Journal of Biomaterials and Nanobiotechnology, 2011, 2, 533-543
doi:10.4236/jbnb.2011.225064 Published Online December 2011 (http://www.scirp.org/journal/jbnb)
533
Self-Assembled Monolayers (SAMs): Which
Perspectives in Implant Dentistry?
Filiberto Mastrangelo1, Giulia Fioravanti2, Raimondo Quaresima2, Raffaele Vinci3, Enrico Gherlone3
1Department of Oral Science, University “G. D’Annunzio” of Chieti, Chieti, Italy; 2Department of Chemistry, Chemical Engineering
and Materials, University of L’Aquila, L’Aquila, Italy; 3Department of Oral Science, University “S. Raffaele” of Milan—Ateneo Vita
e Salute, Milan, Italy.
Received October 5th, 2011; revised November 14th, 2011; accepted November 27th, 2011.
ABSTRACT
Self-assembled monolayers (SAMs) are ordered organic films formed by adsorption of an active organic coating on a
solid surface. Their formation provides an alternative, highly innovative, to current traditional chemical treatments of
the titanium surfaces. For this reason the structural phases, the formation and the growth of SAMs is described from a
surface science point of view. Particulars are given to SAMs on titanium concerning surface morphology, chemical
composition and affinity of specific head group for Ti surfaces (silanes, siloxane, phosphonates and phosphates).
Preparation, coating methodologies, limitations and techniques used for the characterization of SAMs are reported.
For their physicochemical characteristics an d micro-nano scale fea tures some perspectives of using SAMs in biomedi-
cal application are outlined.
Keywords: Ti t anium Surfaces, Implant Dentistry, Osteointegration, Self-Assembling Monolayers, Phosphates
1. Introduction
The biocompatibility of an osteointegrated titanium im-
plant is correlated with its physical, mechanical and
chemical characteristics. Moreover the superficial char-
acteristics have a key role during the initial phases of
osteointegration processes in relationship to titanium
biomaterial and bone tissue [1]. More clinical and re-
search studies were produced in order to modified the
titanium surface with different chemical (acid oxidation,
peroxidation, alkalization, crystalline hydroxyapatite
deposition, electrochemical anodization) and physical
approaches (compactation on particles, ion beam, pressure
or chemical vapour deposition) [2]. With all this methods
a macro, micro and nano-scale surface modification is
obtained [3,4]. To improve the implant success rates the
attention highlighted nano-scale features [5]. Therefore
surface modification techniques such as lithography [6-19]
and self-assembled monolayers (SAMs) were recently
developed and investigated in implant dentistry [20-25].
While the lithography techniques require a considerable
great development prior to clinical translation and appli-
cation on implant surface [26,27] the SAMs are more
known and experimented in medicine [20,21].
2. Self-Assembled Monolayers
2.1. Introduction on Self-Assembling Monolayers
The first preparation and structural characterization of
monolayer assemblies of oriented organic molecules were
described by Nuzzo and Allara in 80s, [28-32] which
dramatically changed surface science.
SAMs structures are ordered organic films in su-
pramolecular chemistry [33-36], directed through non-
covalent interactions (e.g., hydrogen bonding, metal co-
ordination, hydrophobic forces, van der Waals forces,
π-π interactions, and/or electrostatic effects), formed by
the adsorption (chemisorption) of an active organic coat-
ing on a solid surface.
SAM formation provides one easy route towards sur-
face functionalization by organic molecules on selected
metallic (Au, Cu, Ag, Pd, Pt, Hg and C) as well as semi-
conducting surfaces (Si, GaAs, indium coated tin oxide
etc.).
SAMs have shifted the focus of surface science from
metals and metal oxides to surfaces composed of organic
molecules, and allowed studies of surfaces in contact
with solvents and of biologically relevant surfaces. They
can be regarded as the interface between materials with

Self-Assembled Monolayers (SAMs): Which Perspectives in Implant Dentistry? 534
totally different physical and chemical properties: metals,
semiconductors, or other inorganic materials as organic
and biological materials (polymers, biomolecules, other
simpler organic molecules, etc.).
SAMs formation provides an alternative highly inno-
vative to the current chemical treatments towards sur-
face functionalization by amphiphilic molecules, which
could be of great use for several practical applications
such as chemical sensing (biosensors), adhesion (cell or
protein), control of surface properties like wettability and
friction, corrosion inhibition, patterning, semiconductor
passivation, and organic electronics [37-50].
A SAM is a properly organized layer of amphiphilic
molecules with a “head group” at the end having special
affinity for a substrate; on the other end is present a ter-
minal functional group connected by a “tail” (Figure 1).
The end functional groups (tail groups) could be mo-
dulated, and generally properly chosen to improve hy-
drophilic and hydrophobic properties of the substrate.
SAM formation process involves starting with bulk
solution transport, sample surface preparation, surface
adsorption and continuing with the two-dimensional or-
ganization on the substrate [51].
The chemisorption of hydrophilic “head groups” onto a
substrate is followed by a slow two-dimensional organi-
zation of hydrophobic “tail groups”; adsorbate molecules
form either a disordered mass of molecules or form a
“lying down phase”, where alkyl chains are parallel to the
surface or are stacked into a striped phase, before reach-
ing the standing-up phase (Figure 2 ).
The last phase is characterized by a re-arrangement into
a systematic layer (crystalline or semicrystalline), until the
growing left no area on the surface, forming the totally
covered and packed single monolayer [51]. This later
process can involve passage through one or more inter-
mediate surface phases and can often be described using
two-dimensional nucleation and growth models [52].
The kinetics of SAM formation and stability depend on
Figure 1. Representation of SAM structure.
Figure 2. SAM formation.
both preparation conditions and materials adsorbate and
substrate properties.
The head group plays a critical role for the stability and
packing order [53] and different groups (SH, COOH, OH,
NH2) usually results in a decrease in the order of the
monolayer than CH3 group.
The defect density decreases with increasing hydro-
carbon chain length [54].
The final organization properties are dependent on the
chain length, the adsorbate and the substrate. Steric hin-
drance and metal substrate properties affect the packing
film density while chain length involves SAM thickness
[55,56].
An increasing level of attention has been given to the
defects, caused by both external and intrinsic factors,
within monolayer structures.
External factors include the surface preparation
(roughness and surface defects), cleanliness of the sub-
strate, method of preparation, and purity of the adsorbates.
The absorption of various kinds of unwanted molecules
makes SAM highly unstable.
SAMs intrinsically form defects due to the thermody-
namics of formation as it happens in thiol SAMs on gold
that typically exhibit monoatomic vacancy islands due to
extraction of adatoms from the substrate and formation of
adatom-adsorbate moieties.
Limited thermal [57,58] and oxidative stability are also
responsible for curtailing SAMs large scale use.
Due to their versatility and stability the most widely
studied SAM are alkanethiols on gold and silanes on
silicon.
From a biomedical point of view a wide variety of
biomolecules and biomaterials involving proteins, pep-
tides, DNA, carbohydrates, antibodies, and therapeutics,
have been attached to SAMs for several applications [59-
63]. Therefore SAMs are highly promising for implanting
functional molecules on surfaces or to modify chemical-
physical properties of themselves.
In the present study the perspective of using SAMs in
implant dentistry was evaluated in terms of features, li-
mitations, preparation methodology, characterization and
applications.
2.2. Self-Assembling Monolayers on Ti
Commercial pure titanium (cpTi) and its alloys are
widely used in orthopedic, oral and maxillofacial surgery
as load bearing implants because of their superior me-
chanical properties, good biocompatibility with hard hu-
man tissues, and high resistance to corrosion.
CpTi and its alloys are highly reactive metals that
readily passivate to form a protective oxide layer, tena-
cious and stable approximately 10 nanometers thick [64].
The native covering oxide is basically amorphous in

Self-Assembled Monolayers (SAMs): Which Perspectives in Implant Dentistry?535
crystal structure and morphologically homogeneous [65-
69], but this layer is irregular in thickness and composi-
tion, non-crystalline, and typically contaminated with
various foreign elements taken from the surroundings.
The oxide layer provides a highly biocompatible sur-
face and allows for bonding other materials to the metal
surface or bone tissue appearing suitable for dental im-
plants or prostheses.
Few reports of SAMs on Ti [70,71], stainless steel [37],
tantalum [72], zirconium [73,74] or nitinol [37,75] are
present in literature if compared to those on Au.
On Ti surfaces for fabrication of individual monomo-
lecular modification the attaching group of phosphonic
acids or silanes are used.
However, the use of SAMs is strongly related to the
chemical and physical stability of the thin film, which
depend on several factors as:
1) surface morphology and chemical composition;
2) affinity of head group toward metal oxide;
3) coating methodology.
The focus on Ti surfaces used for medical applications
has shifted from surface roughness to surface chemistry
and a combination of chemical manipulations on the po-
rous structure to mimic biological functions, for the pur-
pose of inducing specific cell and tissue responses.
Surface modification of biomedical implants promotes
improved biocompatibility and enhanced implant inte-
gration with the host.
1) Surface morphology and chemical composition
Surface roughness has been shown to be an influenc-
ing parameter for SAM characteristics, as it will deter-
mine the quality of the SAM in terms of its stability, de-
gree of coverage, and order.
It is necessary to consider the topography at various
scales: macro-roughness and micro- to nano-roughness,
which differ for average surface roughness size of the
order of microns to sub-microns up to nanometers, re-
spectively.
To optimize SAMs deposition (in terms of minimizing
defects) surfaces must undergo a basic pre- treatment to
obtain clean and flat substrates. By using a proper sol-
vent (such as acetone, methanol, ethanol or toluene) con-
taminants are removed from the surface.
To obtain a well-ordered and densely packed SAM,
the surface of the substrate should be relatively smoothed
by using mechanical polishing methods (such as silicon
carbide grinding papers and diamond pastes as abrasive).
The process of polishing with abrasives usually starts
with coarse ones and graduates to fine ones.
Also surface chemical composition plays a fundamen-
tal role in SAMs formation, as phosphonic acids or si-
lanes reactions with Ti surface is limited by hydroxyl
adsorption sites to achieve full coverage.
Gas plasma was extensively used in the literature to
pretreat metal oxides before the deposition of SAMs;
oxygen plasma treatment is a common procedure to in-
troduce hydroxyl groups on a Ti surface [76].
Acid etching is the simplest way to obtain hydroxy-
lated Ti surfaces. Conventional chemical treatment con-
sists in using oxygen peroxide or piranha solution (sulfu-
ric acid and oxygen peroxide) to obtain a sufficient den-
sity of hydroxyl groups at the surface of Ti. If chemical
pretreatments are not carefully controlled it is possible to
have surface morphology modification, resulting the
substrate corrosion and formation of a very porous sur-
face, which is undesirable [70].
2) Affinity of head group toward metal oxide
The formation of a well-assembled monolayer depends
on the purity of the adsorbant being used. The presence
of even low levels of contaminants can result in a disor-
dered, non-ideal monolayer.
Silanes/siloxanes and phosphonic acids/phosphonates
are the most commonly organic reagents used for Ti sur-
faces.
 Silanes/Siloxanes
The organosilane derivatives RmSiXn (where X is a
chloride or alkoxy group and R is an organic group that
can carry different functionalities) are known to react
also in cpTi with hydroxylated surfaces to form mono-
layers.
Alkoxysilanes need specific pH values and relatively
high concentration to form stable and densely packed
monolayers, while trichlorosilanes require lower concen-
trations and shorter reaction times.
When alkyltrichlorosilane is used, Si-Cl bonds react
with the OH groups present on the surface of the sub-
strate to form a siloxane network.
The assembly of alkylsilane monolayers is highly sen-
sitive to solvent, temperature, and trace amounts of wa-
ter.
Common long chain alkyl silanes used in the forma-
tion of SAMs are simple hydrocarbon, fluoroalkyl and
end-group substituted silanes. Silanes with one hydroly-
sable group maintain interphase structure after deposition
by forming a single oxane bond with the substrate. Si-
lanes with three hydrolysable groups form siloxane
(silsesquioxane) polymers after deposition, bonding both
with each other as well as the substrate. The minimiza-
tion of water condensation at the substrate can prevent
the random aggregation and reaction among the silanes
and increase attachment to the substrate. Formation of
well-ordered oxane bonds with surface hydroxyl groups
depends on the density or frequency of materials surface
hydroxyl groups [33].
 Phosphoni c acid/Phosphonate s
Phosphonic acids, are somewhat less often character-

Self-Assembled Monolayers (SAMs): Which Perspectives in Implant Dentistry? 536
ized compared to silanes and thiols, but are the becoming
of great practical interest because of their ability to pro-
duce SAMs on a range of metal oxide surfaces [73,77].
Organophosphonates and organophosphates are struc-
turally similar. An organophosphate has four oxygens
with an alkyl group connected via a phosphoester bond.
Phosphonates have three oxygens with a carbon attached
directly to phosphorus. The lack of a hydrolyzable P-O-C
linkage makes phosphonate compounds more stable in
aqueous solution and easier to make SAMs with than
organophosphate compounds.
The reaction of long-chain alkylphosphonic acids with
metal oxide supports leads to dense, well-ordered SAMs
[78,79].
Phosphonates and phosphonic acids form SAMs on Ti
surfaces by the formation of Ti-O-P bonds.
The deposition technique is based on SAMs made
from aqueous alkyl phosphate solutions, which has the
advantage of not using organic solvents [71,80]. Advan-
tages of these SAMs compared to silane ones are a
higher hydrolytic stability under physiological conditions
and the fact that no surface conditioning (i.e., acid treat-
ment) is required to obtain high coverage.
3) Coating methodology
SAMs methodology is divided in two approaches: gas
phase and solution phase deposition [51].
Growth from the gas phase generally requires an ex-
perimental setup with vacuum chambers for better con-
trol of the cleanliness of the environment, the substrate
and the substances and their respective temperatures as
well as the applicability of essentially all the established
techniques known with molecular resolution, used in
surface science to determine the structure.
In gas phase deposition the substrate is located in a
generic surface which allows for cleaning of the surface
by ion sputtering and annealing and, through one addi-
tional port, the adsorbing molecules are dosed with a
controllable flux [81].
In the traditional preparation of SAMs growth from
solution the properly cleaned substrate has to be dipped
into the corresponding diluted solution for a certain pe-
riod of time and the monolayer will assemble [82].
The two principal methods common employed to coat
phosponic acid SAMs on cpTi are (a) pre-treating Ti us-
ing gas plasma followed by solution phase deposition [71,
83] and (b) annealing-based deposition [77,84].
Aerosol sprayed technique is also used to form phos-
phonic acid SAMs onto cpTi surfaces from solution [77].
The spray process was followed by annealing, which
consists in heating a thin film of phosphoric acid on the
Ti surface, giving a strongly bound, ordered alkylphos-
phonate film. The subsequent heat treatment increases
the covalent character of the bond between the metal
substrate and the phosphate or phosphonate anchor
groups [85-89].
A broad variety of organophosphates have been used
for SAMs formation on cpTi by using a tethering by ag-
gregation and growth (T-BAG)/annealing process [90].
Other strategy is based on the adsorption of the alkyl
phosphate ammonium salts from aqueous solution [71].
3. Preparation Methodology
Considering the stability of phosphonic SAMs on cpTi or
its alloys in the follow only this assembling technique
and details will be discuss.
3.1. Cleaning and Hydroxilating Procedure
Prior to deposition, titania substrates were placed in a
highly clean politetrafluoroethylene container and treated
in an ultrasonic bath with water and a proper organic
solvent (i.e. 2-propanol or ethanol) for 10 minutes. It is
very important to place the samples in a vertical position
to remove microscopically small particles, such as silicon
powder, during the sonication. Such small particles can-
not be removed by simply blowing them away, not even
with a strong gas stream. The samples were removed
from the organic solvent and rinsed with copious
amounts of high-purity water; then blow-dried in a ni-
trogen stream followed by an additional cleaning in a
UV-ozone cleaner for 30 minutes or in an oxygen-plasma
cleaner for 2 minutes, right before the assembly process.
This treatment resulted in completely hydrophilic sur-
faces.
3.2. Spray Deposition
The hydroxylated titanium substrates were sprayed (TLC
sprayer and nitrogen) using a 0.75 mM solution of the
phosphonic acid in dry THF (tetrahydrofuran) at room
temperature and allowed to dry at room temperature. The
solvent was then evaporated under ambient conditions.
3.3. Solution Deposition
Immersion of clean titanium surfaces in tetrahydrofuran
(THF) solution of phosphonic acid was carried out im-
mediately after the cleaning because of the extreme sus-
ceptibility of these titanium films to adventitious hydro-
carbon contamination. Upon removal the samples were
rinsed in pure THF for 30 s and finally blown dry with
filtered nitrogen.
3.4. Solution Deposition from Water Soluble
Salts
Alkyl phosphates with different terminal functionalities
can be deposited from aqueous solution by converting
the free (water-insoluble) alkyl phosphoric acids into the
corresponding water-soluble salts. Usually, a 1 mM solu-

Self-Assembled Monolayers (SAMs): Which Perspectives in Implant Dentistry? 537
tion of ammonium salt of the corresponding phosphate
was used. After 48 h, the Ti specimens coated with
phosphate SAMs were rinsed in copious amount of run-
ning water.
3.5. Annealing Process
A strongly surface-bound film of alkanephosphonate can
be formed on the Ti native oxide surface by heating the
material prepared as described above (but before rinsing)
at 120˚C for 18 h. Immersion of treated Ti samples in dry
THF twice, for 5 min each, removed physisorbed phos-
phonic acid. Samples were then dried (room temperature,
0.1 Torr).
Surface coverage of chemisorbed phosphonates could
be enhanced through repeated sequences of solution
deposition, heating (120˚C, 18 h), and rinsing with THF.
4. SAMs Characterization
A SAM for its feature (chemical and topographic
changes) could be considered a nano composite structure.
Therefore it is necessary characterize, with high per-
forming and specific techniques, the morphological evo-
lution of the surface with respect the chemical pre-
treatment conditions and the SAM growth. During char-
acterization the SAMs layer could be altered or modified
by destructive test methods.
Parameters and properties of the Ti substrate, of the
assembled monolayers [69,70] and the corresponding
destructive (DT) or non-destructive measure techniques
(NDT) are reported in Table 1.
5. Discussion
SAMs formation can provides a potential and economic
method for obtaining designable physicochemical fea-
tures of the titanium surface in order to promote the os-
teointegration. The technique appears particularly inter-
esting due to the fact that the SAM can be considered a
“multi compose” physicochemical thin film able to mod-
ify the critical chemical Ti surface characteristics.
The nano-scale structure layer of about several tens of
nanometers (20 - 30 nm) may have a great influence the
physiological and pathological healing process.
The length of the tails can be ruled by the number of
carbon atoms, while the number of hydrophilic end
groups could be modified controlling the hydroxylation
process.
Moreover the roughness of the SAMs structure de-
pends on the functional group and its package. Some
authors [70] found that octadecyltrichlorosilane produced
a great reduction of the pristine roughness, comparable to
the dimensions of the atoms of the functional terminal
group (few units on nanometer).
Furthermore different interactions between cells
growth and implant Ti surfaces could role by the level of
packing order of the chains.
Chemical nature of the terminal groups could favorite
better interaction within bone cells and implant and bio-
mimetics properties.
In order to obtain stable SAMs both the preparation
conditions and the materials properties are critical.
Therefore the substrate must be perfectly clean and the
Table 1. Characterization of a SAM and its substrate: parameters, properties and technique.
Substrate Assembled monolayers Technique DT NDT
Morphology SEM - x
Contaminants-impurities SEM-EDX - x
Roughness Laser Profilometry - x
Thickness of titanium oxide XPS x -
Hydrophilicity/surface wettability Water contact angle - x
Surface decontamination XPS - x
Hydroxilation XPS x
Formation FTIR x -
Nature DRFTIR x -
Thickness AFM x -
No growing area AFM x -
Wettability Water contact angle - x
SEM: Scanning electron microscopy, EDX: Energy dispersive X-ray analysis, XPS: X-ray photoelectron spectroscopy, DRIFT: Diffuse reflectance infrared
Fourier transform spectroscopy, AFM: Atomic force microscopy.

Self-Assembled Monolayers (SAMs): Which Perspectives in Implant Dentistry? 538
adsorbates pure [91]. The preparation conditions support
the necessity of sterility of the implant.
Stable SAMs are obtained with the correct above re-
ported procedures (cleaning, hydroxilating and deposi-
tion for phosphonic acid).
If chemical pretreatments are not carefully controlled
it is possible to have surface morphology modification,
resulting the substrate corrosion and formation of a very
porous surface, which is undesirable [70].
Direct SAMs formation on Ti is limited by the low
surface hydroxyl (OH) group content of the Ti native
oxide surface; only about 15% of surface O is due to OH.
Enhanced surface hydroxylation may be obtained by
physical or chemical treatments.
The reproducibility of the SAM treatment could be
assessed in the same way of the characterization above
reported.
The stability of SAMs under physiological or steriliza-
tion conditions is crucial for successfully using this tech-
nique to coat medical implants [92].
While sulfur-surface (gold, indium coated tin oxide
and so on) self-assembling is used for fabrication of in-
dividual monomolecular modification on the surface, for
Ti surfaces it is necessary to use phosphonic acids or
silanes as attaching groups.
It is known that the modification of Ti surface with
calcium phosphate (CP) and/or hydroxyapatite (HA)
coatings have attracted most research interest because of
the substantial improvements achieved in terms of os-
teointegration.
SAMs can improve the CP or HA coating on titanium
substrates inducing their mineralization with high crys-
tallinity and relatively strong interfacial bonds with the
substrates [93-99].
A crucial aspect to promote a good crystallization of
HA is the strength and the organization of the SAMs film;
these are strongly affected by the influence of Ti surface
properties, such as chemical composition (hydroxylation
of the surface) and morphology (formation of cervices),
obtained by chemical pre-treatments.
The critical role played by crystalline or semicrystal-
line nature of the SAM in order to improve cell and os-
teoactivity must be investigated.
6. Conclusions
The success in implant dentistry is related with its micro
and nano roughness surface characteristics.
Therefore the SAMs films may be an important inno-
vative and alternative technique to the traditional surface
treatments able to improve the healing process.
Although SAM formation provides a simple strategy
to form ultrathin and thermodynamically stable organic
films (also for non-planar feature surfaces) some limita-
tions could restrict their applications. The problems re-
lated with SAMs stability and the reproducibility of the
monolayer treatment must be solved especially in order
to the bone host tissue and the applicability in the oral
and maxillofacial implant surgical technique.
As future trends more designed and built up technique
of SAMs could condition the different physiological and
pathological process. Therefore more experimental stud-
ies of SAMs growth on cpTi and its alloys as well as in
vitro and in vivo animal studies are request.
7. Acknowledgements
GF is grateful to the Italian National Project PRIN2009
(Prot. 2009N9N8RX “Chemistry in Motion”), for the
financial support.
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