Adsorption at solid surfaces 2

• Adsorption is a process in which particles, that is,

atoms, molecules, ions, from one phase are
accumulated at the interface to an adjacent phase.
There is a driving force that attracts them to the
interface.
• Atoms and molecules from a gas or vapor phase may
stick at a solid surface, ions from an electrolytic
solution may be attracted to an electrode, and
surfactants are enriched at the surface of their
aqueous solution.
• Adsorption is the first fundamental step in all surface
confined processes, among which are technologically
so important ones such as heterogeneous catalysis,
corrosion, flotation, thin film growth, and so on. Hence
the great interest in these phenomena and their basic
mechanisms.
• If the adsorption process may be reversed, we speak
about desorption.
• This section is an attempt to give an introduction
to the topic of gas adsorption on solid surfaces by
illustrating a number of important phenomena
that result from the interaction of gas particles
with the substrate surface, such as sticking,
structure formation including substrate
reconstruction, segregation, and film growth as
well as redesorption.
• These processes are, of course, accompanied by
changes in the electronic and vibronic properties
of adsorbate and substrate.
• In previous lecture we discussed that adsorption
and desorption are forward- and backward-
reactions of a dynamic equilibrium at the
interface between two (three-dimensional, 3D)
bulk phases, for instance a gas and a solid
(1)

• the equilibrium constant K is given by

(2)

• where M is a free adsorption site on the solid

surface and kad, kdes are the rate constants of the
adsorption and desorption process, respectively.
• At given gas pressure, the equilibrium constant K
and the rate constants k are temperature
dependent:
(van’t Hoff isobare) (3)

• and
(Arrhenius equation) (4)

• The Gibbs free energy ΔG is often approximated

by the mere energy ΔE, and E* stands for the
activation energy of the adsorption or desorption
process, E*ad, E*des, respectively.
• This temperature dependence enables a
decoupling of the adsorption and desorption
process.
• At sufficiently low temperature Ts of the
substrate, the particles may adsorb, but not
redesorb, because E*des > RTs.
• This permits a dosewise gas adsorption on the
surface in question and its investigation in the
absence of a surrounding gas pressure.
• Similarly, the subsequent desorption into
vacuum, that is, without the presence of a 3D gas
phase, may be studied by controlled increase in
the sample temperature Ts, thereby “activating”
the desorption process.
• A combination of both approaches is to expose
the surface in vacuum only strictly locally either
to a constant or a pulsed influx of particles,
namely, to a collimated continuous or pulsed
beam of atoms or molecules, and to monitor
their adsorption/desorption behavior at a given
surface temperature.
• This beam may even be well prepared in terms of
kinetic and inner energy and the orientation of
the molecules. The figure below illustrates these
scenarios at a solid–gas interface.
Figure 1: Scenario of adsorption on a solid surface. Atomic (Agas)
or molecular (Mgas) particles become bound to the surface (Aad,
Mad). On the atomic scale, the surface offers adsorption sites on
terraces (T), at steps (S) and kinks (K), and at vacancies (V). The
Agas /Mgas exposure can occur via an isotropic background
pressure or a directed particle beam.
 Adsorbate Delivery
• There are various ways how to expose a surface to an
adsorbate. The approach of the adsorbing particles
to the surface/interface requires their mobility and
may happen via diffusion in an isotropic gas phase,
which is described by Fick’s
(5)
laws. Restricted to one
dimension z (normal to the surface) the first and
second Fick’s law

• and
• There are various ways how to expose a surface to an
adsorbate. The approach of the adsorbing particles to
the surface/interface requires their mobility and may
happen via diffusion in an isotropic gas phase, which is
described by Fick’s laws. Restricted to one dimension z
(normal to the surface) the first and second Fick’s law
(5)
and
(6)

refer to stationary and nonstationary conditions,

respectively, with F =flux (particles m−2 s−1), D=diffusion
coefficient (m2 s−1), and dc/dz =concentration gradient.
• The required mobility depends on the
temperature with :
– D∼T3/2 for gases,
– D∼T in liquids,
– and D ∼ exp(−E*diff∕RT) in solids with E*diff
=activation energy of diffusion.
• Typical values for D are in the range of:
– 10−5 (m2 s−1) in gases,
– 10−9 (m2 s−1) in liquids,
– and 10−13 (m2 s−1) in solids.
• Assuming, for instance, an ideal gas of pressure p
the impact rate of particles of mass m onto a
surface of area A per second and unit area is

(7)

• The pressure p of a 3D gas phase is, according to

the ideal gas law, at given volume and
temperature, determined by the number of
enclosed gas particles, which can be controlled
either “batch-wise” by filling a closed volume
(equilibrium pressure) or under “flow conditions”
by a given combination of gas inlet and
“pumping-speed S” of an open vessel (steady
state pressure).
• Highly anisotropic, directed atom or molecular
beams are prepared by effusion cells, for
example, a Knudsen cell.
• At temperature T, the substance M in the
Knudsen-cell acquires its equilibrium vapor
pressure pM within the cell if the cross section of
the exit hole is sufficiently small.
• Assuming further that the vapor pressure within
the cell behaves like an ideal gas, Equation (7) can
be used to calculate the number of particles
traversing the exit hole, that is, the flux Feff
leaving the cell toward the sample.
• Similarly, this particle flux can be determined by
directing the beam into a mass spectrometer

Figure 2 : Experimental setup for thermal

desorption spectroscopy (TDS).
 Figure 3: Experimental setup of a chopped molecular beam experiment.

• The time t the sample surface is actually exposed to

the particle beam can be precisely controlled by
opening (t =0) and closing (t =t) a shutter in front of the
hole, or by means of a chopper, which cuts the beam in
pulses of defined length and frequency
Accommodation, Sticking, and
Coverage
• Not all particles that impinge on the surface do stick. Their
kinetic (in the case of atoms) or total energy (in the case of
molecules), determined by the gas temperature Tgas, may
prevent that they stick on the surface (of area A) but are
rather scattered back. The adsorption rate is thus given by

(8)

• Where the sticking coefficient s is defined as the ratio of

the numbers of sticking and impinging particles

(9)

• and describes the probability of a particle to stick and,

therefore, has a value between 0 and 1.
• On the one hand, s depends on the availability
of adsorption sites or conversely on the
already existing coverage of the surface with
particles (definition see Equations 11 and 12).
• On the other hand, any excess energy of the
incoming particles must eventually be
dissipated at the surface until the average
energy of Aad and the substrate are the same,
otherwise particles may be reflected (Agas,r)
from the surface with
 α is the so-called accommodation coefficient.

• Also ubiquitous surface defects such as steps,

kinks, point defects, and foreign atoms (see
Figure 1) have an enormous influence on the
sticking probability.
• This is elegantly shown with molecular beam
experiments in which, for instance, a Maxwellian
beam of different temperature Tgas is directed in
up-step and down-step direction onto a stepped
surface. This is exemplarily shown in Figure 4
below.
Figure 4: Polar plot of the variation of the initial sticking coefficient for a Maxwellian
beam of H2 molecules on a Ni(997) surface. The beam is directed in the direction either
step up or step down onto the surface at fixed temperature.

• At Tgas =90K huge differences of the initial sticking coefficient

so are found between both directions. A much higher sticking
coefficient in up-step direction shows the dominant influence
of the steps. This difference vanishes with increasing beam
temperature.
• Continued sticking of particles leads to an increase in the
surface coverage until the surface is covered with one
complete monolayer (ML).There are two common ways to
define the coverage. It may either be expressed by the
number of ad-particles per substrate surface atom

(11)

• or by the number of adsorbed particles relative to the

maximal possible number of adsorbed particles

(12)
• 𝜃 is an “absolute coverage” if besides the
known number of substrate surface atoms per
cm2 either the absolute number of ad-
particles per cm2 can be determined or the
lateral distribution of ad-particles with respect
to the substrate surface atoms, that is, the ad-
layer structure, is known.
• The “relative coverage” 𝛿 requires only a
reliable signal that depends linearly on
coverage and clearly indicates when the
saturation coverage is reached, for example,
XPS, AES, or thermal desorption spectra (TDS).
• At sufficiently low temperatures, the amount
of adsorbed particles may exceed 1
monolayer, in that particles “adsorb” on top of
the first, second, and so on saturated layer.
• But these particles are not in direct contact
with the substrate and are more or less
“condensed” on itself.
• The difference in bonding of particles in the
second, third, and so on layer compared to
that of the first layer, is an interesting subject
to study but we will concentrate on the
properties of the first monolayer.
• Under equilibrium conditions, the surface
coverage depends on – besides the nature of
substrate and adsorbate – temperature and
pressure of the gas phase.
• Measurements of the coverage as a function
of pressure at constant temperature result in
“adsorption isotherms,” while such
measurements as a function of temperature
at constant pressure yield “adsorption
isobars” as illustrated in Figure below.
Figure 5: (a) Adsorption isotherms measured at the same temperature on a
“strongly” or “weakly” binding substrate, respectively. The slope at any point
along such an uptake curve yields the sticking coefficient at the corresponding
coverage. (b) Adsorption isobars measured on one substrate at different ambient
pressures p1 <p2 <p3.

• The slope at any point along, for instance, in an

adsorption isotherm represents the sticking coefficient
s (relative to so =s(𝜃 =0) at zero coverage as long as so is
not absolutely known) at the corresponding coverage.
• Structural surface defects tend to enhance
sticking; therefore, steps on a Ru(0001)
surface are populated earlier, that is, already
at lower pressures, than terraces.
• Under nonequilibrium conditions, the sticking
coefficient is measured as the slope of a plot 𝜃
∼NAad as a function of dosage:
(13)

with dosage
(14)

often being given in units of L (Langmuir), with

10−6 Torr s=1 L.
• The slope d𝜃/dD yields again the relative sticking
coefficient at any point along the uptake curve.
The initial slope at 𝜃 =0 gives the initial sticking
coefficient so, which in general decreases with
increasing coverage 𝜃.
Properties of the Adsorbate
 Physisorption, Chemisorption
• The driving force for adsorption is the fact that
the total energy decreases when an adsorbate
particle Agas is brought to the bonding distance of
Aad on the surface.
• This distance dependence of the energy is
described by a “potential” curve whose
characteristics depend on the nature of the
bonding mechanism.
• The two limiting cases are “physisorption” and
“chemisorption”.
• “Physisorption” arises from mere van der Waals
interactions between any kind of matter, for
example, two atoms.
• Ground state fluctuations of the electronic charge
of an atom lead to a fluctuating dipole moment
of the atom, which in turn induces a fluctuating
dipole moment on an adjacent atom.
• Both dynamic dipoles and, thus, both atoms
attract each other until, with decreasing distance
r, their “electron clouds” start to repel each other
(Pauli repulsion).
• Both contributions are combined in the so-called
Lennard-Jones (L J) Potential sketched in Figure 6.

Figure 6: Lennard-Jones Potential and decomposition in

attractive and repulsive contribution.
• In the case of two interacting atoms, the
attractive part of this potential varies with r-6
and dominates at greater distances, while the
short-range repulsive contribution is
proportional to the overlap of the orbitals,
which – in principle resulting in an exponential
increase of the energy with decreasing
distance – is approximated by an r−12
dependence:

(15)
• This potential has two distinct points, a zero at
r =𝜎 and a minimum of depth 𝜀 at ro =21/6 𝜎.
• Both parameters 𝜎 and 𝜀 can be derived from
the virial coefficient of the equation of state of
the respective real gas.
• E(r) can also be determined from a
comparison of experimental and theoretical
surface – atom/molecule scattering results.
• A physisorbed atom on a surface interacts via the
L J-potential with all atoms in the solid. However,
while only the nearest-neighbor surface atoms
cause repulsion, the attraction results from the
summation over all pair interactionswith all
substrate atoms, which leads to a z−3 –
dependence of the attractive contribution (z
perpendicular to the surface).
• Since in this summation the nearest neighbors
are the major contributors, physisorbed species
tend to seek the highest coordinated adsorption
sites on the surface, for example, kink, step, or
hollow sites with as many nearest neighbors as
possible.
• In the case of “chemisorption,” a true chemical
bond is formed between Aad and the substrate
due to overlap of electron orbitals/states.
• This overlap depends on the relative energy and
the nature of the involved orbitals and occurs
only at very short distances, dominantly with
nearest-neighbor atoms.
• The minimum of the “chemisorption potential C”
in Figure 7 occurs, thus, at much shorter
distances and may also be much deeper than the
“physisorption minimum P” indicating a stronger
bond, a real chemical bond involving charge
exchange between the participating atoms.
Figure 7: Potential diagram for atomic adsorption with physisorption and
chemisorptions minimum.
• Within a simple one-electron picture, the possible
orbital interactions between an ad-particle and the
substrate are sketched in Figure 8.

Figure 8: Schematic diagram of hybridization between adsorbate

and substrate electronic states. The five possibilities 1–5 are
explained in the following slides
• The overlap of two unoccupied orbitals (1) above
the Fermi-level EF of the substrate has no
bonding effect, and the overlap of two fully
occupied orbitals (2) is even repulsive, unless the
unoccupied orbitals (3) and the filled orbitals (4)
are so close to the Fermi level that their
hybridization leads to an empty orbital below EF
(3) or an occupied orbital above EF (4).
• Both situations are unstable, and a corresponding
charge flow to ((3)) or from ((4)) the Fermi level
as indicated by the arrows makes both
interactions attractive.
• T
• This charge flow is possible due to the huge
charge reservoir of the substrate and suggests
that the dominantly localized bonding interaction
has, to a certain extent, also a longer ranging
effect on the substrate, in particular, since the
involved valence electron states on the substrate
side are not localized atomic orbitals but
delocalized band states.
• A molecular filled or unfilled orbital therefore
does not only interact with a singled-out surface
atom state but more or less with all valence band
states leading to a broadening and the formation
of a so-called “resonance” (5) in Figure 8. Filling
of the resonance tail below EF may, thus, add to
attraction.
• It is obvious that the hybridization and charge transfer
from/to the ad-particle involved in a chemisorption
bond leads to changes of the properties of both
bonding partners, which manifest themselves in
energetic shifts, population, and depopulation of
electronic states; in altered structural parameters
between atoms of both the ad-particle and the
substrate surface; in changed vibrational properties,
and so on, and in the extreme case in the dissociation
of adsorbed molecules.
• In the latter case, the charge exchange between the
adsorbing molecules and the surface destabilizes the
intramolecular bond such that the molecule dissociates
and the interaction of all molecular fragments with the
surface is energetically favored.
• For instance, diatomic molecules A2,gas such as
H2 or O2 are known to adsorb dissociatively at
room temperature on many surfaces. The final
product are two adsorbed atoms Aad per
adsorbed molecule.
• The same product, of course, can also be
obtained by first dissociating the A2 molecule in
the gas phase and adsorbing the resultant atoms.
• This, however, requires first the “expenditure” of
the full molecular dissociation energy E*diss,
which is then more than recovered by the energy
gain of two separately chemisorbed atoms as
illustrated in Figure 9, namely, .
Figure 9: Potential curves for molecular physisorption (M+A2) and dissociative
chemisorption (M+2A); M=metal, zp, zc =equilibrium distances in the physisorbed
and chemisorbed state, Ep, Ec =physisorption, chemisorption energy. E*ad
=activation barrier between physisorbed and chemisorbed state.
• Direct molecular dissociative adsorption saves
this expenditure, but may proceed stepwise via
several precursor states as illustrated in Figure 10.
• The incoming molecule A2gas may first be trapped
in a molecular physisorbed state A2phys , which via
a small activation energy may convert into a still
molecular chemisorbed state A2chem , which
ultimately, again via a certain activation barrier,
dissociates into two separate chemisorbed atoms
Aad,chem.
• With each step, the respective species comes
closer to the surface and becomes bound more
strongly.
Figure 10: Molecular adsorption may actually proceed via several
precursor states, for example, molecularly physisorbed, and
molecularly chemisorbed until final dissociative chemisorptions
• Originally an adsorbate system was classified as
“physisorbed” or “chemisorbed” by its adsorption
energy.
• A measured adsorption energy or activation
energy of desorption below 30–40 kJ/mol was
taken to be indicative of mere “physisorption,”
while higher values up to several hundreds of kJ
per mol were considered characteristic of
“chemisorption”.
• This definition, however, is too imprecise. Even in
the case of the adsorbed rare gas xenon,
originally considered to be a prototypical
“physisorption system,” both experimental results
and theoretical calculations favor a weak
chemisorption.
• A more precise distinction between
“physisorption” and “chemisorption,” is based on
whether the adsorptive bond is or is not
accompanied by hybridization and charge
redistribution, which for instance, in
photoemission spectroscopy manifests itself in
relative shifts, depopulation, and population of
selected orbitals with respect to others.
• Instead, photoemission spectra of physisorbed
species show, apart from a line broadening,
basically the same rigid shift of all orbitals due to
screening effects.