Recently, novel organic glassy materials that exhibit remarkable stability have been prepared by vapor deposition. The thermophysical properties of these new “stable” glasses are equivalent to those that common glasses would exhibit after aging over periods lasting thousands of years. The origin of such enhanced stability has been elusive; in the absence of detailed models, past studies have discussed the formation of new polyamorphs or that of nanocrystals to explain the observed behavior. In this work, an atomistic molecular model of trehalose, a disaccharide of glucose, is used to examine the properties of vapor-deposited stable glasses. Consistent with experiment, the model predicts the formation of stable glasses having a higher density, a lower enthalpy, and higher onset temperatures than those of the corresponding “ordinary” glass formed by quenching the bulk liquid. Simulations reveal that newly formed layers of the growing vapor-deposited film exhibit greater mobility than the remainder of the material, thereby enabling a reorganization of the film as it is grown. They also reveal that “stable” glasses exhibit a distinct layered structure in the direction normal to the substrate that is responsible for their unusual properties.

1.
M. D.
Ediger
,
C. A.
Angell
, and
S. R.
Nagel
,
J. Phys. Chem.
100
,
13200
(
1996
).
2.
P. G.
Debenedetti
,
AIChE J.
51
,
2391
(
2005
).
3.
P. G.
Debenedetti
and
F. H.
Stillinger
,
Nature (London)
410
,
259
(
2001
).
4.
C. A.
Angell
and
K.
Ueno
,
Nature (London)
462
,
45
(
2009
).
5.
C. A.
Angell
,
J. Non-Cryst. Solids
354
,
4703
(
2008
).
6.
C. A.
Angell
, in
International Seminar on the Dynamics of Glass Transition and Related Topics
, Nov 12–15, 1996,
Kyoto, Japan
[Prog. Theor. Phys. Suppl. Vol. 126, pp
1
8
(
1997
)].
7.
E.
La Nave
,
F.
Sciortino
,
P.
Tartaglia
,
M. S.
Shell
, and
P. G.
Debenedetti
,
Phys. Rev. E
68
, Part 1,
032103
(
2003
).
9.
S.
Sastry
,
P. G.
Debenedetti
, and
F. H.
Stillinger
,
Nature (London)
393
,
554
(
1998
).
10.
C. A.
Angell
,
J. Res. Natl. Inst. Stand. Technol.
102
,
171
(
1997
).
11.
P. K.
Dixon
,
L.
Wu
,
S. R.
Nagel
,
B. D.
Williams
, and
J. P.
Carini
,
Phys. Rev. Lett.
65
,
1108
(
1990
).
12.
R.
Richert
and
C. A.
Angell
,
J. Chem. Phys.
108
,
9016
(
1998
).
13.
M.
Merolle
,
J. P.
Garrahan
, and
D.
Chandler
,
Proc. Natl. Acad. Sci. U.S.A.
102
,
10837
(
2005
).
14.
L.
Berthier
,
G.
Biroli
,
J. P.
Bouchaud
,
L.
Cipelletti
,
D. El
Masri
,
D.
L'Hote
,
F.
Ladieu
, and
M.
Pierno
,
Science
310
,
1797
(
2005
).
15.
K. S.
Schweizer
and
E. J.
Saltzman
,
J. Chem. Phys.
121
,
1984
(
2004
).
16.
V.
Lubchenko
and
P. G.
Wolynes
,
Annu. Rev. Phys. Chem.
58
,
235
(
2007
).
17.
W.
Gotze
and
L.
Sjogren
,
Rep. Prog. Phys.
55
,
241
(
1992
).
18.
A.
Widmer-Cooper
,
P.
Harrowell
, and
H.
Fynewever
,
Phys. Rev. Lett.
Vol. 93, pp.
135701
(
2004
).
19.
M. D.
Ediger
,
Annu. Rev. Phys. Chem.
51
,
99
(
2000
).
20.
K.
Vollmayr
,
W.
Kob
, and
K.
Binder
,
Phys. Rev. B
54
,
15808
(
1996
).
21.
S. F.
Swallen
,
K. L.
Kearns
,
M. K.
Mapes
,
Y. S.
Kim
,
R. J.
McMahon
,
M. D.
Ediger
,
T.
Wu
,
L.
Yu
, and
S.
Satija
,
Science
315
,
353
(
2007
).
22.
K. L.
Kearns
,
S. F.
Swallen
,
M. D.
Ediger
,
T.
Wu
,
Y.
Sun
, and
L.
Yu
,
J. Phys. Chem. B
112
,
4934
(
2008
).
23.
K. L.
Kearns
,
S. F.
Swallen
,
M. D.
Ediger
,
T.
Wu
, and
L.
Yu
,
J. Chem. Phys.
127
,
154702
(
2007
).
24.
K. L.
Kearns
,
T.
Still
,
G.
Fytas
, and
M. D.
Ediger
,
Adv. Mater.
22
,
39
(
2010
).
25.
K. L.
Kearns
,
S. F.
Swallen
,
M. D.
Ediger
,
Y.
Sun
, and
L.
Yu
,
J. Phys. Chem. B
113
,
1579
(
2009
).
26.
K. J.
Dawson
,
K. L.
Kearns
,
L.
Yu
,
W.
Steffen
, and
M. D.
Ediger
,
Proc. Natl. Acad. Sci. U.S.A.
106
,
15165
(
2009
).
27.
E.
Leon-Gutierrez
,
G.
Garcia
,
M. T.
Clavaguera-Mora
, and
J.
Rodriguez-Viejo
,
Thermochim. Acta
492
,
51
(
2009
).
28.
E.
Leon-Gutierrez
,
G.
Garcia
,
A. F.
Lopeandia
,
M. T.
Clavaguera-Mora
, and
J.
Rodriguez-Viejo
,
J. Phys. Chem. Lett.
1
,
341
(
2010
).
29.
E.
Leon-Gutierrez
,
G.
Garcia
,
A. F.
Lopeandia
,
J.
Fraxedas
,
M. T.
Clavaguera-Mora
, and
J.
Rodriguez-Viejo
,
J. Chem. Phys.
129
,
181101
(
2008
).
30.
D. M.
Mattox
,
Handbook of Physical Vapor Deposition Processing
(
Noyes Publications
,
Park Ridge, NJ
,
1998
).
31.
K.
Ishii
,
H.
Nakayama
,
S.
Hirabayashi
, and
R.
Moriyama
,
Chem. Phys. Lett.
459
,
109
(
2008
).
32.
S.
Aasland
and
P. F.
McMillan
,
Nature (London)
369
,
633
(
1994
).
33.
I.
Cohen
,
A.
Ha
,
X. L.
Zhao
,
M.
Lee
,
T.
Fisher
,
M. J.
Strouse
, and
D.
Kivelson
,
J. Phys. Chem.
100
,
8518
(
1996
).
34.
S. K.
Deb
,
M.
Wilding
,
M.
Somayazulu
, and
P. F.
McMillan
,
Nature (London)
414
,
528
(
2001
).
35.
G. N.
Greaves
,
M. C.
Wilding
,
S.
Fearn
,
D.
Langstaff
,
F.
Kargl
,
S.
Cox
,
Q. V.
Van
,
O.
Majerus
,
C. J.
Benmore
,
R.
Weber
,
C. M.
Martin
, and
L.
Hennet
,
Science
322
,
566
(
2008
).
36.
Y.
Katayama
,
T.
Mizutani
,
W.
Utsumi
,
O.
Shimomura
,
N.
Yamakata
, and
K.
Funakashi
,
Nature (London)
403
,
170
(
2000
).
37.
R.
Kurita
and
H.
Tanaka
,
Science
306
,
845
(
2004
).
38.
H.
Tanaka
,
Phys. Rev. Lett.
Vol. 90, pp.
0055701
(
2003
).
39.
H.
Tanaka
,
R.
Kurita
, and
H.
Mataki
,
Phys. Rev. Lett.
92
,
025701
(
2004
).
40.
H. N.
Sheng
,
H. Z.
Liu
,
Y. Q.
Cheng
,
J.
Wen
,
P. L.
Lee
,
W. K.
Luo
,
S. D.
Shastri
, and
E.
Ma
,
Nature Mater.
6
,
192
(
2007
).
41.
S.
Sen
,
S.
Gaudio
,
B. G.
Aitken
, and
C. E.
Lesher
,
Phys. Rev. Lett.
97
,
025504
(
2006
).
42.
O.
Mishima
,
L. D.
Calvert
, and
E.
Whalley
,
Nature (London)
314
,
76
(
1985
).
43.
D. V.
Matyushov
and
C. A.
Angell
,
J. Chem. Phys.
126
,
094501
(
2007
).
44.
J. H.
Crowe
,
J. F.
Carpenter
, and
L. M.
Crowe
,
Annu. Rev. Physiol.
60
,
73
(
1998
).
45.
J. H.
Crowe
,
L. M.
Crowe
,
A. E.
Oliver
,
N.
Tsvetkova
,
W.
Wolkers
, and
F.
Tablin
, in
38th Annual Meeting of the Society-for-Cryobiology, Jul 29, 2001
,
Edinburgh, Scontland
[Cryobiology
43
,
89
(
2001
)].
46.
L. M.
Crowe
,
D. S.
Reid
, and
J. H.
Crowe
,
Biophys. J.
71
,
2087
(
1996
).
47.
J. E.
Curtis
,
T. E.
Dirama
,
G. A.
Carri
, and
D. J.
Tobias
,
J. Phys. Chem. B
110
,
22953
(
2006
).
48.
D. P.
Miller
,
J. J.
de Pablo
, and
H.
Corti
,
Pharm. Res.
14
,
578
(
1997
).
49.
D. P.
Miller
,
J. J.
de Pablo
, and
H. R.
Corti
,
J. Phys. Chem. B
103
,
10243
(
1999
).
50.
P. B.
Conrad
and
J. J.
de Pablo
,
J. Phys. Chem. A
103
,
4049
(
1999
).
51.
R. A.
Riggleman
and
J. J.
de Pablo
,
J. Chem. Phys.
128
,
224504
(
2008
).
52.
A.
Simperler
,
A.
Kornherr
,
R.
Chopra
,
P. A.
Bonnet
,
W.
Jones
,
W. D. S.
Motherwell
, and
G.
Zifferer
,
J. Phys. Chem. B
110
,
19678
(
2006
).
53.
G. A.
Frank
,
J. Phys. Chem. Ref. Data
36
,
1279
(
2007
).
54.
E.
Polak
,
Computational Methods in Optimization
(
Academic
,
New York
,
1971
).
55.
H. J. C.
Berendsen
,
D.
Vanderspoel
, and
R.
Vandrunen
,
Comput. Phys. Commun.
91
,
43
(
1995
).
56.
B.
Hess
,
C.
Kutzner
,
D.
van der Spoel
, and
E.
Lindahl
,
J. Chem. Theory Comput.
4
,
435
(
2008
).
57.
D.
Van der Spoel
,
E.
Lindahl
,
B.
Hess
,
G.
Groenhof
,
A. E.
Mark
, and
H. J. C.
Berendsen
,
J. Comput. Chem.
26
,
1701
(
2005
).
58.
W.
Damm
,
A.
Frontera
,
J.
TiradoRives
, and
W. L.
Jorgensen
,
J. Comput. Chem.
18
,
1955
(
1997
).
59.
See supplementary material at http://dx.doi.org/10.1063/1.3586805 for detailed information on anisotropic characterization, size-effects and statistics for the stable glass.
60.
H.
Nagase
,
N.
Ogawa
,
T.
Endo
,
M.
Shiro
,
H.
Ueda
, and
M.
Sakurai
,
J. Phys. Chem. B
112
,
9105
(
2008
).
61.
C.
Shick
and
G. W. H.
Hohne
,
Thermochim. Acta
311
,
217
(
1998
).
62.
M. T.
Cicerone
and
C. L.
Soles
,
Biophys. J.
86
,
3836
(
2004
).
64.
F. W.
Starr
,
S.
Sastry
,
J. F.
Douglas
, and
S. C.
Glotzer
,
Phys. Rev. Lett.
89
,
125501
(
2002
).
65.
T. E.
Dirama
,
G. A.
Carri
, and
A. P.
Sokolov
,
J. Chem. Phys.
122
,
114505
(
2005
).
66.
P. R.
ten Wolde
and
D.
Chandler
,
Proc. Natl. Acad. Sci. U.S.A.
99
,
6539
(
2002
).
67.
P. J.
Steinhardt
,
D. R.
Nelson
, and
M.
Ronchetti
,
Phys. Rev. B
28
,
784
(
1983
).
68.
J. M.
Leyssale
,
J.
Delhommelle
, and
C.
Millot
,
Chem. Phys. Lett.
375
,
612
(
2003
).
69.
K. J.
Dawson
,
L.
Zhu
,
L. A.
Yu
, and
M. D.
Ediger
,
J. Phys. Chem. B
115
,
455
(
2011
).
70.
F.
Hellman
,
Appl. Phys. Lett.
64
,
1947
(
1994
).
71.
F.
Hellman
,
M. C.
Robson
, and
M. T.
Messer
,
J. Appl. Phys.
75
, Part 2B,
6870
(
1994
).
72.
R. F.
Xiao
,
W. C.
Ho
,
L. Y.
Chow
,
K. K.
Fung
, and
J.
Zheng
,
J. Appl. Phys.
77
,
3572
(
1995
).

Supplementary Material

You do not currently have access to this content.