유기금속 화학 기상증착법으로 실리콘 기판위에 증착된 질소치환 $TiO_2$ 박막의 특성분석

Characterization of Nitrogen-Doped $TiO_2$ Thin Films Prepared by Metalorganic Chemical Vapor Deposition

  • 발행 : 1994.12.01

초록

TiO2 thin films with the substitution of oxygen with nitrogen were deposited on silicon substrate by metalorganic chemical vapor deposition (MOCVD) using Ti(OCH(CH3)2)4 (titanium tetraisopropoxide, TTIP) and N2O as source materials. X-ray diffraction (XRD) results indicated that the crystal structure of the deposited thin films was anatase TiO2 with only (101) plane observed at the deposition temperatures of 36$0^{\circ}C$ and 38$0^{\circ}C$, and with (101) and (200) plane at above 40$0^{\circ}C$. Raman spectroscopic results indicated that the crystal structure was anatase TiO2 in accordance with the XRD results without any rutile, fcc TiN, or hcp TiN structure. No fundamental difference was observed with temperature increase, but the peak intensity at 194.5 cm-1 increased with strong intensity at 143.0 cm-1 for all samples. The crystalline size of the films varied from 49.2 nm to 63.9 nm with increasing temperature as determined by slow-scan XRD experiments. The refractive index of the films increased from 2.40 to 2.55 as temperature increased. X-ray photoelectron spectroscopy (XPS) study showed only Ti 2s, Ti 2p, C 1s, O 1s and O 2s peaks at the surface of the film. The composition of the surface was estimated to be TiO1.98 from the quatitative analysis. In the bulk of the film Ti 2s, Ti 2p, O 1s, O 2s, N 1s and N 2s were detected, and Ti-N bonding was observed due to the substitution of oxygen with nitrogen. A satellite structure was observed in the Ti 2p due to the Ti-N bonding, and the composition of titanium nitride was determined to be about TiN1.0 from the position of the binding energy of Ti-N 2p3/2 and the quatitative analysis. The spectrum of Ti 2p energy level could be the sum of a 4, 5, or 6 Gaussian curve reconstruction, and the case of the sum of the 6 Gaussian curve reconstruction was physically most meaningful. From the results of Auger electron spectroscopy (AES), it was known that the composition was not varied significantly throughout the whole thickness of the film, and silicon oxide was not observed at the interface between the film and the substrate. The composition of the film was possible (TiO2)1-x.(TiN)x or TiO2-2xNx and in this experimental condition x was found to be about 0.21-0.16.

키워드

참고문헌

  1. Appl. Optics v.23 no.20 Physical and Chemical Aspects in the Application of Thin Films on Optical Elements K.H. Guenther
  2. J. Chem Soc. Faraday Trans. 1 v.77 Chemical Vapor Deposition of TiO2 Films Using an Organometallic process and its Photoelectrochemical Behaviour Y. Takahashi;K. Tsuda;K. Sugiyama;H. Minoura;D Makino;M. Tsuiki
  3. Solid State Electron. v.21 C-V Characteristics of Metal-Titanium Dioxide-Silicon Capacitors W.D. Brown;W.W. Grannemann
  4. J. Electrochem Soc. v.137 no.3 Kinetics of Low-Pressure Chemical Vapor Deposition of TiO₂ from Titanium Isopropoxide K.L. Siefering;G. L. Griffin
  5. Thin Solid Films v.226 Investigations of Titanium Oxide Films Deposited by D.C Reactive Magnetron Sputtering in Different Sputtering Pressures L. Meng;M.P. Santos
  6. J. Appl Phys. v.62 no.3 Titanium-Oxide Films Made by RF Diode Sputtering from a Compound Target M.M. Yang
  7. Thin Solid Films v.207 Sol-Gel TiO₂ Thin Films on Silicon Substrates K.A. Vorotilov;E.V. Orlova;V.I. Petrovsky
  8. Thin Solid Films v.201 Deposition of TiO2 Thin Films by Plasma-Enhanced Decomposition of Tetraisopropyltitanate H.J. Frenck;W. Kulisch;M Kuhr;R. Kassing
  9. Thin Solid Films v.239 Influence of Substrate on Structural Properties of TiO₂ Thin Films Obtained via MOCVD G.A. Battiston;R. Gerbasi;M. Porchia;A. Marigo
  10. J. Appl. Phys. v.75 no.1 High Mibility n-type Charge Carriers in Large Single Crystals of Anatase (TiO₂) L. Forro;O. Chauvt;D. Emin;L. Zuppiroli;H. Berger;F Levy
  11. Thin Solid Films v.205 New Amorphous titanium Oxysulfides Obtained in the Form of Thin Films G. Meunier;R. Doroy;A. Levasseur
  12. IEDM Tech. Dig. Electrical Properties of Nitrided-Oxide Systems For Use in Gate Dielectrics and EEPROM S.K. Lai;J. Lee;V K Dham
  13. J. Electrochem. Soc. v.141 no.3 Low temperature Deposition of TiN Using Tetrakis(dimethylamido)-Titanium in an Electron Cyclotron Resonance Plasma Process A. Wever;R. Nikulski;C.P. Klages;M.E. Gross;W.L. Brown;E. Dons;R.M. Charatan
  14. J. Appl Phys. v.70 no.7 Oxidation of titanium Nitride in Room Air and In Dry O₂ H.G. Tompkins
  15. Metal Alkoxides D.C. Bradley;R.C. Mehrotra;D P Guar
  16. JCPDS Power Diffraction File Joint Committee on Power Diffraction Standards
  17. J. Appl Phys. v.75 no.4 Electrical and Optical Properties of TiO₂ Anatase Thin Films H. Tang;K. Prasad;R. Sanjines;P.E. Schmid;F. Levy
  18. Proc. Roy. soc. (London) A v.307 single Crystal Laser Raman Spectroscopy I.R. Beattie;T.R Gilson
  19. J. Raman Spectrosc. v.7 no.6 Raman Spectrum of Anatase, TiO₂ T. Ohsaka;F. Izumi;Y. Fujiki
  20. J. Crystal Growth v.130 Growth and Raman Spectroscopic Characterization of TiO₂ Anatase Single Crystals H. Berger;H. Tang;F. Levy
  21. Thin solid Films v.198 Raman Spectroscopy of Thermally Annealed TiO₂ Thin Films A. Turkovi;M. Ivanda;A. Dra ner;V. Vrane a;M. Per in
  22. Phys. Rev. v.154 no.2 Raman Spectra of TiO₂, MgF₂, ZnF₂, FeF₂, and MnF₂ S.P.S. Porto;P.A. Fleury;T.C. Damen
  23. Elements of X-ray Diffraction(2nd edition) B.D. Cullity
  24. Handbook of X-Ray Photoelectron Spectroscopy(2nd edition) J.F. Moulder;W.F. Stickle;P.E. Sobol;K.D. Bomben
  25. Chem. Phys. Lett. v.90 no.4 Thermal Desorption of H₂ and CO on Pt/TiO₂ J.A. Schreifels;D.N Belton;J M. White;R.L. Hance
  26. Handbook of X-Ray Photoelectron Spectroscopy(2nd edition) J.F. Moulder;W F Stickle;P E. Sobol;K.D. Bomben
  27. J Phys. Chem. v.89 An XPS Investigation of TiO₂ Thin Films on Polycrystalline Pt C.M. Greenlief;J.M White;C S. Ko;R.J. Gorte
  28. Anal Chem v.51 no.4 Two-Dimensional Chemical State Plots: a Standardlized Set for Use in Identifying Chemical States by X-Ray Phototelectron Spectroscopy C.D. Wagner;L.H Gale;R.H Raymond
  29. Practical Surface Analysis by Auger and X-Ray Photoelectron Spectroscopy D. Briggs;M P. Seah
  30. Phys. Rev v.B5 no.12 High-Resolution X-Ray Photoemission Spectrum of the Valence Bands of Gold D.A. Shirley
  31. Anal. Chem. v.36 no.8 Smoothing and Differentiation of Data by Simplified Least Squares Procedures A. Savitzky;M.J E. Golay
  32. Phys. Rev. v.B28 no.6 Vacancy Effects in the X-Ray Photoelectron Spectra of TiNx L. Porte;L. Roux;J. Hanus
  33. J. Phys. Chem. Solids v.30 Charge Transfer in Transition Metal Carbides and Related Compounds Studied by ECSA L Ramqvist;K. Hamrin;G. Johansson;A. Fahlman;C. Nordling
  34. J. Appl. Phys. v.71 no.2 The Influence of Ammonia on Rapid-Thermal Low-Pressure Metalorganic Chemical Vapor Deposited TiNx Films from Tetrakis (Dimethylamido) titanium Precursor onto InP A. Katz;A. Feingolg;S. Nakahara;S.J. Pearton;E. Lane;M. Geva;F.A. Stevie;K Jones
  35. J Appl Phys. v.71 no.12 X-Ray Photoemission Spectra of Reactively Sputtered TiN M. Delfino;J.A. Fair;D. Hodul
  36. Phys. Rev. v.B25 no.12 Photoemission Study of the Electronic Structure of Stoichiometric and Substoichiometric TiN and ZrN H. Hochst;R.D. Bringans;P. Steiner;Th. Wolf
  37. J. Vac Sci Technol. v.A5 no.2 The Structures and Interfaces of TiN Films prepared by Hollow Cathode Discharge Ion Plating Technique L. Pengxing;Z. Meihua;Q. Xuan;L. Xongfang;Y. Fan
  38. J Vac. Sci. Technol. v.A8 no.1 The Characterization of Titanium Nitride by X-Ray Photoelectron Spectroscopy and Rutherford Backscattering M.J. Vasile;A.B. Emerson;F.A. Baiocchi
  39. J Vac. Sci. Technol v.A4 no.6 Low Temperature Oxidation behavior of Reactively Sputtered TiN by X-Ray Phtoelectron Spectroscopy and Contact Resistance Measurements C. Ernsberger;J. Nickerson;T. Smith;A.E. Miller;D. Banks
  40. Surf. Interface Anal. v.6 X-Ray Photoelectron Spectroscopic Studies of the Surface of Sputter Ion Plated Films K.S. Robinson;P.M.A. Sherwood
  41. J. Nucl. Mater v.103-104 Preparation of Titanium Nitride onto Molybdenum, Stainless Steel and Carbon by Gas Absorption and Reactive R.F. Sputtering K. Sato;M. Mohri;T. Yamashina;K. Yabe
  42. Vacuum v.40 no.1,2 Characterization of Ti$N_x$ and Zr$N_x$ Multilayered Structures by Auger Electron Spectroscopy P. Panjan;B. Navinsek;A. Zabkar;J. Fiser;A. Zalar
  43. Vacuum v.42 no.1,2 Quatitative Auger Electron Spectroscopic analysis of Titanium Nitrides J.L. Vignes;J.P. Langeron;G.I. Grigorov;I.N. Martev;M.V. Stoyanova
  44. Surf. Sci. v.128 Kinetics of Nitride Formation on Titanium Targets During Reactive Sputtering J.E. Sundgren;B.O. Johansson;S.E. Karlsson
  45. Surf. Sci. v.149 Qunatitative auger Electron Analysis of Titanium Nitrides P.T. Dawson;K.K. Tzatzov
  46. Surf. Interface Anal. v.14 Quantitative AES and XPS Investigation of Magnetron Sputtered TiNx Films H. Bender;J. Portillo;W. Vandervorst
  47. J Vac. Sci Technol. v.A4 no.6 A Correlation of Auger Electron Spectroscopy, X-Ray Photoelectron Spectroscopy, and Rutherford Backscattering Spectrometry Meassurement on Sputter-Deposited Titanium Nitride Thin Films B.J. Burrow;A.E. Morgan;R.C. Ellwanger
  48. J. Vac. Sci. Technol. v.A4 no.6 Characterization of Nitride Coating by Auger Electron Spectroscopy and X-Ray Photoelectron Spectroscopy S. Hofmann
  49. Handbook of Auger Electron Spectroscopy(2nd edition) L.E. Davis;N.C. MacDonald;P.W. Palmberg;G.E. Riach;R.E. Weber