skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Reaction Acceleration in Thin Films with Continuous Product Deposition for Organic Synthesis

 [1];  [1];  [1]; ORCiD logo [1]
  1. Department of Chemistry, Purdue University, West Lafayette IN 47907 USA
Publication Date:
Sponsoring Org.:
OSTI Identifier:
Grant/Contract Number:
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Angewandte Chemie
Additional Journal Information:
Journal Volume: 129; Journal Issue: 32; Related Information: CHORUS Timestamp: 2017-10-20 15:56:45; Journal ID: ISSN 0044-8249
German Chemical Society
Country of Publication:

Citation Formats

Wei, Zhenwei, Wleklinski, Michael, Ferreira, Christina, and Cooks, R. Graham. Reaction Acceleration in Thin Films with Continuous Product Deposition for Organic Synthesis. Germany: N. p., 2017. Web. doi:10.1002/ange.201704520.
Wei, Zhenwei, Wleklinski, Michael, Ferreira, Christina, & Cooks, R. Graham. Reaction Acceleration in Thin Films with Continuous Product Deposition for Organic Synthesis. Germany. doi:10.1002/ange.201704520.
Wei, Zhenwei, Wleklinski, Michael, Ferreira, Christina, and Cooks, R. Graham. 2017. "Reaction Acceleration in Thin Films with Continuous Product Deposition for Organic Synthesis". Germany. doi:10.1002/ange.201704520.
title = {Reaction Acceleration in Thin Films with Continuous Product Deposition for Organic Synthesis},
author = {Wei, Zhenwei and Wleklinski, Michael and Ferreira, Christina and Cooks, R. Graham},
abstractNote = {},
doi = {10.1002/ange.201704520},
journal = {Angewandte Chemie},
number = 32,
volume = 129,
place = {Germany},
year = 2017,
month = 7

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on July 5, 2018
Publisher's Accepted Manuscript

Save / Share:
  • The synthesis of several new Bi(III) [beta]-diketonate complexes is described. In this method the chelates of the anions of 6,6,7,7.8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione (H(fod)) and 1,1,1,5,5,5-hexafluoro-2,4-pentanedione (H(hfa)) are formed by refluxing 3 equiv of the protonated ligand with 1 equiv of triphenylbismuth. The same reaction with 1,1,1-trifluoro-2,4-pentanedione (H(tfa)) produced a mixed [beta]-diketonate/phenyl ligand complex. The reaction products were characterized by thermogravimetric analysis, mass spectroscopy, nuclear magnetic resonance spectrometry, and gas chromatography/mass spectroscopy. Formation of bismuth-containing thin films using metal-organic chemical vapor deposition was demonstrated using the Bi(III) complex of fod. The films produced using this method were determined to contain 76% bismuth bymore » Auger analysis, and no fluorine contamination was observed. 18 refs., 6 figs., 1 tab.« less
  • Epitaxial Tl{sub 2}Ba{sub 2}CaCu{sub 2}O{sub 8} thin films with excellent electrical transport characteristics are grown in a two-step process involving metal-organic chemical vapor deposition (MOCVD) of a BaCaCuO(F) thin film followed by a postanneal in the presence of Tl{sub 2}O vapor. Vapor pressure characteristics of the recently developed liquid metal-organic precursors Ba(hfa){sub 2}{center_dot}mep (hfa=hexafluoroacetylacetonate, mep=methylethylpentaglyme), Ca(hfa){sub 2}{center_dot}tet (tet=tetraglyme), and the solid precursor Cu(dpm){sub 2} (dpm=dipivaloylmethanate) are characterized by low pressure thermogravimetric analysis. Under typical film growth conditions, transport is shown to be diffusion limited. The transport rate of Ba(hfa){sub 2}{center_dot}mep is demonstrated to be stable for over 85 h atmore » typical MOCVD temperatures (120{degree}C). In contrast, the vapor pressure stability of the commonly used Ba precursor, Ba(dpm){sub 2}, deteriorates rapidly at typical growth temperatures, and the decrease in vapor pressure is approximately exponential with a half-life of {approximately}9.4 h. These precursors are employed in a low pressure (5 Torr) horizontal, hot-wall, film growth reactor for growth of BaCaCuO(F) thin films on (110) LaAlO{sub 3} substrates. From the dependence of film deposition rate on substrate temperature and precursor partial pressure, the kinetics of deposition are shown to be mass-transport limited over the temperature range 350{endash}650{degree}C at a 20 nm/min deposition rate. A ligand exchange process which yields volatile Cu(hfa){sub 2} and Cu(hfa)(dpm) is also observed under film growth conditions. The MOCVD-derived BaCaCuO(F) films are postannealed in the presence of bulk Tl{sub 2}Ba{sub 2}CaCu{sub 2}O{sub 8} at temperatures of 720{endash}890{degree}C in flowing atmospheres ranging from 0{endash}100{percent}O{sub 2}. (Abstract Truncated)« less
  • Lead zirconate titanate (PZT) thin films were deposited by metal-organic chemical vapor deposition (MOCVD) using {beta}-diketonate precursors and O{sub 2} at temperatures below 500 C on variously passivated Si substrates. PZT thin films could not be deposited on bare Si substrates, owing to a serious diffusion of Ph into the Si substrate during deposition. Pt/SiO{sub 2}/Si substrates could partially block the diffusion of Pb, but a direct deposition of PZT thin films on the Pt/SiO{sub 2}/Si substrates resulted in a very inhomogeneous deposition. A TiO{sub 2} buffer layer deposited on Pt/SiO{sub 2}/Si substrates could partially suppress the diffusion of Phmore » and produce homogeneous thin films. However, the crystallinity of PZT thin films deposited on the TiO{sub 2}-buffered Pt/SiO{sub 2}/Si substrate was not good enough, and the films showed random growth direction. PZT thin films deposited on the PbTiO{sub 3}-buffered Pt/SiO{sub 2}/Si substrates had good crystallinity and a- and c-axis oriented growth direction. However, the PZT thin film deposited at 350 C showed fine amorphous phases at the grain boundaries, owing to the low chemical reactivities of the constituent elements at that temperature, but they could be crystallized by rapid thermal annealing (RTA) at 700 C. PZT thin film deposited on a 1,000-{angstrom} PbTiO{sub 3}-thin-film-buffered Pt/SiO{sub 2}/Si substrate at 350 C and rapid thermally annealed at 700 C for 6 min showed a single-phase perovskite structure with a composition near the morphotropic boundary composition.« less
  • Fluorocarbon films of varying composition have been deposited from pulsed and continuous plasmas of octafluorocyclobutane (c-C{sub 4}F{sub 8}) and c-C{sub 4}F{sub 8}/Ar. Continuous plasma deposition rates are a very weak function of applied rf power (may be within experimental error). Pulsed plasma deposition rates are significantly lower than continuous plasma rates at the same average power. The pulsed plasma deposition rates can be attributed almost entirely to the plasma on time during the pulse, but there is a slight dependence on pulse off time. Ar addition affects the deposition rates through a residence time effect, but also affects the depositionmore » chemistry by reducing the degree of C{sub 4}F{sub 8} dissociation, resulting in more fluorinated films. Refractive indices for all films increase approximately linearly with applied rf power, with the pulsed plasma-deposited films falling on the same curve. Carbon 1s x-ray photoelectron spectroscopy shows that the continuous plasma-deposited films become increasingly fluorinated as the rf power is decreased. Pulsed plasma films are more fluorinated than similar average power continuous plasma films: 44% CF{sub 2} for 10/50 (400 W on time, 67 W average power) versus 37% for 50 W continuous. Literature and preliminary gas-phase measurements suggest that the C{sub 4}F{sub 8} is not fully dissociated in either plasma system and that larger species in the gas phase may play a significant role in the deposition mechanisms.« less