Conductivity phenomena in polycrystalline zinc oxide films
Photoconductivity and electric conductivity of polycrystalline zinc oxide thin film under low intensity irradiation
PHOTOCONDUCTIVITY↗
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Hall and photoresponse measurements associated with ultraviolet and near ultraviolet degradation of thin zinc oxide films
Optical and electrical parameters of zinc oxide degradation during exposure to spectral radiation
SOLAR RADIATION↗
Ultraviolet degradation of thin films of zinc oxide
Ultraviolet degradation of zinc oxide thin films
Hayes, J. D.↗
Degradation of thin films of zinc oxide by ultraviolet radiation
Optical transmittance, Hall effect, and spectral photoconductivity measurements on thin films of zinc oxide in vacuum to determine degradation by ultraviolet radiation
Hayes, J. D.↗
Surface acoustic wave/silicon monolithic sensor/processor
A new technique for sputter deposition of piezoelectric zinc oxide (ZnO) is described. An argon-ion milling system was converted to sputter zinc oxide films in an oxygen atmosphere using a pure zinc oxide target. Piezoelectric films were grown on silicon dioxide and silicon dioxide overlayed with gold. The sputtered films were evaluated using surface acoustic wave measurements, X-ray diffraction, scanning electron microscopy, Auger electron spectroscopy, and resistivity measurements. The effect of the sputtering conditions on the film quality and the result of post-deposition annealing are discussed. The application of these films to the generation of surface acoustic waves is also discussed.
Kowel, S. T.↗
Deterministic modeling of hybrid nonlinear effects in epsilon-near-zero thin films
In nonlinear optics, significant effort is concentrated on improving the strength and efficiency of interactions; however, experimentally investigating nonlinear materials is a complex, time-consuming, and costly investment. Moreover, it is often challenging to isolate, study, and optimize material parameters in an experiment due to complexities in the growth process. Recently, epsilon-near-zero materials have received a great deal of attention as promising nonlinear optical materials, but like many up-and-coming materials, the ability to explore and optimize their properties has been challenging. Here, we establish a framework to rapidly evaluate the performance of nonlinear epsilon-near-zero materials for both inter- and intraband effects in silico, requiring only an energy-momentum (E-k) diagram, linear optical properties, and experimental conditions. Measured nonlinear reflection and transmission in gallium-doped zinc oxide films are compared to the numerical framework for both intra- and interband excitation to verify accuracy across wavelength and irradiance while two figures of merit (FoMs) are introduced to quickly evaluate the performance of films without a full numerical framework. This capability is used to predict the performance of highly doped gallium nitride, cadmium oxide, zinc oxide, and indium tin oxide films, and efficient intra- and interband operation conditions are identified. Through this numerical framework and the FoMs, the exploration of unstudied epsilon-near-zero materials is enabled without the need for a nonlinear experiment, thereby accelerating the search for more efficient nonlinear materials and excitation conditions.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
Ferroelectrics everywhere: Ferroelectricity in magnesium substituted zinc oxide thin films
We demonstrate ferroelectricity in Mg-substituted ZnO thin films with the wurtzite structure. Zn 1–x Mg x O films are grown by dual-cathode reactive magnetron sputtering on (111)-Pt // (0001)-Al 2 O 3 substrates at temperatures ranging from 26 to 200 °C for compositions spanning from x = 0 to x = 0.37. X-ray diffraction indicates a decrease in the c-lattice parameter and an increase in the a-lattice parameter with increasing Mg content, resulting in a nearly constant c/a axial ratio of 1.595 over this composition range. Transmission electron microscopy studies show abrupt interfaces between Zn 1–x Mg x O films and the Pt electrode. When prepared at pO 2 = 0.025, film surfaces are populated by abnormally oriented grains as measured by atomic force microscopy for Mg concentrations >29%. Raising pO 2 to 0.25 eliminates the misoriented grains. Optical measurements show increasing bandgap values with increasing Mg content. When prepared on a 200 °C substrate, films display ferroelectric switching with remanent polarizations exceeding 100 μC cm –2 and coercive fields below 3 MVcm –1 when the Mg content is between ~30% and ~7%. Substrate temperature can be lowered to ambient conditions, and when doing so, capacitor stacks show only minor sacrifices to crystal orientation and nearly identical remanent polarization values; however, coercive fields drop below 2 MV/cm. Using ambient temperature deposition, we demonstrate ferroelectric capacitor stacks integrated directly with polymer substrate surfaces.
36 MATERIALS SCIENCE↗
Thin film devices used as oxygen partial pressure sensors
Electrical conductivity of zinc oxide films to be used in an oxygen partial pressure sensor is measured as a function of temperature, oxygen partial pressure, and other atmospheric constituents. Time response following partial pressure changes is studied as a function of temperature and environmental changes.
Canady, K. S.↗
Surface acoustic waves/silicon monolithic sensor processor
Progress is reported in the creation of a two dimensional Fourier transformer for optical images based on the zinc oxide on silicon technology. The sputtering of zinc oxide films using a micro etch system and the possibility of a spray-on technique based on zinc chloride dissolved in alcohol solution are discussed. Refinements to techniques for making platinum silicide Schottky barrier junctions essential for constructing the ultimate convolver structure are described.
Kowel, S. T.↗
Polymer infiltration synthesis of inorganic nanoporous coatings: Does polymer template affect their properties?
Synthesis of all-inorganic metal oxide architectures using polymer templates offers control over their thickness, porosity, and composition. Here, in this study, we provide insights into the synthesis of nanoporous zinc oxide films as a model system via infiltration of polymers that have different mechanisms of interaction with metal oxide precursors such as a polymer of intrinsic microporosity (PIM-1) and representative of the block-copolymers family (polystyrene-polyvinyl pyridine block copolymer). We investigated polymer infiltration process with both gas (diethyl zinc, DEZ, and water vapors) and solution (zinc acetylacetonate, Zn(acac) 2 , dissolved in ethanol) phase precursors. Using quartz crystal microbalance (QCM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) analyses, we systematically studied the effect of polymer template and the form of the metal oxide precursors on the properties of synthesized metal oxide thin coatings. We demonstrate that the infiltration of polymer templates can be efficiently achieved using both gas phase and solution phase precursors. We show that the crystallinity of the synthesized 200 nm ZnO films is mainly affected by the state of the precursor (gas or solution phase) and does not depend on the polymer template type. In turn, the polymer type affects the surface termination of ZnO films. We demonstrate that the surface of porous ZnO coatings synthesized with BCP (here PS-P4VP) is more accessible than the surface of ZnO synthesized with PIM; however, despite the lower surface accessibility for ethanol molecules, ZnO synthesized via infiltration of PIM-1 with solution-phase precursors demonstrates the largest change in resistivity upon its exposure to ethanol vapor at room temperature.
36 MATERIALS SCIENCE↗
Detection techniques for tenuous planetary atmospheres Semiannual report, 1 Jul. - 31 Dec. 1968
Absorption and desorption of oxygen by zinc oxide film irradiated by ultraviolet light
Hoenig, S. A.↗
Local structure of zinc–indium–tin oxide films via grazing-incidence x-ray pair-distribution functions and theoretical methods
A detailed experimental and theoretical study on the local (r ≤ 4.5 Å) atomic structure of amorphous and crystalline zinc–indium–tin oxide (ZITO) thin films using grazing-incidence x-ray Pair-Distribution Functions (PDFs), ab initio Molecular Dynamics (MD), and Empirical Potential Structure Refinement (EPSR) Monte Carlo simulations is presented. High-energy synchrotron x rays, a two-dimensional detector, and different incident angles were used to probe the depth uniformity of five (ZnO) 0.15 (In 2 O 3 ) 0.70 (SnO 2 ) 0.15 films that were deposited via pulsed-laser deposition at growth temperatures (T G ) ranging from 25 to 300 °C. Films deposited at T G ≤ 150 °C were amorphous. The partially crystalline (T G = 200 °C) and fully crystalline (T G = 300 °C) films were highly textured. Both crystalline and amorphous structures were investigated using ab initio MD and EPSR Monte Carlo simulations. The density of the amorphous films determined from the experimental data agreed with MD calculations. Coordination numbers, bond lengths, and distortion for metal–oxygen and for both the edge- and corner-shared In–metal shells up to 4.5 Å obtained from PDF analysis closely agreed with MD and EPSR simulations. There is a pronounced decrease in the edge- and corner-shared In–Zn distances arising from the shorter Zn–O bond length, Zn–O tetrahedral coordination, and In–O–Zn angle in amorphous ZITO compared to its crystalline counterpart. A maximum in electrical mobility was observed for the amorphous film just before crystallization occurred. While the peak is broad, consistent with nearly unchanged overall cation–oxygen coordination in the amorphous films, ESPR results indicate that the tetrahedral coordination follows the conductivity trend.
Grazing Incidence X-ray↗
Thin film oxygen partial pressure sensor
The development is described of a laboratory model oxygen partial pressure sensor using a sputtered zinc oxide thin film. The film is operated at about 400 C through the use of a miniature silicon bar. Because of the unique resistance versus temperature relation of the silicon bar, control of the operational temperature is achieved by controlling the resistance. A circuit for accomplishing this is described. The response of sputtered zinc oxide films of various thicknesses to oxygen, nitrogen, argon, carbon dioxide, and water vapor caused a change in the film resistance. Over a large range, film conductance varied approximately as the square root of the oxygen partial pressure. The presence of water vapor in the gas stream caused a shift in the film conductance at a given oxygen partial pressure. A theoretical model is presented to explain the characteristic features of the zinc oxide response to oxygen.
Wortman, J. J.↗
Switching kinetics in ferroelectric zinc magnesium oxide thin films
The switching kinetics of RF-magnetron reactively sputtered ~200 nm thick Zn 1-x Mg x O (ZMO) ferroelectric thin films with x = 0.41 and x = 0.27 prepared on Pt/Ti/SiO 2 /Si substrates were studied at applied fields near the coercive fields, ranging from 3.4 to 5.1 MV cm -1 , and at temperatures ranging from room temperature to 100 °C. Polarization reversal in ZMO followss the Kolmogorov-Avrami-Ishibashi kinetics model for nucleation and growth at applied fields near the coercive field, and obeys an individual column switching (ICS) model at higher applied fields required to switch most of the spontaneous polarization. Switching in the high-applied field regime can be described using either the Gaussian or inverse gamma distribution functions depending on the mole fraction of magnesium in the film. The switching current transients of the high-Mg content ZMO film (x = 0.41) are always bi-modal, whereas the low Mg composition film (x = 0.27) is described by the Gaussian distribution initially following wake-up, and becomes bimodal with continued cycling. Rayleigh-like behavior of the dielectric constant revealed a simultaneous increase of the irreversible and decrease of the reversible contributions to the dielectric constant, which was ascribed to an increase in the density of mobile domain walls with cycling and resulted in faster switching.
30 DIRECT ENERGY CONVERSION↗
Wake up and retention in zinc magnesium oxide ferroelectric films
Zn 0.64 Mg 0.36 O (ZMO) is a newly discovered ferroelectric oxide with the wurtzite structure. Epitaxial Zn 0.64 Mg 0.36 O films from 0.036 to 0.5 μm in thickness are grown on Pt/sapphire with the crystallographic c-axis out of plane. At room temperature, the remanent polarization is ~80 μC/cm 2 and the coercive field is ~3 MV/cm. The coercive field is strongly temperature dependent up to 240 °C with a pseudo-activation energy of 23 ± 0.3 meV, suggesting that polarization reversal occurs through an extrinsic process such as domain wall motion. ZMO films can be woken up in 20 electric field cycles on driving near the coercive field; they wake up in a single loop at fields in excess of 4 MV/cm. A thermally activated fluid imprint process, with a pseudo-activation energy of 67 ± 8 meV, enlarges the coercive field by several hundred kV cm –1 after switching the polarization. Additionally, ZMO films exhibit excellent retention characteristics; no reduction in the polarization is observed up to 1000 h from room temperature to 200 °C bakes. Here, this current early generation of ZMO films can survive several thousand switching cycles before dielectric breakdown occurs.
36 MATERIALS SCIENCE↗
Thickness scaling and ferroelectric switching in wurtzite structure zinc magnesium oxide thin films
This study reports the thickness scaling of sputtered ferroelectric Zn 0.61 Mg 0.39 O (ZMO) thin films down to 43 nm. Encapsulated IrO 2 /ZMO/Ir capacitors exhibited switchable polarizations exceeding 50 μC cm −2 and coercive fields that increased from 3.9 to 4.4 MV cm −1 as the thickness decreased. Switching kinetics are best described by the simultaneous non-linear nucleation and the growth model. Bimodal switching is prevalent at low thicknesses, with the fastest switching times measured to be approximately 400 ns. Device encapsulation made ZMO switching kinetics more abrupt, potentially due to changes in the concentration of atmosphere-induced defects such as hydroxides. These results demonstrate stable ferroelectricity and sub-microsecond switching in sub-50 nm wurtzite ZMO, highlighting its potential as a low-voltage ferroelectric for integrated nonvolatile memory applications.
36 MATERIALS SCIENCE↗
Fabrication of nanoporous doped metal oxide coatings via selective infiltration of a block copolymer template: The case of Al-doped zinc oxide
Conductive nanoporous conformal coatings are important for various applications including touchscreens, displays, and electrochromic windows, though design of such coating with controlled porosity and composition remains challenging. We propose a sequential infiltration synthesis (SIS) method for the fabrication of nanoporous conductive aluminum-doped zinc oxide (AZO) films by infiltrating block copolymer (BCP) templates, specifically polystyrene-block-polyvinyl pyridine (PS-b-P4VP), with diethyl zinc and trimethyl aluminum precursors. Tunability of both porosity and electrical conductivity is achieved by precisely controlling the swelling behavior of the polymer templates and adjusting the number of SIS cycles. Further, our results reveal that porosity levels can reach up to 80 %, with resistivity as low as ~7.83 Ωcm. Using conductive atomic force microscopy (C-AFM) and Hall effect measurements, we show that lower concentrations of aluminum doping relative to zinc (around 1: 17) results in higher conductivity of the AZO films. Additionally, AZO is based on zinc oxide (ZnO) which is cost-efficient, abundant and less toxic than commonly used transparent conductive oxides such as indium tin oxide (ITO) and fluorine-doped tin oxide (FTO). Therefore, this novel approach opens new possibilities for creating highly porous, conformal, conductive AZO coatings with customizable porosity and composition, making them ideal candidates for diverse optoelectronic applications.
36 MATERIALS SCIENCE↗