Molecular Layer Deposition of Titanicone Films using TiCl4 and Ethylene Glycol or Glycerol: Growth and Properties

被引：106
作者：
Abdulagatov, Aziz I. [1 ]
Hall, Robert A. [1 ]
Sutherland, Jackson L. [1 ]
Lee, Byoung H. [1 ]
Cavanagh, Andrew S. [2 ]
George, Steven M. [1 ,3 ]
机构：
[1] Univ Colorado, Dept Chem & Biochem, Boulder, CO 80309 USA
[2] Univ Colorado, Dept Phys, Boulder, CO 80309 USA
[3] Univ Colorado, Dept Chem & Biol Engn, Boulder, CO 80309 USA
来源：
CHEMISTRY OF MATERIALS | 2012年 / 24卷 / 15期
基金：
美国国家科学基金会;
关键词：
molecular layer deposition; thin films; hybrid organic-inorganic; titanium oxide; atomic layer deposition; POLYMER THIN-FILMS; SOLAR-CELLS; TRIMETHYLALUMINUM; BIOCOMPATIBILITY; MULTILAYERS; FABRICATION; MECHANISMS; SURFACES; GLYCIDOL; CRYSTAL;
D O I：
10.1021/cm300162v
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
Molecular layer deposition (MLD) techniques were used to grow titanium-containing hybrid organic inorganic films known as "titanicones" using F. titanium tetrachloride (TiCl4) and either ethylene glycol (EG) or glycerol (GL). The surface chemistry for titanicone MLD was self-limiting versus TiCl4 and either EG or GL exposures. Quartz crystal microbalance (QCM) measurements observed a film growth rate of similar to 83 ng/cm(2)/cycle using TiCl4 and EG from 90 to 115 degrees C. The growth rate then decreased significantly at 135 degrees C. X-ray reflectivity (XRR) studies yielded a growth rate of similar to 4.5 angstrom/cycle with a constant density of similar to 1.8 g/cm(3) from 90 to 115 degrees C. The growth rate measured using XRR also decreased to 1.5 angstrom/cycle at 135 degrees C. Titanicone films were grown using TiCl4 and GL at higher temperatures between 130 and 210 degrees C. GL should increase the bridging between the polymer chains in the titanicone film and change film properties and improve film stability. The film growth rates decreased with temperature from 49 ng/cm(2)/cycle at 130 degrees C to 34 ng/cm(2)/cycle at 210 degrees C. XRR studies were consistent with a temperature-dependent film growth and measured growth rates of 2.8 angstrom/cycle at 130 degrees C and 2.1 angstrom/cycle at 210 degrees C. Nanoindentation experiments revealed that the elastic modulus and hardness of the titanicone films grown using GL were much higher than titanicone films grown using EG. Annealing the titanicone films to 600 degrees C in air removed the carbon constituents and yielded TiO2 films with a density of similar to 3.3 g/cm(3) that is slightly higher than the density of TiO2 ALD films grown at 115 degrees C. The titanicone films absorbed light in the ultraviolet, and the absorption threshold was consistent with an optical bandgap of similar to 3.6 eV. Prolonged ultraviolet exposures on the titanicone films produced TiO2 films with a low density of 2.7 g/cm(3).
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页码：2854 / 2863
页数：10
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