Beruflich Dokumente
Kultur Dokumente
Surface reactions
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DOI: 10.1002/smll.200600103
1. Introduction
There has been considerable activity and progress in the While in some cases the attachment of reactive tethers facil-
development of methods for the controlled attachment of itates direct reaction of such molecules with the surface,[6, 7]
organic molecules to silicon surfaces, largely motivated by this approach has significant limitations. A more general
the promise of fabricating hybrid devices and sensors.[1–5] A and flexible strategy involves the formation of a functional
major challenge in this area is the coupling of complex func- monolayer, followed by a coupling reaction. Several such se-
tional molecules such as molecular switches or biomolecules quential reaction schemes have been reported for molecular
to the surface while retaining their functionality and pre- monolayers on silicon surfaces.[8–13] However, these studies
serving the chemical and electronic integrity of the surface. were carried out using macroscopic surface science probes,
precluding the examination of the quality of the resulting
surfaces at the molecular scale.
Recently we have developed a new method for forming
[*] Dr. B. J. Eves, Dr. C. Fan, Dr. G. P. Lopinski molecular monolayers on H-terminated Si surfaces using
Steacie Institute for Molecular Sciences photochemical reactions in the gas phase.[14] This approach
National Research Council
involves the generation of gas-phase radicals that abstract H
100 Sussex Drive, Ottawa, K1A 0R6 (Canada)
Fax: (+ 1) 613-991-4278 atoms from the surface, creating Si dangling bonds. These
E-mail: Gregory.Lopinski@nrc-cnrc.gc.ca reactive sites can lead to monolayer formation via two
Dr. B. J. Eves mechanisms: a propagating radical chain reaction, leading
Institute for National Measurement Standards to the formation of molecular islands, or direct reaction of
National Research Council, Ottawa (Canada) radicals with the dangling bonds, resulting in the formation
small 2006, 2, No. 11, 1379 – 1384 < 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 1379
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ACHTUNGREequipped with both STM and HREELS. An G.LK3000 P. Lopinski et al.
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Surface Reactions of Amines and Hydrogen/Silicon Substrates
SPECIAL SECTION
due to the free terminal amine rather than the formation of
bending modes associated with the three CH2 groups in the a Si N bond.
molecule, whereas the 1120 cm 1 peak is a combination of Figure 2 shows STM images illustrating the evolution of
C C and C N stretching modes. The weak peak at 850 cm 1 the surface morphology with increasing reaction time. The
likely contains contributions from both the NH2 wag image in Figure 2 a shows the typical state of the surface
mode[18] and also the Si N stretch[19] (ob-
served at 810 cm 1 for allylACHTUNGREamine, which
reacts by forming a Si N bond[14]). In
summary, the observed vibrational spec-
trum is consistent with diaminopropane
bonding to the surface through one of its
amine groups, resulting in the formation
of a Si N bond, and leaving its remaining
amine group free for further reaction.
The formation of the amine-terminat-
ed surface upon UV photochemical reac-
tion can be explained on the basis of our
previous work on gas-phase photochemi-
cal reactions with H/SiACHTUNGRE(111) and an under-
standing of the photodissociation products
of diaminopropane. Although photodisso-
ciation data for 1,3-diaminopropane are
Figure 2. Constant-current occupied-state STM images ( 2.5 V, 30 pA, 18 1 18 nm) of a
not available, we note that methylamine H/SiACHTUNGRE(111) surface after a UV photochemical reaction with 1,3-diaminopropane (1 Torr) for
has four main dissociation pathways when a) 72 s and b) 144 s.
irradiated with 194–244 nm photons: H +
CH3NH, H + CH2NH2, CH3 + NH2, H2 +
CH3N.[20] The majority (75 %) dissociates
into CH3NH and H radicals. The cleavage of the N H bond after reaction for 72 s. A single monoatomic height step
has also been reported as the main dissociation route for n- edge is seen to run through the image. The terraces are cov-
butylACHTUNGREamine, n-amylamine, and n-hexylamine irradiated by a ered with numerous protrusions (2–3 F in height) that
mercury arc lamp.[21] Therefore, it is likely that the main appear to cover 50 % of the surface. The image is consis-
photodissociation product for diaminopropane is tent with the HREELS spectrum of the same sample in Fig-
NH2C3H6NH and H. The amine and H atom radicals pro- ure 1 d, which indicates a substantial amount of diaminopro-
duced by photolysis of the reactant gas can abstract H pane on the surface. The observation of a fairly strong Si H
atoms from the silicon surface, creating reactive Si radicals mode in the spectrum is in line with the significant area of
(dangling bonds). The amine radicals can then add directly the surface that appears to remain unreacted. Many of the
at these reactive sites, via formation of a Si N bond. It is protrusions are isolated and the remainder do not appear to
important to note that this mechanism makes it highly un- be correlated with one another. This is in contrast to images
likely that both amine groups on the molecule will react observed for surfaces partially reacted with alkenes where
with the surface. The amines only react after losing a hydro- the monolayer growth proceeds via formation of irregularly
gen and becoming a radical and then only with dangling shaped island structures due to a propagating radical-chain
bonds on the surface. reaction mechanism.[25] Rather the absence of islands is ex-
The significant broadening of the HREELS elastic peak pected for the direct addition of amine radicals at isolated
upon addition of the amine suggests that the reaction has al- Si dangling bonds.
tered the free-carrier density in the near-surface region of Upon doubling the reaction time to 144 s (Figure 2 b),
the silicon substrate. HREELS is sensitive to changes in the the surface appears to be mostly covered with only relative-
electron density at the surface of semiconductors due to ly small unreacted regions remaining. It is difficult to re-
coupling to the free-carrier plasmon mode, the energy of solve the individual molecular features within the reacted
which depends on the carrier density.[22, 23] For carrier densi- regions, which appear rather flat and have a height variation
ties in the range of 1016–1018 cm 2, losses associated with of < 1 F. The HREELS spectrum corresponding to this re-
coupling to the plasmon mode show up as a broadening of action duration (Figure 3 a) shows that the Si H bend and
the elastic peak.[23, 24] The increase in carrier density suggest- stretch modes are substantially reduced, with the bend
ed by the broadening of the elastic peak can be attributed mode barely observable above background. Further expo-
to band-bending induced by amine functionalization of the sure of the surface to diaminopropane results in only a
surface. As the amine group is expected to be an electron small amount of additional molecules being added to the
donor this would result in bending the bands into accumula- surface, with little change observed in the HREELS spec-
tion (on the n-type samples used here). We note that allyl- trum. The image in Figure 2 b also allows us to address the
ACHTUNGREamine, which binds through a Si N bond, does not show possibility of multilayer formation. Since photodissociation
this broadening effect,[14] which indicates that the effect is of diaminopropane leads to the formation of gas-phase radi-
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Surface Reactions of Amines and Hydrogen/Silicon Substrates
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After reaction with 1,3-diaminopropane for 6 s, the ble to image the same area over the course of the experi-
HREELS spectrum (Figure 4 b) reveals weak (note the mul- ment, however, the images represent typical areas on the
tiplication factor of 12 000 relative to the elastic peak) but surface at each stage. The clean H/SiACHTUNGRE(111) surface (Fig-
clearly observable peaks associated with the C H methyl- ure 5 a) has few defects and is indicative of the quality of
ene stretches and the N H stretch of the terminal amine. surfaces that can be routinely achieved. After reaction with
These new features are consistent with the reaction of di- 1,3-diaminopropane, a number of bright isolated features
ACHTUNGREaminopropane with the surface and the formation of termi- are observed (Figure 5 b). Large areas of clean H/SiACHTUNGRE(111)
nal amine groups on the surface. The peaks due to Si H are visible, consistent with the HREELS data in Figure 4,
remain largely unchanged, suggesting that only a small which shows only a slight decrease in the Si H peak intensi-
number of molecules have been attached and that the re- ty after reaction for 6 s. In fact, by counting the number of
mainder of the surface has not been adversely affected by observed features the coverage is determined to correspond
the reaction. In fact, STM images of this surface (shown in to only 0.5 % of a monolayer. There is no indication of Si
Figure 5 b) indicate that the coverage of adsorbed species is dangling bonds being present on the surface. A close exami-
nation of the image shows
that there are at least two
different features with dif-
ferent apparent heights on
the surface. This is made
clear by plotting a histo-
gram of the apparent
height of these features
(Figure 5 d). Approximate-
ly 65 % of the features ex-
hibit an apparent height of
3 F with the remainder
appearing somewhat small-
er ACHTUNGRE(2 F). Therefore the
STM imaging at low cover-
age reveals that the photo-
chemical reaction of 1,3-di-
ACHTUNGREaminopropane is likely
more complicated than
suggested above from the
analysis of higher coverage
HREELS spectra. The ma-
jority features are likely
due to molecules that have
reacted by losing a H atom
from one of the amine
groups and reacting with a
Figure 5. STM images (25 1 25 nm ) of H/SiACHTUNGRE(111) at various stages of the sequential reaction: a) clean
2
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Acknowledgements
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