Thin Films: From Organic Monolayers to Ceramic Coatings

1
Thin Films From Organic Monolayers to Ceramic
Coatings   Professor Chaim N. Sukenik Department
of Chemistry and Institute for Nanotechnology and
Advanced Materials Bar Ilan University, Ramat
Gan, Israel   Contact Information tel
972-3-5318072 fax [phone] mobile
972-5-889-8811 e-mail sukenc_at_mail.biu.ac.il
2

• Professor Chaim Sukenik
• organic/inorganic thin film coatings
  biomaterials
• high performance polymers and composites
  ceramics
• tel [phone] fax [phone] e-mail
  sukenc_at_mail.biu.ac.il
• http//www.biu.ac.il/ESC/ch/faculty/sukenik/suke
  nint.html
• Biography
• Ph.D., Chemistry, Cal Tech, 1976 NSF
  Postdoctoral Fellow, UCLA, 1977
• Faculty Case Western Reserve University
  (1977-1995)
• At Bar Ilan University since 1995
• Director of Minerva Center for Nanoscale
  Particles and Films as Tailored Biomaterial
  Interfaces, Bar Ilan Center for Advanced
  Materials and Nanotechnology and Marie Curie
  Training Site for the Fabrication of Nanoscale
  Materials.
• Research Overview
• Reaction chemistry at ordered interfaces
  patterning nanoscale assemblies
• monolayers as ultra-thin barrier layers on
  metals, alloys and polymer composites surface
  modification to control biocompatibity ceramic
  thin films

3
Conformal, spontaneously formed coatings adhere
to surfaces with complex geometry uniformly thin
films with significant chemical versatility
1) In situ chemistry includes attachment of
radio-isotopes, drugs, bio-molecules, and
multi-layer structures. 2) Uniform monolayers
well-suited for in situ spectroscopic monitoring
of interfacial chemistry.
anchoring via siloxanes, thiols, amines,
carboxylates, phosphonates, others
4
(No Transcript)
5
Successful reaction conditions Pb(OAc)4, NaI, in
HOAc/H2O (75/25) at 80 oC Ca(NO3)2 (air), NaI, in
neat HOAc at 85 oC
Note The alkyl benzene substrate does not
iodinate the phenyl ether is fully iodinated in
minutes/hours.
6
Creation and Characterization of n-Alkylthiol
and n-Alkylamine Self-Assembled Monolayers on
316L Stainless Steel  Chuan-Min Ruan, Thomas
Bayer, Sergio Meth and Chaim N. Sukenik (Thin
Solid Films, 2002)
7
Surface Modification of Stainless Steel with
Siloxane-Anchored Thin Films Sergio Meth and
Chaim N. Sukenik (Thin Solid Films, 2003)
8
Functionalized Surfaces for Deposition of Oxide
Films

• Immerse substrate in solution of organic
  surfactant

• Immerse substrate in ceramic precursor solution

• Ceramic layer deposits on SAM

9
Monolayers and Organic/Inorganic Nanoscale Thin
Films
Patterned functionalized film as template for
TiO2 deposition
In situ functionalization
Self-Assembled Monolayers
10
Solution Deposition Conditions

• TiCl4 (0.5 M) in HCl (6 N), 80 ?C
• 0.05 M titanium lactate in aqueous HCl (pH 1.9),
  70 ?C
• LPD Methods
• 0.30 M H3BO3 and 0.10 M (NH4)2TiF6 initial pH
  is 3.88, ambient temperature
• 0.15 M H3BO3 and 0.05 M (NH4)2TiF6 initial pH is
  adjusted (w/HCl or other acid) to 2.88, 50 C

Advantages Low temperature deposition
conditions good for non-planar substrates
simple and cheap equipment.
11
LPD titania films substrate effects
12
Growth Kinetics of TiO2
TiO2 by Method 1 pH 3.88, RT Deki 22h (300
nm)
TiO2 by Method 2 pH 2.88, 50 C Koumoto 3h
(380 nm) Koumoto 6h (550 nm) Koumoto 20h (1000
nm)
Method 1 provides amorphous films Method 2
provides anatase films
13
Protect Polymer/Composite from Heat and/or
Abrasion
14
PMR-15 coated with TiO2 (via LPD method 2)