Non-Drude Behavior in Indium-Tin-Oxide Nanowhiskers and Thin Films Investigated by Transmission and Reflection THz Time-Domain Spectroscopy

A comparative study of indium-tin-oxide (ITO) nanowhiskers (NWhs) and thin films as transparent conductors in the terahertz frequency range are conducted. We employ both transmission-type and reflection-type terahertz time-domain spectroscopies (THz-TDTS and THz-TDRS) to explore the far-infrared optical properties of these samples. Their electrical properties, such as plasma frequencies and carrier scattering times, are analyzed and found to be fitted well by the Drude-Smith model over 0.1-1.4 THz. Further, structural and crystalline properties of samples are examined by scanning electron microscopy and X-ray diffraction, respectively. Non-Drude behavior of complex conductivities in ITO NWhs is attributed to carrier scattering from grain boundaries and impurity ions. In ITO thin films, however, the observed non-Drude behavior is ascribed to scattering by impurity ions only. Considering NWhs and thin films with the same height, mobility of the former is ~ 125 cm2V-1s-1, much larger than those of the ITO thin films, ~ 27 cm2 V-1 s-1. This is attributed to the longer carrier scattering time of the NWhs. The dc conductivities ( ~ 250 Ω-1 cm-1) or real conductivities in the THz frequency region of ITO NWhs is, however, lower than those of the ITO thin films ( ~ 800 Ω-1 cm-1) but adequate for use as electrodes. Partly, this is a reflection of the much higher plasma frequencies of thin films. Significantly, the transmittance of ITO NWhs ( ≅ 60%-70%) is much higher ( ≅ 13 times) than those of ITO thin films in the THz frequency range. The underneath basic physics is that the THz radiation can easily propagate through the air-space among NWhs. The superb transmittance and adequate electrical properties of ITO NWhs suggest their potential applications as transparent conducting electrodes in THz devices.

[1]  Matthew C. Beard,et al.  Carrier Localization and Cooling in Dye-Sensitized Nanocrystalline Titanium Dioxide , 2002 .

[2]  S. Koh,et al.  Microstructure and Electrical Properties of Indium Oxide Thin Films Prepared by Direct Oxygen Ion‐Assisted Deposition , 2000 .

[3]  Nicholas C. Harris,et al.  Nanoscale characteristics of single crystal zinc oxide nanowires , 2011, 2011 11th IEEE International Conference on Nanotechnology.

[4]  A. L. Patterson The Scherrer Formula for X-Ray Particle Size Determination , 1939 .

[5]  Fu-Rong Chen,et al.  Four-probe electrical-transport measurements on single indium tin oxide nanowires between 1.5 and 300 K , 2009, Nanotechnology.

[6]  Masanori Hangyo,et al.  Measurement of optical properties of highly doped silicon by terahertz time domain reflection spectroscopy , 2001 .

[7]  Handong Sun,et al.  UV light emitting transparent conducting tin-doped indium oxide (ITO) nanowires , 2011, Nanotechnology.

[8]  Chan-Shan Yang,et al.  THz conductivities of indium-tin-oxide nanowhiskers as a graded-refractive-index structure. , 2012, Optics express.

[9]  Xiao Wei Sun,et al.  Terahertz dielectric response and optical conductivity of n-type single-crystal ZnO epilayers grown by metalorganic chemical vapor deposition , 2010 .

[10]  Jingshan Luo,et al.  Temperature-dependent terahertz conductivity of tin oxide nanowire films , 2012 .

[11]  E. F. Schubert,et al.  Light‐Extraction Enhancement of GaInN Light‐Emitting Diodes by Graded‐Refractive‐Index Indium Tin Oxide Anti‐Reflection Contact , 2008 .

[12]  Weili Zhang,et al.  Terahertz dielectric properties and low-frequency phonon Resonances of ZnO nanostructures , 2007 .

[13]  Peichen Yu,et al.  Broadband and omnidirectional antireflection from conductive indium-tin-oxide nanocolumns prepared by glancing-angle deposition with nitrogen , 2009 .

[14]  Jiro Kitagawa,et al.  Propagation Characteristics of Terahertz Electrical Signals on Micro-Strip Lines Made of Optically Transparent Conductors , 2005 .

[15]  Victor F. Weisskopf,et al.  Theory of Impurity Scattering in Semiconductors , 1950 .

[16]  A. Yamamoto,et al.  Terahertz characterization of semiconductor alloy AlInN: negative imaginary conductivity and its meaning. , 2009 .

[17]  A. Nadarajah,et al.  Terahertz characterization of zinc oxide nanowires using parallel-plate waveguides , 2011, 2011 11th IEEE International Conference on Nanotechnology.

[18]  Hanspeter Helm,et al.  Nanostructured gold films as broadband terahertz antireflection coatings , 2008 .

[19]  M. Beard,et al.  Electronic Coupling in InP Nanoparticle Arrays , 2003 .

[20]  Wen-Chau Liu,et al.  Implementation of an indium-tin-oxide (ITO) direct-Ohmic contact structure on a GaN-based light emitting diode. , 2011, Optics express.

[21]  Dielectric Response of Soft Modes in Ferroelectric Thin Films , 2003 .

[22]  M. Khazan,et al.  Convertible transmission-reflection time-domain terahertz spectrometer , 2001 .

[23]  C. Pan,et al.  Terahertz spectroscopic study of vertically aligned InN nanorods , 2007 .

[24]  V. Sundström,et al.  Far-infrared response of free charge carriers localized in semiconductor nanoparticles , 2009 .

[25]  C. Pan,et al.  Improved broadband and quasi-omnidirectional anti-reflection properties with biomimetic silicon nanostructures. , 2007, Nature nanotechnology.

[26]  Sun Wenfeng,et al.  Measurement of Refractive Index for High Reflectance Materials with Terahertz Time Domain Reflection Spectroscopy , 2009 .

[27]  Xiang Zhang,et al.  Introduction to THz Wave Photonics , 2009 .

[28]  M. Brett,et al.  Indium tin oxide nanowhisker morphology control by vapour–liquid–solid glancing angle deposition , 2012, Nanotechnology.

[29]  David G. Cooke,et al.  Transient terahertz conductivity in photoexcited silicon nanocrystal films , 2006 .

[30]  T. Löffler,et al.  Indium–tin–oxide-coated glass as dichroic mirror for far-infrared electromagnetic radiation , 2002 .

[31]  Chan-Shan Yang,et al.  Effects of two-photon absorption on terahertz radiation generated by femtosecond-laser excited photoconductive antennas. , 2011, Optics express.

[32]  Charles A Schmuttenmaer,et al.  Conductivity of ZnO nanowires, nanoparticles, and thin films using time-resolved terahertz spectroscopy. , 2006, The journal of physical chemistry. B.

[33]  Tsung-Yuan Tsai,et al.  On a GaN-Based Light-Emitting Diode With an Indium–Tin–Oxide (ITO) Direct-Ohmic Contact Structure , 2011, IEEE Photonics Technology Letters.

[34]  Q. Wan,et al.  Single-crystalline tin-doped indium oxide whiskers: Synthesis and characterization , 2004 .

[35]  Nanostructured indium-tin-oxide films fabricated by all-solution processing for functional transparent electrodes. , 2011, Optics express.

[36]  M. R. Freeman,et al.  Terahertz conductivity of thin gold films at the metal-insulator percolation transition , 2007 .

[37]  P. Taday,et al.  Detection and identification of explosives using terahertz pulsed spectroscopic imaging , 2005 .

[38]  N. V. Smith,et al.  Classical generalization of the Drude formula for the optical conductivity , 2001 .

[39]  M. Chaker,et al.  Highly transparent and conductive nanometric Indium Tin Oxide for pulse shaping applications , 2011, 2011 ICO International Conference on Information Photonics.

[40]  T. Yoshie,et al.  Design of subwavelength-size, indium tin oxide (ITO)-clad optical disk cavities with quality-factors exceeding 10⁴. , 2011, Optics express.

[41]  Ci-Ling Pan,et al.  The complex refractive indices of the liquid crystal mixture E7 in the terahertz frequency range , 2010 .

[42]  P. Yu,et al.  Frequency-Dependent Complex Conductivities and Dielectric Responses of Indium Tin Oxide Thin Films From the Visible to the Far-Infrared , 2010, IEEE Journal of Quantum Electronics.

[43]  D G Cooke,et al.  Optical modulation of terahertz pulses in a parallel plate waveguide. , 2008, Optics express.

[44]  Yia-Chung Chang,et al.  Combined micro- and nano-scale surface textures for enhanced near-infrared light harvesting in silicon photovoltaics , 2011, Nanotechnology.

[45]  Alberto Piqué,et al.  Electrical, optical, and structural properties of indium–tin–oxide thin films for organic light-emitting devices , 1999 .

[46]  Z. Qiao,et al.  Correlation of lattice distortion with optical and electrical properties of In2O3:Sn films , 2004 .

[47]  Wen-Yang Chang,et al.  Optical panel with full multitouch using patterned indium tin oxide. , 2011, Optics letters.

[48]  Peter Uhd Jepsen,et al.  Investigation of aqueous alcohol and sugar solutions with reflection terahertz time-domain spectroscopy. , 2007, Optics express.

[49]  Ci-Ling Pan,et al.  Optical properties and potential applications of ɛ-GaSe at terahertz frequencies , 2009 .

[50]  Hao-Chung Kuo,et al.  Efficiency Enhancement of GaAs Photovoltaics Employing Antireflective Indium Tin Oxide Nanocolumns , 2009 .

[51]  H. Bandulet,et al.  Terahertz conductivity of the metal-insulator transition in a nanogranular VO2 film , 2010 .

[52]  Peichen Yu,et al.  Enhanced angular characteristics of indium tin oxide nanowhisker-coated silicon solar cells. , 2011, Optics express.

[53]  T. H. Isaac,et al.  Tuneable Fabry–Perot etalon for terahertz radiation , 2008 .

[54]  S. Franzen,et al.  Indium Tin Oxide Plasma Frequency Dependence on Sheet Resistance and Surface Adlayers Determined by Reflectance FTIR Spectroscopy , 2002 .

[55]  J. Yu,et al.  Glancing angle deposited ITO films for efficiency enhancement of a-Si:H/μc-Si:H tandem thin film solar cells. , 2011, Optics express.

[56]  M. Hamasha,et al.  Behavior of Sputtered Indium–Tin–Oxide Thin Film on Poly-Ethylene Terephthalate Substrate Under Stretching , 2011, Journal of Display Technology.

[57]  Xingyuan Liu,et al.  Optical and electrical properties of Vanadium doped Indium oxide thin films. , 2008, Optics express.

[58]  Ci-Ling Pan,et al.  Temperature-dependent optical constants and birefringence of nematic liquid crystal 5CB in the terahertz frequency range , 2008 .

[59]  Martin Kempa,et al.  Phase-sensitive time-domain terahertz reflection spectroscopy , 2003 .

[60]  K. Unterrainer,et al.  Metallic wave-impedance matching layers for broadband terahertz optical systems. , 2007, Optics express.

[61]  Chennupati Jagadish,et al.  Carrier lifetime and mobility enhancement in nearly defect-free core-shell nanowires measured using time-resolved terahertz spectroscopy. , 2009, Nano letters.

[62]  A. Azad,et al.  Optical and dielectric properties of ZnO tetrapod structures at terahertz frequencies , 2006 .

[63]  G. Exarhos,et al.  Discovery-based design of transparent conducting oxide films , 2007 .

[64]  A. Meldrum,et al.  Ultrafast percolative transport dynamics in silicon nanocrystal films , 2011 .

[65]  V. Sundström,et al.  Charge transport in nanostructured materials for solar energy conversion studied by time-resolved terahertz spectroscopy , 2010 .

[66]  K. Bertness,et al.  Noncontact measurement of charge carrier lifetime and mobility in GaN nanowires. , 2012, Nano letters.