Surface Science 500 (2002) 879–903

www.elsevier.com/locate/susc

Organic functionalization of group IV semiconductor

surfaces: principles, examples, applications, and prospects
Stacey F. Bent *
Department of Chemical Engineering, Stanford University, Stanford, CA 94305-5025, USA
Received 5 July 2000; accepted for publication 22 June 2001

Abstract
Organic functionalization is emerging as an important area in the development of new semiconductor-based materials
and devices. Direct, covalent attachment of organic layers to a semiconductor interface provides for the incorporation of
many new properties, including lubrication, optical response, chemical sensing, or biocompatibility. Methods by which
to incorporate organic functionality to the surfaces of semiconductors have seen immense progress in recent years, and in
this article several of these approaches are reviewed. Examples are included from both dry and wet processing envi-
ronments. The focus of the article is on attachment strategies that demonstrate the molecular nature of the semicon-
ductor surface. In many cases, the surfaces mimic the reactivity of their molecular carbon or organosilane counterparts,
and examples of functionalization reactions are described in which direct analogies to textbook organic and inorganic
chemistry can be applied. This article addresses the expected impact of these functionalization strategies on emerging
technologies in nanotechnology, sensing, and bioengineering. Ó 2001 Elsevier Science B.V. All rights reserved.

Keywords: Single crystal surfaces; Silicon; Germanium; Diamond; Chemisorption; Alkenes; Infrared absorption spectroscopy;
Scanning tunneling microscopy

1. Introduction ubiquitous. Semiconductor-based devices can now

The microelectronics revolution that was started
fifty years ago has grown into an industry that
drives much of the world’s technology today. It
is responsible for a nearly $1 trillion worldwide
electronics market. Microelectronics use semicon-
ductor materials as their basic building block.
These semiconducting solids––such as silicon,
gallium arsenide, and germanium––have become
*
Tel.: +1-650-723-0385; fax: +1-650-723-9780.
E-mail address: stacey.bent@stanford.edu (S.F. Bent).
be found in everything from automobiles and
home appliances, to means of communication and
equipment in our doctor’s office.
The rapidity with which microelectronics tech-
nologies have advanced is unprecedented. For
example, the number of electronic components on
a single silicon chip doubles every 18 months, and
computer memory that used to cost thousands
of dollars can now be fabricated for only pennies.
The widespread availability of microelectronic-
controlled machines depends upon these revolu-
tionary advances. Many of these advances
have resulted from miniaturization of the most

0039-6028/01/$ - see front matter Ó 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 0 3 9 - 6 0 2 8 ( 0 1 ) 0 1 5 5 3 - 9
880 S.F. Bent / Surface Science 500 (2002) 879–903

fundamental building blocks of electronic devices,
in which more and more active units are packed
into smaller and smaller areas on the semicon-
ductor chip. Integrated circuits now contain nearly
one billion transistors on a chip less than a square
inch in size [1,2].
As we enter a new century, the sizes of micro-
electronic devices have gotten so small that the
active elements now approach molecular dimen-
sions. For example, it is predicted by an industry
guideline known as the Technology Roadmap for
semiconductors [3] that by the year 2014, lateral
device dimensions will reach 35 nm (350 A ); ver-
tical dimensions will be even smaller. Because
molecules themselves are on the order of a few
tenths of nanometers in size, it follows that future
technologies increasingly will depend upon the
functionality of individual molecules and atoms.
Surface phenomena have always been a
cornerstone of the microelectronics industry. Pro-
cesses such as epitaxy [4], chemical vapor deposi-
tion, etching, oxidation and passivation [5], which
are used routinely in the industry, involve chemical
or physical processes occurring at the surface of
the semiconductor wafer. However, with the rapid
miniaturization of devices, understanding of the
atomic-level phenomena underlying these pro-
cesses becomes even more critical. The sizes that
microelectronics are projected to reach in the near
future means that a given material in a device
might be just a few layers thick. As a result, much
of the functionality of a device will be due to
physical processes that occur within a few molec-
ular layers of some interface, such as a buried in-
terface, e.g. between Si/SiO2 or Si/metal, or an
outer surface exposed to ambient. For this reason,
research on the interfacial chemistry at semicon-
ductor surfaces has seen a tremendous amount of
growth over the past decade, and promises to be
an increasingly important field in the future.
The importance of atomic level surface chemis-
try is highlighted in the growing field of organic
functionalization of semiconductors. An area that
has been researched extensively over the past few
years, surface functionalization or organic modi-
fication is the process of depositing layers of or-
ganic molecules (i.e. those that contain carbon) at
semiconductor surfaces. Fig. 1 illustrates a semi-

Fig. 1. Illustration of organic molecules attached to a silicon substrate in the initial stages of film deposition. Layered organic/
semiconductor materials are being explored for possible application in sensor development, molecular electronics, and biocompatible
implants.
 S.F. Bent / Surface Science 500 (2002) 879–903
conductor surface upon which organic molecules
have been attached. The motivation to deposit
organic layers on a semiconductor stems from a
desire to impart some property of the organic
material to the semiconductor device. Over the
same time period during which semiconductor
(typically Si, Ge, GaAs) based devices were un-
dergoing rapid size scaling, revolutionary advances
also were made in the development of new solid
state organic materials. Organic molecules com-
prise more than 95% of all known chemical com-
pounds. Carbon can form a myriad of molecules
differing in shape, size and composition [6]. For
example, the organic molecules attached to the
surface in Fig. 1 will exhibit certain properties
based on the types and specific groupings of atoms
in the molecules. As a result, organic materials
offer engineers great flexibility in designing and
creating unique molecular properties, that can
then be exploited to provide new capabilities in
optical, electronic, and mechanical function as well
as in chemical and biological activity.
An especially promising approach is to combine
organic materials with conventional semicon-
ductor materials [7]. Microelectronics technology
provides an opportunity to create hybrid devices
exploiting the best properties and features of both
organic and inorganic materials. As an example,
consider a chemical or biological sensor built with
a mixed organic/semiconductor design. Organic
molecules such as those shown in Fig. 1 can be
deposited on a silicon substrate. The organic layer
may be terminated with a variety of end groups
that respond to different chemical or biological
stimuli. A ‘‘sensing’’ response occurs if a species of
interest binds to the end group, causing trans-
duction of signal within the organic layer. If this
signal can be coupled into the silicon substrate,
then all of the capabilities of silicon-based micro-
electronic circuitry––such as signal amplification,
processing and storage––become available. The
end product is a chip-based chemical or biological
sensor.
Hybrid organic/semiconductor materials also
are being explored for use in molecular electronics
and computing and for imparting biocompatibility
to semiconductor devices for implantation. Or-
ganic materials are also finding use in more con-
881
ventional microelectronics processing, such as for
new-generation dielectric materials for metal in-
terconnect isolation, or for surface passivation and
protection.
Fortunately, the surfaces of most semiconduc-
tors of interest for microelectronics have charac-
teristics that enable organic molecules to be
attached by a number of different chemical reac-
tions. These attachment chemistries provide an
insightful view of the reactivity of semiconductor
surfaces. They also demonstrate how the wealth of
chemical understanding that has been developed
over the past century within the field of organic
chemistry can now be used to manipulate semi-
conductor surfaces to impart properties useful for
a variety of applications. The focus of this article is
on several different approaches that have been
taken to functionalize semiconductor surfaces with
organic molecules. The list of attachment reactions
covered in this article is not intended to be com-
prehensive, but rather a selected group of systems
has been chosen for the level of insight they pro-
vide into the molecular nature of semiconductor
surfaces. The article will use these examples to il-
lustrate some general principles describing the
chemistry at semiconductor surfaces. For more
complete technical reviews on the subject of at-
tachment reactions at semiconductor surfaces, the
reader is referred to Refs. [8–11].
2. The silicon surface
We will begin with an investigation into the
structure of the silicon surface. Silicon is the pre-
dominant semiconductor material used in the
microelectronics industry, due in part to several
important properties. Silicon can be produced
in single crystalline form at better than
99.999999999% purity, it forms an excellent oxide
at its surface, and its electronic properties can be
tuned dramatically by substituting only a small
fraction of silicon atoms in the lattice with another
element in a process called ‘‘doping’’. Silicon is a
covalent solid that crystallizes into a diamond
cubic lattice structure, illustrated in Fig. 2. In a
covalent solid, bonding is produced by overlap of
the highly directional electronic orbitals of the
882 S.F. Bent / Surface Science 500 (2002) 879–903

dices, which designate the particular orientation at

which the bulk is terminated. The top surface in
Fig. 2, e.g., has the (1 0 0) orientation. Both the
(1 0 0) and (1 1 1) surfaces undergo extensive re-
constructions, i.e. their surface atomic geometry
differs significantly from that of the bulk. More-
over, the two surfaces have markedly different
surface structures [14,15]. The Si(1 0 0) surface re-
constructs into a ð2  1Þ structure, where ð2  1Þ
designates the new periodicity of the surface atoms.
The Si(1 0 0)-2  1 surface, illustrated in Fig. 3(a),
consists of pairs of silicon atoms in adjacent rows
that have bonded to each other, thereby reducing
Fig. 2. The diamond cubic lattice is the crystal structure found
the number of dangling bonds. These pairs of sili-
for diamond, silicon and germanium. Each atom is bonded to con atoms are called dimers. Si(1 1 1), on the other
four neighboring atoms in a tetrahedral geometry. hand, reconstructs into a complex (7  7) structure
that contains 49 surface atoms in the new unit cell.
It is useful to consider in more detail the
atoms. Like carbon, its group IV homolog, silicon bonding of the dimers on the Si(1 0 0)-2  1 sur-
atoms hybridize into a tetrahedral bonding con- face, because they play such an important role in
figuration. In the bulk solid, the diamond cubic
lattice allows silicon atoms to achieve this tetra-
hedral configuration. At the surface of the mate-
rial, however, the bulk is truncated, so the stable
bulk tetrahedral bonding is disturbed.
The reactivity of the silicon surface is controlled
in part by the unsatisfied bonding orbitals, or so-
called dangling bonds, that remain upon truncat-
ing the bulk. A surface silicon atom that is bonded
to only two other silicon atoms instead of four, as
shown at the top surface of the crystal illustrated
in Fig. 2 for example, would have two dangling
bonds. Dangling bonds contain single electrons,
whereas normal covalent bonds contain two spin-
paired electrons. At the surface, atoms can read-
just to minimize the total free energy of the system
and eliminate the dangling bonds. This process is
referred to as surface ‘‘reconstruction’’. The energy
minimization is a trade-off between energy gained
by forming new local bonds (to eliminate the
dangling bonds) with energy lost because of bond Fig. 3. Two surfaces of silicon that are important in organic
strain that results from its new configuration. This functionalization chemistry. (a) The clean Si(1 0 0)-2  1 sur-
energy trade-off often leads to complex surface face, with rows of silicon dimers lining the surface. These di-
reconstructions [12–15]. mers play an important role in the chemistry of organic
molecules at this surface. (b) The hydride-terminated Si(1 1 1)
The crystallographic faces of silicon that are
surface. The golden spheres represent silicon atoms; hydrogen
most important industrially are the Si(1 0 0) and the atoms are shown in white. The hydrogen–silicon bonds are the
Si(1 1 1) surfaces. The numbers in parentheses refer important molecular group in hydrosilylation attachment
to a crystallographic notation known as Miller in- chemistry, discussed in the text.
 S.F. Bent / Surface Science 500 (2002) 879–903
Fig. 4. Illustration of a r bond and a p bond in a double-
bonded molecule. The r bond (green) is cylindrically symmetric
around the molecular axis, while the two lobes of the p bond
(red and blue) are separated by a nodal plane. The molecule
shown is ethylene.
the reactivity of this surface toward organic mole-
cules. The Si(1 0 0)-2  1 dimers are attached by
something akin to a double bond [16]. In the lan-
guage of chemical bonding, a double bond consists
of two types of bonds: a r bond (one that has
symmetry around the axis connecting the two
atoms) and a p bond (one with a nodal plane along
the axis) [17]. Fig. 4 provides an illustration of a r
and a p bond in a molecule; note that the p bond
has two lobes.
However, in contrast to the p bond in the mol-
ecule shown in Fig. 4 (ethylene), the p bond be-
tween the silicon atoms is sufficiently weak that the
dimer is not held in a symmetric configuration.
Instead, the energy of the Si(1 0 0)-2  1 surface
can be reduced even further if the dimer moves
from a symmetric configuration to one in which
the dimer is tilted. Hence, at low temperatures, the
dimers of the Si(1 0 0)-2  1 surface are observed
to be tilted [14]. At higher temperatures, thermal
energy induces a rapid change in the direction of
the tilt which causes the dimers to appear sym-
metric, as represented in Fig. 3(a). The presence of
the p bond in the silicon dimer and the dimer
tilting will both be important in understanding the
reactivity of the surface.
Even after reconstruction, both the Si(1 0 0)-
2  1 and Si(1 1 1)-7  7 surfaces are highly reac-
tive. Both surfaces are typically cleaned and
prepared in an ultrahigh vacuum environment
(p ¼ 1010 Torr) by bombarding the surface with
argon ions to sputter away surface layers and/or
883
heating to temperatures near 900 °C. The resulting
surfaces are not stable in air, instead quickly oxi-
dizing to form an SiO2 layer. Hence, experiments
on the clean Si(1 0 0)-2  1 and Si(1 1 1)-7  7 sur-
faces must be performed in vacuum, and the
organic reactants for functionalization are intro-
duced in vapor form into the vacuum chamber.
On the other hand, silicon surfaces can be
rendered relatively stable in air (i.e. relatively re-
sistant to oxidation) by coating the surface with
hydrogen. A number of recipes have been devel-
oped to terminate the silicon surface with Si–H
(silicon hydride) groups. An excellent overview of
this process is given by Weldon et al. [5]. The
most common methods involve exposure to di-
lute, aqueous hydrofluoric acid solutions, and
these wet etch procedures are used both at
bench-top research laboratories and large-scale
microfabrication facilities alike. Not only does
terminating a silicon surface with hydrogen atoms
render it passivated toward many reactions, but it
also changes the surface structure. Because the
reconstructed surface contains some weak Si–Si
bonds, replacement of these with strong Si–H
bonds can relax the surface reconstructions. One
important surface for organic functionalization
reactions is that of hydride-terminated Si(1 1 1).
Due to the strong bonding and passivating nature
of hydrogen at the interface, Si(1 1 1) that is hy-
dride terminated does not reconstruct, revealing
instead a nearly bulk-like periodicity of the sur-
face silicon atoms [18]. The structure of the
hydride-terminated Si(1 1 1) surface is shown in
Fig. 3(b).
Both the bare and hydrogen-terminated silicon
surfaces have been used as substrates for organic
functionalization. Because of their different rela-
tive reactivities, most of the reactivity studies of
bare silicon are performed under ultrahigh vacuum
conditions while reactions with hydride-termi-
nated silicon involve wet chemical methods. De-
spite the different approaches and surface
structures, however, a unifying feature in all of
these attachment chemistries is the molecular
nature of the chemistry, which in turn allows
some common principles to be formulated for
functionalization chemistry at semiconductor sur-
faces.
884 S.F. Bent / Surface Science 500 (2002) 879–903

3. Principles of cycloaddition chemistry at semicon- p bonded molecules come together to form a new
ductor surfaces cyclic molecule, losing two p bonds and making
two new r bonds in the process. The reactions are
The covalent nature of the semiconductor sur- designated by how many p electrons of each re-
face permits its reactivity to be described within a actant molecule are involved in the reaction. Two
molecular framework. This covalency leads to a types of cycloaddition reactions are shown in Fig.
reactivity that is often quite distinct from that of 5. In the first, known as a ½2 þ 2 reaction (i.e. two
metals. On metals, bonding may not be strongly p electrons in the ethylene molecule þ two p
site specific. This characteristic is markedly differ- electrons in the other ethylene molecule), two
ent from that of a surface such as silicon, where alkenes come together to form a new four-mem-
bonding is both localized and directional. To a bered ring. The second type of cycloaddition in
significant degree, the reactivity of semiconductor Fig. 5 is the ½4 þ 2 reaction, also known as the
surfaces can be understood by drawing analogies Diels–Alder reaction [19]. This important reaction
to known molecular systems, and in particular to is named after Otto Diels and Kurt Alder, who
systems in organic chemistry. In this section, this received the Nobel Prize in Chemistry in 1950
molecular analogy is developed to understand for their studies of this reaction. Here, a ‘‘diene’’
and predict one class of organic reactions that molecule with two neighboring (conjugated) p
can be applied to surface functionalization of the
Si(1 0 0)-2  1 surface. These are known as cyclo-
addition reactions. In Section 4, examples of cy-
cloaddition chemistry will be described. Then in
Section 5, some of the same principles developed
for surface cycloaddition reactions will be ex-
tended to other classes of organic reactions used to
functionalize silicon.
The Si(1 0 0)-2  1 reconstructed surface, shown
in Fig. 3(a), to some extent mimics an organic
reagent. As described above, the dimers of the
Si(1 0 0)-2  1 surface are attached by two bonds: a
r bond and a p bond (Fig. 4) [16]. The p bond
across the dimer is quite weak, but nevertheless its
presence provides a nice way of describing the di-
mer [17]. Because of these two bonds, it is useful to
draw analogies between the Si dimer and a car-
bon–carbon double bond, since C and Si are both
in the same group (group IV) of the periodic table.
Carbon–carbon double bonds, known as alkenes,
are a very well studied functional group in organic
chemistry. The simplest alkene molecule, ethylene,
is the molecule displayed in Fig. 4.
A number of reactions are known which can
form bonds with an alkene group. One syntheti-
cally useful class of these reactions are ‘‘cycload-
dition’’ reactions. Cycloadditions are widely used Fig. 5. Cycloaddition reactions are an important class of re-
in organic synthesis as a means of forming new actions for forming new ring compounds in organic chemistry.
The ½2 þ 2 cycloaddition between two alkenes forms a four-
carbon–carbon bonds and new carbon rings be- membered ring, while the ½4 þ 2 cycloaddition between an
cause of their versatility and high stereoselectivity alkene and a diene forms a six-membered ring. The designations
[19–21]. Cycloadditions are reactions in which two refer to the number of p electrons involved in the reaction.
 S.F. Bent / Surface Science 500 (2002) 879–903 885

bonds such as butadiene reacts with an alkene

(ethylene) to form a new six-membered ring. In
Fig. 5, the p bond and the r bond are each rep-
resented by a line, so that the double bond of
ethylene is shown with two lines while the product
cyclobutane, which contains only r bonds, is
shown with single lines.
The cycloaddition reactions in Fig. 5 are subject
to what are know as the Woodward–Hoffman se-
lection rules. These selection rules stem from an
analysis based on frontier orbital theory which
examines the symmetries of the highest occupied
and lowest unoccupied molecular orbitals (HOMO
and LUMO, respectively) of the reactants as they
come together to form the reaction product.
Frontier orbital theory was formulated by Wood-
ward and Hoffman [22]. Professor Hoffman was
awarded the Nobel Prize in Chemistry in 1981,
Fig. 6. Examination of two cycloaddition reactions by frontier
together with Professor Fukui of Kyoto Univer-
orbital analysis. The frontier orbitals under consideration are
sity, for his contributions in this area. The resulting the highest occupied molecular orbital (HOMO) and the lowest
Woodward–Hoffman selection rules are widely unoccupied molecular orbital (LUMO). The blue and red lobes
used for predicting how readily an organic reaction represent the mathematical sign of the molecular orbital, such
will occur. Such an analysis is illustrated in Fig. 6 that blue combines with blue and red combines with red.
Mixing the orbitals leads to a symmetry forbidden reaction, as
for ½4 þ 2 and ½2 þ 2 cycloaddition reactions. In
in the case of the ½2 þ 2 reaction.
cycloaddition reactions, the frontier p orbitals
(characterized by positive and negative lobes, surface. We can therefore formulate the following
shown in different colors in Fig. 6) must overlap ‘‘in guiding principle. To the extent that the simple
phase’’ for the reaction to be symmetry allowed. picture of surface Si@Si double bonds is valid,
Because of the particular properties of these p similar symmetry selection rules as developed for
orbitals in the ½2 þ 2 reaction, ½2 þ 2 cycloaddi- organic reactions should apply to the surface. On
tions are found to be ‘‘symmetry forbidden’’. That the other hand, as the analogy of the dimer as a
is, the Woodward–Hoffman symmetry rules dic- true double bond becomes less accurate, deviations
tate that this reaction should not occur without from the symmetry selection rules will be expected.
significant energy activation. In fact, in organic Indeed, this prediction has been borne out in a
chemistry this reaction is largely limited to number of recent studies of cycloaddition reac-
synthesis involving photochemical activation. tions on Si(1 0 0)-2  1 [23–51], as well as on the
The ½4 þ 2 reaction, in contrast, has frontier or- related surfaces of Ge(1 0 0)-2  1 [52–55] and
bital properties (shown in Fig. 6) that make it C(1 0 0)-2  1 [56–58]. These studies are described
‘‘allowed’’ by symmetry considerations. Indeed, in Section 4.
Diels–Alder reactions are commonly used in or-
ganic synthesis as a means of forming new C–C
bonds and ring structures. 4. Examples
If the analogy that we have drawn between the
Si@Si dimer on the Si(1 0 0)-2  1 surface and an 4.1. Examples of [2 þ 2] cycloaddition reactions on
alkene group is reasonable, then certain parallels silicon
might be expected to exist between cycloaddition
reactions in organic chemistry and reactions that The first examples of what can be categorized
occur between alkenes or dienes and the silicon as ½2 þ 2 type cycloaddition reactions occurring
886 S.F. Bent / Surface Science 500 (2002) 879–903
between an alkene and a silicon surface were re-
ported the late 1980’s. Alkenes such as ethylene, as
well as the related alkyne (triply bonded) molecule
acetylene, were reacted with the clean Si(1 0 0)-
2  1 surface in vacuum [31,46–51,59–69]. The
alkenes were found to chemisorb at room tem-
perature, forming stable species like that shown in
Fig. 7(c) that ‘‘bridge-bonded’’ across the silicon
dimers on the surface. The reaction proceeded by
formation of two new r bonds between Si and C
atoms, hence the bonding was referred to as ‘‘di-
sigma’’ bonding. In addition, it was shown that
while the p bonds of the alkene and of the Si–Si
dimer are broken, the r bonds remain intact
[65,66,68]. With this kind of reaction product
formed, one can draw a direct analogy with the
surface adsorption of the alkene (Fig. 7) and the
½2 þ 2 cycloaddition reaction shown in Fig. 5(a).
Fig. 7. A ½2 þ 2 reaction at the silicon surface occurs between an alkene molecule and the silicon dimer. The product is bridge-bonded
across the dimer.
Just as two ethylene molecules (CH2 @CH2 ) react
to form a four-membered cyclobutane ring, eth-
ylene reacts with the silicon dimer (Si@Si) on the
Si(1 0 0)-2  1 surface to form a four-membered
Si2 (CH2 Þ2 ring with the surface.
Interestingly, the surface ½2 þ 2 cycloaddition is
a relatively fast reaction, occurring readily with
most alkenes at room temperature [9]. This high
reactivity would not be expected for a true, sym-
metric 2 þ 2 reaction, which formally is symmetry
forbidden and is slow for the analogous homoge-
neous reaction [21,22]. The symmetry analysis
shown in Fig. 6, however, applies to a system in
which the Si dimer is symmetric and closely mimics
an alkene. This is the pathway illustrated in Fig.
7(a). However, the Si dimer is not symmetric in its
lowest energy configuration. The lowest energy
state of the Si(1 0 0)-2  1 surface is actually one in
 S.F. Bent / Surface Science 500 (2002) 879–903
which the silicon dimers are tilted. It has been
proposed that this low symmetry (tilted) geometry
allows the reaction to proceed through an asym-
metric pathway in which the alkene approaches
the dimer from one side, as shown in Fig. 7(b)
[10,31,64,69]. This asymmetric approach is of a
8 atoms wide. The orientation of the
lower symmetry and can occur with little or no
energetic barrier. This example serves as an inter-
esting case of a solid state effect in the silicon
(tilting of the dimers) controlling a surface reac-
tion (via relaxation of the symmetry constraints).
The result of the ½2 þ 2-like reaction is a tightly
bonded organic group, directly attached to the
silicon surface through strong Si–C bonds ( 82
kcal/mol each [25]), as illustrated in Fig. 7(c).
Furthermore, as reported above, the reaction
occurs readily for many alkenes. Consequently,
½2 þ 2 cycloaddition has attracted much attention
as a means to functionalize the Si(1 0 0)-2  1 sur-
face. Many beautiful examples have been reported
of silicon surfaces functionalized by means of ½2 þ
2 chemistry using alkene or dialkene precursors.
One example is the work by Hamers and co-
workers. In 1997, this group began a series of
studies showing that this type of attachment chem-
istry can be used to form well-ordered monolayer
organic films across the surface of silicon [31–36].
By adsorbing cyclopentene (the molecule shown in
Fig. 8) at room temperature in vacuum, layers that
are ordered in registry with the underlying silicon
surface lattice could be generated [32,35].
Fig. 8. The cyclopentene molecule.
887
The experiments by Hamers and coworkers
were performed on a Si surface that was inten-
tionally cut slightly (4°) off-axis from the (1 0 0)
crystal face. This miscut has the effect of producing
a stepped surface, where between each step resides
a terrace
dimer rows on the terraces is indicated schemati-
cally in Fig. 9(a). Fig. 9(b) shows a scanning
tunneling microscope (STM) image of the clean 4°
miscut Si(1 0 0) surface [35]. In the picture, each
oblong white feature is an image of a Si–Si dimer.
It is readily seen that on the flat terrace regions, the
Si@Si dimers all maintain the same orientation
with respect to the step. If cyclopentene molecules
are now adsorbed on this surface, and if they bond
across the dimer, as expected for a ½2 þ 2 cyclo-
addition, we would expect to see rows of bound
cyclopentene that follow the underlying silicon
rows. In fact, the STM images obtained after cy-
clopentene exposure clearly show ordered molec-
ular adsorption of cyclopentene at this surface. In
Fig. 9(c), the white features (larger than those in
Fig. 9(b)) are images of individual adsorbed cy-
clopentene molecules. These images offer beautiful
evidence for the degree of molecular order that can
be achieved in this reactive system. Long range
order on a length scale of millimeters was con-
firmed by measuring the retention of orientational
anisotropy across the length of the silicon sample
using polarized vibrational spectroscopy [32].
These studies provide support for the use of cy-
cloaddition chemistry at the Si(1 0 0)-2  1 surface
as a method to prepare ordered monolayer organic
films.
The success in forming ordered overlayers is
especially significant in light of the following
characteristics of this system. As with ethylene,
cyclopentene was found to react at the Si(1 0 0)-
2  1 surface with near unity reactivity, i.e., each
gas molecule that collides with the surface has an
almost perfect chance of sticking and bonding at
the surface. Furthermore, diffusion is expected to
be very slow in these systems at room temperature,
suggesting that once the molecules have bonded to
the surface, they remain at or near the same site on
the surface [9]. The formation of ordered over-
layers in the absence of significant surface mobility
is in contrast to the behavior of other growth
888 S.F. Bent / Surface Science 500 (2002) 879–903
Fig. 9. (a) Schematic illustration of the oriented rows of silicon
dimers present on a clean Si(1 0 0) surface that has been inten-
tionally miscut by 4°. (b) STM images of this surface, and (c)
the same surface after adsorption of cyclopentene. Figure re-
printed from Ref. [35] with permission from Elsevier Science.
systems. In most common methods of semicon-
ductor film growth, such as molecular beam epit-
axy (MBE) or chemical vapor deposition (CVD),
diffusion of the depositing species at the surface is
a requisite for the formation of good overlayers
[1]. Motion of atoms or molecules to find the op-
timal binding sites is necessary for conformal film
coverage. This is usually achieved by holding the
substrate at an elevated temperature. These cy-
clopentene films, therefore, do not grow like or-
dinary metal or semiconductor crystals. Rather,
the strong and directional bonding at the interface
is sufficient to direct the molecules into the neces-
sary sites, so that the semiconductor surface acts as
a template for the placement of the organic mol-
ecules. The effect is one in which the structure of
the underlying surface is propagated into ordered
overlayers of organic molecules.
Ordered overlayers are not achieved in all
systems, however, and it appears that a certain
rigidity and molecular size is necessary to form
well-ordered films, as evident in the following ex-
ample. Although Hamers et al. have shown that
other alkenes and dialkenes (such as 1,5-cyclo-
octadiene, displayed in Fig. 10) could be used to
produce ordered monolayer films through the
same ½2 þ 2 attachment [33], a number of other
alkenes investigated did not adsorb with a high
degree of order. For example, cyclohexadiene and
cyclooctatetraene, both illustrated in Fig. 10, while
reacting readily with the Si(1 0 0)-2  1 surface, did
not form ordered films on Si(1 0 0)-2  1 [34,36].
This reduced packing may stem from either disor-
der in the configurations of individual adsorbates
or from too low a final (saturation) coverage of
molecules at the surface. Rigidity of the organic
molecule, generally provided by a ring structure,
was found to help in the formation of ordered lay-
ers. In addition, having a single type of functional
group or a single means of bonding to the surface
was advantageous, because molecules that bind in
several different configurations do not maintain the
degree of order necessary for close packing [34].
In addition to forming densely packed organic
layers, the ½2 þ 2 cycloaddition reaction can be
used to generate a chiral surface, according to a
recent study by Lopinski et al. [39]. Chirality refers
to the handedness of a molecule, and chirality
plays an enormously important role in the chem-
istry of natural products. A chiral molecule is one
that cannot be superimposed on its mirror image
similar to a human hand or a conch shell. For
example, in Fig. 11, there is no way to take the
image of either the molecule or the hand on the left
side of the picture and superimpose it with the
 S.F. Bent / Surface Science 500 (2002) 879–903
Fig. 10. The 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,5-cyclooctadiene, and cyclooctatetraene molecules.
corresponding image on the right (the mirror im-
age). Both objects are chiral. Chiral molecules that
share the same stoichiometry and bonding se-
quence but are non-superimposable are known as
enantiomers. An example is the molecule pictured
in Fig. 11. Nature makes broad use of enan-
tiomeric species, and most biochemical processes
select for one enantiomer over another. For
example, biological enzymes distinguish between
enantiomers.
Lopinski et al. have demonstrated the formation
of a synthetic chiral surface by adsorbing the
molecule 1SðþÞ-3-carene on the Si(1 0 0)-2  1
surface [39]. Carene, illustrated in Fig. 12(a), is a
chiral, two-ringed molecule containing a C@C
double bond and a three-carbon-atom ring (cy-
clopropane). Carene initially adsorbs by ½2 þ 2
cycloaddition between the alkene group and the
silicon dimer. The final adsorbed state is believed
889
to bridge across two dimers by reacting also at the
cyclopropane group. Calculated structures for ca-
rene molecule adsorbed at a Si(1 0 0)-2  1 surface
are indicated in Fig. 12. The structure in Fig. 12(b)
is of the ½2 þ 2 cycloaddition product; that in Fig.
12(c) is of carene bridging across two dimers.
The carene molecule was chosen in the study
because it contains a bulky dimethyl group that
geometrically hinders adsorption at one face of the
molecule. This so-called steric hindrance forces the
½2 þ 2 reaction to take place with only one facial
orientation of the molecule. Lopinski et al. verified
that the reaction was enantiospecific, i.e. produced
only one of the possible chiral products, using
scanning tunneling microscopy. The STM image
allows the determination of absolute chirality of
adsorbed molecules, as shown in earlier work from
the same group [38]. The resulting carene adsor-
bate contains chiral centers and produces a chiral
890 S.F. Bent / Surface Science 500 (2002) 879–903
Fig. 11. A chiral molecule or object (such as the human hand)
is one that cannot be superimposed on its mirror image.
surface [39]. This result is significant because of its
implications for sensor development using organ-
ically modified surfaces. In molecular recognition,
distinguishing between enantiomers of molecules
requires a chiral probe. Hence, if organic layers on
silicon are to be used to achieve molecular recog-
nition, particularly in biological systems, chiral
surfaces such as this one must be utilized.
Fig. 12. Structures of (a) the 1SðþÞ-3-carene molecule; (b) carene molecule bonded by ½2 þ 2 cycloaddition across the silicon dimer; (c)
carene molecule bonded in a bridging configuration across two silicon dimers. Both adsorbed structures are chiral. Figure adapted with
permission from Ref. [39]. Copyright 1999 American Chemical Society.
4.2. Examples of Diels–Alder reactions on silicon
In 1997, a series of papers was published in
which the ½4 þ 2 (Diels–Alder) cycloaddition re-
action product (Fig. 5(b)) was first predicted and
observed to occur on the Si(1 0 0)-2  1 surface.
Konecny and Doren performed a theoretical study
in which they predicted that Diels–Alder reactions
should occur across silicon dimers on a Si(1 0 0)-
2  1 surface, just as they do across C@C double
bonds in a molecule [23,24]. Their prediction
was based on ab initio calculations of the reaction
of a model conjugated diene (1,3-cyclohexadiene,
shown in Fig. 10) with a silicon surface.
In the calculations, the silicon surface was
modeled by a silicon cluster containing nine silicon
atoms and featuring the silicon dimer, as shown
in Fig. 13. This silicon cluster and related larger
clusters have been shown to provide adequate
models of the silicon surface while remaining
computationally tractable. Doren et al. followed
the reaction of cyclohexadiene with the silicon
cluster, and examined two possible reaction path-
ways: a ½4 þ 2 reaction or a ½2 þ 2 reaction
[23,24]. Fig. 13 illustrates the two possible reaction
products for a related molecule, 1,3-butadiene (see
Fig. 5). The calculations showed that there is a
substantial thermodynamic driving force (54 kcal/
mol) to form the product of a ½4 þ 2 reaction
between cyclohexadiene and the silicon dimer.
This is significantly more energy than is gained in
 S.F. Bent / Surface Science 500 (2002) 879–903 891

Fig. 13. In ab initio theoretical studies of silicon surface reactivity, the Si(1 0 0)-2  1 surface is modeled using a nine silicon atom
cluster. Two possible outcomes for the reaction of the Si cluster with 1,3-butadiene are shown: the product of the Diels–Alder reaction
and the product of the ½2 þ 2 reaction.

the competing ½2 þ 2 reaction (39 kcal/mol). In

addition, the calculations predicted that the reac-
tion should occur with little or no energetic barrier
across a symmetric silicon dimer, consistent with
the Woodward–Hoffman rules for a ½4 þ 2 reac-
tion [23,24].
Studies by Teplyakov et al. provided the ex-
perimental evidence for the formation of the
Diels–Alder reaction product at the Si(1 0 0)-2  1
surface [26,27]. A combination of surface-sensitive
techniques was applied to make the assignment,
including surface vibrational spectroscopy, ther-
mal desorption studies, and synchrotron-based
X-ray absorption spectroscopy. Vibrational spec-
troscopy in particular provides a molecular ‘‘fin-
gerprint’’ and is useful in identifying bonding and
structure in the adsorbed molecules. Fig. 14 pro-
vides an example of a vibrational spectrum used to Fig. 14. Measured vibrational spectra giving information on
assign the bonding of the butadiene molecule at a the bonding of butadiene at the Si(1 0 0)-2  1 surface. The
peaks shown in the spectrum correspond to absorption of light
surface. The peaks shown in the spectrum corre- at the energies of vibration over the spectral region for carbon–
spond to absorption of light at the energies of vi- hydrogen bond stretches. The units of energy are in wave-
bration (in a unit of reciprocal centimeters, or number, or cm1 .
cm1 , called wavenumber) for carbon–hydrogen
bonds in the molecules. Because there are multiple
C–H bonds present in the molecule, the spectrum can be assigned. An analysis of the vibrational
contains multiple peaks. By comparing the spec- spectra of adsorbed butadiene on Si(1 0 0)-2  1 in
trum for the butadiene molecule (Fig. 14(a)) with which several isotopic forms of butadiene (i.e.,
the spectrum for reacted butadiene (Fig. 14(b)), some of the H atoms were substituted with D
the bonding configuration of the reacted molecule atoms) were compared showed that the majority of
892 S.F. Bent / Surface Science 500 (2002) 879–903
butadiene molecules formed the Diels–Alder re-
action product at the surface. Very good agree-
ment was also found between the experimental
vibrational spectra obtained by Teplyakov et al.
[26,27] and frequencies calculated for the Diels–
Alder surface adduct by Konecny and Doren
[23,24]. Later studies by Hovis et al. using scan-
ning tunneling microscopy confirmed the Diels–
Alder product in this system and quantified the
formation of a small ½2 þ 2 side product [34].
Both the ½2 þ 2 and ½4 þ 2 products of reaction
between a diene and the Si(1 0 0)-2  1 surface
have a number of features that are desirable for
surface functionalization. As shown in Fig. 13,
both reactions produce organic molecules that are
strongly bound to the silicon surface through two
covalent Si–C bonds. The high strength of these
bonds means that the organic layer at the surface
is typically stable to temperatures in excess of one
to two hundred degrees celsius [30]. In addition,
both of the cycloaddition reaction products be-
tween the diene and the surface retain one double
bond in the organic layer. This remaining double
bond (alkene group) can be used as a starting
point for further derivatization of the surface. For
example, the alkene group in the first layer can act
as the attachment point for the second layer, a new
functional group in the second layer as the at-
tachment point for the third layer, and so on. In
this way, there is the potential to perform con-
trolled, layer-by-layer synthesis of organic films
on the Si(1 0 0)-2  1 surface.
4.3. Down the periodic table: solid state effects on
cycloaddition chemistry
It is intriguing that the analogs of key reactions
in organic chemistry––such as the Diels–Alder and
½2 þ 2 cycloadditions––occur across the silicon
dimer on the Si(1 0 0)-2  1 surface. These results
lend support to the analogy that was drawn be-
tween a dimer on Si(1 0 0)-2  1 and the C@C
double bond. The success of this analogy, in turn,
advances the concept of describing the reactivity of
a covalent surface within a molecular framework.
It has therefore been a challenge to both experi-
mentalists and theoreticians to test the limits of
this molecular framework by probing the gener-
ality of the surface cycloaddition reaction. In other
words, one can ask whether cycloaddition reac-
tions also occur on the surfaces of related covalent
materials. The closest homologs to silicon for
comparison are carbon and germanium, also in
group IV of the periodic table.
Both carbon (in its diamond form) and germa-
nium are of technological interest. Silicon germa-
nium alloys, for example, are used for high
frequency devices in applications such as wireless
communications [70,71]. Diamond has received
much attention for its unique combination of
material properties, such as high thermal conduc-
tivity, wide optical transparency, hardness and
chemical inertness [72].
Like Si(1 0 0), the (1 0 0) crystallographic face of
both Ge [73] and diamond [74] undergo a ð2  1Þ
reconstruction to form rows of surface dimers.
These dimers each are believed to have some de-
gree of double-bond character, with a strong r
bond and a partial p bond [73,74]. However, the
surfaces differ in the strength of the p bond and
the degree of tilt that is observed in the dimers.
The dimers on both the Si and Ge surfaces tilt due
to the weakness of the p bond. In the case of
Si(1 0 0)-2  1, the dimers are observed in their
tilted form only at low temperature, as discussed
previously, whereas on Ge(1 0 0)-2  1, the dimers
are tilted at both low and moderate temperatures
[14]. An appropriate picture of the dimers on these
surfaces is that shown in Fig. 7(b). In contrast, the
diamond dimer is essentially different. Due to good
p bond formation between C atoms, the diamond
surface forms symmetric dimers, best described by
the picture in Fig. 7(a), over a large temperature
range [74].
Over the past few years, researchers have begun
to probe for detailed parallels between the surface
chemistry of Si(1 0 0) with that of Ge(1 0 0) and
C(1 0 0), with special consideration paid to the role
of the surface dimers. The first published studies
focused on Ge surfaces. Adsorption studies of
alkene-containing molecules such as ethylene [52],
butadiene [53], cyclopentene [54], and cyclohex-
adiene [55] at the Ge(1 0 0)-2  1 surface in ul-
trahigh vacuum revealed that like Si, Ge(1 0 0)
can participate in cycloaddition chemistry. Both
½2 þ 2 and ½4 þ 2 reaction products have been
 S.F. Bent / Surface Science 500 (2002) 879–903
observed experimentally. Theoretical investiga-
tions by Musgrave and coworkers have also re-
vealed close parallels in energetics between
cycloaddition reactions on Si(1 0 0) vs Ge(1 0 0).
Namely, on both surfaces, the ½4 þ 2 cycloaddi-
tion product is more stable by
15–20 kcal/mol C(1 0 0)-2  1 surface was found to form predom-
than the ½2 þ 2 cycloaddition product [25]. In-
deed, experimental studies of Diels–Alder reac-
tions on Ge(1 0 0)-2  1 show close similarities in
bonding (based on the vibrational spectra) with
the Si-based product [53]. Although the formation
of well-ordered monolayers, as in the case of sili-
con, has not yet been reported, it might be ex-
pected that the proper choice of molecular
precursor will lead to similarly packed monolayers
on Ge.
Unlike on Si, however, the Diels–Alder reaction
was found to be reversible on Ge(1 0 0)-2  1,
leading to loss (by desorption) of the organic layer
upon heating the surface to 300 °C [53]. The re-
verse of the Diels–Alder reaction is called the
retro-Diels–Alder reaction, and it also finds close
parallels in molecular organic chemistry. This
difference between Si and Ge surfaces in the be-
havior of the organic layer upon heating is a sig-
nificant one. It is the result of a fundamental
difference in the strength of the bonds formed be-
tween carbon and silicon atoms versus carbon and
germanium atoms. A C–Ge bond is weaker than a
C–Si bond by almost 10 kcal/mol [25] and bond
for bond, an organic molecule bound to Ge will be
held less tightly than one bound to Si. Exploiting
the reversibility of the attachment reaction on Ge
due to its weaker bonding is being considered as a
way to spatially pattern organic layers on the
surface [53].
Recently, there have been reports of both ½4 þ 2
and ½2 þ 2 cycloaddition reactions occurring on
the diamond(1 0 0)-2  1 surface [56–58]. Unlike
germanium or silicon, the diamond surface allows
direct comparison to be made between chemistry in
a molecular system (i.e. organic chemistry) versus
chemistry on the surface of an extended solid (i.e.
surface chemistry). First, both reactions directly
involve carbon atoms. Second, like the corre-
sponding alkene, the carbon–carbon dimer on
the diamond(1 0 0)-2  1 surface is symmetric. In
agreement with this analysis, studies by Russell
893
and coworkers [56,57] and by Hossain et al. [58]
have shown that the carbon dimers on the dia-
mond(1 0 0) surface behave like C@C double
bonds toward organic cycloaddition reactions. For
example, the reaction between butadiene and the
inantly the Diels–Alder product. The resulting six-
membered ring tethered to the surface exhibited
remarkable similarities to cyclohexene, which is
the Diels–Alder product of the related reaction
between butadiene and ethylene, shown in Fig. 5
[56]. Recent theoretical calculations by Fitzgerald
and Doren have investigated the butadiene/dia-
mond(1 0 0) reaction system, and their results are
consistent with formation of a majority ½4 þ 2
product with a minor ½2 þ 2 product [75].
Studies of ½2 þ 2 reactions on diamond provide
further insight into the reactivity of covalent solids
[57] and further evidence for a solid state effect on
surface reactivity in these systems. Recall that
½2 þ 2 cycloadditions are not generally observed
in molecular systems because they are symmetry
forbidden according to the Woodward–Hoffman
rules. At the surfaces of Si and Ge solids, ½2 þ 2
reactions are believed to occur because the surface
dimers tilt, providing an asymmetric reaction ap-
proach (transition state) that relaxes the symmetry
restrictions [31,69]. Because on diamond the di-
mers do not tilt [74], it would be expected that the
diamond surface, of all the group IV surfaces,
would behave most like its C@C analog. Follow-
ing the Woodward–Hoffman selection rules, a
½2 þ 2 reaction along a symmetric reaction path-
way would be unlikely to occur. Consistent with
this expectation, it was found that while cyclo-
pentene does undergo ½2 þ 2 addition on C(1 0 0),
the reaction probability is three orders of magni-
tude lower than that on Si(1 0 0) or Ge(1 0 0) [57].
Hence the structure of the surface exerts a strong
influence on the surface reactivity.
5. Further applications: functionalization of hydride-
terminated Si surfaces
Both ½2 þ 2 and ½4 þ 2 cycloaddition reactions
have now been demonstrated as a means of
functionalizing the surfaces of three covalent
894 S.F. Bent / Surface Science 500 (2002) 879–903
semiconductor solids: C, Si, and Ge. Although
work is ongoing, the results already seem to be
quite general for alkenes and dienes reacting on
these surfaces. Cycloaddition chemistry is a good
method for forming organic layers on semicon-
ductor substrates. By proper choice of organic
reagent, a variety of useful surface layers can be
engineered, including molecular monolayers ex-
hibiting good stability, chirality, and a high degree
of order. The understanding of cycloaddition re-
actions at semiconductor surfaces is now reaching
a level where scientists can begin to apply these
reactions to the rational design of organic/semi-
conductor interfaces.
Conceptually, the framework for describing cy-
cloaddition reactions in organic chemistry appears
to apply moderately well to reactions at these
surfaces. These parallels allow one to apply the
broad knowledge base available from organic
chemistry to tailor the reactions at the surface in
order to obtain targeted products. Furthermore,
the general principles that have can be developed
for the cycloaddition systems can be extended to
understand an even broader range of reactions at
semiconductors. For example, it is evident that
the surface structure plays a role in influencing
surface selection rules and reaction pathways. It
has also been shown that at these covalent sur-
faces, the formation of strong directional bonds
with rigid organic molecules allows the production
of ordered overlayers, even in the absence of dif-
fusion.
There are many additional applications in which
these guiding principles and a molecular approach
to designing surface reactions can be used to
functionalize semiconductor surfaces. One area of
application that exhibits great promise is the so-
lution-based functionalization of hydrogen-termi-
nated silicon surfaces. Even before vacuum-based
cycloaddition methods began to be exploited for
attaching organic groups to semiconductor sur-
faces (see Section 4), remarkable advances were
made in solution-based functionalization chemis-
try. In these so-called ‘‘wet-chemical’’ methods,
monolayers of organic films could be obtained on
silicon that imparted outstanding resistance to
oxidation and provided superb protection and
passivation to the underlying substrate.
Solution-based functionalization chemistry ex-
hibits a number of advantages over the vacuum
approaches. These include a much simpler appa-
ratus and the potential for significantly higher re-
action rates due to higher reactant fluxes present in
the liquid. In addition, for certain applications, the
solution-based method may be easier to integrate
into an existing processing protocol. On the other
hand, the degree of control over surface cleanliness
and structure, and the ability to perform in situ
diagnostics, may be reduced for this method
compared to a vacuum approach. For some ap-
plications, the surface control and range of at-
tachment configurations that are possible by the
vacuum-based approach may prove critical. For
example, in the development of molecular elec-
tronics, the electrical properties will depend upon
the structural properties of the surface and the
specific interfacial bonding, which can be well
controlled in a vacuum environment. In other
applications, the substrate being modified may not
be able to withstand the harsher treatment used
in solution processing. The choice of using wet
chemistry (solution based) vs dry chemistry (vac-
uum based) ultimately will depend upon the needs
of the particular application, and both methods
continue to be actively pursued.
Most solution based functionalization ap-
proaches use the hydride-terminated silicon surface
as a starting point. Hydride-terminated silicon,
particularly the H:Si(1 1 1) surface, can be gener-
ated with a high degree of order and atomic flat-
ness, and can be rendered quite passive against
oxidation and contamination [5]. The structure of
the H:Si(1 1 1) surface is shown in Fig. 3(b). The
hydride-terminated surface does not require vac-
uum conditions either for its preparation or sub-
sequent reaction [5].
Recall that for the Si(1 0 0)-2  1 surface, the
important functional group was the Si@Si dimer,
for which analogies were drawn to alkene chem-
istry. On the H:Si(1 1 1) surface, the group of in-
terest for functionalization is typically the Si–H
bond. The literature on organosilicon chemistry
(i.e., the chemistry of molecules with C–Si bonds)
includes many known reactions for Si–H bonds.
One major class of these reactions is ‘‘hydrosily-
lation’’, whereby the silicon-hydrogen bond adds
 S.F. Bent / Surface Science 500 (2002) 879–903 895

across an alkene (C@C) or alkyne (CBC) group.

Examples in which this chemistry is used to func-
tionalize silicon surfaces are described in the fol-
lowing sections.

5.1. Hydrosilylation chemistry at the H:Si(1 1 1)

surface

The first report of a densely packed organic

monolayer bound directly to silicon through Si–C
bonds was based upon the hydrosilylation reaction
on the H:Si(1 1 1) surface [76,77]. In pioneering
work, Chidsey and coworkers demonstrated that
long-chain 1-alkenes (those with the double bond
at one end of the chain) could be attached to hy-
drogen-terminated silicon surfaces at 100 °C in the
presence of a molecule called a radical initiator
[76,77]. A radical initiator is a species used to
create free radicals in reactions. Chidsey et al.
proposed that the surface attachment mechanism
was analogous to the hydrosilylation reaction in
solution phase chemistry. In the proposed surface
mechanism (illustrated in Fig. 15), the radical ini-
tiator starts the reaction by abstracting H from a
surface Si–H bond, producing a silicon dangling
bond (which is also referred to as a silicon radical).
In Fig. 15, a surface dangling bond is designated
by an orbital with a dot, where the dot represents
a single, unpaired electron. The silicon dangling
bond then reacts with the alkene molecule, form-
ing a new Si–C bond at the surface and leading to
the attachment of the organic molecule, which it-
self is left with a carbon radical as shown in Fig.
15. This surface bound organic radical is thought
to abstract a hydrogen atom either from an unre-
acted alkene molecule or from a neighboring Si–H
group on the surface. The net reaction sequence
produces a stable, closed-shell organic group
bound directly to the Si(1 1 1) surface.
Studies by Chidsey and coworkers [76,77]
showed a remarkable stability and robustness to
the organic monolayers formed by this process. A
number of diagnostic techniques were used to
characterize the monolayers, including vibrational
spectroscopy, X-ray spectroscopy and reflectivity,
ellipsometry and wetting measurements. These
showed that the monolayers were tightly packed,
with a density close to 90% that of crystalline hy-
Fig. 15. Proposed mechanism for surface hydrosilylation. Ini-
tial loss of silicon hydride generates a silicon dangling bond.
Reaction between the silicon and an alkene molecule leads to an
attached alkyl radical, which may abstract a hydrogen atom
from a neighboring silicon [84].
drocarbons. More importantly, the organic layers
formed by hydrosilylation were stable in a number
of environments, including boiling water, organic
solvents, acids and bases, and air. The silicon
substrate was found to be protected by the
monolayer against oxidation after many weeks of
exposure to air [76,77].
After the reports of the radical-initiated hydro-
silylation process, a number of different ap-
proaches for functionalization based on this
reaction were developed [8,77–79]. It was shown
that the reaction could proceed not just with a
radical initiator, but also with other methods for
generating the initial silicon radical (dangling
bond). The use of heat (>150 °C) succeeded by
thermally breaking the Si–H bond, although the
monolayers produced by this method were of a
lower quality [77]. Another method involved use of
acidic molecules (called Lewis acids) to catalyze
the reaction [78,79]. Related approaches using
896 S.F. Bent / Surface Science 500 (2002) 879–903
reactions of organometallic species (molecules
involving both organic groups and metal atoms)
to functionalize silicon surfaces through the Si–H
bonds were also shown to work [80–83].
5.2. Radical chain reactions
A recent revisit of the proposed reaction mech-
anism for radical-initiated hydrosilylation [76,77]
has led to two beautiful demonstrations of silicon
functionalization in which the reaction propagates
along the surface, leaving attached organic mole-
cules in its wake. This occurs because the reaction
is ‘‘self-propagating’’. In a self-propagating reac-
tion, one reaction causes a subsequent reaction to
occur, which starts the next reaction, and so
on. Recall that in the surface hydrosilylation
mechanism (Fig. 15), the process is initiated by
generating a silicon dangling bond on the hydride-
terminated surface. Reaction of this silicon dan-
gling bond with an alkene molecule leads to a
surface-bound organic group containing a carbon
radical, which must abstract a hydrogen atom in
order to become a stable, closed shell species. If the
adsorbate abstracts a hydrogen atom from a
neighboring Si–H group, a new silicon dangling
bond is produced, which can begin the reaction a
new. This process is also known as a radical chain
reaction.
This proposed radical-chain reaction mecha-
nism was recently confirmed in hydrosilylation
experiments performed in vacuum. In one report,
Cicero et al. prepared hydride-terminated Si(1 1 1)
surfaces using standard wet-etch methods, then
introduced the sample into an ultrahigh vacuum
chamber [84]. In vacuum, the tip of a STM was
used to generate isolated silicon dangling bond
sites surrounded by silicon hydride groups [85,86].
This surface was then exposed to styrene, a mol-
ecule which consists of an alkene group attached
to a benzene ring, as shown in Fig. 16. In the STM
image of Fig. 17(A), islands of adsorbed styrene
are observed on the silicon surface in areas sur-
rounding the locations of the initial dangling
bonds, which are designated by black dots [84]. In
other words, one dangling bond on the surface led
to the deposition of many styrene molecules. This
result supports the presence of a radical-chain
Fig. 16. The styrene molecule.
reaction during which hydrogen atoms are
abstracted from neighboring silicon atoms. The
observation of bunched-up islands of styrene ra-
ther than one-dimensional lines is attributed to a
‘‘random walk’’ propagation of the reaction. Cic-
ero et al. suggest that the reaction stops at a silicon
atom that no longer has any neighboring hydrogen
atoms [84]. Note that this system provides another
clear example of the localization of the reaction
and limited mobility of the organic molecules at
silicon surfaces. If the styrene molecules were
mobile, the bunching effect would not be observed.
In another report, Lopinski and coworkers have
used the same concept of the radical-initiated hy-
drosilylation reaction on the Si(1 0 0)-2  1 surface
to induce self-directed growth of molecular
‘‘wires’’ on the surface [87]. On the Si(1 0 0)-2  1
surface, the radical chain reaction propagates
primarily along the direction of the dimer row,
leading to ‘‘lines’’ of organic adsorbates, as shown
in Fig. 17(B). Molecular assemblies as long as 130
A (corresponding to 34 styrene molecules) were
observed. Lopinski et al. suggested that by using
different reactant alkenes and seed conditions at the
surface, this reaction may be used to engineer more
complex molecular nanostructures on silicon.
5.3. Photoinitiation and photopatterning
Another interesting extension of the hydrosily-
lation reaction involves photoinitiation. Chidsey
and coworkers have shown that shining ultraviolet
 S.F. Bent / Surface Science 500 (2002) 879–903 897

Fig. 17. (A) STM image of hydrocarbon islands formed by radical-initiated hydrosilylation chemistry of styrene on H-terminated
Si(1 1 1) [84] (reprinted with permission from Ref. [84]. Copyright 2001 American Chemical Society). (B) STM image of hydrocarbon
lines formed by the same mechanisms on H-terminated Si(1 0 0)-2  1. The four images show the propagation of the styrene nano-
structures with increasing styrene exposure [87] (reprinted from Ref. [87] with permission from nature).

light on the H:Si(1 1 1) surface while exposing the
surface to a 1-alkene also led to the formation of
organic monolayers [88,89]. Buriak and coworkers
have used the photoinitiation of hydrosilylation in
an exciting application of this process [90]. They
have examined functionalization reactions on po-
rous silicon, which is a cousin of single-crystalline
silicon. Porous silicon contains a complex array of
pores at the surface, generating a surface structure
of silicon reminiscent of stalagmites [8]. Porous
silicon is generated by specialized etching of crys-
talline silicon, and like crystalline silicon, can be
hydride terminated. In contrast to crystalline sili-
con, though, porous silicon is a strong emitter of
light (called ‘‘luminescence’’). In fact, it luminesces
in response to electrical, optical, and chemical
stimuli, making it of great interest for use in light
emitting devices.
Buriak et al. demonstrated that the hydrosily-
lation reaction of alkenes could be induced by
visible white light on photoluminescent samples of
hydride-terminated porous silicon [8,90]. Using a
simple optical setup in which light was only shined
on certain regions of the silicon, they showed that
using the photoreaction, they could form patterns
of organic layers on the surface. Regions that were
898 S.F. Bent / Surface Science 500 (2002) 879–903
exposed to white light in the presence of alkene
molecules became covered with organic groups,
whereas regions that were kept dark remained
terminated with hydrogen. Subsequently, the po-
rous silicon was etched in basic solution. Areas of
the substrate that were functionalized remained
intact because the organic layer acted to protect
the underlying silicon, but areas that were hydride
terminated were destroyed during the etch process.
A sample that had been subjected to this treat-
ment is shown in Fig. 18 while being illuminated
with ultraviolet light. Some regions of the sample
appear orange. These are the areas that were
photochemically coated with the organic layer; the
orange light is the visible luminescence that occurs
when alkyl-functionalized porous silicon is ex-
posed to ultraviolet light. The dark regions of the
sample reflect areas that do not photolumines-
cence. These are areas that were not hydrosilylated
and were etched in the basic solution. This simple
example serves to demonstrate the potential of
organic functionalization in manipulating the
properties of a silicon substrate. Adding the ability
Fig. 18. Photograph of a porous silicon sample that was
photopatterned using the light-promoted hydrosilylation reac-
tion. The orange regions of the pattern are coated with an or-
ganic layer that protected the surface against etching, allowing
the underlying silicon to luminescence. The dark blue regions
were unprotected, and after etching they no longer lumines-
cence (reproduced with permission of Wiley-VCH from Ref.
[90]).
to pattern these attached organics, as shown in the
work by Buriak and coworkers [90], only expands
the possibilities for future device applications.
6. Prospects
The microelectronics industry is headed toward
increasingly miniaturized devices. Within the next
decade or two, the industry will be facing the ne-
cessity to fabricate atomic-scale devices. As semi-
conductor devices continue their downward trend
in size, the importance of interfacial phenomena
and atomic scale manipulation will continue to
rise.
The tools available to surface chemists and
surface physicists already enable an unprecedented
level of control in the ability to modify surfaces at
the atomic level. New capabilities in both the ex-
perimental and theoretical arenas will give scien-
tists and engineers increasing power to manipulate
surfaces in order to design specific functionality.
The benefits of this molecular-level surface engi-
neering will be felt in many areas of microelec-
tronic fabrication––in atomic layer deposition, in
surface passivation, in deposition of ultrathin di-
electrics, for example. It will then go beyond ex-
isting processing and into the realm of new
uncharted territory. For example, signs are already
appearing of molecular electronics and molecular
computing [91].
One of the emerging areas in interface science is
organic functionalization of semiconductors. This
technology provides the opportunity to create
hybrid devices exploiting the properties and fea-
tures of both organic and inorganic materials. The
addition of organic layers at the interface provides
for myriad possibilities, including the incorpora-
tion of lubrication, optical response, chemical
sensing, or biocompatibility properties to semi-
conductor surfaces. Thus, the field of organic
modification ties directly into a number of tech-
nological areas that will become of increasing im-
portance.
One area of impact is nanotechnology. Nano-
technology refers to the development of materials,
systems and devices with a characteristic length
scale of 1–100 nm. For comparison, a H atom is
 S.F. Bent / Surface Science 500 (2002) 879–903
roughly 0.1 nm in diameter. Such molecular-scale
materials are being explored for many applications
in which novel electronic, optical or mechanical
properties are desired. One example is a so-called
molecular computer, in which switches and mem-
ory components will be constructed out of mole-
cules instead of patterned out of silicon.
Nanotechnology in effect relies upon manipulating
atoms into specific locations in order to construct
such novel devices. It is evident that methods being
developed for organic functionalization can be
used to produce films of molecules on semicon-
ductor surfaces with nanometer scale thicknesses,
i.e. one molecule high. Achieving nanometer scale
control in the lateral direction is also possible. One
example is the use of radical-initiated hydrosily-
lation of alkenes to form self-limiting islands or
lines of organic material several approximately 10–
100 nm in size [84,87]. Other possibilities include
writing complex patterns in attached organic lay-
ers with the tip of a STM [45], or utilizing poly-
merization in the organic layer. The opportunities
to make contributions in the area of nanotech-
nology by creative use of functionalization strate-
gies are vast.
Another area closely tied to organic function-
alization is molecular recognition and chemical
or biological sensing. Organic molecules are key
players in molecular recognition. Coupling organic
molecules to semiconductor solids provides op-
portunity to fabricate integrated chip-based sen-
sors. In such a scheme, the organic layer provides
the molecular recognition function, while the
semiconductor provides capabilities for signal
processing, data storage, logic, and even wireless
communication. Using this approach, the fabri-
cation of compact sensor that can be used out in
the field and communicate data remotely can be
envisioned. Key to such a device is the attachment
of an organic layer on the semiconductor sub-
strate, where the organic layer can be engineered
with a variety of end groups designed for molec-
ular recognition. It remains a challenge to develop
strategies for incorporating molecular receptors of
a general nature onto the semiconductor surface.
Even bioengineering stands to gain significantly
from advances made in organic surface modifica-
tion. Surface modification is known to play a de-
899
cisive role in influencing cell growth [92,93]. For
example, interfacial properties can be used either
to inhibit or to accelerate cell adhesion or cell
growth. Strategies utilizing patterned organic lay-
ers that combine adhesion proteins, cell growth
factors, and inhibiting molecules can be used to
direct two-dimensional cell growth. It has been
demonstrated, for example, that the direction of
axon extension from nerve cells can be controlled
by printing lm-scale lines of proteins on glass
surfaces [94,95]. Directed cell growth, in turn, can
be used for tissue engineering. Organic modifica-
tion can also be used to impart biocompatibility
to semiconductor-based devices designed to be
implanted into living organisms.
There are clearly a large number of applications
for which organic functionalization of semicon-
ductor surfaces can have a great impact. Each of
these applications requires a deep understanding
of how to modify the semiconductor surfaces
controllably. Methods to incorporate organic
functionality to the surfaces of semiconductors
have seen immense progress in recent years. We
have shown in this review how direct, covalent
attachment of organic molecules at the surface is
being used to bind organic layers onto semicon-
ductors. Methods developed for both dry and wet
environments can impart excellent control of the
interfacial properties. For example, organic layers
can be deposited which protect the underlying
substrate from attack by etchants, impart chiral
properties to the surface, or add new optical
properties to silicon.
A number of challenges remain, however, before
many of the futuristic applications––in nanotech-
nology, sensing, and others areas––can be realized
using this technology. One future need is to in-
crease the degree of control over both the selec-
tivity (i.e., in producing one product over
competing products) and the degree of order in the
organic layer. This in turn requires a deeper un-
derstanding of the driving forces that control the
attachment reactions. Evidence points to the im-
portance of both the reaction rates (kinetics) and
the energetic stability of the products (thermody-
namics) in controlling these reaction systems.
Therefore, it is important to understand how to
design the system (by choice of reaction conditions
900 S.F. Bent / Surface Science 500 (2002) 879–903
or molecular precursors) in order to manipulate
the product distribution. More work is also needed
in determining the detailed reaction mechanisms.
One of the key challenges is the ability to deposit
multiple organic layers in a controllable fashion.
So far, most of the work in organic functional-
ization by covalent Si–C attachment has focused
on the initial monolayer. There are some nice ex-
ceptions, however, such as the work by Bitzer and
Richardson [96]. It is clear that many applications
require flexibility in the deposition of multiple
layers. In order to extend the organic modification
to allow for next-layer attachment, a bifunctional
or polyfunctional organic molecule must be used
for the first layer. This layer, in turn, will retain a
reactive functional group for further attachment.
This review, and indeed most of the work on or-
ganic functionalization by a covalent Si–C linkage,
has focused on the alkene functional group. Re-
search on other functional groups is in its infancy.
There is clearly a great need not only for under-
standing how different functional groups react at
the semiconductor surface, but also for learning
how to direct the reaction of a polyfunctional
molecule in a stepwise fashion.
The application of organic chemistry at semi-
conductor surfaces for forming organic monolay-
ers and thin films is becoming an important and
growing area. By focusing on the molecular nature
of the surface, the functionalization methods ulti-
mately will provide the potential for control over
the monolayer bonding and order at the surface.
The impact of these studies on emerging technol-
ogies in microelectronics, sensing, and photonics is
expected to be significant in the coming decades.
Acknowledgements
The author expresses appreciation for the many
fruitful interactions with students and colleagues
that contributed immensely to this review. Thanks
are also due to Prof. Charles Musgrave, Collin
Mui, George Wang, Michael Filler, and Michael
Manzo for their contribution to the figures, and to
Prof. Jillian Buriak, Prof. Christopher Chidsey,
Prof. Robert Hamers and Dr. Robert Wolkow for
graciously providing permission to reprint their
figures. The National Science Foundation (Grants
nos. DMR-9896333 and CHE-9900041) and the
Beckman Foundation are gratefully acknowledged
for financial support which made this review pos-
sible. The author also thanks the Camille and
Henry Dreyfus Foundation for support through a
Camille Dreyfus Teacher–Scholar award.
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