Deposition and characterisation of functional ITO thin films

Polycrystalline tin-doped indium oxide (ITO) thin films were prepared by Pulsed Laser Deposition (PLD) with an ITO (In\(_2\)O\(_3\)-10 wt.% SnO\(_2\)) target and deposited on borosilicate glass substrates. By changing independently the thickness, the deposition temperature and the oxygen pressure, a variety of microstructures were deposited. The impact on thin film physical properties of different gas dynamics is stressed and explained. Films deposited at room temperature (RT) show poorer opto-electrical properties. The same is true for films deposited at low or high oxygen pressure. It is shown that films grown with 1 to 10 mT Oxygen pressure at 200 °C show the best compromise in terms of transmittance and resistivity. The influence of the thickness, the substrate temperature and the oxygen pressure on the microstructure and ITO film properties is discussed. A practical application (a Dye Sensitized Solar Cell) is proposed.

[1]  C. Erginsoy.  Neutral Impurity Scattering in Semiconductors , 1950 .

[2]  David B. Geohegan,et al.  Time-resolved imaging of gas phase nanoparticle synthesis by laser ablation , 1998 .

[3]  J. Maudes,et al.  Sprayed SnO2 films: Growth mechanism and film structure characterization , 1980 .

[4]  Wen-Fa Wu,et al.  Effect of oxygen concentration in the sputtering ambient on the microstructure, electrical and optical properties of radio-frequency magnetron-sputtered indium tin oxide films , 1996 .

[5]  V. F. Korzo,et al.  Electrophysical properties of indium oxide pyrolytic films with disordered structure , 1973 .

[6]  F. Shinoki,et al.  Optical properties of r.f. reactive sputtered tin-doped In2O3 films , 1979 .

[7]  Andreea Trache,et al.  Atomic Force Microscopy (AFM) , 2008, Current protocols in microbiology.

[8]  P. Champness,et al.  The identification of asbestos , 1976 .

[9]  C. Afonso,et al.  Expansion dynamics of the plasma produced by laser ablation of BaTiO3 in a gas environment , 1997 .

[10]  J. A. Greer,et al.  Large-area pulsed laser deposition: Techniques and applications , 1995 .

[11]  P. Willmott,et al.  Pulsed laser vaporization and deposition , 2000 .

[12]  David B. Williams,et al.  The measurement and calculation of the X‐ray spatial resolution obtained in the analytical electron microscope , 1990 .

[13]  F. O. Adurodija,et al.  Highly conducting indium tin oxide (ITO) thin films deposited by pulsed laser ablation , 1999 .

[14]  Ronald P. Howson,et al.  Pressure stability in reactive magnetron sputtering , 1988 .

[15]  X. W. Sun,et al.  Pulsed laser deposited crystalline ultrathin indium tin oxide films and their conduction mechanisms , 1998 .

[16]  H. Börner,et al.  Large area pulsed laser deposition of YBCO thin films on 3-inch wafers , 1994 .

[17]  Y. Shigesato,et al.  Lattice Defects in O+ Implanted Tin-Doped Indium Oxide Films , 1993 .

[18]  F. Smits.  Measurement of sheet resistivities with the four-point probe , 1958 .

[19]  S. J. PERRY,et al.  Low Temperature , 1881, Nature.

[20]  M. T. Bhatti,et al.  Characterization of rf-sputtered indium tin oxide thin films , 2004 .

[21]  P. Schattschneider,et al.  Treating retardation effects in valence EELS spectra for Kramers-Kronig analysis. , 2008, Ultramicroscopy.

[22]  J. Woollam,et al.  Spectroscopic ellipsometry studies of indium tin oxide and other flat panel display multilayer materials , 1994 .

[23]  Nevill Mott,et al.  Metal-insulator transitions , 1974 .

[24]  T. E. Haynes,et al.  Study of the effect of ion implantation on the electrical and microstructural properties of tin-doped indium oxide thin films , 1993 .

[25]  Nevill Mott,et al.  Conduction in glasses containing transition metal ions , 1968 .

[26]  J. Preece,et al.  HREELS studies of gold nanoparticles with dialkyl sulphide ligands , 2002 .

[27]  A. Klein,et al.  Electronic and chemical properties of tin-doped indium oxide (ITO) surfaces and ITO/ZnPc interfaces studied in-situ by photoelectron spectroscopy. , 2006, The journal of physical chemistry. B.

[28]  A. Saxena,et al.  Thickness dependence of the electrical and structural properties of In2O3:Sn films , 1984 .

[29]  N. Zaluzec,et al.  Atomic sputtering in the Analytical Electron Microscope , 1989 .

[30]  I. Hamberg,et al.  High Quality Transparent Heat Reflectors Of Reactively Evaporated Indium Tin Oxide , 1982, Photonics West - Lasers and Applications in Science and Engineering.

[31]  Xindi Wu,et al.  Large‐area, two‐sided superconducting YBa2Cu3O7−x films deposited by pulsed laser deposition , 1991 .

[32]  Alberto Piqué,et al.  Indium tin oxide thin films for organic light-emitting devices , 1999 .

[33]  Q. Jia,et al.  Indium tin oxide on InP by pulsed laser deposition , 1995 .

[34]  S. Schiller,et al.  Reactive d.c. high-rate sputtering as production technology , 1987 .

[35]  Alireza Salehi,et al.  The effects of deposition rate and substrate temperature of ITO thin films on electrical and optical properties , 1998 .

[36]  M. Olsson,et al.  THIN FILMS ENGINEERING OF INDIUM TIN OXIDE: LARGE AREA FLAT PANEL DISPLAYS APPLICATION , 2006 .

[37]  K. No,et al.  Effects of oxygen partial pressure on the microstructure and electrical properties of indium tin oxide film prepared by d.c. magnetron sputtering , 1995 .

[38]  J. Talvacchio,et al.  Pulsed Laser Deposition (PLD) of Oriented Bismuth Titanate Films for Integrated Electronic Applications , 1992 .

[39]  Greg P. Smestad,et al.  Education and solar conversion:: Demonstrating electron transfer , 1998 .

[40]  R. Vook.  Structure and growth of thin films , 1982 .

[41]  V. Berardi,et al.  Diagnostics of YBa2Cu3O7−δ laser plume by time‐of‐flight mass spectrometry , 1994 .

[42]  L. Reimer,et al.  Contribution to the contamination problem in transmission electron microscopy. , 1978, Ultramicroscopy.

[43]  J. F. Flintoff,et al.  High-quality optical and epitaxial Ge films formed by laser evaporation , 1989 .

[44]  R. Egerton,et al.  Beam-Induced Damage to Thin Specimens in an Intense Electron Probe , 2005, Microscopy and Microanalysis.

[45]  F. O. Adurodija,et al.  The electro-optical properties of amorphous indium tin oxide films prepared at room temperature by pulsed laser deposition , 2002 .

[46]  N. Browning,et al.  The impact of surface and retardation losses on valence electron energy-loss spectroscopy. , 2008, Ultramicroscopy.

[47]  H. Köstlin,et al.  Optical and electrical properties of doped In2O3 films , 1975 .

[48]  W. A. Phillips,et al.  Electrical and optical properties of amorphous indium oxide , 1990 .

[49]  R. K. Hart,et al.  The contamination of surfaces during high-energy electron irradiation , 1970 .

[50]  E. Burstein.  Anomalous Optical Absorption Limit in InSb , 1954 .

[51]  Richard F. Haglund,et al.  Resistivity and oxygen content of indium tin oxide films deposited at room temperature by pulsed-laser ablation , 1999 .

[52]  E. M. Peterson,et al.  Kinetics of decomposition of amorphous hydrogenated silicon films , 1979 .

[53]  Alexander Ehrlich,et al.  The Hall Effect , 1997 .

[54]  M. Marezio.  Refinement of the crystal structure of In2O3 at two wavelengths , 1966 .

[55]  P. Moreau,et al.  Relativistic effects in electron-energy-loss-spectroscopy observations of the S i / S i O 2 interface plasmon peak , 1997 .

[56]  P. Thilakan,et al.  Studies on the preferred orientation changes and its influenced properties on ITO thin films , 1997 .

[57]  Frank J. Bachner,et al.  Properties of Sn‐Doped In2 O 3 Films Prepared by RF Sputtering , 1975 .

[58]  S. S. Harilal.  Expansion dynamics of laser ablated carbon plasma plume in helium ambient , 2001 .

[59]  P. Schattschneider,et al.  The influence of relativistic energy losses on bandgap determination using valence EELS. , 2007, Ultramicroscopy.

[60]  R. B. Tahar,et al.  Optical, structural, and electrical properties of indium oxide thin films prepared by the sol-gel method , 1997 .

[61]  K. J. Lethy,et al.  Influence of substrate temperature on the properties of laser ablated indium tin oxide films , 2007 .

[62]  M. Ohring.  The Materials Science of Thin Films , 1991 .

[63]  K. Ellmer,et al.  Reactive magnetron sputtering of tin-doped indium oxide (ITO): influence of argon pressure and plasma excitation mode , 2001 .

[64]  V. Cimalla,et al.  Dependence of the photoreduction and oxidation behavior of indium oxide films on substrate temperature and film thickness , 2001 .

[65]  J. Pankove,et al.  Absorption Edge of Impure Gallium Arsenide , 1965 .

[66]  John B. Goodenough,et al.  X-ray photoemission spectroscopy studies of Sn-doped indium-oxide films , 1977 .

[67]  K. Zakrzewska,et al.  Scattering of charge carriers in transparent and conducting thin oxide films with a non-parabolic conduction band , 1989 .

[68]  J. Seto.  The electrical properties of polycrystalline silicon films , 1975 .

[69]  H. Waal,et al.  Tin oxide coatings: Physical properties and applications , 1981 .

[70]  Scott A. Barnett,et al.  Laser‐induced plasmas for primary ion deposition of epitaxial Ge and Si films , 1985 .

[71]  Akio Suzuki,et al.  Highly conducting transparent indium tin oxide films prepared by pulsed laser deposition , 2002 .

[72]  C. Granqvist,et al.  Band-gap widening in heavily Sn-dopedIn2O3 , 1984 .

[73]  R. Pommier,et al.  Sprayed films of indium tin oxide and fluorine-doped tin oxide of large surface area☆ , 1981 .

[74]  A. Savitzky,et al.  Smoothing and Differentiation of Data by Simplified Least Squares Procedures. , 1964 .

[75]  Abhai Mansingh,et al.  Band gap narrowing and the band structure of tin-doped indium oxide films , 1989 .

[76]  S. Evans,et al.  Relative differential subshell photoionisation cross-sections (MgKα) from lithium to uranium , 1978 .

[77]  A. Banerjee,et al.  Annealing characteristics of tin oxide films prepared by spray pyrolysis , 1980 .

[78]  H. Dislich,et al.  Amorphous and crystalline dip coatings obtained from organometallic solutions: Procedures, chemical processes and products , 1981 .

[79]  David C. Paine,et al.  A study of low temperature crystallization of amorphous thin film indium–tin–oxide , 1999 .

[80]  L. Laude,et al.  Pulsed laser deposition of high quality ITO thin films , 1996 .

[81]  Ho-Chul Lee.  Electron scattering mechanisms in indium–tin-oxide thin films prepared at the various process conditions , 2006 .

[82]  A. Méndez-Vilas.  Electron Energy Loss Spectroscopy , 2012 .

[83]  Nadezhda M. Bulgakova,et al.  Gas-dynamic effects of the interaction between a pulsed laser-ablation plume and the ambient gas: analogy with an underexpanded jet , 1998 .

[84]  S. Uekusa,et al.  Micrograin structure influence on electrical characteristics of sputtered indium tin oxide films , 1993 .

[85]  R. Boxman,et al.  Influence of a parallel electric field on the conductivity of a growing indium oxide film , 1996 .

[86]  Jun Yuan,et al.  Effects of microstructure on the optical properties of tin-doped indium oxide thin films studied by electron energy loss spectroscopy , 1995 .

[87]  Li-Jian Meng,et al.  Properties of indium tin oxide films prepared by rf reactive magnetron sputtering at different substrate temperature , 1998 .

[88]  H. Hoffmann,et al.  Optical and Electrical Properties of RF-Sputtered Indium-Tin Oxide Films , 1983, June 16.

[89]  L. Reimer.  Electron Energy‐Loss Spectroscopy in the Electron Microscope , 1997 .

[90]  T. Ma,et al.  High‐quality transparent conductive indium oxide films prepared by thermal evaporation , 1980 .

[91]  H. Geistlinger.  The influence of chemisorption on the defect equilibrium of metal oxide thin films , 1996 .

[92]  Masatoshi Imada,et al.  Metal-insulator transitions , 1998 .

[93]  M. Grätzel,et al.  Optical properties of tin‐doped indium oxide determined by spectroscopic ellipsometry , 1996 .

[94]  Henry J. Snaith,et al.  Advances in Liquid‐Electrolyte and Solid‐State Dye‐Sensitized Solar Cells , 2007 .

[95]  S. Pennycook,et al.  Plume-induced stress in pulsed-laser deposited CeO2 films , 1999 .

[96]  R. Dingle.  XCIV. Scattering of electrons and holes by charged donors and acceptors in semiconductors , 1955 .

[97]  P. Huibers,et al.  Multispectral Determination of Soap Film Thickness , 1997 .

[98]  H. Kwok,et al.  Preparation of indium tin oxide films at room temperature by pulsed laser deposition , 1993 .

[99]  B. Chiou,et al.  Mechanical properties of r.f. magnetron sputtered indium tin oxide films , 1997 .

[100]  S. Shimada,et al.  Preparation and properties of tin-doped indium oxide thin films by thermal decomposition of organometallic compounds , 1986 .

[101]  Sang Yeol Lee,et al.  Properties of ITO films on glass fabricated by pulsed laser deposition , 2003 .

[102]  J. W. Orton,et al.  REVIEW ARTICLE: The Hall effect in polycrystalline and powdered semiconductors , 1980 .

[103]  J. C. Roustan,et al.  Fabrication and characterization of ITO thin films deposited by excimer laser evaporation , 1996 .

[104]  Yuzo Shigesato,et al.  Electrical and structural properties of low resistivity tin‐doped indium oxide films , 1992 .

[105]  F. O. Adurodija,et al.  Real-time in situ crystallization and electrical properties of pulsed laser deposited indium oxide thin films , 2005 .

[106]  R. Savu,et al.  Low-temperature, self-nucleated growth of indium–tin oxide nanostructures by pulsed laser deposition on amorphous substrates , 2006 .

[107]  S. Muranaka.  Crystallization of Amorphous In2O3 Films during Film Growth , 1991 .

[108]  J. Speck,et al.  GROWTH-RELATED STRESS AND SURFACE MORPHOLOGY IN HOMOEPITAXIAL SRTIO3 FILMS , 1996 .

[109]  D. Mergel,et al.  Oxygen incorporation in thin films of In2O3:Sn prepared by radio frequency sputtering , 2000 .

[110]  M. Shiojiri,et al.  Electron Microscopic Studies of Structure and Crystallization of Amorphous Metal Oxide Films , 1979 .

[111]  U. Diebold,et al.  The surface and materials science of tin oxide , 2005 .

[112]  R. Vest,et al.  Indium tin oxide films from metallo-organic precursors , 1988 .

[113]  J. Greer.  High quality YBCO films grown over large areas by pulsed laser deposition , 1992 .

[114]  Y. Yang,et al.  Refractive indices of textured indium tin oxide and zinc oxide thin films , 2006 .

[115]  U. Bangert,et al.  Electron energy loss spectroscopy of defects in diamond , 2007 .

[116]  R. Grigorovici,et al.  Optical Properties and Electronic Structure of Amorphous Germanium , 1966, 1966.

[117]  A. Mitwalsky,et al.  Microstructure and etching properties of sputtered indium—tin oxide (ITO) , 1991 .

[118]  F. O. Adurodija,et al.  High quality indium tin oxide films by combined pulsed laser ablation and in-situ pulsed laser irradiation , 2000 .

[119]  R. L. Weiher,et al.  Optical Properties of Indium Oxide , 1966 .

[120]  Zakya H. Kafafi,et al.  Indium tin oxide thin films grown on flexible plastic substrates by pulsed-laser deposition for organic light-emitting diodes , 2001 .

[121]  Z. Jarzȩbski.  Preparation and Physical Properties of Transparent Conducting Oxide Films , 1982, May 16.

[122]  Hoi Sing Kwok,et al.  Role of the oxygen atomic beam in low-temperature growth of superconducting films by laser deposition , 1989 .

[123]  Ray F. Egerton,et al.  Electron Energy-Loss Spectroscopy , 1997, Microscopy and Microanalysis.

[124]  I. Hamberg,et al.  Evaporated Sn‐doped In2O3 films: Basic optical properties and applications to energy‐efficient windows , 1986 .

[125]  Takurou N. Murakami,et al.  Counter electrodes for DSC: Application of functional materials as catalysts , 2008 .

[126]  J. Silcox,et al.  Visibility of Single Heavy Atoms on Thin Crystalline Silicon in Simulated Annular Dark-Field STEM Images , 1988 .

[127]  P. Ossi,et al.  Cluster growth in an ablation plume propagating through a buffer gas , 2008 .

[128]  S. Naseem,et al.  Effects of oxygen partial pressure on the properties of reactively evaporated thin films of indium oxide , 1988 .

[129]  D. Dobrev.  Ion-beam-induced texture formation in vacuum-condensed thin metal films☆ , 1982 .

[130]  W. Möller,et al.  Real-time evolution of the indium tin oxide film properties and structure during annealing in vacuum , 2004 .

[131]  D. Newbury,et al.  Trace elemental analysis at nanometer spatial resolution by parallel-detection electron energy loss spectroscopy. , 1993, Analytical chemistry.

[132]  D. Newbury,et al.  Microanalysis to nanoanalysis: measuring composition at high spatial resolution , 1990 .

[133]  M. Stöger-Pollach,et al.  Optical properties and bandgaps from low loss EELS: pitfalls and solutions. , 2008, Micron.

[134]  David M. Paganin,et al.  X-ray interactions with matter , 2006 .

[135]  D. Paine,et al.  Study of the effect of Sn doping on the electronic transport properties of thin film indium oxide , 1993 .

[136]  B. K. Gupta,et al.  Preparation and intrinsic absorption in the band edge in chemically sprayed In2O3 layers , 1977 .

[137]  C. Kittel.  Introduction to solid state physics , 1954 .

[138]  Gousuke Shiraishi,et al.  Elimination of droplets using a vane velocity filter for pulsed laser ablation of FeSi2 , 2002 .

[139]  T. Sedgwick,et al.  Chemical Vapor Deposited Polycrystalline Silicon , 1972 .

[140]  Y. Hayashi,et al.  Doping mechanisms of tin-doped indium oxide films , 1992 .

[141]  Hoi Sing Kwok,et al.  Low Resistivity Indium Tin Oxide Films by Pulsed Laser Deposition , 1993 .

[142]  A. Banerjee,et al.  Optical and electronic properties of zinc oxide films prepared by spray pyrolysis , 1985 .

[143]  W. Phillips,et al.  Precise measurements of oxygen content: Oxygen vacancies in transparent conducting indium oxide films , 1991 .

[144]  P. Tiemeijer.  Measurement of Coulomb interactions in an electron beam monochromator , 1999 .

[145]  E. J. Moore.  Quantum-Transport Theories and Multiple Scattering in Doped Semiconductors. I. Formal Theory , 1967 .

[146]  Aa Wheeler,et al.  Handbook of Crystal Growth, Vol 1b , 1993 .

[147]  R. T. Tung.  Recent advances in Schottky barrier concepts , 2001 .

[148]  Hoi Sing Kwok,et al.  Generation of high‐energy atomic beams in laser‐superconducting target interactions , 1989 .

[149]  Á. Barna,et al.  Formation Processes of Vacuum-Deposited Indium Films and Thermodynamical Properties of Submicroscopic Particles Observed by In Situ Electron Microscopy , 1969 .

[150]  Min Han,et al.  Cluster formation dynamics in a locally-confined gas layer mixed with the plume ablated by pulsed laser irradiation , 1999 .

[151]  M. Grätzel,et al.  A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films , 1991, Nature.

[152]  H. Enoki,et al.  The intermediate compound in the In2O3-SnO2 system , 1991 .

[153]  L. Murr,et al.  Nucleation and growth characteristics of palladium and indium thin films , 1972 .

[154]  Richard L. Petritz,et al.  Theory of Photoconductivity in Semiconductor Films , 1956 .

[155]  S. Fähler,et al.  Calculations and experiments of material removal and kinetic energy during pulsed laser ablation of metals , 1996 .

[156]  J. Costa-Quintana,et al.  Coulomb (or Strong) Correlation Effects in the Band Structure of Eu2O3 , 1982 .

[157]  H. W. Kraner,et al.  Microstructure and Electro‐Optical Properties of Evaporated Indium‐Oxide Films , 1983 .

[158]  Kunihiro Fukui,et al.  Indium-tin oxide thin films prepared by chemical vapor deposition , 1991 .

[159]  F. O. Adurodija,et al.  Low-temperature growth of low-resistivity indium-tin-oxide thin films by pulsed laser deposition , 2000 .

[160]  L. Thomas.  High spatial resolution in stem x-ray microanalysis , 1982 .

[161]  J. Marshall.  Carrier diffusion in amorphous semiconductors , 1983 .

[162]  Hiroshi Morikawa,et al.  Crystallization and electrical property change on the annealing of amorphous indium-oxide and indium-tin-oxide thin films , 2000 .

[163]  A. Rabenau,et al.  X-Ray and Optical Measurements in the In2O3-SnO2 System , 1979, March 16.

[164]  Richard H. Bube,et al.  Optical and electrical properties of ZnO films prepared by spray pyrolysis for solar cell applications , 1979 .

[165]  J. Manifacier,et al.  In2O3 : (Sn) and SnO2 : (F) films - application to solar energy conversion part II — Electrical and optical properties , 1979 .

[166]  T. Maruyama,et al.  Indium-Tin Oxide Thin Films Prepared by Thermal Decomposition of Metallic Complex Salts , 1988 .

[167]  Li Mei,et al.  PULSED LASER DEPOSITION OF THIN FILMS , 2000 .

[168]  John C. C. Fan,et al.  Effect of O2 pressure during deposition on properties of rf‐sputtered Sn‐doped In2O3 films , 1977 .

[169]  R. L. Weiher.  Electrical Properties of Single Crystals of Indium Oxide , 1962 .

[170]  R. Synowicki,et al.  Spectroscopic ellipsometry characterization of indium tin oxide film microstructure and optical constants , 1998 .

[171]  L. Murr,et al.  Electron microscopy of nucleation and growth of indium and tin films , 1972 .

[172]  A. Dubois,et al.  Étude par diffraction de rayons X de films à base d'oxydes d'étain et d'indium , 1973 .

[173]  J. P. Fillard,et al.  Optical and electrical properties of SnO2 thin films in relation to their stoichiometric deviation and their crystalline structure , 1977 .

[174]  B. Chiou,et al.  Properties of radio-frequency magnetron sputtered ITO films without in-situ substrate heating and post-deposition annealing , 1994 .

[175]  P. Thilakan,et al.  Investigations on the Annealing Effects on Reactively Deposited ITO Thin Films , 1997 .

[176]  I. Jones.  Chemical microanalysis using electron beams , 1992 .

[177]  W. A. Knox.  Contamination formed around a very narrow electron beam. , 1976, Ultramicroscopy.