Article

Cite This: J. Phys. Chem. C 2018, 122, 11385−11391 pubs.acs.org/JPCC

Water Adsorption on Hydrophilic and Hydrophobic Surfaces of

Silicon
Lei Chen,† Xin He,‡ Hongshen Liu,‡ Linmao Qian,*,† and Seong H. Kim*,†,‡
†
Tribology Research Institute, State Key Laboratory of Traction Power, Southwest Jiaotong University, Chengdu 610031, China
‡
Department of Chemical Engineering and Materials Research Institute, The Pennsylvania State University, University Park,
Pennsylvania 16802, United States
*
S Supporting Information
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ABSTRACT: The isotherm thickness and hydrogen-bonding interactions of

water layers adsorbed on hydrophilic and hydrophobic surfaces were quantified
and compared. The hydrophilic and hydrophobic surfaces were modeled with an
OH-terminated native oxide layer on silicon and a HF-etched silicon terminated
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with hydrogen, respectively. The silicon substrate allows the use of attenuated total
reflection infrared (ATR-IR) spectroscopy for quantitative measurement of
adsorbed water without interferences from the gas phase water. On the hydrophilic
Si−OH surface, the average thickness of the strongly hydrogen-bonded water layer
increases up to ∼2 molecular layers as relative humidity (RH) increases, beyond
which the weakly hydrogen-bonded structure is dominant. On the hydrophobic
Si−H surface, the adsorbed water layer consists predominantly of the weakly
hydrogen-bonded structure and its average thickness remains less than a
monolayer even at RH = 90%. The differences in the thickness and structure of adsorbed water layers on hydrophilic versus
hydrophobic surfaces found from ATR-IR measurements provide critical insights needed for better understanding of various
physical processes affected by water adsorption in ambient conditions.

■ INTRODUCTION
Most inorganic materials exposed to ambient air adsorb water,
and such adsorbed water layers can play a crucial role in
biology,1,2 materials science,3,4 and tribology.5−7 The unique
properties of water in the liquid state stem from its large dipole
moment, high polarizability, and hydrogen bonding capabil-
ity.8,9 In the case of water adsorbed on solids, additional
interactions with the solid surface make its property or
structure deviate from the liquid water.10,11 Understanding
the structure of interfacial water is of fundamental interest in
many physical processes such as separation of hydrophilic
surfaces or macromolecules in water,12 fabrication of uniform
films in atomic layer deposition,13 or control of surface wear
and interfacial friction of solid materials.14−16
The isotherm thickness and structure of adsorbed water films
can vary substantially depending on the surface chemistry and
the relative humidity (RH).17 On hydrophilic silicon oxide
surfaces, the adsorbed water layer can form strongly hydrogen-
bonded or ordered structures, which was often denoted as
solid-like water, ice-like water, or quasi-ice.18,19 The formation
of ordered structures is in agreement with density functional
theory (DFT) and molecular dynamics (MD) simulations.20−22
With the increase of RH (or partial pressure of water vapor),
more disordered or liquid-like structure grows in the adsorbed
water layer. The double-layer structure was also reported for
mica and metal surfaces.23−25 At hydrophobic surfaces, MD
simulations showed that water molecules have a diffusive
behavior due to the lack of strong interactions with the
surface.26 For example, simulations predicted that water
molecules on graphite do not have any hydrogen bond
interactions with the surface.27
This article reports spectroscopic evidence on differences in
structural configuration of water molecules adsorbed on
hydrophilic and hydrophobic surfaces of silicon. The thickness
and hydrogen-bonding interactions of water adsorbed on
hydrophilic native oxide surface (terminated with Si−OH,
water contact angle < 5°) and hydrophobic HF-etched surface
(terminated with SiH, water contact angle ≈ 83°) were
measured as a function of RH using attenuated total reflectance
infrared (ATR-IR) spectroscopy. The silicon substrate allows
the use of ATR-IR spectroscopy for measurement of adsorbed
water without interferences from the gas phase water. Also,
silicon is a technically important material in various scientific
and engineering applications.28−32 One advantage of ATR-IR
over other techniques such as polarization-modulation
reflection−absorption infrared spectroscopy (PM-RAIRS) is
that it allows quantitative determination of the adsorbed water
layer thickness.33 In the past, silane-based self-assembled
monolayers (SAMs) were frequently used for modification of
silicon surfaces; however, the use of SAMs complicates spectral
analysis due to ingress of water to subsurface sites.17,34,35 For
this reason, the Si−OH surface of the native oxide on Si and the
Received: February 22, 2018
Revised: May 2, 2018
Published: May 4, 2018

© 2018 American Chemical Society 11385 DOI: 10.1021/acs.jpcc.8b01821

J. Phys. Chem. C 2018, 122, 11385−11391
The Journal of Physical Chemistry C Article

Figure 1. ATR-IR spectra of the O−H stretching region of water adsorbed on (a) Si−OH and (b) Si−H surfaces at RHs of 15%, 30%, 45%, 60%,
75%, and 90%. The insets schematically show the Si−OH functional groups on a native oxide layer and the SiH groups on the HF-etched surface. Si,
blue; O, red; H, gray. The O−H stretching region is fitted with two components: strongly H-bonded water (blue lines centered at 3200−3275 cm−1)
and weakly H-bonded water (green lines centered at 3400−3450 cm−1). Note the log(1/R) full-scale for Si−OH in (a) is four times larger than that
for Si−H in (b). (c) ATR-IR spectra of the SiH stretch region of Si−H and Si−OH surfaces measured in dry nitrogen. Peak deconvolution is shown
in Figure S2 in the SI. (d) ATR-IR spectrum of bulk liquid water on the Si−OH surface.

Si−H surface obtained right after the HF etching were used to
model hydrophilic and hydrophobic surface chemistry,
respectively. The ATR-IR analysis of these surfaces quantita-
tively shows how the isotherm thickness and hydrogen-bonding
interactions in the adsorbed water layer vary with the surface
chemistry of silicon-based materials.
at the surface of fused quartz are hydroxylated, then the areal
density of OH groups is roughly 5/nm2.38
A Thermo-Nicolet Nexus 670 spectrometer equipped with a
MCT-A detector and a Harrick ATR setup was used to collect
ATR-IR spectra of water layers on those two surfaces as RH
varied from 0% (dry nitrogen) to 90% at room temperature

■
EXPERIMENTAL DETAILS
A double-side-polished p-doped Si(100) wafer (∼725 μm
thick) was cut into the ATR crystal shape (50 mm × 10 mm,
with 45° bevel-cut and polish in both ends for IR entrance and
exit). The total reflection of IR beams from the probe surface
was ∼35 times. One crystal was prepared by cleaning with the
RCA-1 solution (aqueous solution with H2O2 and NH3, 80
°C), rinsing with DI water, and drying with nitrogen. After that,
the crystal was exposed to UV/O3 for 30 min, which produced
an organic-contaminant-free native oxide surface.36 This sample
is named as “Si−OH”. Another ATR crystal was treated with
wet etching in hydrofluoric acid (∼40 wt % HF in aqueous
solution) for about 5 min, followed by rinsing with DI water
and drying with nitrogen. This crystal is denoted as “Si−H”. X-
ray photoelectron spectroscopy (XPS) analysis confirmed that
the oxygen content at the surface is below the detection limit
(see Figure S1 in the Supporting Information, SI). The water
contact angles were measured to be <5° on the Si−OH surface
and ∼83° on the Si−H surface (measured immediately after
HF treatment). When the silicon oxide surface is saturated with
hydroxyl groups, the water contact angle decreases to 0°.17
Using the Cassie equation, it is estimated that the Si−OH
surface is ∼98% saturated with silanol groups.37 If all Si atoms
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(20.8 ± 0.5 °C). After cleaning, the silicon crystal was promptly
mounted to the ATR assembly and purged with dry nitrogen
until there was no change in the OH stretch and H2O bending
vibration regions. The single beam spectrum collected in dry
nitrogen (RH = 0%) was used as a background spectrum for all
subsequent data collections. The spectra were collected with a 4
cm−1 resolution and averaged over 100 scans. At an incident
angle of 45°, the effective penetration depth of the evanescent
wave was 482 nm at 1635 cm−1.39
■ RESULTS AND DISCUSSION
The ATR-IR spectra of adsorbed water layers measured during
the stepwise increase of RH from 9% to 90% on the hydrophilic
Si−OH and hydrophobic Si−H surfaces are reported in Figure
1a,b. The SiH stretching vibration region of the ATR-IR spectra
(Figure 1c) confirms the presence of SiH (2082 cm−1) and
SiH2 (2103 and 2121 cm−1) species at the Si−H surface.40,41
After water adsorption measurement at 90% RH, the area of
SiH stretching vibration peak is still >98% of the peak area
measured before the 9% RH exposure (see Figure S2 in
Supporting Information). This result implies that the oxidation
of the Si−H surface due to exposure to water vapor at room
temperature is negligible over the duration of the measurement
time (typically, ∼5 h for a full series from 9% RH to 90% RH
measurements), and most SiH groups remain intact. For
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comparison, the ATR-IR spectrum of liquid water is also shown
in Figure 1d. Note that the spectral feature of the bulk liquid is
not sensitive to the surface chemistry since the penetration
depth of evanescent wave into liquid water is several orders of
magnitude larger than the thickness of the adsorbed water
layer.42
The difference in hydrogen-bonding interactions of water
molecules adsorbed on Si−OH and Si−H surfaces are
manifested as variances in peak shape of the O−H stretch
mode in the range from 3000 to 3800 cm−1 (Figure 1a,b).43,44
As the strength of hydrogen bonding interaction increases, the
O−H stretching peak position shows a larger red-shift.45
Although the exact peak shape is a complicated function of
hydrogen bond dynamics,46 the O−H stretch mode of water in
this region can be fitted with two main components: (I) the
strongly hydrogen-bonded configuration at 3200−3275 cm−1
and (II) the weakly hydrogen-bonded configuration at 3400−
3450 cm−1.37,46,47 The IR spectrum of ice water measured at
<273 K has a major peak centered at ∼3220 cm−1 (same as
peak-I) with a relatively narrow full-width-half-maximum
(fwhm) of ∼275 cm−1.48,49 Based on this comparison, the
peak-I component is often called the ice-like or solid-like
structure; in short, it just means more ordered or networked water
due to strong hydrogen bond interactions. Then, the peak-II
component could be called the disordered structure to contrast
with the peak-I component.
This argument can be used to analyze the ATR-IR spectral
features of adsorbed water on hydrophilic Si−OH and
hydrophobic Si−H surfaces. On the Si−OH surface, peak-I
(blue line in Figure 1a) is dominant over peak-II (green line) at
low RH conditions, implying that most adsorbed water
molecules have strong hydrogen-bonding interactions and
assume the solid-like configuration. As RH increases, the
weakly hydrogen-bonded disordered structure (peak-II) grows
along with the solid-like configuration. This is in good
agreement with previous reports on the water adsorption on
silicon oxide surface50 and other hydrophilic surfaces.51,52 In
contrast, the Si−H surface shows much larger intensity of the
peak-II component (green line in Figure 1b) compared to the
peak-I component (blue line) in the entire RH range studied
(Figure 1b), indicating that the weakly hydrogen-bonded
disordered structure is dominant at all times.
Comparison with the ATR-IR spectrum of bulk liquid water
(Figure 1d) reveals that the structural configurations of the
adsorbed water layers on the hydrophilic Si−OH and
hydrophobic Si−H surfaces (Figure 1a,b) are drastically
different from that of the liquid water.17 The relative ratio of
peak-I to peak-II is calculated from the areas of the
deconvoluted peaks at various RH conditions. This ratio for
the bulk liquid water is ∼0.72 in Figure 1d (marked with a
dotted line in Figure 2). With the increase of RH, the I/II ratio
of the water layer adsorbed on Si−OH decreases from ∼3 at
RH = 9% to ∼1.5 at RH = 90% (Figure 2). This result indicates
that on the hydrophilic Si−OH surface, the water layer mostly
assumes the strongly hydrogen-bonded solid-like network at
low RHs, and then its structure gradually changes toward the
bulk liquid network as RH approaches the saturation point. In
contrast, the I/II ratio of the water layer on the Si−H surface
remains relatively constant at 0.3−0.5 in the entire RH range
(Figure 2). On the hydrophobic Si−H surface, the solid-like
structure is minor, and its relative abundance does not change
with RH. These results are congruent with MD simulation
results.27
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Figure 2. Area ratio of peak-I (centered at 3200−3275 cm−1) and
peak-II (centered at 3400−3450 cm−1) as a function of RH on the
hydrophilic Si−OH and hydrophobic Si−H surfaces (estimated from
Figure 1a,b). The solid lines are drawn to guide eyes. The dotted line
marks the area ratio of those two peaks for bulk liquid water
(estimated from Figure 1d). The ATR-IR measurements were
repeated 5 times for the Si−OH surface and 4 times for the Si−H
surface.
Not only the structural configuration but also the thickness
of adsorbed water depend greatly on the outermost surface
chemistry.17 In ATR-IR, the thickness of the adsorbed water
layer (d) can be estimated by comparing the integrated areas of
adsorbed species (Aads) with the peak area of bulk water (Abulk)
with consideration of the penetration depth (dbulk) of the
evanescent IR beam:53
A ads A λ
d= dbulk = ads
Abulk Abulk 2π (n1 sin θ − n2 2)1/2
2 2
(1)
Here, λ is the wavelength of IR, θ is the incident angle of the IR
beam (45°), and n1 and n2 are the refractive indices of the
substrate and bulk water, respectively. The exact refractive
index of the adsorbed layer is not known, but it is assumed here
to be the same as the bulk value. The adsorbed water layer
constitutes with the more-ordered (peak-I) and disordered
(peak-II) components; so the total thickness of absorbed water
layer (d) can be expressed as the sum of the ordered water
thickness (dordered) and disordered water thickness (ddisordered).
The thickness of each component was calculated using eq 1
with the refractive index of bulk ice (n2 = 1.30)54 and the area
of peak-I for dordered; and the refractive index of bulk liquid (n2 =
1.33)55 and the area of peak-II for ddisordered. Figure 3 displays
the thickness (d) of the adsorbed water layer on the Si−OH
and Si−H surfaces. The calculated thickness is compared with
the molecular diameter of water (2.82 Å),50 which could be
taken as the thickness of one monolayer.
On the hydrophilic Si−OH surface (Figure 3a), the total
thickness (d) of the adsorbed water layer grows rapidly to
about a full monolayer at RH ≈ 9%, then slowly in the
intermediate RH region (for example, 20−70%), and then fast
again as RH approaches saturation (up to ∼4 molecular layers
at 90% RH). Based on the calculated thickness of the ordered
(dordered) and disordered (ddisordered) components, the structural
configuration of the adsorbed water layer could be deduced.
The first monolayer formed at low RH is highly ordered; this
must be due to strong hydrogen bond interactions with the
surface OH groups. The ordered structure induced by the
interactions with the surface appears to propagate up to ∼2
layers, consistent with the water configuration at a fully
hydroxylated surface calculated in MD simulations.21 A similar
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Figure 3. Adsorption isotherm of adsorbed water on (a) hydrophilic
Si−OH and (b) hydrophobic Si−H surfaces. The circle and triangle
symbols represent the total thickness of the adsorbed water layer
calculated based on eq 1. The solid line is drawn to guide eyes. The
average and standard deviation values of adsorbed water thickness are
estimated from the ATR-IR measurements repeated 5 times on the
Si−OH surface and 4 times on the Si−H surface. Note that the
thickness is an estimation based on eq 1; the value will vary depending
on how dbulk is defined in eq 1. The number of layers is calculated by
dividing the average thickness with the average diameter of water
molecule (2.82 Å).
trend was also observed on metal and metal oxide surfaces both
in experimental measurements and MD simulations, except the
degree of order in the first monolayer.55−58 The disordered
structure on the hydrophilic Si−OH surface becomes
significant when RH increases above 60%. Because the ordered
structure is induced by the surface OH groups, the disordered
structure is expected to be formed on top of the ordered layer,
not under the ordered layer.
On the hydrophobic Si−H surface (Figure 3b), the
calculated average thickness of the adsorbed water layer
remains less than half a monolayer in RH ≤ 75% conditions.
Previously, PM-RAIRS found that water does not adsorb on the
CH3-terminated hydrophobic SAMs on gold (water contact
angle >100°) even at near-saturation RH.33 In the case of the
Si−H surface, the silicon substrate with high polarizability may
reduce the water contact angle to 83°, compared to the CH3-
terminated SAM surface. However, this may not be sufficient to
hold a full monolayer of water on the Si−H surface (Figure 3b).
Considering the lack of hydrogen bonding interactions between
the water molecule and the Si−H surface, the physisorbed
water molecules are likely to form clusters via hydrogen
bonding interactions with each other.59 Such clusters may form
around defect sites at the Si−H surface (such as a trace amount
of Si−OH groups). Since the concentration of oxidized Si sites
is below the detection limit of XPS (Figure S1) and the average
Figure 4. Schematic illustrating the structural of adsorbed water layer on (a) hydrophilic Si−OH and (b) hydrophobic Si−H surfaces. The dotted
yellow lines represent hydrogen bonds. Note that illustration is not to scale. In (a), the water layer adsorbed on the hydrophilic Si−OH surface
grows up to full coverage at RH < 10% with highly ordered structures. Inset in (b) shows the schematic of clusters of water molecules on the
hydrophobic Si−H surface.
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thickness of the adsorbed water molecules from ATR-IR is
nearly half a monolayer (Figure 3b), the water clusters near
defect sites must be three-dimensional (3D) islands, instead of
two-dimensional patches covering a large area of the surface.
The structural configuration of the adsorbed water layers
implicated by the ATR-IR data is schematically illustrated in
Figure 4. On the hydrophilic Si−OH surface, the water
molecules in the ordered layer are under strong influences of
the surface hydroxyl groups, and the disordered layer exists at
the air-side of the adsorbate layer (Figure 4a). This
configuration is congruent with the structures previously
proposed from other spectroscopic observations19,49,60 and
MD simulations.61,62 The ordered water is likely to be a fully
connected network at the monolayer coverage, based on MD
simulations predicting the formation of 2D ice-like water
layer.63,64 In the case of the hydrophobic Si−H surface, the
adsorbed water layer is very little, and they are likely to exist in
clusters.65 Those clusters may be formed near defect sites that
may have some polarity or contain OH groups. Based on the
spectral shape of the OH stretch mode, the structure of these
clusters appears to be highly disordered or dynamically
changing, regardless of RH conditions of the environment
(Figure 2).66 The total averaged thickness is less than the full
monolayer coverage even at 90% RH.67 This is due to the lack
of hydrogen bonding interactions with the Si−H surface.
The ATR-IR analysis of water adsorption provides the
structure and thickness information on the physisorbed water
layers on the hydrophilic Si−OH and hydrophobic Si−H
surfaces in equilibrium with the gas phase water, which could be
related to various physical processes occurring such surfaces.
For example, the protein adsorption on biomaterials is a
function of surface wettability.68 Hydrophilic surfaces with a
water contact angle less than 60° show a resistance to protein
adsorption, whereas a hydrophobic surface can readily adsorb
proteins in aqueous solution.68 This could be attributed to the
hydrogen bond strength of water molecules at or near the
surface (Figure 4). At the hydrophilic surface, water molecules
are associated into a strongly hydrogen bonded network, which
may not be displaced easily. In contrast, the weakly associated
disordered water layers near the hydrophobic surface could be
easily displaced by protein molecules, changing the interfacial
energy. Furthermore, the lack of hydrogen bonding interactions
between water molecules and a hydrophobic surface may be the
main cause for the formation of a lower density “depleted”
interface at the hydrophobic surface in liquid water.69,70 The
energetic instability of such interfaces may play a significant role
in collapsing or coagulation of hydrophobic particles in aqueous
solution.71,72
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The strongly hydrogen-bonded water structure would play a
pivotal role in interfacial water flow. MD simulations showed
that a hydrodynamic slip of water can occur even on
hydrophilic surfaces depending on the surface density of
hydrophilic sites.73 If the OH groups on the Si−OH surface are
assumed to be distributed in a hexagonal array pattern (a close-
packed array with equal distance among each other), then the
areal density of 5/nm2 would correspond to the distance
between the nearest OH groups of ∼0.48 nm.38 This is ∼1.7
times the size of the water molecule.50 Because the silica surface
is known to be a nonslip surface for water, this distance might
be too far to allow the slip of water molecules among adjacent
OH sites,73 but it is close enough to induce a strongly hydrogen
bonded network covering the entire surface, as evidenced by
ATR-IR (Figures 1−3).
Also, the structure of the adsorbed water layer is found to be
important in nanotribology. The adhesion and friction forces
measured at nanoscale are found to be strongly dependent on
the amount of ordered water layer formed around the annulus
of the contact area on the hydrophilic surface, which is a
function of RH in the environment. However, they are much
smaller and relatively independent of RH on the hydrophobic
surface because the adsorbed water layer is so thin (less than a
monolayer in average, Figure 3) and its structure does not
change (Figure 2).74−76 Another example is water-assisted
mechanochemical reactions of silicon materials. Compared to
the disordered water layer, the ordered water layer appears to
facilitate mechanochemical reactions that lead to hydrolysis of
silicon oxide surfaces, which is manifested as surface wear.77,78
A similar mechanism may pertain to the mechanochemical wear
of multicomponent silicate glass materials.79 The mechano-
chemical wear of hydrophilic silicon increases with the growth
of the ordered water layer, but this is somewhat suppressed
upon the growth of disordered water layers at high RH.80,81
■
CONCLUSIONS
The structure and isotherm thickness of physisorbed water
layers strongly depend on the surface chemistry of the substrate
and RH in the surrounding environment. ATR-IR analysis of
the adsorbed water in equilibrium with the gas phase provided
the spectroscopic evidence for the strongly hydrogen-bonded
ordered network of water molecules on the hydrophilic Si−OH
surface and the lack or rarity of such structures on the
hydrophobic Si−H surface. As RH increases, the thickness of
the ordered water layer on the hydrophilic Si−OH surface
reaches a full monolayer at <10% RH and continues growing up
to about two monolayers. In contrast, the disordered structure
component grows slowly with RH, reaching a monolayer
coverage at RH > 60%, and increases fast as RH approaches the
saturation value. The water layer on the hydrophobic Si−H
surface is highly disordered and less than a monolayer
(probably forming isolated clusters) even at RH = 90%.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jpcc.8b01821.
XPS measurements on Si−H and Si−OH surfaces, ATR-
IR analysis of the SiH stretch region of the Si−H surface
(PDF)
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Article
■ AUTHOR INFORMATION
Corresponding Authors
*E-mail: linmao@swjtu.edu.cn.
*E-mail: shkim@engr.psu.edu.
ORCID
Seong H. Kim: 0000-0002-8575-7269
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was financially supported by the Natural Science
Foundation of China (51505391, 51527901) and the
Fundamental Research Funds for the Central Universities
(2682016CX026). ATR-IR measurements were carried out
with the support from the National Science Foundation of the
USA (Grant No. DMR-1609107 and CMMI-1435766).
■
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11391 DOI: 10.1021/acs.jpcc.8b01821

J. Phys. Chem. C 2018, 122, 11385−11391