IRG-C: Oxide Glasses: Surfaces and Thin Film Interfaces

Senior Participants: Ashcroft (Phys), Ast (MS&E), Baker (MS&E), Blakely (MS&E),
Dieckmann (MS&E), J. Silcox (A&EP) Umbach (MS&E), Zehnder (T&AM). 3 Graduate Students, 1
Research Associate.
This IRG is concerned with the structure and properties of glass, particularly at and near surfaces and
interfaces. IRG-C uses a broad range of approaches and tools to explore the complexity of useful
engineered glass systems and to develop fundamental insights into these materials. To this end, we
are focusing on a set of calcium aluminosilicate (formed from mixtures of SiO2, Al2O3 and CaO)
glasses around the anorthite ([Ca0.5AlO2] 0.5 - [SiO2] 0.5) composition. They are of interest both
because they are good model glassesthe simplest glasses that have the physical attributes of
complex technological glassesand because they are closely related to the advanced glasses used in,
for example, computer displays. Surprisingly, given their technological utility, much of the fundamental surface behavior of these glasses is either not understood or not yet explored. When the ratio
of Al2O3 to CaO is maintained at 1:1, a fully linked network structure like that of SiO2 is obtained;
this network is preserved even when the SiO2 content is systematically varied over a wide range. An
important collaboration with scientists at Cornings R&D laboratories has been developed and they
have prepared high purity samples of calcium aluminosilicates for IRG-C research. IRG-Cs recent
efforts have been focussed on studies of these
model glasses and the initial results suggest that this
will be an incredibly rich area in which to work.
Recent Accomplishments
Tracer diffusion studies: In Dieckmanns previous IRG-C work with other glasses,1,2 exposure
of the glass surface to moist air at elevated
temperatures results in a near-surface zone tens of
microns thick that is likely due to water-induced
structural relaxations. In the calcium
aluminosilicates, Dieckmann has now seen that
the rate of formation of this zone depends strongly on composition and on temperature. The diffusivity of 22Na- decreases sharply with decreasing
50 nm
SiO2 content, both in the modified zone and in the
bulk, possibly because AlO2 acts as a deep trap
for Na+, with the trapping increasing as the glass
Fig. 1: Non-contact AFM image of structure relaxes.
fracture surface of anorthite glass. Inset
AFM on fracture surfaces: Umbach and Blakely
shows typical nanometer scale features.
have used non-contact AFM to study the
nanoscale surface structure of calcium aluminosilicate glasses fractured in ultra-high vacuum.
These surfaces are free of mechanical damage from polishing and free from extrinsic
contaminants. Fig. 1 shows a typical fracture surface for anorthite glass. There appear to be
characteristic structures at several length scales. Hillocks of width 15 to 20 nm contain distinct
features with a lateral length scale of 5 nm (see the inset of Fig. 1). Similar characteristic length
scales are observed in commercial display glasses. The origin of these features may be associated
with the fracture process or may reflect some underlying structural unit of the glass itself.

Electron beam induced precipitation of metal in glass. In developing techniques to perform

quantitative chemical analysis of glasses at the nanometer scale with STEM, Silcox has found
that, like other glasses3, calcium aluminosilicates are sensitive to electron beam radiation
damage4. The precipitation of metals is one form of damage, arising from the excitation of lowlying levels in non-bridging oxygen atoms. This precipitation effect has been exploited to write
metal lines as fine as 20 in width on the surface of glass wafers.
Adhesion of thin metal films to glass: The work of Backhaus-Ricoult (CNRS, France) suggests
that adhesion of thin metal films to these glasses will depend sensitively on the interfacial
oxygen content. Baker has developed bilayer decohesion tests and analytical models for
interpreting those tests, which will now be used to correlate interfacial fracture toughness with
interfacial chemistry.
Surface roughness in dry etching: The dry etching of glass is of interest for (i) shaping glasses
with roughnesses suitable for miniaturized opto-electronic devices and (ii) nanoscale patterning
to enhance properties such as adhesion and orientation of deposited thin films. As a preliminary
investigation of etch-induced surface roughness, the Ast group studied a glass-ceramic system
containing 70 vol% SiO2. A comparison of the dry etching of green glass with that of the glass
ceramic made it possible to separate chemical (i.e. composition) from microstructural (i.e.
devitrification) effects. It was found that those elements in the glass that form non-volatile
fluoride compounds limit the etch rate and that smoother surfaces can be achieved in systems
which phase separate on the scale of 10 nm5.
Ion-bombardment-induced nanoscale corrugations: In a collaborative project with IRG-D,
Umbach, Blakely, and Headrick have previously demonstrated that off-normal ion-sputtering can
produce quasi-periodic corrugations on SiO2 with wavelengths of 20 to 120 nm and amplitudes
of ~1 nm. A model to explain these observations has recently been developed. In this model, ionassisted viscous relaxation confined to the surface is the dominant mechanism for smoothing the
surface during erosion, playing a role analogous to that which surface diffusion plays for
crystalline surfaces. In the reporting period, corrugations similar to those observed on SiO2 have
also been found to form on a multicomponent silicate glass.
Theory of glass formation: The Ashcroft group recently developed a model of the packing
aspects of three components fluids6, which is important for systems that form practical glasses
from melts. The study establishes the concentration ratios and dimension ratios (for constituent
particles) necessary for effective potentials to favor such systems.
Future Research Directions
Calcium aluminosilicates: IRG-C will continue to explore the surprisingly strong composition
dependence of the properties of these glasses. Further Na tracer diffusion experiments will be
conducted and Ca diffusion experiments will begin within a few months. Impurity transport
across the surface will also be investigated by electrostatically bonding the glass to a Si wafer.
Any impurities that diffuse into or out of the Si can be analyzed with deep level transient
spectroscopy (DLTS). We will use analytical STEM to determine if these glasses shows
compositional variations at the characteristic length scales observed in the AFM images. In order
to distinguish the effects of the fracture process from compositional and structural effects, AFM
will be performed on fracture surfaces of fused silica, crystalline quartz and crystalline anorthite.
The etch rates and corresponding nanoscopic and mesoscopic roughnesses of the calcium
aluminosilicates as a function of glass composition and etch process will be investigated. The

effects of interface chemistry on metal film adhesion as a function of glass composition will be
studied. With the acquisition of a new FTIR microscope, IRG-C will be able to characterize all
the glasses it studies for water content and structural relaxations. This new capability will be
particularly useful for the diffusion experiments, where the width of the modified zone can be
determined directly by cross-sectional IR microscopy.
Theory: Glass formation: Application by Ashcroft of a variational approach (via the GibbsBogolyubov inequality) to the Helmhotz energies of systems with more realistic interactions will
allow a better understanding of those fluid mixtures which form glasses and those which do not.
Adhesion: As an alternative to previous first-principles calculations of metal-glass interactions
where the metal and glass were both in solid form, Ashcroft intends to study the wetting
properties of a multicomponent glass forming liquid in the presence of a substrate whose
interactions with the constituents of the liquid are known.
References for IRG-C
1. L. Tian, R. Dieckmann, C.-Y. Hui, Y.-Y. Lin, and J. G. Couillard, Effect of water
incorporation on the diffusion of sodium in Type I silica glass, J. Non-Cryst. Sol. (submitted
for publication).
2. L. Tian, R. Dieckmann, C.-Y. Hui, and J. G. Couillard, Effect of water incorporation on the
diffusion of sodium in an alkaline-earth boroaluminosilicate glass, J. Non-Cryst. Sol.
(submitted for publication).
3. N.Jiang, J.Qiu and J.Silcox, Precipitation of nanometer scale Zn crystalline particles in ZnOB2O3-SiO2 glass during electron irradiation, Appl. Phys. Lett 77 3956-3958 (2000).
4. N. Jiang and J. Silcox, Electron radiation damage in multi-component glasses J.Appl. Phys.,
submitted for publication.
5. J. Liu, N. Nemchuk, D. G.Ast, J. G. Couillard, Etch rate and surface morphology of plasma
etched glass substrates, to be published in the Proceedings of MRS 2000 Fall Meeting,
Boston, Mass.
6. A. Koenig and N. W. Ashcroft, Structure and effective interactions in three-component hard sphere
fluids, Physical Review E (submitted for publication).