125]  Sangeneni Mohan,et al.  Optical properties of electron-beam evaporated TiO2 films deposited in an ionized oxygen medium , 1990 .

[126]  M. Perego,et al.  Energy band alignment of HfO2 on Ge , 2006 .

[127]  R. Dutton,et al.  Perspectives paper: First principles modeling of high-k gate dielectrics , 2001 .

[128]  Sharma,et al.  Pressure-induced phase transformations in HfO2 to 50 GPa studied by Raman spectroscopy. , 1993, Physical review. B, Condensed matter.

[129]  V. Ozoliņš,et al.  Incorporating first-principles energetics in computational thermodynamics approaches , 2002 .

[130]  P. Kirsch,et al.  Electrical and spectroscopic comparison of HfO2/Si interfaces on nitrided and un-nitrided Si(100) , 2002 .

[131]  Ji-Cheng Zhao,et al.  Hf-Si binary phase diagram determination and thermodynamic modeling , 2000 .

[132]  C. Musgrave,et al.  First-principles calculations of structural and electronic properties of monoclinic hafnia surfaces , 2006 .

[133]  Gennadi Bersuker,et al.  Scanning transmission electron microscopy investigations of interfacial layers in HfO2 gate stacks , 2006 .

[134]  Safa Kasap,et al.  Principles of electronic materials and devices , 2000 .

[135]  N. Umezawa Effects of capping HfO2 with multivalent oxides toward reducing the number of charged defects , 2010 .

[136]  R. Johnson,et al.  Status of silicon carbide (SiC) as a wide-bandgap semiconductor for high-temperature applications: A review , 1996 .

[137]  Horst Schreiber,et al.  Crystal phase transition of HfO2 films evaporated by plasma-ion-assisted deposition. , 2008, Applied optics.

[138]  D. Kwong,et al.  Physical and electrical characteristics of HfN gate electrode for advanced MOS devices , 2003, IEEE Electron Device Letters.

[139]  Jane P. Chang,et al.  An accurate determination of barrier heights at the HfO2∕Si interfaces , 2004 .

[140]  W. Besling,et al.  Diffusion Barrier Deposition on a Copper Surface by Atomic Layer Deposition , 2002 .

[141]  Y. Kamata,et al.  High-k/Ge MOSFETs for future nanoelectronics , 2008 .

[142]  S. Spiga,et al.  Band alignment at the La2Hf2O7∕(001)Si interface , 2006 .

[143]  Jane P. Chang,et al.  Generation of oxide nanopatterns by combining self-assembly of S-layer proteins and area-selective atomic layer deposition. , 2008, Journal of the American Chemical Society.

[144]  Yasuhiro Shimamoto,et al.  Rutile-type TiO2 thin film for high-k gate insulator , 2003 .

[145]  Gerbrand Ceder,et al.  First-principles study of native point defects in hafnia and zirconia , 2007 .

[146]  I. Parkin,et al.  Atmospheric-pressure chemical vapor deposition of group IVb metal phosphide thin films from tetrakisdimethylamidometal complexes and cyclohexylphosphine , 2004 .

[147]  S. Zou,et al.  Field emission from hafnium oxynitride films prepared by ion beam-assisted deposition , 2005 .

[148]  Inversion-type enhancement-mode HfO2-based GaAs metal-oxide-semiconductor field effect transistors with a thin Ge layer , 2008 .

[149]  J.C. Lee,et al.  Area dependence of TDDB characteristics for HfO2 gate dielectrics , 2002, IEEE Electron Device Letters.

[150]  R. Ramprasad,et al.  First-principles study of the valence band offset between silicon and hafnia , 2007 .

[151]  J. Kwo,et al.  GaAs-based metal-oxide semiconductor field-effect transistors with Al2O3 gate dielectrics grown by atomic layer deposition , 2004 .

[152]  Crystalline phases, microstructures and electrical properties of hafnium oxide films deposited by sol-gel method , 2005 .

[153]  C. Choy,et al.  Growth and characterization of Hf-aluminate high-k gate dielectric ultrathin films with equivalent oxide thickness less than 10 Å , 2003 .

[154]  H. Morkoç,et al.  Oxides, Oxides, and More Oxides: High-κ Oxides, Ferroelectrics, Ferromagnetics, and Multiferroics , 2009 .

[155]  T. Ma,et al.  Temperature dependence of channel mobility in HfO/sub 2/-gated NMOSFETs , 2004, IEEE Electron Device Letters.

[156]  Jeffrey T. Roberts,et al.  Chemical vapour deposition of the oxides of titanium, zirconium and hafnium for use as high-k materials in microelectronic devices. A carbon-free precursor for the synthesis of hafnium dioxide , 2000 .

[157]  A. Kuwabara,et al.  Ab initio lattice dynamics and phase transformations of ZrO2 , 2005 .

[158]  K. Kukli,et al.  Conductance transient, capacitance–voltage and deep-level transient spectroscopy characterization of atomic layer deposited hafnium and zirconium oxide thin films , 2003 .

[159]  P. Ye,et al.  Enhancement-mode InP n-channel metal-oxide-semiconductor field-effect transistors with atomic-layer-deposited Al2O3 dielectrics , 2007 .

[160]  J.C. Lee,et al.  The electrical and material characterization of hafnium oxynitride gate dielectrics with TaN-gate electrode , 2004, IEEE Transactions on Electron Devices.

[161]  Alexander L. Shluger,et al.  The interaction of oxygen vacancies with grain boundaries in monoclinic HfO2 , 2009 .

[162]  Pascale Mazoyer,et al.  Evolution of materials technology for stacked-capacitors in 65 nm embedded-DRAM , 2005 .

[163]  V. Misra,et al.  Electrical properties of Ru-based alloy gate electrodes for dual metal gate Si-CMOS , 2002, IEEE Electron Device Letters.

[164]  Jane P. Chang,et al.  Plasma etching of Hf-based high-k thin films. Part III. Modeling the reaction mechanisms , 2009 .

[165]  Bengt Hallstedt,et al.  Thermodynamic assessment of the Silicon — Oxygen system , 1992 .

[166]  H. Seo,et al.  Epitaxial and polycrystalline HfNx (0.8⩽x⩽1.5) layers on MgO(001): Film growth and physical properties , 2005 .

[167]  Y. F. Loo,et al.  Deposition of HfO2 Films by Liquid Injection MOCVD Using a New Monomeric Alkoxide Precursor, [Hf(dmop)4] , 2005 .

[168]  D. Kwong,et al.  Thermally robust HfN metal as a promising gate electrode for advanced MOS device applications , 2004 .

[169]  R. Grimes,et al.  Dielectric polarizability of ions and the corresponding effective number of electrons , 1998 .

[170]  Jane P. Chang,et al.  Electronic structure and band alignment at the HfO2∕4H-SiC interface , 2007 .

[171]  Zuimin Jiang,et al.  Thin HfO2 films grown on Si(100) by atomic oxygen assisted molecular beam epitaxy , 2004 .

[172]  Po-Tsun Liu,et al.  An interfacial investigation of high-dielectric constant material hafnium oxide on Si substrate☆ , 2005 .

[173]  Mikko Ritala,et al.  Tailoring the dielectric properties of HfO2–Ta2O5 nanolaminates , 1996 .

[174]  G. Humphrey The Heats of Formation of TiO, Ti2O3, Ti3O5 and TiO2 from Combustion Calorimetry1 , 1951 .

[175]  K. S. Coleman,et al.  Energy-band alignment of HfO2/SiO2/SiC gate dielectric stack , 2008 .

[176]  M. Gutowski,et al.  Low-temperature Polymorphs of ZrO2 and HfO2. A Density Functional Theory Study , 2005 .

[177]  Paul H. Fuoss,et al.  Grazing-incidence small angle x-ray scattering studies of phase separation in hafnium silicate films , 2003 .

[178]  Wilfried Vandervorst,et al.  Nucleation and growth of atomic layer deposited HfO2 gate dielectric layers on chemical oxide (Si–O–H) and thermal oxide (SiO2 or Si–O–N) underlayers , 2002 .

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

[180]  Degradation mechanisms of electron mobility in metal-oxide-semiconductor field-effect transistors with LaAlO3 gate dielectric , 2009 .

[181]  A. Nakao,et al.  Sol−Gel Fabrication of Dielectric HfO2 Nano-Films; Formation of Uniform, Void-Free Layers and Their Superior Electrical Properties , 2005 .

[182]  J. K. Dewhurst,et al.  Relative stability of ZrO 2 and HfO 2 structural phases , 1999 .

[183]  J. Bae,et al.  The growth-temperature-dependent interface structure of yttria-stabilized zirconia thin films grown on Si substrates , 2010, Journal of physics. Condensed matter : an Institute of Physics journal.

[184]  T. Venkatesan,et al.  Low Leakage Current Transport and High Breakdown Strength of Pulsed Laser Deposited HfO2/SiC Metal-Insulator-Semiconductor Device Structures , 2007 .

[185]  Yee-Chia Yeo,et al.  Metal gate technology for nanoscale transistors—material selection and process integration issues , 2004 .

[186]  O. Marty,et al.  Annealing and doping effects on the structure of europium-doped HfO2 sol–gel material , 2003 .

[187]  E. Cartier,et al.  Oxygen transport and reaction mechanisms in rhenium gate contacts on hafnium oxide films on Si , 2006 .

[188]  M. Heyns,et al.  Extrinsic interface formation of HfO2 and Al2O3∕GeOx gate stacks on Ge (100) substrates , 2009 .

[189]  Lee,et al.  Ab initio calculation of the thermodynamic properties and atomic temperature factors of SiO2 alpha -quartz and stishovite. , 1995, Physical review. B, Condensed matter.

[190]  Jaan Aarik,et al.  Phase transformations in hafnium dioxide thin films grown by atomic layer deposition at high temperatures , 2001 .

[191]  A. Stesmans,et al.  Energy band alignment at the (100)Ge/HfO2 interface , 2004 .

[192]  G. Girolami,et al.  Titanium, zirconium, and hafnium tetrahydroborates as "tailored" CVD precursors for metal diboride thin films , 1988 .

[193]  Metal-oxide-semiconductor field-effect-transistors on indium phosphide using HfO2 and silicon passivation layer with equivalent oxide thickness of 18 Å , 2009 .

[194]  T. White,et al.  Structure and optical properties of solution deposited TiO2 films , 2006 .

[195]  John D. Wright,et al.  Sol-Gel Materials , 2000 .

[196]  David-Wei Zhang,et al.  First principles calculations of oxygen vacancy passivation by fluorine in hafnium oxide , 2006 .

[197]  Byung Jin Cho,et al.  Physical and electrical characterization of HfO2 metal-insulator-metal capacitors for si analog circuit applications , 2003 .

[198]  M. Ramon,et al.  Film properties of ALD HfO2 and La2O3 gate dielectrics grown on Si with various pre-deposition treatments , 2004 .

[199]  C. Musgrave,et al.  First-Principles Investigation of Hydroxylated Monoclinic HfO2 Surfaces , 2006 .

[200]  G. Apostolopoulos,et al.  MBE lanthanum-based high-k gate dielectrics as candidates for SiO2 gate oxide replacement , 2004 .

[201]  M. Mouis,et al.  Carrier transport in HfO/sub 2//metal gate MOSFETs: physical insight into critical parameters , 2006, IEEE Transactions on Electron Devices.

[202]  Youngdo Won,et al.  Initial reaction of hafnium oxide deposited by remote plasma atomic layer deposition method , 2005 .

[203]  Jane P. Chang,et al.  Electrical characteristics of postdeposition annealed HfO2 on silicon , 2005 .

[204]  C. Mahata,et al.  Reliability of ultra-thin titanium dioxide (TiO2) films on strained-Si , 2008 .

[205]  Piero Pianetta,et al.  Hafnium oxide/germanium oxynitride gate stacks on germanium: Capacitance scaling and interface state density , 2009 .

[206]  R. Wallace,et al.  High-κ gate dielectrics: Current status and materials properties considerations , 2001 .

[207]  Eng Fong Chor,et al.  Enhanced device performance of AlGaN/GaN HEMTs using HfO2 high-k dielectric for surface passivation and gate oxide , 2007 .

[208]  Yuebing Zheng,et al.  Microstructure-dependent band structure of HfO2 thin films , 2006 .

[209]  D. Kwong,et al.  ALD(HfO2)x(Al2O3)1-x high-k gate dielectrics for advanced MOS devices application , 2003 .

[210]  P. Chalker,et al.  TOPICAL REVIEW: Some recent developments in the chemical vapour deposition of electroceramic oxides , 2003 .

[211]  P. McIntyre,et al.  Interfacial characteristics of HfO2 films grown on strained Si0.7Ge0.3 by atomic-layer deposition , 2004 .

[212]  Chun-Yen Chang,et al.  Impact of post-deposition-annealing on the electrical characteristics of HfOxNy gate dielectric on Ge substrate , 2005 .

[213]  Karlheinz Schwarz,et al.  The interface between silicon and a high-k oxide , 2004, Nature.

[214]  Improved electrical and surface characteristics of metal-oxide-semiconductor device with gate hafnium oxynitride by chemical dry etching , 2006 .

[215]  Preparation of hafnium oxide thin films by sol–gel method , 2008 .

[216]  J. Bacsa,et al.  Deposition of ZrO2 and HfO2 thin films by liquid injection MOCVD and ALD using ansa-metallocene zirconium and hafnium precursors , 2008 .

[217]  V. Narayanan,et al.  Lattice-matched, epitaxial, silicon-insulating lanthanum yttrium oxide heterostructures , 2002 .

[218]  Hideki Takeuchi,et al.  Observation of bulk HfO2 defects by spectroscopic ellipsometry , 2004 .

[219]  Jane P. Chang,et al.  Effect of Nitrogen on the Electronic Properties of Hafnium Oxynitrides , 2006 .

[220]  Eduard A. Cartier,et al.  Physical and electrical characterization of Hafnium oxide and Hafnium silicate sputtered films , 2001 .

[221]  Tobias Erlbacher,et al.  Tunneling atomic-force microscopy as a highly sensitive mapping tool for the characterization of film morphology in thin high-k dielectrics , 2008 .

[222]  V. Paraschiv,et al.  SELECTIVE REMOVAL OF HIGH-K GATE DIELECTRICS , 2009 .

[223]  O. Richard,et al.  Atomic layer deposition of hafnium oxide on germanium substrates , 2005 .

[224]  K. Yong,et al.  MOCVD and characterization of Hf-silicate thin films using HTB and TEMAS , 2007 .

[225]  K. Saraswat,et al.  Effects of crystallization on the electrical properties of ultrathin HfO2 dielectrics grown by atomic layer deposition , 2003 .

[226]  Hong Ma,et al.  π‐σ‐Phosphonic Acid Organic Monolayer/Sol–Gel Hafnium Oxide Hybrid Dielectrics for Low‐Voltage Organic Transistors , 2008 .

[227]  A. Chin,et al.  Improved High-Temperature Leakage in High-Density MIM Capacitors by Using a TiLaO Dielectric and an Ir Electrode , 2007, IEEE Electron Device Letters.

[228]  Dean-Mo Liu,et al.  Structural evolution and optical properties of TiO2 thin films prepared by thermal oxidation of sputtered Ti films , 2000 .

[229]  H. Kumigashira,et al.  Chemical reaction at the interface between polycrystalline Si electrodes and HfO2∕Si gate dielectrics by annealing in ultrahigh vacuum , 2005 .

[230]  Evgeni P. Gusev,et al.  Structure and stability of ultrathin zirconium oxide layers on Si(001) , 2000 .

[231]  Jack C. Lee,et al.  HfO2-based InP n-channel metal-oxide-semiconductor field-effect transistors and metal-oxide-semiconductor capacitors using a germanium interfacial passivation layer , 2008 .

[232]  Jane P. Chang,et al.  The effect of aluminum oxide incorporation on the material and electrical properties of hafnium oxide on Ge , 2008 .

[233]  H. Funakubo,et al.  Characterization of Hafnium Oxide Thin Films by Source Gas Pulse Introduced Metalorganic Chemical Vapor Deposition Using Amino-Family Hf Precursors , 2003 .

[234]  J. Kwo,et al.  GaAs MOSFET with oxide gate dielectric grown by atomic layer deposition , 2003, IEEE Electron Device Letters.

[235]  J. Abelson,et al.  In situ spectroscopic ellipsometry analyses of hafnium diboride thin films deposited by single-source chemical vapor deposition , 2007 .

[236]  A. Chroneos,et al.  Mechanisms of nonstoichiometry in HfN1−x , 2009 .

[237]  M. Sung,et al.  A new patterning method using photocatalytic lithography and selective atomic layer deposition. , 2004, Journal of the American Chemical Society.

[238]  J. Robertson,et al.  Bonding, energies, and band offsets of Si-ZrO2 and HfO2 gate oxide interfaces. , 2004, Physical review letters.

[239]  P. Kofstad,et al.  On the Defect Structure of ZrO2 and HfO2 , 1963 .

[240]  Albert Chin,et al.  Effect of surface NH3 anneal on the physical and electrical properties of HfO2 films on Ge substrate , 2004 .

[241]  H. Seo,et al.  Growth and physical properties of epitaxial HfN layers on MgO(001) , 2004 .

[242]  D. Schlom,et al.  Thermodynamic stability of binary oxides in contact With silicon , 1996 .

[243]  R. Waser,et al.  Thin Films of HfO2 for High-k Gate Oxide Applications from Engineered Alkoxide- and Amide-Based MOCVD Precursors , 2007 .

[244]  H. Iwaia,et al.  Trend of CMOS downsizing and its reliability , 2002 .

[245]  Evgeni P. Gusev,et al.  Microstructure and thermal stability of HfO2 gate dielectric deposited on Ge(100) , 2004 .

[246]  D. Kwong,et al.  Thermal response of Ru electrodes in contact with SiO2 and Hf-based high-k gate dielectrics , 2005 .

[247]  S. Maikap,et al.  Characteristics of ultrathin HfO2 gate dielectrics on strained-Si0.74Ge0.26 layers , 2003 .

[248]  Raghaw Rai,et al.  Thermodynamic stability of high-K dielectric metal oxides ZrO2 and HfO2 in contact with Si and SiO2 , 2002 .

[249]  John Robertson,et al.  Defect energy levels in HfO2 high-dielectric-constant gate oxide , 2005 .

[250]  J. Dai,et al.  Nitridation of hafnium oxide by reactive sputtering , 2006 .

[251]  J. Abelson,et al.  Hafnium diboride thin films by chemical vapor deposition from a single source precursor , 2005 .

[252]  S. Desgreniers,et al.  High-density ZrO 2 and HfO 2 : Crystalline structures and equations of state , 1999 .

[253]  K. Sasaki,et al.  Influence of Sputtering Parameters on the Formation Process of High-Quality and Low-Resistivity HfN Thin Film , 1999 .

[254]  Electrical properties of HfOxNy thin films deposited by PECVD , 2006 .

[255]  M. Eizenberg,et al.  Effect of composition and chemical bonding on the band gap and band offsets to Si of HfxSi1−xO2 (N) films , 2010 .

[256]  Yue Kuo,et al.  Electrical reliability aspects of HfO2 high-k gate dielectrics with TaN metal gate electrodes under constant voltage stress , 2006, Microelectron. Reliab..

[257]  J.C. Lee,et al.  Optimized NH/sub 3/ annealing Process for high-quality HfSiON gate oxide , 2004, IEEE Electron Device Letters.

[258]  Sang Heup Moon,et al.  Atomic layer deposition of an HfO2 thin film using Hf(O-iPr)4 , 2009 .

[259]  Ryan M. Martin,et al.  Plasma etching of Hf-based high-k thin films. Part II. Ion-enhanced surface reaction mechanisms , 2009 .

[260]  G. Apostolopoulos,et al.  Interface trap density in amorphous La2Hf2O7/SiO2 high-κ gate stacks on Si , 2005 .

[261]  S. Pearton,et al.  Dry Etching of Electronic Oxides, Polymers, and Semiconductors , 2005 .

[262]  C. Shih,et al.  Investigations of GaN metal-oxide-semiconductor capacitors with sputtered HfO2 gate dielectrics , 2009 .

[263]  Pulsed laser deposition and characterization of Hf-based high-k dielectric thin films , 2007 .

[264]  Alfred Kersch,et al.  Stabilization of the high-k tetragonal phase in HfO2: The influence of dopants and temperature from ab initio simulations , 2008 .

[265]  C. Musgrave,et al.  Atomic Layer Deposition of HfO 2 Using Alkoxides as Precursors , 2004 .

[266]  P. McIntyre,et al.  Size-dependent polymorphism in HfO2 nanotubes and nanoscale thin films , 2009 .

[267]  John Robertson,et al.  Band offsets of high K gate oxides on high mobility semiconductors , 2006 .

[268]  J. Aarik,et al.  Influence of substrate temperature on atomic layer growth and properties of HfO2 thin films , 1999 .

[269]  B. Lee,et al.  Temperature dependence of the work function of ruthenium-based gate electrodes , 2006 .

[270]  R. Gordon,et al.  Atomic layer deposition of transition metals , 2003, Nature materials.

[271]  S. Laux,et al.  Comments on "Monte Carlo simulation of transport in technologically significant semiconductors of the diamond and zinc-blende structures. II. Submicrometer MOSFETs" [with reply] , 1991 .

[272]  K. Kukli,et al.  Analytical TEM characterization of the interfacial layer between ALD HfO2 film and silicon substrate , 2005 .

[273]  Yasuhiro Shimamoto,et al.  Remote-charge-scattering limited mobility in field-effect transistors with SiO2 and Al2O3∕SiO2 gate stacks , 2005 .