SURFACE AND INTERFACE ANALYSIS

Surf. Interface Anal. 27, 835–839 (1999)

Surface Electrical Resistivity and Wettability

Study of Fused Silica

B. C. Senn, P. J. Pigram and J. Liesegang*

Department of Physics and Centre for Materials and Surface Science, La Trobe University, Bundoora VIC 3083, Australia

The effect of heat treatment on the room-temperature surface electrical conductivity of a fused silica plate
has been investigated. Water-drop contact-angle measurements were used to assess the area ratio of SiOH
(silanol) to Si–O–Si (siloxane) groups generated on the surface. Electrical resistivity values ranging from
1012 to 1016 Z.m were also measured as a function of the generated surface hydration. Three conduction
regimes were identified corresponding to the following states of a fused silica surface: strongly hydrated, fully
hydroxylated and increasingly dehydroxylated. The conductivity behaviour is interpreted consistently with
previously proposed charge conduction mechanisms involving combinations of protonic and ionic conduction.
A surface region dielectric constant variation of 3.8–3.2 is also determined for 20–250 ° C heat treatments.
Resistivity measurements for samples treated above 430 ° C are interpreted in terms of the presence of NaY
ions and indicate a surface activation energy of ~0.21 eV for labile NaY ions to be oxidized and surface
pinned. Copyright  1999 John Wiley & Sons, Ltd.
KEYWORDS: silica; electrical resistivity; wettability; hydroxylation; contact angle

INTRODUCTION thermal conductivity and other physical and chemical

The physical properties of silica are known to be
influenced by surface dehydration (dehydroxylation)
treatment.1 The study of the surface electrical resistivity of
silica following such treatments is important because the
behaviour of the charge carriers located at the surface is
believed to have a major influence on conductivity in that
region2,3 as well as on other properties such as catalysis
and adsorbency. Silica .SiO2 / is a useful material for
studying the electronic processes involved in conduction
when its surface structure has been modified. The
relationship between water adsorption and the electrical
conduction mechanism of silica is of particular importance
in emerging ionic humidity sensor applications.4 In this
study a fused silica plate was investigated using an
electrical conductivity technique developed in previously
reported work5,6 in order to study the effect of surface
modification on electrical conduction in the surface region.
The results have been used to determine the nature of
charge carrier transport in the surface region of the
material.
The surface properties of silica have been the sub-
ject of numerous investigations with varied, inconclu-
sive results. Silica has been tested in many different
forms, including natural transparent (quartz) crystals cut
into plates7 dried gels and powders,8,9 all of which have
been processed using different mechanical, chemical and
thermal procedures10 and different surface preparation
techniques.1,11 Samples may vary widely in surface mor-
phology, water content, defect density, alkali ion content,
* Correspondence to: J. Liesegang, Department of Physics and Cen-
tre for Materials and Surface Science, La Trobe University, Bundoora,
Victoria 3083, Australia.
E-mail: J.Liesegang@latrobe.edu.au
CCC 0142–2421/99/090835–05 $17.50
Copyright  1999 John Wiley & Sons, Ltd.
properties.1,12 The structure of silica is also known to
be dependent on the thermal and chemical history of the
sample.13,14
The silica surface
A number of different functional groups involving Si–O
bonds have been identified on the surface or in the
internal structure of silica.1,15 The most commonly
reported of these groups include single isolated silanol
groups (Fig. 1(a)), geminal silanol (silanediol) groups
(Fig. 1(b)), silanetriol groups (Fig. 1(c)), vicinal silanol
groups (Fig. 1(d)) and siloxane bridges formed on a silica
surface by thermally induced dehydroxylation (Fig. 1(e)).
A large surface concentration of silanol groups makes
a silica surface hydrophilic. A predominance of silox-
ane groups, however, makes the surface hydrophobic.16,17
Before dehydroxylation of a fully hydroxylated silica sur-
face may occur, physisorbed water must be removed.
Dehydration commences at relatively low temperatures
(up to 190 š 10 ° C.18 At ¾200 ° C, all physisorbed water
will be removed, leaving only single, geminal and vicinal
silanol groups and siloxane bridges. Neighbouring vicinal
groups have been shown to desorb easily as water.19 – 21
At a temperature of ¾450–500 ° C, all the vicinal groups
condense, producing water vapour with only single and
geminal groups remaining. The isolated and geminal
hydroxyl groups that remain represent ¾25–30% of the
initial fully hydroxylated surface.1,10,19 Strained siloxane
bridges are formed by thermally induced condensation of
hydroxyl groups to ¾500 ° C. Between ¾600 and 900 ° C,
the isolated and geminal hydroxyl groups are removed.
At temperatures between 1000 and 1100 ° C, only single
silanol and stable siloxane bridges remain. Almost com-
plete dehydroxylation occurs in this temperature region,
Received 24 September 1999
Revised 22 March 1999; Accepted 23 March 1999
836 B. C. SENN ET AL.
Figure 1. Different types of relevant functional groups found on
fused silica surfaces.
with a large percentage of stable siloxane bridges existing
on the surface18 (Fig. 2).
Contact angle measurements and surface silanol area
coverage
The sessile water-drop contact angle () provides informa-
tion about wettability, surface energy, surface roughness
and surface heterogeneity. It is also a sensitive measure of
surface contamination. When the focus is the wettability of
the solid, advancing angles .A / and receding angles .R /
become important. In determining the variation of surface
silanol area coverage with temperature, the equilibrium
contact angle () may be used.22 A heterogeneous sur-
face composed of two homogeneous components may be
described in terms of contact angle by Cassie’s equation,23
which leads to a fractional coverage representation7 for
silica of
cos  0.749
aSiOH D .1/
0.251
Conduction mechanisms for silica surfaces
The conduction mechanism on a silica surface is known to
depend on the type of surface species involved. Anderson
and Parks24 showed that the mechanism on silica gels was
conditional on the surface coverage of adsorbed water
Figure 2. Relevant functional groups on silica produced at various treatment temperatures.
Surf. Interface Anal. 27, 835–839 (1999)
and that protons were the dominant charge carriers. They
stated that when complete coverage of physisorbed water
was observed at the surface, the charge transport was
dominated by HC hopping via an H3 OC ion releasing an
HC to a nearby H2 O molecule, causing ionization and
the formation of another H3 OC ion. The result is HC
hopping off from one water molecule to another. If all
water is removed from the surface, only free protons may
be formed, which migrate by hopping from site to site
across the silanol groups on the surface. When only partial
water coverage exists at the surface, the H2 O molecules
become hydrogen bonded to the silanol groups and HC
may be transferred from one of these silanol groups to a
water molecule to form H3 OC . Transfer of HC between
water molecules located in clusters also may take place.
Anderson and Parks also were able to relate measured
change in resistivity () to change in dielectric constant
(ε) (see Ref. 24, Eqn (7)), which is rewritten in the form
 D 0 exp.e2 /8εε0 rkTR / .2/
where 0 is a pseudo-constant involving carrier concen-
tration and carrier mobility, k is Boltzmann’s constant, e
is the carrier ionic charge, TR is the temperature (room)
at which resistivity was measured and r is the usual
bond length Si–OH in the surface (¾0.16 nm25 ). The
present work will also use this relationship together with
data obtained for .T/, where T is treatment tempera-
ture, to determine the variation of dielectric constant ε.T/
in the surface region of silica as a function of treatment
temperature.
Other notable surface species that have been found in
the surface of quartz following heat treatment are alkali
ions,26,27 in particular NaC ions. It may be noted that 2 ppm
of bulk Na produces 2% of surface Na after 1000 ° C treat-
ment and that such a level of contamination characterizes
‘high purity’ silica. Such ions therefore might be expected
to influence the conductivity of silica surfaces that have
undergone high-temperature treatment. Such a presence
of NaC ions has been reported both by Wood et al.26
using secondary ion mass spectrometry (SIMS) and by
Fowkes and Burgess,28 who reported that even the purest
silica traps 1013 atoms cm 2 within 10 nm of the sur-
face, creating negative (oxide) ionic charge at the surface.
These in turn provide additional pathways for ionic trans-
port. Later we show how resistivity measurements in the
present work, performed on samples treated at >430 ° C,
have been used to estimate a surface activation energy for
NaC ions to diffuse into a bonded oxide surface site.
Copyright  1999 John Wiley & Sons, Ltd.
 SURFACE RESISTIVITY AND WETTABILITY OF FUSED SILICA 837

EXPERIMENTAL Resistivity measurement

The plate was removed from the contact angle apparatus

Preparative procedure for fused silica surfaces
A fused silica window of dimensions 70 ð 45 ð 3 mm
(Spectra-Physics; flatness /3) was cleaned following a
method reported previously7,29 using ethanol and dried
nitrogen and then thoroughly rinsed with deionized water.
The plate then was placed in a beaker of deionized
water and boiled for 4–6 h. The beaker then was filled
with deionized water until it overflowed, to remove any
contaminants present on the water surface after boiling.
This procedure was repeated for each measurement to
obtain a clean, fully rehydroxylated surface. A ‘steam
test’ involving the condensation of steam from a beaker
of boiled water onto the silica plate was used to determine
if it was sufficiently free of contamination and fully
hydroxylated.7,29 Fringes were inspected to determine the
level of contamination at the plate surface.
and frictionally charged. Electrical contact was made by
encasing one end of the plate in indium foil (0.5 µm thick)
and attaching a metal chain. The sample was lowered
into a coaxial metal cylindrical capacitor arrangement
that contained an inner cylinder insulated from an outer
cylinder, the latter being earthed. Induced charge on the
inner electrode was then monitored as sample charge
decayed with time using an electrometer. Refer to Refs 5
and 6 for a full description of experimental details. All
measurements were carried out at room temperature and
a relative humidity of ¾25%.
Contact angle measurement
The method used by Lamb and Furlong7 was used for
contact angle measurements of sessile water drops placed
on the treated silica surface after cooling. Results obtained
were in close agreement with those reported in figs 3 and
5 of Ref. 7 (see Fig. 3 below).

Heat treatment procedure

After cleaning, the plate was placed in a specially designed
sample holder under vacuum (¾2ð10 6 hPa) and lowered
into a tube furnace (Sephco Industrial Heating). The
method of Lamb and Furlong7 was used for heat treating
the sample in the range 20–840 ° C. It was heated to each
desired temperature for a ¾24 h before being annealed
back to room temperature. The entire sample plus sample
holder was then purged with dry nitrogen. The sample
was removed under a nitrogen blanket from the holder
and the resistivity was measured at room temperature (see
below). A drop formed by manipulation of a micrometer-
driven syringe was then placed on the sample surface
and contact angles were measured using the sessile drop
method. Contact angles (both advancing and receding) as
a function of drop base width were measured and it was
found that there was no appreciable variation of either
contact angle with drop size for drops in the base width
range 4–8 mm. This sequence was carried out for each
selected treatment temperature between 25 and 840 ° C.
RESULTS
The measurements of contact angle and resistivity for
various heat treatment temperatures are summarized in
Table 1.
Room-temperature .TR / electrical resistivity measure-
ments for the silica plate show three distinct zones
(labelled I, II and III) as surface structure changes with
increasing heat treatment temperature T; these resistivities
are plotted along with the contact angle measurements in
Fig. 3. The data in Zone I indicate a strong influence on
conductivity of physisorbed water on the surface.24 Zone II
shows little variation in conductivity as dehydroxylation
commences. In zone III, a slight increase in conductivity
is observed in the region where siloxane groups begin to
form at ¾500 ° C.
Figure 3 shows that the gradual loss of physisorbed
water (i.e. up to 200 ° C or contact angle <5° ) is associ-
ated with a significant decrease in conductivity. A ther-
mal treatment at 200 ° C results in complete removal of

Table 1. Summary of measured contact angle and resistivity results taken at room
temperature, following various heat treatments of a fused silica surface
Average Average
Treatment advancing receding Fraction of SiOH groups on the
temperature Resistivity .Ðm/ contact angle contact angle silica surface estimated from
š10 ° C š8% š1° š1° contact angle measurement

25 1.60 ð 1012 0.0 0.0 1.00 š 0.1

98 2.68 ð 1013 1.5 0.0 0.99 š 0.1
133 2.03 ð 1014 2.6 0.0 0.99 š 0.1
149 8.84 ð 1014 2.8 0.0 0.99 š 0.1
194 3.44 ð 1015 4.3 0.0 0.99 š 0.1
251 6.05 ð 1015 6.4 0.0 0.99 š 0.1
319 6.74 ð 1015 8.8 0.0 0.98 š 0.1
428 7.20 ð 1015 11.4 0.0 0.98 š 0.1
515 3.60 ð 1015 13.0 2.1 0.96 š 0.1
658 3.00 ð 1015 25.3 9.6 0.81 š 0.1
731 3.54 ð 1015 34.6 13.4 0.65 š 0.1
841 1.39 ð 1015 39.7 17.3 0.52 š 0.1

Copyright  1999 John Wiley & Sons, Ltd. Surf. Interface Anal. 27, 835–839 (1999)
838 B. C. SENN ET AL.
Figure 3. Graphs of both log(resistivity) () and water drop
equilibrium contact angle () vs. treatment temperature. The
equilibrium contact angle  was obtained from the advancing
and receding contact angles via cos  D [cos A C cos R ]/.2r /,
where roughness factor r D 1 was used30,31 .
physisorbed water, revealing a complete layer of silanol
groups on the surface.7 An Arrhenius plot (Fig. 4) of log 
vs. 1/T (with T in kelvin) gives a linear correlation, which
when interpreted in terms of Eqn (2) is given empirically
by
ε.T/ D 176.7[ln..T/ C 18.4] 1 .3/
This result thus allows an evaluation of the variation
of the dielectric constant in the surface region of the
silica sample with treatment temperature, assuming a
room-temperature value of 3.8. Figure 5 shows such
variation using our .T/ data fitted with a polynomial.
Figure 4. Arrhenius plot of log(room temperature resistivity) versus 1/T , where T is the treatment temperature.
Surf. Interface Anal. 27, 835–839 (1999)
The population of SiOH groups on the surface is only
marginally reduced for further thermal treatments up to
430 ° C, so little variation in resistivity is expected and
noted in Fig. 3.
A much greater and more rapid loss of SiOH groups
is known to occur above 500 ° C.7 Although a decrease in
resistivity is observed for this region, it is relatively small
in comparison with the silanol loss. This tends to indicate
that the conduction may now begin to be influenced
by extraneous factors. We suggest that the influence of
labile NaC ions diffusing to the surface, in increasing
numbers depending on the treatment temperature, provides
the explanation for this phenomenon. It is therefore of
interest again to make an Arrhenius plot, the linearity of
which we suggest may be interpreted through an activation
energy for NaC of ¾0.2 eV. This activation presumably
refers to the hopping of near-surface sodium ions into
subsurface sites, where they are pinned to O ions. Such
oxide ions provide hopping sites for mobile protons from
physisorbed water, there being more of them generated at
higher treatment temperatures, resulting in the observed
decrease in resistivity in zone III.
CONCLUSIONS
The electrical resistivity results for fused silica as pre-
sented are consistent with the mechanism offered by
Anderson and Parks24 for a silica-gel surface. As adsorbed
water content is increased, conductivity is increased;
therefore, when a complete layer of physisorbed water
exists on a silica surface, the hopping of protons between
neighbouring water molecules provides the conductive
path for charge transport. We have evaluated the change
Copyright  1999 John Wiley & Sons, Ltd.
 SURFACE RESISTIVITY AND WETTABILITY OF FUSED SILICA
Figure 5. Graph of dielectric constant in the surface region of silica () vs. treatment temperature, as deduced from present resistivity
data. The curve is simply a polynomial fit.
in surface region dielectric constant, which is concomitant
with the heat treatment, indicating a decrease from 3.8
to 3.2 over the treatment temperature range 20–250 ° C.
When physisorbed water coverage is not complete, H3 OC
diffusion of hydroxyl groups dominates and proton hop-
ping between adjacent water molecules in clusters also
occurs, thus causing the charge carrier conduction to be
lower than that for complete coverage by physisorbed
water. When only hydroxyl groups are present on the
fused silica surface, the HC ions gained through hydroxyl
dissociation hop between adjacent sites allows limited
REFERENCES
1. R. K. Iler, The Chemistry of Silica, Chapt. 6. Wiley, Chichester
(1979).
2. J. J. Bikerman, Physical Surfaces, p. 428. Academic Press,
New York (1970).
3. M. Muroya and S. Kondo, Bull. Chem. Soc. Jpn. 47, 1533
(1974).
4. E. Traversa, Sensors Actuators B 23, 135 (1995).
5. J. Liesegang, B. C. Senn and E. R. Smith, J. Appl. Phys. 77,
5782 (1995).
6. J. Liesegang and B. C. Senn, J. Appl. Phys. 80, 6336
(1996).
7. R. N. Lamb and D. N. Furlong, J. Chem. Soc. Faraday Trans.
1 78, 61 (1982).
8. J. H. Anderson and K. A. Wickersheim, Surf. Sci. 2, 252,
(1964).
9. R. Guermeur, C. Jacolin, F. Biquard and C. Blanc, Surf. Sci.
255, 157 (1991).
10. A. Vidal, H. Balard, E. Papirer, M. Czernichowski, R. Erre,
P. Levitz, H. Van Damme, J. P. Gallas, J. F. Hemedy,
J. C. Lavalley, O. Barres, A. Burneau, Y. Grillet, A. Tuel,
H. Hommel and A. P. Legrand, Adv. Colloid Interface Sci. 33,
91 (1990).
11. E. Borello, A. Zecchina and C. Morterra, J. Phys. Chem. 71,
2938 (1967).
12. S. P. Zhdanov, L. S. Kosheleva and T. I. Titova, Langmuir 3,
960 (1987).
13. C. Morterra and M. J. D. Low, J. Phys. Chem. 73, 321
(1969).
14. S. Kondo, H. Yamauchi, Y. Kajiyama and T. Ishikawa, J.
Chem. Soc. Faraday Trans. 1 80, 2033 (1984).
Copyright  1999 John Wiley & Sons, Ltd.
839
conduction to occur. This is the least conductive path for
charge transfer.
When a combination of siloxane and silanol groups
resides on the surface (i.e. for treatment above 430 ° C),
a reduced conductivity is found. This in part may result
from HC transfer from silanol groups to siloxane groups;
however, the variation of resistivity with treatment tem-
perature observed would suggest that a more likely cause
is the surface migration of labile NaC ions that are pinned
to oxide ions at the surface. Such oxide ions then provide
hopping sites for protons from physisorbed water.
15. H. E. Bergna, The Colloid Chemistry of Silica, Advances
in Chemistry Series 234, pp. 21 35. American Chemical
Society, Washington, DC (1994).
16. G. J. Young, J. Colloid Sci. 13, 67 (1958).
17. G. J. Young and T. P. Bursh, J. Colloid Sci. 15, 361 (1960).
18. L. T. Zhuravlev, Colloids Surf. 74, 71 (1993).
19. O. Sneh and S. M. George, J. Phys. Chem. 99, 4639 (1995).
20. D. W. Sindorf and G. E. Maciel, J. Am. Chem. Soc. 105, 1487
(1983).
21. R. L. White and A. Nair, Appl. Spectrosc. 44, 69 (1990).
22. A. B. D. Cassie, Discuss. Faraday Soc. 3, 11 (1948).
23. R. N. Wenzel, J. Phys. Chem. 53, 1466 (1949).
24. J. H. Anderson and G. A. Parks, J. Phys. Chem. 72, 3662
(1968).
25. A. F. Wells, Structural Inorganic Chemistry, 4th Edn,
Chapt. 23. Oxford University Press, Oxford (1975).
26. B. J. Wood, R. N. Lamb and C. L. Raston, Surf. Interface
Anal. 23, 680 (1995).
27. I. Enculescu and B. Iliescu, Cryst. Res. Technol. 32, 870
(1997).
28. F. M. Fowkes and T. E. Burgess, in Clean Surfaces Sympo-
sium, ed. by G. Goldfinger. North Carolina State University,
Dekker, New York (1970).
29. R. M. Pashley, PhD Thesis, Imperial College, London (1978).
30. E. Wolfram and R. Faust, Wetting, Spreading and Adhesion,
ed. by J. F. Padday, Chapt. 10. Academic Press, London
(1978).
31. R. E. Johnson and R. H. Dettre, Surface and Colloid Science,
ed. by E. Matijevic and F. Elrich, Chapt. 2. Wiley, New York
(1969).
Surf. Interface Anal. 27, 835 839 (1999)