Fabrication of ZrO2 and ZrN Films by Metalorganic Chemical Vapor Deposition Employing New Zr Precursors

The application of new zirconium precursors for the fabrication of ZrO2 and ZrN thin films by metalorganic chemical vapor deposition (MOCVD) is presented. The all-nitrogen coordinated Zr precursors exhibit improved thermal properties for vapor phase fabrication of thin films. The growth of ZrO2 thin films was realized by the combination of the Zr complex with oxygen, while the formation of ZrN thin films was achieved for the first time employing a single source precursor (SSP) approach. This was enabled by the presence of nitrogen containing ligands which contributes to the formation of the ZrN phase without the need for any additional nitrogen source in contrast to classical film growth processes for ZrN thin films. In the first step the newly developed precursors were evaluated thoroughly for their use in MOCVD applications, and in the next step they were utilized for the growth of ZrO2 and ZrN thin films on Si(100) substrates. Polycrystalline ZrO2 films that crystallized in the monoclinic phase and the...

[1]  Tsutomu Suzuki,et al.  Effects of substrate temperature on the ion conductivity of hydrated ZrO2 thin films prepared by reactive sputtering in H2O atmosphere , 2012 .

[2]  I. A. Siddiquey,et al.  A rapid method for the preparation of silica-coated ZrO2 nanoparticles by microwave irradiation , 2011 .

[3]  T. Troczynski,et al.  An innovative technique to simply fabricate ZrO₂-HA-TiO₂ nanostructured layers. , 2011, Colloids and surfaces. B, Biointerfaces.

[4]  M. Kiani,et al.  Characterization of ion beam sputtered ZrN coatings prepared at different substrate temperatures , 2011 .

[5]  A. Ney,et al.  Evaluation of Homoleptic Guanidinate and Amidinate Complexes of Gadolinium and Dysprosium for MOCVD of Rare-Earth Nitride Thin Films , 2011 .

[6]  Se Stephen Potts,et al.  Bis(cyclopentadienyl) zirconium(IV) amides as possible precursors for low pressure CVD and plasma-enhanced ALD , 2010 .

[7]  M. Signore,et al.  Physical properties evolution of sputtered zirconium oxynitride films: effects of the growth temperature , 2009 .

[8]  A. Devi,et al.  Homoleptic gadolinium guanidinate: a single source precursor for metal-organic chemical vapor deposition of gadolinium nitride thin films. , 2009, Journal of the American Chemical Society.

[9]  Se Stephen Potts,et al.  MOCVD of Zirconium Oxide from the Zirconium Guanidinate Complex [ZrCp′{η2-(iPrN)2CNMe2}2Cl] , 2009 .

[10]  Se Stephen Potts,et al.  Synthesis of zirconium guanidinate complexes and the formation of zirconium carbonitride via low pressure CVD , 2009 .

[11]  A. Devi,et al.  Synthesis, characterization, and thermal properties of homoleptic rare-earth guanidinates: promising precursors for MOCVD and ALD of rare-earth oxide thin films. , 2008, Inorganic chemistry.

[12]  S. Koveshnikov,et al.  In0.53Ga0.47As based metal oxide semiconductor capacitors with atomic layer deposition ZrO2 gate oxide demonstrating low gate leakage current and equivalent oxide thickness less than 1nm , 2008 .

[13]  S. Isotani,et al.  X-ray photoelectron spectroscopy analysis of zirconium nitride-like films prepared on Si(100) substrates by ion beam assisted deposition , 2008 .

[14]  L. Gauckler,et al.  Microstructures of CGO and YSZ Thin Films by Pulsed Laser Deposition , 2008 .

[15]  R. Odedra,et al.  Liquid injection MOCVD and ALD of ZrO2 using Zr–cyclopentadienyl precursors , 2007 .

[16]  Ying Wang,et al.  Investigation of Zr-N thin films for use as diffusion barrier in Cu metallization , 2007, Microelectron. J..

[17]  P. Ehrhart,et al.  Synthesis and characterisation of zirconium-amido guanidinato complex: a potential precursor for ZrO2 thin films. , 2007, Dalton transactions.

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

[19]  R. Waser,et al.  Liquid‐Injection MOCVD of ZrO2 Thin Films using Zirconium Bis(diethlyamido)‐bis(di‐tert‐butylmalonato) as a Novel Precursor , 2006 .

[20]  C. Rowley,et al.  Synthesis and thermolysis of aluminum amidinates: a ligand-exchange route for new mixed-ligand systems. , 2006, Inorganic chemistry.

[21]  M. Yashima,et al.  XPS study of the phase transition in pure zirconium oxide nanocrystallites , 2005 .

[22]  R. Fischer,et al.  Tantalum complexes with all nitrogen coordination sphere: mixed amido-, imido-, guanidinato complexes of tantalum and their thermal behaviour. , 2005, Dalton transactions.

[23]  J. Olsson,et al.  Low-resistivity ZrNx metal gate in MOS devices , 2005 .

[24]  G. Yap,et al.  The insertion of carbodiimides into Al and Ga amido linkages. Guanidinates and mixed amido guanidinates of aluminum and gallium. , 2005, Inorganic chemistry.

[25]  A. Bartasyte,et al.  New sterically hindered Hf, Zr and Y β-diketonates as MOCVD precursors for oxide films , 2004 .

[26]  Liling Hu,et al.  Influence of N2:(N2 + Ar) flow ratio and substrate temperature on the properties of zirconium nitride films prepared by reactive dc magnetron sputtering , 2003 .

[27]  Heng-Ghieh Yang,et al.  Systematic study of the evolution of texture and electrical properties of ZrNx thin films by reactive DC magnetron sputtering , 2003 .

[28]  G. Yap,et al.  Synthesis and structural investigation of N,N',N' '-trialkylguanidinato-supported zirconium(IV) complexes. , 2003, Inorganic chemistry.

[29]  K. Starbova,et al.  Thin ZrO2 sol–gel films for catalytic applications , 2003 .

[30]  T. Aizawa,et al.  Mechanical properties of zirconium films prepared by ion-beam assisted deposition , 2003 .

[31]  Esther Kim,et al.  Atomic Layer Deposition of Hafnium and Zirconium Oxides Using Metal Amide Precursors , 2002 .

[32]  P. Chalker,et al.  Novel Mononuclear Alkoxide Precursors for the MOCVD of ZrO2 and HfO2 Thin Films , 2002 .

[33]  P. Uggowitzer,et al.  ZrN, ZrxAlyN and ZrxGayN thin films – novel materials for hard coatings grown using pulsed laser deposition , 2001 .

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

[35]  D. Barreca,et al.  Zirconium Dioxide Thin Films Characterized by XPS , 2000 .

[36]  Á. Kiss,et al.  Thick target γ-ray yields for light elements measured in the deuteron energy interval of 0.7–3.4 MeV , 2000 .

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

[38]  Allain,et al.  Optical sensors for the determination of concentrated hydroxide , 2000, Analytical chemistry.

[39]  D. Gilmer,et al.  Anhydrous Metal Nitrates as Volatile Single Source Precursors for the CVD of Metal Oxide Films , 1998 .

[40]  I. Milošev,et al.  Zirconium Nitride by XPS , 1998 .

[41]  N. Travitzky,et al.  Vacuum arc deposition and microstructure of ZrN-based coatings , 1997 .

[42]  Dejun Fu,et al.  Structure, electrical and chemical properties of zirconium nitride films deposited by dc reactive magnetron sputtering , 1997 .

[43]  G. Bertrand,et al.  Zirconia coatings realized by microwave plasma-enhanced chemical vapordeposition , 1997 .

[44]  P. Fragnaud,et al.  Thin film solid oxide fuel cells , 1996 .

[45]  P. Mayr,et al.  Zirconium carbonitride films produced by plasma-assisted metal organic chemical vapour deposition , 1995 .

[46]  J. M. Sanz,et al.  Interaction of oxygen with ZrN at room temperature: An XPS study† , 1994 .

[47]  E. Kótai,et al.  Computer methods for analysis and simulation of RBS and ERDA spectra , 1994 .

[48]  H. Suhr,et al.  Thin zirconium nitride films prepared by plasma-enhanced CVD , 1992 .

[49]  R. Gordon,et al.  Solution-phase reactivity as a guide to the low-temperature chemical vapor deposition of early-transition-metal nitride thin films , 1990 .

[50]  Williams,et al.  Zirconium nitride-a new material for Josephson junctions. , 1985, Physical review. B, Condensed matter.

[51]  D. Milam,et al.  Optical coatings for laser fusion applications , 1980 .

[52]  M. Balog,et al.  The chemical vapour deposition and characterization of ZrO2 films from organometallic compounds , 1977 .

[53]  M. Balog,et al.  Thin films of metal oxides on silicon by chemical vapor deposition with organometallic compounds. I , 1972 .

[54]  A. C. Dumbri,et al.  Preparation and Properties of Pyrolytic Zirconium Dioxide Films , 1971 .

[55]  M. Gros-Jean,et al.  Gaseous Phase Study of the Zr-Organometallic ALD Precursor TEMAZ by Mass Spectrometry , 2009 .

[56]  I. Povey,et al.  Chemical vapour deposition of ZrO2 thin films monitored by IR spectroscopy , 1994 .

[57]  D. C. Bradley,et al.  765. Metallo-organic compounds containing metal–nitrogen bonds. Part I. Some dialkylamino-derivatives of titanium and zirconium , 1960 .