Thin films with self-assembled nanostructures are important in applications such as catalysis and biosensor technology. A major technique used to prepare such films is sol-gel processing. This technique involves depositing a complex fluid on a substrate by dip, spin, or spray coating, followed by allowing the film to evaporate and form self-assembled nanostructures. Since the composition of the film during coating is central to understanding how changing chemical and physical conditions affect the properties and microstructures of the films, we investigate the rheological properties of the entrained fluid film and its subsequent impact on the steady state film thickness during the evaporation-induced self-assembly process. We perform systematic experiments to measure the meniscus shape and film thickness during sol-gel dip coating. We observe that the experimental data of film thickness lie way below the Landau-Levich-Derjaguin prediction from the classic film-coating results. To explain this discrepancy, we present a thin film model based on the lubrication approximation with an evaporation effect. Our results show that evaporation-induced self-assembly leads to rheological variations in the entrained film and, consequently, alters the film thickness. The predicted film thickness based on the evaporation-induced rheology variation model compares well with the experiments.

1.
C. J.
Brinker
,
A. J.
Hurd
,
R. R.
Schunk
,
G. C.
Frye
, and
C. S.
Ashley
, “
Review of sol-gel thin film formation
,”
J. Non-Cryst. Solids
147–148
,
424
(
1992
).
2.
Y.
Lu
,
R.
Ganguli
,
C. A.
Drewien
,
M.
Anderson
,
C. J.
Brinker
,
W.
Gong
,
Y.
Guo
,
H.
Soyez
,
B.
Dunn
,
M.
Huang
, and
J.
Zink
, “
Continuous formation of supported cubic and hexagonal mesoporous films by sol-gel dip-coating
,”
Nature
389
,
364
(
1997
).
3.
G. A.
Ozin
,
E.
Chomski
,
D.
Khushalani
, and
M. J.
MacLachlan
, “
Mesochemistry
,”
Curr. Opin. Colloid Interface Sci.
3
,
181
(
1998
).
4.
D.
Zhao
,
P.
Yang
,
N.
Melosh
,
J.
Feng
,
B. F.
Chmelka
, and
G. D.
Stucky
, “
Continuous mesoporous silica films with highly ordered large pore structures
,”
Adv. Mater. (Weinheim, Ger.)
10
,
1380
(
1998
).
5.
P.
Schmidt-Winkel
,
C. J.
Glinka
, and
G. D.
Stucky
, “
Microemulsion templates for mesoporous silica
,”
Langmuir
16
,
356
(
2000
).
6.
S. C.
Christiansen
,
D.
Zhao
,
M. T.
Janicke
,
C. C.
Landry
,
G. D.
Stucky
, and
B. F.
Chmelka
, “
Molecularly ordered inorganic frameworks in layered silicate surfactant mesophases
,”
J. Am. Chem. Soc.
123
,
4519
(
2001
).
7.
S.
Chia
,
U.
Jun
,
F.
Tamanoi
,
B. S.
Dunn
, and
J. I.
Zink
, “
Patterned hexagonal arrays of living cells in sol-gel silica films
,”
J. Am. Chem. Soc.
122
,
12095
(
2000
).
8.
F.
Nishida
,
J. M.
McKiernan
,
B.
Dunn
,
J.
Zink
,
C.
Brinker
, and
A.
Hurd
, “
In situ fluorescence probing of the chemical changes furing sol-gel thin film formation
,”
J. Am. Ceram. Soc.
78
,
1640
(
1995
).
9.
M.
Huang
,
B. S.
Dunn
, and
J. I.
Zink
, “
In situ Luminescence probing of the chemical and structural changes during formation of dip-coated lamellar phase sodium dodecyl sulfate sol-gel thin films
,”
J. Am. Chem. Soc.
122
,
3739
(
2000
).
10.
D.
Grosso
,
F.
Babonneau
,
P. A.
Albouy
,
H.
Amenitsch
,
A. R.
Balkenende
,
A.
Brunet-Bruneau
, and
J.
Rivory
, “
An in situ study of mesostructured CTAB-silica film formation during dip coating using time-resolved SAXS and interferometry measurements
,”
Chem. Mater.
14
,
931
(
2002
).
11.
D.
Doshi
,
A.
Gibaud
,
N.
Liu
,
D.
Sturmayr
,
A. P.
Malanoski
,
D. R.
Dunphy
,
H.
Chen
,
S.
Narayanan
,
A.
MacPhee
,
J.
Wang
,
S. T.
Reed
,
A. J.
Hurd
,
F.
van Swol
, and
C. J.
Brinker
, “
In-situ x-ray scattering study of continuous silica-surfactant self-assembly during steady-state dip coating
,”
J. Phys. Chem. B
107
,
7683
(
2003
).
12.
D.
Qu
,
E.
Ramé
, and
S.
Garoff
, “
Dip-coated films of volatile liquids
,”
J. Appl. Phys.
14
,
1154
(
2002
).
13.
S.
Das Gupta
,
J. A.
Schonberg
, and
P. C.
Wayner
, Jr.
, “
Use of the augmented Young-Laplace equation to model equilibrium and evaporating extended menisci
,”
J. Colloid Interface Sci.
157
,
332
(
1993
).
14.
P. C.
Wayner
, Jr.
, “
Spreading of a liquid film with a finite contact angle by the evaporation/condensation process
,”
Langmuir
9
,
294
(
1993
).
15.
S.
Moosman
and
G. M.
Homsy
, “
Evaporating menisci of wetting fluids
,”
J. Colloid Interface Sci.
73
,
212
(
1980
).
16.
J. B.
Freund
, “
The atomic detail of an evaporating meniscus
,”
Phys. Fluids
17
,
022104
(
2005
).
17.
A. J.
Hurd
and
L.
Steinberg
, “
The physics of evaporation-induced assembly of sol-gel
,”
Granular Matter
3
,
19
(
2001
).
18.
P. W. K.
Rothemund
, “
Using lateral capillary forces to compute by self-assembly
,”
Proc. Natl. Acad. Sci. U.S.A.
97
,
984
(
2000
).
19.
S. E.
Rankin
,
L. J.
Kasehagen
,
A. V.
McCormick
, and
C. W.
Macosko
, “
Dynamic Monte Carlo simulation of gelation with extensive cyclization
,”
Macromolecules
33
,
7639
(
2000
).
20.
L. J. D.
Frink
and
F.
van Swol
, “
Stress isotherms of porous thin materials: Theoretical predictions from a nonlocal density functional theory
,”
Langmuir
15
,
3296
(
1999
).
21.
Y.
Lu
,
R.
Ganguli
,
C. A.
Drewien
,
M. T.
Anderson
,
C. J.
Brinker
,
W.
Gong
,
Y.
Guo
,
H.
Soyez
,
B.
Dunn
,
M. H.
Huang
, and
J. I.
Zink
, “
Continuous formation of supported cubic and hexagonal mesoporous films by sol-gel dip-coating
,”
Nature
389
,
364
(
1997
).
22.
L. H.
Ouyang
,
D. L.
Rode
,
T.
Zulkifli
, and
B.
Abraham-Shrauner
, “
Hydrogenated amorphous and microcrystalline GaAs films prepared by radio-frequency magnetron sputtering
,”
J. Appl. Phys.
91
,
3459
(
2002
).
23.
S. F.
Kistler
and
P.
Schweizer
,
Liquid Film Coating—Scientific Principles and Their Technological Implications
(
Kluwer Academic
, Dordrecht,
1997
).
24.
J.
Ratulowski
and
H. C.
Chang
, “
Marangoni effects of trace impurities on the motion of long gas bubbles in capillaries
,”
J. Fluid Mech.
210
,
303
(
1990
).
25.
K. J.
Ruschak
, “
Coating flows
,”
Annu. Rev. Fluid Mech.
17
,
65
(
1985
).
26.
L. E.
Scriven
, “
Dynamics of a fluid interface
,”
Chem. Eng. Sci.
12
,
98
(
1960
).
27.
V. G.
Levich
,
Physicochemical Hydrodynamics
(
Prentice-Hall
,
Englewood Cliffs, NJ
,
1962
).
28.
L.
Landau
and
B.
Levich
, “
Dragging of a liquid by a moving plate
,”
Acta Physicochim. URSS
17
,
42
(
1942
).
29.
B.
Deryaguin
, “
On the thickness of the liquid film adhering to the walls of a vessel after emptying
,”
Acta Physicochim. URSS
20
,
349
(
1943
).
30.
F. P.
Bretherton
, “
The motion of long bubbles in tubes
,”
J. Fluid Mech.
10
,
166
(
1961
).
31.
J. A.
Tallmadge
, “
A withdrawal theory for Ellis model fluids
,”
AIChE J.
12
,
1011
(
1966
).
32.
S. H.
Davis
, “
Thermocapillary instabilities
,”
Annu. Rev. Fluid Mech.
19
,
403
(
1987
).
33.
M. R. E.
Warner
,
R. V.
Craster
, and
O. K.
Matar
, “
Surface patterning via evaporation of ultrathin films containing nanoparticles
,”
J. Colloid Interface Sci.
267
,
92
(
2003
).
34.
K. D.
Danov
,
N.
Alleborn
,
H.
Raszillier
, and
F.
Durst
, “
The stability of evaporating thin liquid films in the presence of surfactant. I. Lubrication approximation and linear analysis
,”
Phys. Fluids
10
,
131
(
1998
).
35.
A. A.
Darhuber
,
S. M.
Troian
,
J. M.
Davis
,
S. M.
Miller
, and
S.
Wagner
, “
Selective dip-coating of chemically micropatterned surfaces
,”
J. Appl. Phys.
88
,
5119
(
2000
).
36.
V. S.
Ajaev
,
G. M.
Homsy
, and
S. J. S.
Morris
, “
Dynamic response of geometrically constrained vapor bubbles
,”
J. Colloid Interface Sci.
254
,
346
(
2002
).
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