Section A - Collaborative Research Project (CRP)
State of the art, aims and objectives
The process of self-assembly of large functional molecules on surfaces is the single most important step in
creating thin films of complex organic molecules for a number of applications in molecular sensing,
enantioselective catalysis and recognition structures, and in the rapidly developing fields of molecular devices,
such as optoelectronic and logic circuits [1]. In order to use molecular layers in laterally structured
arrangements, i.e. in device applications, the control of supramolecular self-organisation on surfaces is of
central importance. To this aim, it is important to combine the ability to synthesise molecules and fabricate
templates and substrates with a detailed understanding of the balance between intermolecular forces and
molecule-substrate interactions. This may be achieved using powerful surface sensitive techniques, such as
electron spectroscopies (photoemission, absorption) and scanning tunnelling microscopy (STM). Indeed, a
considerable effort is currently being devoted to the microscopic description of molecule/surface conformation,
bonding and electronic states in individual (functionalised) molecules and supramolecular networks [2].
However, most of these studies have focused on planar metallic or semiconducting surfaces, and very little
work is done using functionalised substrates and templates [3]. The latter are not only useful to tune particular
network geometries and properties, but are indeed required for a massive, parallel supramolecular selfassembly in technological applications and devices.
Supramolecular self-organisation is driven by long-range dipolar interactions and short-range ionic or hydrogen
bonding between molecules. Within the limits of growth kinetics, the resulting network depends on the general
properties of the molecule and the details of the functional groups, although particular configurations may be
induced by the electronic structure of the surface [4], or forced by the morphology in a templated substrate [3].
The latter is the case of vicinal surfaces with one-dimensional arrays of steps, which are natural templates to
self-assemble one-dimensional molecular structures attached to surface steps [5]. Such one-dimensional
assemblies are the simplest supramolecular networks, and hence ideal to investigate molecule-molecule and
substrate-molecule interactions, supramolecular growth kinetics, as well as the physical and chemical
properties of the resulting one-dimensional molecular arrays.
Vicinal surfaces are easily obtained by a macroscopic tilt or miscut (1º to 15º) with respect to a high-symmetry
surface, resulting in one-dimensional step superlattices on the nanometer scale. Using noble metal surfaces as
model systems, Ortega’s, Michel’s and Greber’s groups have pioneered the work on the basic description of
the electronic states of vicinal surfaces within the last few years [6]. Noble metal vicinal surfaces are found to
exhibit complex reconstructions and varying electronic properties as a function of miscut and step type, which
can thus become tuning parameters to tailor one-dimensional supramolecular assemblies. The on-going “MOLVIC” Collaborative Research Project (CRP) aimes at characterising and systematically testing such noble metal
vicinal surfaces as one-dimensional templates for supramolecular assembly. It is focused on fundamental
aspects, such as the structural stability of the template upon molecule adsorption, the identification of ordered
phases (arrays) and their geometric and electronic properties. Our approach encompasses a characterisation of
individual molecule properties (conformation, electronic levels), and molecule-molecule as well as moleculesurface interactions within the assembly. We focus on a restricted number of molecules, in particular those
which exhibit weak molecule-molecule and molecule-surface interactions, such as fullerenes, and pentacene,
simple synthetic molecules likely to force linear hydrogen bonding (benzodiguanamine) and chiral molecule,
such as D- and L-cysteine and tartaric acid.
The knowledge acquired during the current CRP is a major step towards a true customisation of onedimensional molecular assemblies. The new CRP will expand towards a wide variety of molecules with a
higher degree of functionalization: PMMA, diynes, aminoacids, phthalocyanines, functionalised and doped
(“endo-“) fullerenes, and aromatic molecules with different symmetries and functional groups, such as PTCDI
and NTCDI. Most of these will be specifically synthesised by the associated group in Toulouse [AP1] and the
new partner in Kiel [IP5]. The new CRP will also incorporate sophisticated techniques for a more detailed
electronic and crystallographic characterisation, namely SPALEED [IP3], photoelectron diffraction and timeand spin-resolved photoemission [IP6], circular dichroism in absorption and photoemission [IP4], and a
combination of laser illumination and photoelectron spectroscopy, in order to address molecular switching
processes in adsorbed layers [IP4].
Hydrogen bonding in supramolecular chemistry will be investigated by using aromatic molecules, synthesised
by Gourdon, with linear symmetry and varied end groups. We will test one-dimensional supramolecular
assembly via homogeneous symmetric bonding, e.g, using di-imide or di-amine-like molecules [7,IP1],
asymmetric bonding introducing asymmetric end groups, e.g, pyrazole-carboxylic-like molecules [IP1].
Moreover, we will coadsorb molecules for heterogeneous bonding, e.g, mixing amine and imine groups [8].
Ionic and dipole-like molecule/molecule and substrate/molecule bonding can be explored with molecular
chains of fullerenes and endofullerenes. Functionalized fullerenes, such as PCBA will likely introduce
molecule/molecule hydrogen bonding and strong changes in molecule/surface interaction. Moreover, we intend
to step towards the preparation of N@C60 spin-chains, where the spins of the isolated nitrogen atom are
expected to order and are used to detect the magnetic properties of the environment [9, IP6]. On the other hand,
based on the variety of ordered patterns achieved with C60 and C70 fullerenes on Au(111) vicinals [IP1,IP2], we
will use such patterns as templates for “chemistry on the surface”. Herges will provide, on the one hand, retinal
molecules with functional groups for appropriate surface attachment, which will be used to test light-induced
isomerization of one-dimensional, self-assembled retinals (IP6), and on the other hand, appropriate molecules
for linear polymerization of polyacetylenes and proteins. Diynes can be polymerised to form polyacetylenes
which are semiconducting molecular wires consisting of a single C-C backbone. Their conductivity depends on
the substitution and the environment which makes the material “designable” and interesting for molecular
electronics. Oxazolidine-2,5-diones, malonic acid monoazides and -isocyanato carboxylic esters form
proteins if heated, irradiated, initiated by amines. The preparation of isolated, linear stretched protein chains on
a surface so far has not been achieved, and might contribute to answering fundamental questions in protein
folding. Oxazolidine-2,5-dione crystals are known to polymerise in a chain reaction once initiated nucleophilic
attack, and malonic acid monazides react by photochemical initiation. It might be possible to initiate the
polymerisation using the STM tip and control the formation of the protein chain.
In order to access the full range of system interactions, molecular assemblies above and below the
supramolecular level will be explored. Weak molecule-molecule interactions, such as dipole- or substratemediated, characterize dilute phases, but also dense aromatic hydrocarbon layers, such as pentacene, where the
hydrogen bond is not formed. The latter are particularly sensitive to surface state-mediated interactions [4], and
hence vicinal surfaces with tunable electronic properties may be ideal to tailor the growth of ordered adlayers.
Au vicinal surfaces are ideal for testing the full range of system interactions due to the presence of
reconstructed patterns that force coverage-dependent ordered phases in the 5-10 nm range. These in turn can be
studied with reciprocal space techniques, such as angle resolved PES, SPALEED and surface X-ray diffraction
[IP3]. However, due to the inherent complexity, with large unit cells and weak molecule-molecule interactions
we will combine high resolution structural and spectroscopic capabilities in the same Lab system, such as PES
and SPALEED [IP3], PES and STM [IP1,IP2]. Different kinds of interactions, other than the one mediated by
surface electronic states, are to be explored [IP1,IP3,IP4], such as the formation of an adsorption-induced strain
superlattice [10], which may also modify the surface electronic structure [11]. Besides the -conjugated
molecules, dilute phases of C60, C70 fullerenes and endofullerenes (N,K,Na) on a variety of vicinal surfaces will
be investigated [IP1,IP6]. Beyond weak hydrogen or ionic bonding, the strong covalent molecule-molecule
interaction will be tested in polymerised chains [IP2]. There is an enormous interest in this kind of system,
since one-dimensional bands and hence, one-dimensional electron conduction is expected. In this CRP vicinals
will be used as templates for molecules which can be polymerised. We will test the formation of insulating
wires of PMMA and conducting 1D assemblies of diynes and amino acids, taking advantage of the step dipole
moment. Polymerisation will be induced either with electrons (holes) from the STM tip or by illumination.
Strategy and work plan (for details see individual work-plans)
As a general scientific strategy, we aim at determining the hierarchy of forces that drive supramolecular selfassembly, by a detailed analysis of the structural and the electronic properties in a number of different cases.
The current CRP is aimed at providing the electronic and structural characterisation for a wide variety of noble
metal vicinal surfaces and templates, and a selective group of molecular assemblies. We have already acquired
a remarkable control and knowledge of the general substrate properties [5], necessary to assess the role of the
substrate in determining both the substrate/molecule interaction, and the morphology of assemblies with
molecules of higher functionalisation. The extended CRP will focus on the full range of molecule/molecule
interactions and hence varied molecular functionalisations will be tested. For aromatic chains with hydrogen
bonding, we define a double strategy, i.e. varying the chemical nature of the end groups (diaminotriazine,
imide), and the strength of the bonding by combining molecules or by asymmetric functionalisation [7,8]. For
C60 and C70 fullerenes the whole range of interactions can be tuned by functionalisation (hydrogen bonding,
polar groups), external doping (ionic, dipolar, magnetic), and polimerisation. The covalent bonding will be
intensively investigated in one-dimensional chains of aminoacids, proteins and dyines.
Such a thorough and complex approach requires a strong collaborative research, and a continuous exchange of
personnel, materials and information among the different groups. Moreover, collaborative experiments using
European synchrotron radiation facilities naturally forces parallel, coordinated work at home labs. The overall
CRP strategy is sketched below. Every box contains the characteristic strengths and research to be carried out
at home Labs in each group: types of molecules to be synthesised or searched, the distinct technique to be
used, and the specific issues. At this level, the CRP work is necessary, since exchange of substrates and
molecules (green and black lines, respectively) is needed. Small boxes define a direct collaborative research,
namely, electronic/structural characterisation through photon/electron spectroscopies at European syncrotrons
(BESSY, SLS, Elettra, ESRF), as well as joint home lab experiments with exchange of personnel (Kiel, Berlin,
San Sebastian). From this Figure, the European added value of the CRP is evident.
1.- Supramolecular self-organisation of aromatic molecules: AP1(synthesis)
a) Lab Work: IP1(STM+ARPES), IP3 (SPALEED, ARPES, SXRD), IP4 (XRCD for chirality).
b) Lab Collaboration: IP1+IP2, using 4K-STM (molecule conformation) and HR-ARPES (ordered phases).
c) Lab Collaboration IP3+IP4, using XRCD to study chirality
d) Synchrotron Collaboration IP1+IP2+IP3+IP4+IP6 (absorption/photoelectron spectroscopy, XRCD)
2.- Supramolecular self-assembly of fullerenes:
a) Lab work: IP6 (XPD, spin-resolved, time-resolved PES for fullerenes and magnetic endofullerenes), IP1
(STM+ARPES for dilute phases and functionalised fullerenes by IP5)
b) Synchrotron Collaboration IP1+IP2+IP6 (photoelectron spectroscopy, XRCD).
3.- Polymerisation:
Lab collaboration: IP2+IP5 (Synthesis, light induced and tip-induced polymerisation, 4K-STM)
4.- Light-induced isomerization:
Lab and synchrotron collaboration: IP4+IP5+IP6 (synthesis, light induced isomerization, XRCD,XPD).
Bibliography:
[1] "Molecular Electronics: Science and Technology”, eds. A. Aviram and M. Ratner, Annals of the New York
Academy of Sci. vol. 852, New York 1998; Heath et al., Science 280, 1716 (1998); Chen et al., Science 286,
1550 (1999); Collier et al., Science 289, 1172 (2000); see also the special issue Science 295, 2395-2421
(2002).
[2] S. M. Barlow and R. Raval Surf. Sci. Rep. 50, 201 (2003); F. Rosei et al., Prog. Surf. Sci. 71, 95 (2003); V.
Humblot et al., Prog. Surf. Sci. 76, 1 (2004).
[3] J. N. Crain et al., J. Appl. Phys. 90, 3291 (2001); R. Otero et al. Angewandte Chemie, International
Edition 43, 2092 (2004) and Nature Materials 3, 779–782 (2004).
[4] S. Lukas et al., Phys. Rev. Lett. 88, 028301 (2002); J. Repp et al, Phys. Rev. Lett. 85, 2981 (2000); E. C. H.
Sykes et al., J. Am. Chem. Soc. 127, 7255 (2005).
[5] See Annual report of the on-going “MOL-VIC” CRP.
[6] Ortega: J. Phys. Cond. Mat. 15, S3281 (2003), Phys. Rev. Lett. 84, 6110 (2000), Phys. Rev. Lett. 87,
107601 (2001), Phys. Rev. Lett 95, 066805 (2005); Greber: Phys. Rev. Lett. 88, 237601 (2002); 90, 177402
(2003); 92, 016803 (2004); 92, 196805 (2004); Michel: Phys. Rev. Lett. 93, 137602 (2004).
[7] D. L. Keeling et al., Nanoletters 3, 9 (2003); D. Laliberté et al., J. Org. Chem. 69, 1776 (2004).
[8] J. A. Theobald et al., Nature 424, 1029 (2003).
[9] T. Almeida Murphy et. al., Phys. Rev. Lett. 77 (1996) 1075, W. Harneit, Phys. Rev. A 65 (2002) 032322.
[10] C. Cohen et al, Surf. Sci. 490, 336 (2001).
[11] D. Sekiba et al, Phys. Rev. Lett. 94, 0168081 (2005).
Deliverables and milestones (referred to individual work-plans)
End of the on-going CRP (2006): Fully characaterized vicinal surfaces and templates, characterization of
molecular assemblies of planar (benzodiguanamine, PTCDI, NTCDI) molecules with hydrogen-bonding,
fullerenes with ionic interactions, and pentacene (substrate mediated interactions) on some vicinals. Chirality
on cysteine. General CRP workshop and kick-off meeting
1st year: New equipment set-up and testing. Synthesis of new molecules from IP5 and AP1. First experiments
for the structural characterization of one-dimensional assemblies of aromatics with symmetric and asymmetric
bonding (IP1, IP3, IP4) , functionalized fullerenes and endofullerenes (IP1,IP6) and their polimerisation (IP2).
2nd and 3rd year: Full characterization of supramolecular one-dimensioanl assemblies of aromatics (AP1, IP1,
IP3, IP4) and functionalized fullerenes and endofullerenes (IP1,IP6), light isomerization (IP4, IP6) and chain
polimerisation (IP2,IP5).
Overall budget of the CRP
BUDGET
ITEMS
EUROCORES
Funding
Agency (EFA)
Estimate of Funding
PI 1 Ortega
Ministerio de
Educación y Ciencia
(Spain)
(in Euros)
Salary costs
Ph.D.
student(s)
Post-doc.
Researcher(s)
Senior
researcher (s)
Technician(s)
Estimate of Funding
PI 2 Berndt
Deutsche
Forshungsgemeinshaft
(Germany)
(in Euros)
Estimate of Funding
PI 3 Michel
Ministerio de
Educación y Ciencia
(Spain)
(in Euros)
3 x 56000 = 168000
2x35360=70720
Estimate of Funding
PI 4 Horn
Deutsche
Forshungsgemeinshaft
(Germany))
(in Euros)
Estimate of Funding
PI 5 Herges
Deutsche
Forshungsgemeinshaft
(Germany))
(in Euros)
3 x 56000 = 168000
3 x 48000 = 144000
Estimate of Funding
PI 6 Greber
Swiss National Science
Foundation
(Switzerland)
(in Euros)
Estimate of
TOTAL Funding
(in Euros)
238753
789473
Guest Prof:
20000
32246
20000
32246
Equipment per
item
item 1
UV source + optics
19700
item 2
item 3
Item 4
Item 5
Travel
conferences,
worksh.,visits
Consumables
/ Runn. Costs
Including
analysis costs
Publication,
Dissem. Cost
Overheads
if applicable
Electron analyzer
133400
Quad. mass spectrom.
12000
UHV chamb. and gaug.
20000
Ion, turbo and rotary
pumps, gate valves
20000
High Intens. Light
sourc., fiber optic lamp
21000
Evaporator comp.
6000
HPLC software
8000
245100
Transfer rod: 5000
12000
12000
6000
14000
6300
50300
12000
15000
6000
32000
93000
2000
0
Channeltrons 5000
23 000
3000
19%
26927
0
20%
66860
19%
29906
5000
123693
Others
Travel to synchrcotron
3000
187306
T O T A L
214700
171647
168000
0
administrative coordin.
2000
219000
403159
5000
1363812
Description of the Collaboration:
SCIENTIFIC TRACK RECORD
The project is structured as an interdisciplinary effort aimed at understanding supramolecular assembly through a
combination of preparation and analysis techniques. The collaborating groups contribute and share their know-how in
vicinal surface preparation and chemical synthesis, state-of-the-art experimental techniques, and a considerable
experience in materials science and surface/interface research. The current, on-going CRP combines the expertise of
the groups in nanostructured template preparation (Ortega, Michel), molecule synthesis (Gourdon), single molecule
manipulation and spectroscopy (Berndt) and electronic structure characterisation (Horn, Ortega, Michel), and theory
(Joachim). The new CRP will be strengthened by two new groups: strong synthetic chemistry capabilities (Herges),
and one of the leading groups worldwide for surface structural characterisation and analysis (Greber). The
combination of expertise in the new team will make it possible to expand the CRP research to new classes of
molecular systems, and novel aspects such as molecular magnetism, molecular chirality, and electron dynamics.
Theoretical support will be provided by prestigious groups out of the CRP (see IP1.B4 and IP2.B4).
Ortega has devoted most of his research career to the field of electronic states in nanostructures. Related to this
project, during the recent six years, Ortega, together with Michel and Greber, has paved the way on the
fundamental understanding of electronic states in vicinal surfaces using angle resolved photoemission. This is
demonstrated by the large number of high profile papers (8 PRL’s) published by these authors on the subject
(see CV’s). The search performed by Ortega currently extends to a variety of one-dimensional structures with
tailored electronic properties: from step and facet arrays in noble metal surfaces to adsorption-induced atom
chain structures and stripes. As a side effect of this broad research, Ortega posseses a large collection of about
30 different vicinal single crystal surfaces (Au,Cu,Ag,Si,Ge) which are at the disposal of the other CRP
members. Using some of these surfaces, Ortega’s group is currently carrying out individual STM as well as
collaborative spectroscopy/STM experiments with Berndt, Michel and Horn on self-assembly of aromatic
molecules (synthesized by Gourdon) and fullerenes. Ortega’s group scientific quality output reflects in the 6
PRLs published since 2000.
Berndt has an extensive experience in the field of low-temperature tunneling microscopy and spectroscopy.
Among the different fields pursued in recent years, we must mention high-resolution spectroscopy of noble
metal surface states, resulting in an accurate determination of lifetimes of surface state electrons. We were able
of observing the Kondo effect over a single magnetic adatom and have demonstrated the modification of
electronic structure of a single in atomic resonators fabricated by atom manipulation. Recently, we investigated
STM-induced luminescence from quantum wells and studied transport to single atoms and molecules. A second
focus of our work is tunneling microscopy of molecules. We have observed the self-assembly of
supramolecular clusters and chains and have demonstrated the feasibility of separating a racemic mixture of
chiral molecules into enantiomerically pure domains by molecular manipulation with the STM. Recently, we
have studied the conformational changes of large molecules (lander, C90H98) upon adsorption in collaboration
with the group in Toulouse. Since 2000 we have published 9 articles in Phys. Rev. Lett. (one in print), one in
Nature, one in Science.
The scientific activity of Michel has been devoted during the last ten years to the investigation of the structural
and electronic properties of complex surface system, paying special attention to the role of the electronic
energy in the stabilization of surface phases. To this end, different experimental techniques have been applied
to characterize the properties of surfaces and interfaces, developing a true multitechnique approach to the
problems. This includes surface x-ray diffraction, photoelectron diffraction, inelastic He atom scattering, and
angle-resolved photoemission. This work has given rise to several important publications in the field (see list of
most relevant papers). Since 1999, Michel, Ortega and Greber have worked in the analysis of vicinal metal
surfaces. The current CRP has extended this work to the analysis of the self assembly of organic molecules on
vicinal surfaces and has already obtained promising results.
Electronic structure investigations are at the center of interest in the group of Horn. Low-dimensional systems
such as metallic quantum wells on semiconductors, and terrace structures on clean surfaces on the one hand,
and on the other hand, complex quasicrystalline alloy phases which exhibit perfect atomic order despite the
absence of translational symmetry, have been studied using angle resolved photoemission as well as scanning
tunneling microscopy and spectroscopy. This work has revealed general features of the electronic states in such
systems, with relevance to a broad range of material systems. The group has recently used circular cichroism in
core level photoemission to identify chiral centers in adsorbed molecules, an interesting subject in the context
of this proposal.
Focus of research of Herges is the synthesis of carbon rich materials and the design of photoswitchable
compounds to construct molecular machines such as photochemically driven pincers, motors, ion pumps, and
chemical synthesizers. The Herges group achieved the first rational synthesis of a short section of a carbon
nanotube and the first synthesis of a Möbius annulene. The scientific record is documented by a number of
publications in reputed journals (20 papers in Angew. Chem. one publication in Science and in Nature).
Greber's research activity in the past five years has been generally focused on the interplay between electronic
structure and morphology in low dimensional systems, using a multitechnique approach. Related to this CRP, it
is of particular importance, on the one hand, his contributions in the field of novel, self-assembled
nanostructures, such as boron nitride layers (e.g. nanomesh) and fullerene chains on vicinal surfaces.
Furthermore the angle scanned photoelectron diffraction technique was applied to the determination of the
absolute chirality of molecules. The quality of scientific output is reflected in the abundant number of high
profile articles, e.g., six Phys.Rev.Letters and two Science in the past five years.
The scientific activity of Gourdon during the past 7 years has been focused on the design, synthesis and
structural studies of molecular devices for single molecule experiments by UHV STM and AFM. One of the
key points has been the development of molecular landers, in which a rigid polyaromatic part is lifted above a
metallic substrate by molecular spacers. It has allowed the first demonstration of molecular moulding, the
measurement of contact conductance on a single molecule, the study of single molecule mechanics and
switching etc..
EXPERTISE AND CONTRIBUTIONS EXPECTED FROM EACH GROUP TO THE CRP
Ortega: Expertise on vicinal surface and template fabrication. Expertise on electronic structure analysis from
stepped and facetted surfaces with angle-resolved photoemission. The expected contributions are: providing
customised templates, characterising electronic properties of templates and molecular assemblies by combining
STM and angle-resolved photoemission in the home Lab in San Sebastian, collaborating in synchrotron
radiation experiments.
Berndt: Expertise on atomic and molecular manipulation using low-temperature STM. 2D-chiral molecular
structures. Determination of local electronic structure by tunnelling spectroscopy and photonemission STM.
The expected contributions are: testing tailored templates for molecular self-organisation, characterising the
assemblies and assessing local electronic structure. The low-temperature capabilities of the STM (operation at 5
and 50 K) allow to suppress mobility, which usually prevents tunnelling spectroscopy with sub-molecular
spatial resolution at ambient or moderately low (150 K) temperatures.
Michel: Expertise on vicinal surface and template fabrication. Expertise on electronic and structural analysis
with core-level photoemission, angle-resolved photoemission, photoelectron diffraction, surface x-ray
diffraction and x-ray standing waves. The expected contribution is the accurate characterisation of the structure
and the electronic properties of templates and complex molecular assemblies with those techniques, using also
synchrotron radiation laboratories.
Horn: Expertise and contribution will cover the analysis of molecular adsorbate electronic structure, and
adsorbate geometry using valence level photoemission, core level photoelectron diffraction, and x-ray
absorption techniques. The use of circularly polarised x-rays will provide insight into the influence of the
adsorption and assembly process on chiral centers of adsorbed layers.
Herges: Expertise on synthesis of complex organic molecules and supramolecular structures, namely tube- and
belt-like aromatic and Moebius aromatic compounds. The contribution to this project will be the synthesis and
structural characterisation of functionalised fullerenes and related compounds suitable for the formation of onedimensional supramolecular structures on vicinal surfaces.
Greber: Expertise on vicinal and chiral surfaces and formation of molecular arrays. Expertise on angle scanned
X-ray Photoelectron diffraction (XPD), applied to molecular systems, with access to a state of the art
experiment on a synchrotron light source. Full access to a surface science lab with XPS, LEED, STM, 2PPE,
and Spin-Polarized Photoemission.
Gourdon: Expertise on design and synthesis of molecules for nanosciences such as wires, switches, templates
or mechanical molecular devices. The expected contribution is to provide specifically designed molecules for
adsorption on various metallic templates.
EUROPEAN ADDED VALUE
The European added value of the CRP is strongly reflected in the variety of groups from different countries
involved, and in the strong necessity of the collaborative research (see “Strategy and Workplan” in section A).
There are good complementarities between the teams, showing that the collaborative project constitutes a
coherent body, able to generate synergies. From the multitude of experimental approaches, the diversity of
methods of analysis, and the acces to the different national facilities, it is clear that no similar research project
could be undertaken at national level, indicating the need of a collaborative European project and the existence
of a European added value from the collaboration. It is also remarkable that state of the art European
Synchrotron Radiation Facilities (ESRF, BESSY, Elettra, SLS) are deeply involved in such collaborative
research.
Section B - Individual Projects (IP)
IP1-B1 PI: Enrique Ortega, Universidad del País Vasco, San Sebastian
One-dimensional self assembly of aromatic molecules and functionalized fullerenes
1.- Aims and Objectives
The general objective of IP1 is studying one-dimensional supramolecular self-organization in a variety of
molecule/vicinal surface systems, with the triple aim of:
a) Identifying the underlying microscopic mechanisms that drive the self-assembly process, determining
the kinetic limiting parameters and the specific role played by substrates, molecules and functional groups.
b) Providing a thorough characterisation of structural and electronic properties of such one-dimensional
supramolecular assemblies.
c) As a result, defining the appropriate combinations of substrates, molecules, and functional groups, and
the procedures to obtain one-dimensional supramolecular structures with desired properties.
2.- Methodology
We will utilize a variety of molecule/surface systems trying to cover the widest possible range of
molecule/molecule and substrate/molecule interactions. That will provide the necessary knowledge in order to
to proceed with the refined selection of substrates, molecules and functional groups for a customized system.
The experimental approach is based on a powerful combination of variable temperature Scanning Tunneling
Microscopy and High-Resolution Angle Resolved Photoemission within the same experimental chamber. A
more accurate study of individual molecule conformations will be carried out in collaboration with IP2 (4K
STM), whereas synchrotron radiation studies (absorption, Photoemission) will be done in collaboration with
IP2, IP3, IP4 and IP6 at the SLS, Elettra, and BESSY facilities.
Initially we plan to work with a limited number of vicinal substrates and templates, and explore other substrates
depending on the results obtained. The selected group comprise Au(111) vicinals with different
electronic/structural properties (step arrays, facets and kinks) and Ag overlayers on Cu(111) vicinals. We will
focus on two groups of molecules which, in principle, define two distinct types of interactions with the
substrate, i.e., aromatic chains with functionalized end groups (pi-bonding to the surface) and fullerenes (ionic
bonding). For aromatic molecules (synthesized by AP1) we fix the linear geometry and vary the chemical
nature of the end groups (diaminotriazine, imide), and the strength of the intermolecular bonding by combining
different molecules or by asymmetric end-group functionalisation (acid-N). For fullerenes we plan to introduce
hydrogen bonding using molecules with functional acid (PCBA), and polar (INDAN, BINDAN, synthesized by
IP5), and also tune the ionicity by external doping (with alkali metals, endofullerenes).
Succesive experiments for each group of molecules will increase the degree of complexity, i.e., from the
simplest linear, symmetric aromatic molecules and plain fullerenes on step arrays we will move towards coadsorbtion of molecules and endofullerenes and the use of complex Ag/Cu nanostructured templates.
2.- Work plan, milestones and deliverables
2.1.- Expected outcome of the ongoing CRP (end of 2006):
a) Template characterization: The extensive work in surface/template fabrication and characterization will
provide a variety of one-dimensional structures with well-characterized geometry, chemical composition and
electronic properties. We will be able of selecting geometry and electronic properties in vicinal surfaces and
templates by selecting surface and step type and density [1], as well as chemical contrast in two-phase striped
structures [2]. Nonetheless, based on the stability of the substrate/template upon molecule adsorption, we are
already defining a selective set of surfaces/templates for prospective experiments with molecules (see Figure 1).
These comprise:
i) Au(778), canonical example of an step array (36 Å periodicity) with a high degree of homogeneity over
huge areas of the surface. Electronic states are quasi-one-dimensional minibands of electrons confined in
terraces [1].
ii) Au(788), same as Au(778), but with a perpendicular, ordered fcc/hcp reconstruction pattern (70 Å
periodicity) along terraces, thereby defining a square mesh. (Figure 1).
i) Au(433), faceted structure with single 36 Å terraces that are separated by step bunches and confine
surface electrons [1]. (Figure 1)
ii) Ag/Cu(111): adsorption of Ag on vicinal Cu(111) surfaces lead to a variety of structures such as stripes,
facets and overlayers. At the submonolayer regime, besides the chemical contrast, we find exotic electronic
states and reconstruction patterns (misfit dislocations) that vary as a function of step spacing and coverage [2].
We plan a careful, thorough study using Ag wedges and well-oriented curved Cu crystals (Figure 2).
Fig. 1: Characteristic STM images from
vicinal Au(111) surfaces to be used as
substrates for one-dimensional
supramolecular self-assembly. Left,
Au(788) (step arrays+fcc/hcp periodic
patterns) and right, Au(433) (periodic
faceting). On top, schematic sideview
description of the surfaces.
Figure 2: STM images (100 nm2) showing the variety of Ag/ Cu nanostructures with distinct structural and
electronic properties that can be produced by Ag deposition on vicinal Cu(111) surfaces by varying Ag thickness,
step type and surface orientation. In the right panel we show the schematic description of the wedge/curved
crystal approach that permits step type, density and coverage variation in a single sample.
a)
Molecular assemblies: The current CRP work (STM/Photoemission/Absorption in collaboration with
partners at Kiel, Berlin and Madrid), using plain fullerenes and linear, planar aromatic molecules with a whole
variety of vicinal surfaces and templates, is expected to provide the clues about the basic experimental
procedures, such as measurement conditions and limitations, as well as fundamental knowledge on the stability
of substrates upon molecule adsorption and the kinetic parameters for different assemblies.
2.2. First year (2007):
Overall set-up of the High Resolution Photoemission System: The correct characterisation of complex
molecular structures which exhibit a succession of long-range, ordered phases require the combined use of
powerful techniques. This will be achieved in Ortega’s group by combining, in a single vacuum system,
Scanning Tunneling Microscopy/Spectroscopy (STM, structural properties) and High Resolution, Angular
Photoemission (HR-ARPES, electronic properties). The latter will be incorporated in the existing chamber and
tested with current molecule/surface systems: fullerene and benzodiguanamine on Au vicinals.
The combination of STM/HR-PES is of particular importance in the study of diluted, ordered phases, induced
by weak molecule/molecule interactions, such as dipole interactions, or forced by the structure (reconstruction
patterns) or the electronic states of the substrate. Dilute ordered phases are inherently complex, i.e., they exhibit
large unit cells (beyond 50 Å) and small interacting energies (in the meV range), thereby requiring both STM in
real space and HR-ARPES with high wave vector (angular) and energy resolution in reciprocal space.
Fig. 3: Differnt types of functionalized
molecules to be tested for onedimensional supramolecular assembly.
From left to right and from top down:
Benzodiguanamine, 4-{[4-(pyridin-4ylethynyl)phenyl]ethynyl}benzoic acid,
PCBA, INDAN, BINDAN
First deliverable: Full characterization of fullerenes and benzodiguanamine assemblies on Au vicinals and
Ag/Cu templates
2.2. Second-Third year (2008-2009):
a) Planar aromatic molecules (Fig. 2): Synthesized by AP1. Currently we are working on aromatic molecules
with symmetric end group functionalisation: benzodiguanamine (amine end-group) adsorption on Au(778) and
Au(788), and plan to generalize the study to PTCDI and NTCDI (imine end-group) and to Au(433) and Ag/Cu
stubstrates. We will investigate all coverage regimes, from dilute to monolayer saturation by means of the
STM/HR-PES approach. Absorption/Photoemission experiments in collaboration with IP3 and IP4 are alredy
being planned and will be implemented at BESSY/ELETTRA.
Secondly we plan to study asymmetric hydrogen bonding introducing the study of linear pyrazole-carboxyliclike molecules with asymmetric single end-group (acid, pyridine), such as the one shown in Fig. 3, and also
perform coadsorption experiments of imide and amine-like molecules, which are expected to strengthen the
molecule/molecule interaction [3].
In a more advanced phase, the strategy of coadsorbing distinct molecules to strengthen intermolecular
interactions will be tested in Hexa-tert-butylphenilbenzene- like molecules with amine and pyridine end groups.
These are bulky molecules that are expected to exhibit weak substrate-molecule interactions (see AP1-C1).
Second deliverable: Full characterization of NTCDI, PTCDI, and pyrazole-carboxylic-like on Au vicinals and
Ag/Cu templates. Full characterization of coadsorbed NTCDI-benzodiguanamine on Au vicinals and Ag/Cu
templates. Test of molecules of the family of Hexa-tert-butylphenilbenzene with pyridine, imine end groups,
and coadsorption on Au vicinals and Ag/Cu templates.
b) C60 and C70 fullerenes: Our current STM/Photoemission/Absorption experiments of C60 and C70 fullerenes
on Au(788) encourage the use of functional groups and doping to modify molecule/molecule interactions. The
fcc/hcp reconstruction pattern of Au(788) forces a periodic, selective clustering in fcc patches during
monolayer completion [4]. These exhibit different degrees of substrate-induced metallicity, as revealed in
photoemission/absorption experiments [5]. In a first step we will use synthetic PCBA, with an acid end-group
expected to create stronger hydrogen bonding between molecules. As dopants, we will use alkali metals (K,
Na). Photoemission/Absorption will be done in collaboration with IP2 and IP6 in the SLS.
In a more advanced phase we will test other fullerene functionalizations, such as the polar BINDAN and
INDAN molecules (synthesized by IP5), or thiol groups.
Third deliverable: Full characterization of functionalized and doped fullerene assemblies on Au vicinals and
Ag/Cu templates.
3.- Justification of major budget items
Self-assambled supramolecular structures exhibit an inherent degree of complexity, namely large, complex
building-blocks (unit cells) and small interaction energies. In practice, systems are difficult to characterize with
standard electron diffraction techniques, and hence the combination of powerful, sensitive techniques in both
real (STM) and reciprocal space (photoemission) is necessary. The current proposal is intended to incorporate
state-of-the-art high resolution, angular Photoemission (HR-ARPES) to the current set-up in San
Sebastian, which includes Variable Temperature STM and standard electron diffraction techniques. The HRARPES equipment consists on a display-type electron analyzer that allowing simultaneous measurement of
angle-resolved spectra within a  5º range, a plasma-discharge lamp and a monochromator. Only the full
equipment ensures energy resolution below 10 meV and angular resolution down to 0.1º. The former is
necessary for the small interacting energies (narrow bands and gaps), whereas the latter is critical to resolve
band structures for extended states in large unit cells (for instance, to explore substrate mediated interactions):
in fact, with the standard photon energy of 21 eV, the angular resolution becomes 0.005 Å-1, and hence
assuming 10 points per Brillouin zone, the equivalent spatial resolution goes beyond 10 nm.
2.- References
[1] A. Mugarza, A. Mascaraque, V. Pérez-Dieste, V. Repain, S. Rousset, F. J. García de Abajo and J. E.
Ortega, Phys. Rev. Lett 87, 107601 (2001); A. Mugarza and J. E. Ortega, J. Phys. Cond. Mat. 15, S3281 (2003);
J. E. Ortega , M. Ruiz-Osés, J. Cordón, A. Mugarza, J.Kuntze, and F. Schiller, New Journal of Phys. 7, 101
(2005).
[2] J. Lobo, E. G. Michel, A. Bachmann, S. Speller, J. Kuntze, and J. E. Ortega, Phys. Rev. Lett. 93, 137602
(2004); F. Schiller, J. Cordón, M. Ruiz-Osés, and J. E. Ortega, Phys. Rev. Lett 95, 066805 (2005).
[3] J. A. Theobald et al., Nature 424, 1029 (2003).
[4] N. Néel, J. Kröger, and R. Berndt, Adv. Mater., accepted for publication (2005).
[5] F. Schiller et al. (unpublished).
IP1 - B.2
CRP Acronym: MOL-VIC
PI Name & Institution: Enrique Ortega, Universidad del País Vasco
IP Nr:1
Funding Agency: Ministerio Educación y Ciencia (Spain)
Outline Proposal Nr(s).:
BUDGET ITEMS
must be consistent with the rules set by
the relevant national funding agencies
Duration
where
appropriate
in month,
including start
date
YEAR 1 Funding
YEAR 2
Funding
YEAR 3
Funding
TOTAL Funding
(in Euros) [other
currencies]
(in Euros) [other
currencies]
(in Euros) [other
currencies]
(in Euros) [other
currencies]
Short Description
of each budget item where
appropriate
Salary position
Ph.D. student
Post-doc. researcher
senior researcher
Technician
student stipend / student assistant
Equipment per item
item 1
133400
item 2
133400
item …
Electron analizer
Travel
conferences, workshops, travel to
fieldwork, visits
(including networking within the CRP)
Conferences, workshops
4000
4000
4000
12000
Small parts, samples,
evaporation material
4000
4000
4000
12000
26866
1520
1520
29906
Consumables / Running Costs
including analysis costs
Publication, Dissemination Costs
Overheads
19%
if applicable
Others
including access to large infrastructures,
shiptime, etc. (please specify)
T O T A L
168266
9520
9520
187306
IP1.- B3 RELATED PROJECTS
In general all the research work in San Sebastian is related to the study of electronic states in low dimensional
systems, such as quantum wells, vicinal surfaces and, in general, laterla nanostructures. More information can
be found at the Lab web page: http://dipc.ehu.es/nanolab
There are two differnt on-going projects related to the subject of the present proposal.
The first one “One-dimensional molecular self-assembly on vicinal surfaces”is the current CRP of the SONS
Eurocores. It represents the fundamental, basic search on molecules/templates, which is necessary to carry out
the projected activities of the new CRP SONS Eurocores.
The second one “Caracterización experimental de la respuesta electrónica y óptica de nanoestructuras y
sistemas de baja dimensionalidad” is a Spanish Ministry funded project on similar subjects, where molecular
structures are investigated in the context of the electronic and optical response. It is a collaborative research
work with different theoretical groups in San Sebastian, and from which we obtained a partial funding for the
HR-PES equipment (30000 Euro)
Ther is also an on-going collaboration with Prof. Nazario Martin from the Faculty of Chemistry of the
Universidad Complutense de Madrid, who synthesizes fullerenes and PCBA molecules that are being currently
tested in San Sebastian.
IP1.- B4 OTHER SCIENTIFIC COLLABORATIONS
In the context of the physics of low dimensional, metallic structures we keep a long-time collaboration with
Prof. Himpsel’s group in the University of Wisconsin and the Synchrotron Radiation Center in Madison,
Wisconsin. In such collaboration we basically focus on electronic states of Au/Si systems and magnetic layers.
In the context of magnetic overlayers and nanostructures we keep an on-going collaboration with Prof.
Daehne’s and Prof. Laubschat’s groups, from Berlin and Dresden, respectively. In the latter case, we take
advantage of the collaboration to punctually carry out photoemission experiments in BESSY an at the Lab in
Dresden.
With respect to theory, Ortega’s group is strongly linked to the Solid State theory group in San Sebastian
(http://dipc.ehu.es/group/index.htm), such as A. Rubio (first principles elctronic structure, spectroscopy) and F.
J. García de Abajo (electrodynamics). Related to this project, we plan to collaborate with A. Arnau (STM
modelling) and D. Sánchez-Portal (molecular dynamics).
IP2-B1 PI: Richard Berndt, Universität Kiel
a) Aims and objectives
IP2 aims at the fabrication of linear molecular structures with controllable properties such as specific nearest-neighbour
separation between molecules suitable for polymerization and thus for fabrication of unfolded proteins and other linear
polymers with pronounced one-dimensional character of the electronic states. Moreover, the ordering of chiral molecules on
a chiral vicinal surface will be investigated. We will further study geometric and electronic properties of endohedral
fullerenes at the single-molecule level.
b) Methodologies / Experiments
Pristine metal vicinal surfaces as well as molecular templates developed during the previous funding period will be used,
thereby providing a full variety of length scales and chemical affinities. Molecules will be custom-designed within the
network in IP5 and AP1. Endohedral fullerenes will be analysed together with IP6. The systems are analysed by scanning
tunnelling microscopy and spectroscopy at low temperatures (4 K, 50 K, 80 K).
c) Workplan
(1) C60 meshes and wires as templates
We propose to use Au(788)-C60 and Au(433)-C60 as templates to guide subsequent adsorption of functional units. We
have fabricated fullerene nanomeshes of rectangular fullerene islands (comprised of four fullerene chains, four to five
C60 molecules each) on Au(788) with an extraordinarily high periodicity in two dimensions [1]. On Au(433) we have
achieved an alternation of long and narrow fullerene and gold stripes [2].
(1.1) Polymerisation of fullerene nanostructures
Polymerisation of C60 layers on surfaces is of considerable interest concerning the use of fullerenes as material-resistive
masks for high-resolution photolithography [3]. Typical distances between our fabricated fullerene nanostructures are
10 to 50 nm. Since Rao et al.
[4] first demonstrated polymerisation of C60 films by UV irradiation at room temperature,
there have been several reports on fullerene dimers or polymers formed by various methods such as photoirradiation,
high-pressure compression at high temperature, alkaline-metal doping, and electron impact [5]. The light-induced
chemical reaction, which leads to the dimerisation of fullerene molecules is of the [2+2]-cycloadditional type
[6,7]. The polymerisation was found to occur below a certain threshold wavelength and only when the molecules were
able to rotate, i.e., above the merohedral temperature, which is usually around 250 K [8]. We will therefore use UV
irradiation (160 - 370 nm, 0.1 W/cm2) to achieve polymerisation of the fullerene nanostructures on Au(788) and
Au(433). A UV lamp with these specifications was successfully used by Nakayama and coworkers to polymerise a
fullerene layer [9].
(1.2) “Linear protein”
We propose to adsorb suitably functionalised amino acid (lysine) on the fullerene nanowires in order to achieve a linear
arrangement. Adsorption of amino acids on solid surfaces under ultra-high vacuum conditions has been shown for, e.g.,
Cu(110) [10,11]. A subsequent irradiation of the adsorbate system with UV light (see specifications in (1.1)) will
induce polymerisation of the amino acid molecules, which may lead to the formation of an unfolded protein. If
successful this preparation would open an avenue for fascinating experiments on protein folding.
(2) Polymer formation from diynes and oxazolidin-2,5-dion
In addition to the approach presented above, which relies on C60 templates we will explore an alternative route to
prepare linear molecular wires and proteins. We will adsorb diynes synthesised by IP5 on vicinal surfaces in an attempt
to fabricate linear arrays, which are then then polymerised by UV light irradiation (see specifications of the UV lamp in
(1.1)). As a result polyacetylenes are obtained, which are semiconducting molecular wires consisting of a single C-C
backbone. These ultimately thin molecular chains may be used as wires in molecular electronics. Moreover, we expect
oxazolidin-2,5-dion to arrange in linear arrays. Again, polymerisation will be attempted with the goal to fabricate an
unfolded protein. If it turns out that the molecules do not stick to the surface then they can be chemically modified
(attachment of an aromatic residue) by IP5 to meet the adsorption requirements.
(3) Adsorption of chiral molecules on chiral metal surfaces
Chiral assemblies are particularly interesting for their ability to induce enantioselectivity in catalytic reactions [12] and
for their unique optical [13] and electronic properties [14]. A way to trigger enantioselectivity is to use vicinal, kinked
surfaces that are intrinsically chiral substrates for adsorption [15]. But also achiral substrates can become chiral, either
by adsorption of chiral molecules as in the case of tartaric acid on Cu(110) [12] or by chiral restructuring upon
adsorption, as demonstrated for (achiral) hexa-tert-butyl-decacyclene (HtBDC, C60H66) molecules on Cu(110) [16].
Such local restructuring has been proposed to be one of the key ingredients in understanding phenomena as chiral
recognition, which are believed to be fundamentally relevant for enantiospecific catalysis [17]. Here we propose to
adsorb chiral molecules (tartaric acid, Cu-tetra-3,5 di-ter-butyl-phenyl porphyrin (CuTBPP)) onto Au(16,14,15). This is
a first attempt to study a surface with a high density of kinks, and hence potential chirality. Indeed, the miscut angle of
the substrate has been chosen to tune single-domain, zig-zag, reconstructed terraces, with preferential adsorption sites
at corners. Depending on the observations, other kinked surfaces will be tested to optimise domain size.
(4) Investigation of endohedral fullerenes
Endohedral fullerenes, which are closed-cage carbon molecules with embedded atoms or molecules are expected to be
important for molecular electronics [18]. As a consequence the fabrication of endohedral fullerene wires is of
importance. To fabricate arrangements of endohedral fullerene chains, adsorption on Au(788) will be performed as a
first experiment. In cooperation with IP6 we will investigate the adsorption of endohedral fullerenes on surfaces. While
IP6 will study structural aspects of the adsorption and the electronic properties of H2@C60 (a hydrogen molecule is
incorporated in a fullerene cage) with photoemission, we aim at the discrimintation of the electronic structure of single
H2@C60 from C60 with low-temperature scanning tunnelling microscopy and spectroscopy. In particular we plan to
analyse the vibrational properties of H2 in C60 cages using inelastic tunnelling spectroscopy.
d) Deliverables
Month 12:
IP2 reports on progress in polymerisation of fullerene nanostructures on vicinals.
IP2 reports on adsorption of amino acids and diynes .
Month 24:
IP2 reports on adsorption of oxazolidin-2,5-dion.
IP2 reports on polymer formation of molecules mentioned above.
Month 36:
IP2 reports on adsorption of chiral molecules on chiral surfaces.
IP2 reports on adsorption of endohedral fullerenes on vicinals and the whole project.
e) Justification for budget items
Staff: The complexity of the planned experiments along with the interdisciplinary aspect of the work requires a post
doctoral researcher.
Equipment: To induce polymerisation an UV lamp (Lot-Oriel, 160-370 nm, 0.1 W/cm2) is required along with a power
supply. The light will be focussed onto the sample in ultra-high vacuum using UV-grade lenses (Melles Griot), which
can be approached to the sample by a translation stage (MDC).
References
[1] N. Néel, J. Kröger, and R. Berndt, Adv. Mater., accepted for publication (2005).
[2] N. Néel, J. Kröger, and R. Berndt, Appl. Phys. Lett., submitted (2005).
[3] A. F. Hebard, C. B. Eom, R. M. Fleming, Y. J. Chabal, A. J. Muller, S. H. Glarum, G. J. Pietsch, R. C. Haddon, A. M.
Mujsce, M. A. Paczkowski, G. P. Kochanski, Appl. Phys. A: Solids Surf. 57, 299 (1993).
[4] A. M. Rao, P. Zhou, K.-A. Wang, G. T. Hager, J. M. Holden, Y. Wang, W.-T. Lee, X.-X. Bi, P. C. Eklund, D. S.
Cornett, M. A. Duncan, and I. J. Amster, Science 259, 955 (1993).
[5] M. S. Dresselhaus, G. Dresselhaus, and P. C. Eklund, Science of Fullerenes and Carbon Nanotubes (Academic, New
York, 1996), p. 106, and references therein.
[6] M. R. Pederson and A. A. Quong, Phys. Rev. Lett. 74, 2319 (1995).
[7] C. H. Xu and G. E. Scuseria, Phys. Rev. Lett. 74, 274 (1995).
[8] W. I. F. David, R. M. Ibberson, J. C. Matthewman, K. Prassides, T. J. S. Dennis, J. P. Hare, H. W. Kroto, R. Taylor, and
D. R. M. Walton, Nature (London) 353, 147 (1991).
[9] T. Nakayama, J. Onoe, K. Nakatsuji, J. Nakamura, K. Takeuchi, and M. Aono, Surf. Rev. Lett. 6, 1073 (1999).
[10] E. M. Marti, S. M. Barlow, S. Haq, and R. Raval, Surf. Sci. 501, 191 (2002).
[11] Q. Chen and N. V. Richardson, Nature Materials 2, 324 (2003).
[12] M. Ortega Lorenzo, C. J. Baddeley, C. Muryn, and R. Raval, Nature (London) 404, 376 (2000).
[13] T. Verbiest, S. Van Elshocht, M. Kauranen, L. Hellemans, J. Snauwaert, C. Nuckolls, T. J. Katz, and A. Persoons,
Science 282, 913 (1998).
[14] K. Ray, S. P. Ananthavel, D. H. Waldeck, and R. Naaman, Science 283, 814 (1999).
[15] Ch. McFadden, P. Cremer, A. Gellmann, Langmuir 12, 2483 (1996).
[16] M. Schunack, L. Petersen, A. Kühnle, E. Lægsgaard, I. Stensgaard, I. Johannsen, and F. Besenbacher, Phys. Rev. Lett.
86, 456 (2001).
[17] A. Kühnle, T. R. Linderoth, B. Hammer, and F. Besenbacher, Nature (London) 415, 891 (2002).
[18] S. Kobayashi, S. Mori, S. Iida, H. Ando, T. Takenobu, Y. Taguchi, A. Fujiwara, A. Taninaka, H. Shinohara, and Y.
Iwasa, J. Am. Chem. Soc. 125, 8116 (2003).
IP2 - B.2
CRP Acronym: MOL-VIC
PI 2 Berndt, Kiel University:
IP Nr: 2
Funding Agency:
Outline Proposal Nr(s).:
BUDGET ITEMS
must be consistent with the rules set by
the relevant national funding agencies
Duration
where
appropriate
in month,
including
start date
YEAR 1
Funding
YEAR 2
Funding
YEAR 3
Funding
TOTAL Funding
Short Description
of each budget item where appropriate
(in Euros) [other
currencies]
(in Euros) [other
currencies]
(in Euros) [other
currencies]
(in Euros) [other
currencies]
Complex experiments with
interdisciplinary aspects
56000
56000
56000
UV-lamp setup for polymerisation
experiments
19700
Salary position
Ph.D. student
Post-doc. researcher
168000
senior researcher
Technician
student stipend / student assistant
Equipment per item
item 1
19700
item 2
item …
Travel
conferences, workshops, travel to
fieldwork, visits
(including networking within the CRP)
4000
4000
4000
12000
5000
5000
5000
15000
Consumables / Running Costs
including analysis costs
Publication, Dissemination Costs
Overheads
if applicable
Others
including access to large infrastructures,
shiptime, etc. (please specify)
T O T A L
84700
65000
65000
214700
IP2.- B3 RELATED PROJECTS
As evident from our recent publications our work revolves around spectroscopy of individual atoms, molecules
and clusters. In terms of funding, the only project related to MOLVIC is Scanning Tunnelling Microscopy of
metal-chalcogenides and organic molecules in the framework of the “DFG Forschergruppe 353”. More
information can be found at the Lab web page: http://www.ieap.uni-kiel.de/surface/ag-berndt/.
IP2.- B4 OTHER SCIENTIFIC COLLABORATIONS
We have a number of scientific collaborations which are reflected by the more recent publications. S. Crampin
(Bath, UK) is performing various electronic structure calculations related to our experimental results. P.
Johansson (Örebro, Sweden) performs numerical modelling of light emission from the STM and of the impact of
the STM tip on electronic states. W. Hofer (Liverpool, UK) supports us with total energy calculations for our
transport experiments on single atoms. M. Brandbyge (Copenhagen, Denmark) calculates inelastic effects in
molecular transport related to our recent experiments on single molecules (unpublished work). N Lorente
(Toulouse, France) investigates molecular interactions in order to interpret our data on orbital shifts of organic
molecules in two-dimensional meshes. The group of P. Echenique (San Sebastian) has provided continuous
backing in interpreting electron dynamics at surfaces.
There is an on-going collaboration with R. Wiesendanger (Hamburg, Germany) on spin-polarised tunnelling.
Locally, in Kiel, we cooperate with groups in the theoretical physics department, from the “Technische Fakultät”
and from the chemistry department in an initiative for a “Sonderforschungsbereich” on switching processes of
organic molecules at surfaces.
IP3-B1 PI: Enrique García Michel, Universidad Autónoma Madrid
Substrate-mediated self-assembly of organic molecules: structural and electronic properties
1-IP AIMS AND OBJECTIVES:
Building up a functional structure exploiting self-organization requires a detailed understanding of the self-organization
process itself. Both physical and chemical properties and the equilibrium structure of a self-organized system depend on the
interactions between the molecular components and with the supporting substrate. Controlling the self-organization process
requires to understand the interactions at nanoscopic level (intermolecular and molecule-substrate), their hierarchy and the
influence of kinetic parameters. Taking into account the complexity of the self-organization process, and the wide range of
interactions playing a role, it is important to analyze a variety of model systems, which can provide information on each
aspect of the process. The main goal of this IP is to understand the different modes of intermolecular interactions mediated by
the substrate. This means that we are considering dilute systems (where the mean intermolecular distance is beyond the reach
of direct interactions), and /or molecular species which do not exhibit stronger direct interactions, like hydrogen bonding.
This kind of systems are less common than supramolecular structures where direct bonding takes place, but can be very
interesting.
There exist different mechanisms for substrate-mediated interactions. A long-time known mechanism for atomic selfassembly is long-range (10–30 nm) surface-state-mediated adatom interaction 1, which is known to operate on metal
surfaces2. The adatom acts as an impurity, and the surface state electrons try to screen it. This produces surface state Friedel
oscillations. Not all wave vectors contribute to the screening process, because of the cutoff at the Fermi energy 3. As a result
the local density of states at the Fermi energy oscillates around the impurity with a wavelength of F/2=/kF, where F is the
Fermi wavelength and kF the Fermi wave vector. The variation of the local density of states at E F due to standing-wave
formation modifies the adsorption energy of the adsorbates. Regions of high local density of states are favoured for adatoms.
Thus, the interaction between the adsorbates, and consequently their mutual distance, is determined by the LDOS at EF. The
interaction energy decays as 1=r2 where r is the distance between two adatoms, and oscillates with a period of F/2, half of the
Fermi wavelength of the surface-state electrons. A first goal of this IP is checking the extension of this mechanism to
supramolecular ordering. Preliminary results for pentacene adsorption on Cu(110) indicate that a surface-state mediated
interaction might be playing a crucial role in the formation of pentacene superstructures. We expect that surface state
mediated interaction dominates the supramolecular ordering for adequate metallic substrates and for molecules which are not
suitable for directional intermolecular interactions, as hydrogen bonds. This is the case of simple aromatic molecules like
pentacene or anthracene, but also of more complex molecules. The use of vicinal noble metal surfaces provides us with an
additional degree of freedom, because the properties of the surface state can be tuned by changing the miscut angle 4, and thus
different regimes can be probed. In turn, this can be used to understand the details of the interaction. For instance, although
there is no known case of formation of supramolecular ordering mediated by the electrons confined at the terraces, this is
certainly possible, and it will be explored along this IP by using vicinal noble metal surfaces.
A second mechanism for substrate-mediated self-ordering is related to the existence of elastic interactions. In general, the
formation of periodic structures involves an energy cost, related to the formation of boundaries. Models based on linear
elasticity theory predict that the elastic energy gained in the bulk by the formation or alternate domains with different surface
stress might be sufficient to pay back the energy cost of boundary formation. This mechanism seems to be acting in the
faceting of vicinal surfaces and in the formation of stripes upon oxygen adsorption on Cu(110) 5. The case of N on Cu(100) is
somewhat more complex, but can be explained on the same grounds. There is also direct evidence for the effect of local
surface strain on the bonding strength for adsorbates6. It is a natural extension of all these observations that the local strain
field modifies the adsorption energy of more complex molecules. Obviously, the mechanism is not straightforward, since any
modification of the strain will also affect the local electronic structure7. In this IP we intend to explore the role of local strain,
1
K.H. Lau and W. Kohn, Surf. Sci. 75, 69 (1978).
J. Repp et al, Phys. Rev. Lett. 85, 2981 (2000).
3 P. Hyldgaard and M, Persson, J. Phys. Cond. Matt 12, 13 (2000).
4 J.E. Ortega et al. Phys. Rev. Lett. 84, 6110 (2000).
5 V. Repain et al, Phys. Rev. Lett.84, 5367 (2000) ;K. Kern et al, Phys. Rev. Lett. 67, 855 (1991).
6 M. Gsell et al, Science 280, 717 (1998).
7 D. Sekiba et al, Phys. Rev. Lett. 94, 016808 (2005).
2
and substrate structure modification upon adsorption, in the formation of complex, long-range ordered superstructures.
Vicinal surfaces already characterized along the current CRP offer an excellent playground for studies of this kind, since the
terrace size and other structural parameters of the substrate can be tuned.
2-METHODOLOGIES/EXPERIMENTS:
The complexity of the physical effects analysed requires a multi-technique approach in order to probe simultaneously the
structural and electronic properties of the system. The generic objective of the IP (to understand the mechanisms which rule
the self-organization of diluted systems) requires the analysis of two different properties: Structural properties, to determine
the nature of the long-range order in the self-organized systems, including both the superstructure geometry and the possible
modifications of the substrate structure, and electronic properties, to understand the role of the electronic structure in the
self-organization process.
Low-energy electron diffraction (LEED) will be used to study the long range order of superstructures grown on vicinal
templates. LEED has many advantages with respect to other structural techniques, like its high surface sensitivity and its
readiness as a conventional laboratory technique. Its main disadvantage is the possible sensitivity of organic molecules to the
electron beam, and also the complexity of the superstructures induced by molecular self-assembly, which tend to exhibit large
unit cells. Both problems are to be overcome by the use of spot-profile LEED (SPALEED). On the one hand, the use of
channeltron amplification enables the use of much lower electron currents (in the range of 500 pA). On the other hand, the
large transfer width of SPALEED enhances the resolution and facilitates the analysis of complex superstructures. An
SPALEED apparatus will be available soon in our laboratory, and it will be integrated with our current ARPES spectrometer,
already operational, which comprises a high-flux He-plasma UV source, a hemispherical electron analyzer and a cryogenic
manipulator with 5 degrees of freedom. The energetic resolution of this setup is 30 meV and the angular resolution is 0.5º
(equivalent to a k-space resolution of 0.03 Å-1 approximately, which enables us to probe unit cells in the range of 3-4 nm. The
integration in the same apparatus of ARPES and SPALEED constitutes a powerful combination of probes of reciprocal space,
sensitive to both structural and electronic properties. While STM provides local structural information, such as molecular
adsorption sites and conformation, SPALEED is sensitive to long range order. We note that a crucial step for the success of
our approach is the combination of the structural information provided by SPALEED and by STM (IP1, IP2).
While SPALEED is the technique best adapted for the overall problems we are going to face, we are also familiar with other
structural techniques, which will be used if necessary. In particular, surface x-ray diffraction can be useful to analyze the
minor modifications induced in the substrate by molecular adsorption. Photoelectron diffraction (IP6) is also useful whenever
there is no long-range order, but there is a well-defined local molecular adsorption geometry. It is also sensitive to local
modifications of the substrate induced by the adsorption.
3-WORK PLAN AND MILESTONES
We consider both scientific activities and instrument implementation.
SCIENTIFIC ACTIVITIES
Activity 1: Template production and characterization (YEAR 1)
The goal is to obtain templates which offer different periodicities and electronic structures, suitable to test the molecular
assembly for a variety of controlled situations. We restrict ourselves to substrates without a direct chemical reaction with the
adsorbates, since the deposited molecular species should remain stable. The substrates of choice are single-crystalline vicinal
noble metal surfaces. A previous characterization by STM of the substrate properties will be undertaken by IP1 and IP3, or it
has already been done along this project. In any case, an in situ characterization with LEED and SPALEED will enable a
quantitative analysis of the substrate structure and the availability of templates with reproducible properties.
Milestone: obtaining a broad range of well-characterized substrates with tunable structural and electronic properties.
Activity 2: Molecular assembly: structural properties (YEAR 1-2)
Molecular assembly will be analyzed using the substrates obtained from Activity 1. We are experienced in the use of vicinal
noble metal surfaces. The variety of structural parameters which can be modified (terrace size, nature of the step, azimuthal
orientation of the step, etc) will facilitate the selection of the substrate most adequate for each type of molecule. For instance,
one dimensional self assembling along terraces requires a terrace size significantly larger than the molecular size.
Furthermore, tuning the terrace size by changing the miscut angle modifies also the surface electronic structure in a controlled
manner, which can be used to test the mechanisms of the substrate mediated interaction.
Activity 2.1: Substrate mediated molecular assembly
We plan to analyze the nature of the assembling process by studying aromatic molecules adsorbed on vicinal surfaces with
large terraces. The terrace widths will be used to tune the substrate electronic properties and find a correlation with the
molecular superstructures observed.
Milestone: obtaining long-range ordered self-organized structures for aromatic molecules for different terrace widths.
Characterization of their structural properties using SPA-LEED.
Activity 2.2: Structural modifications of the substrate after adsorption
An important aspect of the molecule-surface interaction is the structural modification of the substrate to optimize adsorbatesubstrate chemical bonding. This effect can become very important, giving rise to a true deformation of the substrate to adapt
it to the molecule. The structure can be analyzed using SPALEED; but it is possible that an analysis using photoelectron
diffraction (IP3) is needed, since this technique is better adapted to the analysis of local deformations.
Milestone: developing routine tools to characterize the substrate deformation for simple aromatic molecules of different
lengths.
Activity 3: Molecular assembly: electronic properties (YEAR 2-3)
Angle resolved photoemission will be used to study the electronic structure of the template and of the molecular
superstructure. The main goal of this IP is to understand and evaluate the substrate mediated interaction. To this end, an
analysis of the electronic structure before and after adsorption is crucial. As already observed by us, a long-range ordered
molecular superstructure can either induce new surface states, or modify the periodicity, filling and reciprocal space location
of already existing surface states. All these changes induce a more favourable electronic structure, which in turn facilitates the
formation of certain molecular superstructures.
Milestone: developing routine tools to characterize substrate deformation for aromatic molecules of different lengths.
INSTRUMENT IMPLEMENTATION
Activity 4: put into operation of new UHV chamber (YEAR 1)
Design, acquisition and put into operation of a ultra-high vacuum chamber dedicated to the exposure to molecular adsorbates.
The chamber should have an independent pumping system, evaporators of Knudsen cell type, a manipulator compatible with
the current transfer system of the chamber and a quadrupole mass spectrometer (QMA), which will be used to test the purity
of the residual gas and the adsorbates. A conventional LEED apparatus will be installed as well for a rapid test of
superstructure formation.
Milestone: put into operation of a UHV chamber dedicated to molecular exposure.
Activity 5: put into operation of SPALEED diffractometer (YEAR 1)
Put into operation of low-energy electron diffractometer with spot profile analysis, adapted to the study of complex surface
periodicities. Development of adequate software tools.
Milestone: put into operation of the SPALEED apparatus.
4-JUSTIFICATION FOR BUDGET ITEMS
The development of the scientific objectives described above requires very strict experimental conditions. In particular, the
process of molecular evaporation must be done in a dedicated UHV chamber, in order to avoid damage to the instruments of
the main chamber and to guarantee controlled preparation conditions. Sample preparation (ion gun, sample heating) are
needed in this chamber also. A QMS is also required to guarantee the quality and cleanliness of the molecular evaporations.
An important budget item is the application for the salary of a postdoctoral researcher. The development of the activities
described in the project represents a significant increase of the work load, which cannot be undertaken without additional
manpower. The postdoctoral researcher hired will take care of the operation of the SPALEED, data acquisition and analysis,
with support from the rest of group. He/she will also be involved in the whole research activities related to this IP.
IP3 - B.7
CRP Acronym: MOL-VIC
Outline Proposal Nr(s).: 05-SONSOP-014
BUDGET ITEMS
must be consistent with the rules set by
the relevant national funding agencies
Salary position
Post-doc. researcher
Equipment per item
Item 1
Item 2
Item 3
E.G: Michel, Universidad
Autónoma de Madrid
Funding Agency: Minist. de
Educación y Ciencia (Spain)
IP Nr:3
Duration
where
appropriate
in month,
including start
date
24,1.1.2008
YEAR 1
Funding
YEAR 2
Funding
YEAR 3
Funding
TOTAL Funding
Short Description
of each budget item where appropriate
(in Euros) [other
currencies]
(in Euros) [other
currencies]
(in Euros) [other
currencies]
(in Euros) [other
currencies]
35360
35360
Salary of post-doc researcher
70720
Quadrupole Mass Spectrometer
UHV chamber and UHV gauge
Turbo and rotary pumps, gate
valve
Transfer rod
20000
20000
12000
20000
20000
5000
5000
Conferences, workshops,
2000
2000
2000
6000
Small parts, samples, evaporation
material
2000
2000
2000
6000
Publication, Dissemination Costs
Publication costs
Overheads
19%
0
9310
1000
9948
1000
7668
2000
26927
1000
1000
1000
3000
Item 4
Travel
conferences, workshops, travel to
fieldwork, visits
(including networking within the CRP)
Consumables / Running Costs
12000
including analysis costs
if applicable
Others
Travel to synchrotron radiation
facilities
including access to large infrastructures,
shiptime, etc. (please specify)
T O T A L
59310
63308
49028
171647
IP3.- B3 RELATED PROJECTS
We have successfully conducted during last years a significant number of research projects and research contracts, both at
national and international levels. An important scientific production is derived from this activity: more than 80 publications
in international journals since 1997, a similar number of contributions to conferences (many of them invited and frequently
chairing sessions), six PhD thesis successfully finished, and two more being currently done.
The current MOL-VIC application is the continuation of our on-going MOL-VIC project. With the exception of
this project, which we do not describe here, there is no direct relationship with other already funded or applied for
projects, besides the fact that all the projects are related to the investigation of the electronic structure of surfaces and
interfaces. In particular, the role of the electronic energy in the stabilization of low-dimensional structures has been
analyzed in several different model systems, a topic related in part to our contribution to MOL-VIC. In recent years our
research has focused in two different topics related in part to the subject of this application:
1- Role of electronic effects in the formation of collective states at surfaces. In this general topic we have
analyzed
a) 2D structural phase transitions and electronic effects: we have studied several model systems, like
K/Si(100), where different effects compete to determine the metallic character of the surface, giving rise to a complex
experimental phenomenology. We have also studied the surface of Sn/Si(111) as a function of coverage in the range of
formation of a solid solution of (3x3)R30º structur. We observe in this surface a metal/semiconductor transition as a
functions of coverage, related to the existence of a small charge transfer between Sn and Si at low coverage.
b) Surface charge density waves: several years ago, the existence of a surface CDW in Sn/Ge(111) and
Pb/Ge(111) was proposed. We have studied these two systems using several different techniques. Our analysis of the
evolution of the electronic structure of the system with temperature, of the structure of the low temperature phase, and
finally the observation of a soft phonon related with the transition, allowed us to demonstrate that the phase transition is
much more complex than expected, but it is not related to CDW stabilization.
2-Quantum confinement effects at surfaces
a) Quantum Well Status and electronic growth: in previous works we have demonstrated the existence of
several periodicities of QWS, and we have also studied other properties of these systems. More recently, we have
analyzed the use of QWS as a sensitive probe to analyze final state bands.
b) Electronic structure of laterally nanostructured systems: we have studied the electronic structure of Cu(223)
and Ag/Cu(223). In this case, the layer of Ag generates a surface with facets which produces lateral confinement of the
electron surface states. We have also studied as model system the stepped surfaces of Cu(111), where we detect a
change in the nature of the electron wave function of the surface state, related to the lateral periodicity of the surface.
Self-organization at surfaces has been exploited as a way to produce long-range ordered nanostructures.
IP3.- B4 OTHER SCIENTIFIC COLLABORATIONS
We participate in several different international collaboration programmes. Through these programmes we have
successfully developed collaborations with the following groups (we exclude here collaborations within the
MOL-VIC project):
2- K. Wandelt, at the Institute for Theoretical and Physical Chemistry of the University of Bonn,
Germany.
3- P. Soukiassian, at the University of Paris-Sud and CEA, in France.
4- T. Balasubramanian, at the synchrotron radiation laboratory Max-Lab, in Sweden.
5- H. Ascolani, at the Atomic Center of Bariloche (Argentina).
6- G. Panaccione, at the TASC laboratory of CNR in Trieste (Italy).
25
IP4-B1 PI: Karsten Horn, Fritz Haber Institut, Berlin
Low-dimensional molecular arrangements – electronic structure and chirality
1. Aims and Objectives
At the center of interest in the group “PI Horn” is the characterization of the electronic structure of low-dimensional
systems in its relation to morphology and molecular conformation on flat and stepped surfaces. Starting from a
general characterization of complex organic molecules as demonstrated in previous work, we will move towards
complex systems in which dimensionality is imprinted on the overlayers by means of suitable vicinal surfaces. The
experimental methods are core and valence level photoelectron spectroscopy assisted by scanning tunnelling
microscopy to ascertain the desired conformation of the overlayer-substrate system.
Of particular interest in the continuation of the project will be two aspects of molecular structures on surfaces: a)
the chiral nature of adsorbed species, and b) the change in molecular confirmation upon excitation with electrons
and UV light. Both aspects within the general MOL-VIC framework are discussed in the detailed work plan
below.
2. Methodology/Experiments
The group has studied several molecular adsorbates on metal and semiconductor surfaces with a view to identifying
the bonding interaction of simple organic molecules with metal and semiconductor surfaces. Recently, interest has
moved on to identifying the chiral nature of molecules and molecular fragments on surfaces. Chirality is a fascinating
aspect of molecular structure, not only from a fundamental point of view1 (e.g. a single handedness of practically all
biologically active molecules), but also in view of applications.
Enantiomeric purity of chemical products is of central importance in
any production, for example2 (remember for example the
thalidomide tragedy). Heterogeneous catalytic processes for enantioselective synthesis have important advantages over conventional
homogenous ones. The induction of a chiral preference by coadsorption of so-called chiral “modifier” molecules is an important
step in the heterogeneous catalytic conversion of pro-chiral reagents
into one of the possible optical isomers.3
The problem is that the characterization of the chiral nature of
adsorbed molecules is difficult; the usual method of optical rotation
fails because of the low concentration of scatterers, and (on metal
surfaces) because of the optical properties of the substrate. Certain
spatial arrangements of molecules have been studied in STM, which
are clearly induced by the chiral nature of the adsorbate. However,
the detection of chiral centers by means of the widely used electron
spectroscopies has so far proven elusive.
Utilizing the access to circularly polarized x-rays at the BESSY
storage ring, we have used circular dichroism in core level
photoemission to identify the (R,R) and (S,S) forms of butanediol on
Si(100)4. In both cases, a sizeable dichroic signal was found in the
C15 spectra, which erased upon changing the enantiomer, and was
absent when studying the achiral (R,S)-form of the molecules. There
is a complication in such experiments due to an influence of the
experimental geometry which may induce dichroism not related to
the adsorbate, but this was avoided using a specific high symmetry
geometry. Consider the data in Fig. 1 which clearly show the
Fig. 1: a) Schematic view of the experimental
geometry for circular dichroism experiments. b)
Photoelectron spectra of the C 1s levels for the
stereoisomers of 2,3-butanediol excited by right
(dashed, blue) and left-circularly polarized (solid
line, red) light. forms. c) Difference signal for the
three stereoisomers. From ref. 4 .
26
reversal of dichroism in adsorbed butanediol. Work on adsorbed tartaric acid, the molecule in which Pasteur found
the first evidence for such chirality, has begun and is expected to yield important data on the interplay between the
chirality and different structural arrangements on the surface (mono- and bitartrate); this system is useful since, in
contrast to butanediol, detailed structural data exist.
Within the second topic, i.e. change in molecular conformation upon excitation with electrons and photons, work has
been carried out on the characterization of biphenyl, in collaboration with the group of Prof. Dujardin, Paris. Prof
Dujardin's group has recently demonstrated that in biphenyl adsorbed on Si(100), reversible molecular increments
can be induced by resonant electronic excitation – different reversible and bistable movements were selectively
activated by tuning the electron energy5. Such molecular switching may open up interesting applications in the field
of molecular electronics. Our photoemission and NEXAFS data (work in progress) may serve to identify the bonding
mechanism and conformation. Ultimately, we aim at using selective UV irradiation to induce movements in this socalled “molecular nanomachine”.
3. Work plan and milestones
In the continuation of the project, four topics are at the center of interest. First, in all systems to be studied,
photoelectron spectroscopy will be used to elucidate the electronic structure of the adsorbed molecules, which is
central to an understanding of all aspects of the formation of supramolecular assemblies. From simple molecules
such as stilbene and tartaric acid discussed below in a separate context, to the complex ones such as oxazolidin-2,5diones carboxy-hydroxamic acids preprared by Herges (IP 5), valence level spectra supported by quantum chemical
calculations will shed light on the bonding mechanism and the influence of configurational changes in the adsorbed
phase on the molecular orbital structure. Second, the aspect of molecular chirality on surfaces will be addressed on
vicinal surfaces. We have recently studied the clean and metal-covered
Si(557) surface, which consists of regular terraces, with a view to
identifying the causes for a large anisotropy observed in electronic
transport measurements. This vicinal template, and similar metal ones,
will be used to study quasi-one-dimensional structures of chiral
molecules on surfaces. Moreover, this work will be extended to vicinal
surfaces where chiral centers in the clean surface can be prepared by a
suitable miscut of the surface, to produce kinks. This will yield insight
into the action of the surface to induce chirality in more complex organic
molecules. This work will be carried out in a combination of STM and
photoemission studies, using mainly silicon surfaces as templates. A
close collaboration with IP 1 – Ortega for the use of well-defined vicinal
surfaces, and with IP 2 –Berndt for the STM characterization of such
chiral systems is mandatory for the successful realization of this project.
Fig. 2: Molecular models for cis- and
A third topic is the attempt to induce chirality into adsorbed achiral
trans-stilbene.
layers by using a kind of "doping" method. Recently, evidence was
found for a process in which a small amount of chiral molecules may act to switch an entire achiral layer of succinic
acid into a chiral form6. This surprising, apparently long-range action of a small amount of chiral modifiers may be
important for the use in heterogenous catalysis, and may also shed light on the process of molecular recognition
which probably needs an "amplification" stage.
The fourth topic relates to the switching of molecules on surfaces induced, for example, by illumination with near-uv
radiation. A number of studies have shown that a cis-trans isomerization in stilbene occurs in the gas phase (see
molecular models in Figure 2), and mechanisms for this process have been proposed 7. This process may also occur,
although following a different pathway, on solid surfaces, suggesting a variety of applications. The IP Horn is
located in the Department of Molecular Physics of the Fritz-Haber-Institute, where laser sources are available to
study such switching process as a function of several parameters (illumination wavelength, pulse length, polarization
etc.) Starting from an analysis of pure cis- and trans-stilbene on surfaces, ways to identify the molecular
conformation from its valence level spectrum, and from the adsorption geometry interpreted from NEXAFS will be
27
explored. This will lead to detecting such molecular switching processes in adsorbed stilbene. While these initial
studies may also be carried out on flat surfaces, the continuation of the project, with various functional groups
attached to the stilbene main building blocks, will benefit from the use of linear structures. Again, this work requires
the characterization of the layers by STM, either in the home lab or in collaboration with IP 2, since the
conformational changes induced by light are likely to be strongly influenced by terrace width and atomic structure of
the substrate at steps and kinks, in the sense of a steric hindrance.
Milestones:
-
completion of the study on the chiral nature of different structures of tartaric acid on Cu(110)
-
clarification of the "doping" action of chiral molecules in achiral adsorbed layers
-
investigation of complex adsorbed molecules, e.g. oxazolidin-2,5-diones and carboxy-hydroxamic acids
-
identification of the cis- and trans- conformation of stilbene on surfaces
-
demonstration of molecular switching induced by light in adsorbed stilbene layers
-
study of stilbene with functional endgroups.
Deliverables – see work plan
4. Justification for budget items
This work needs a fully dedicated postdoctoral researcher to tackle the complexity of the experiments involved,
and the command of the different experimental efforts and interpretation methods.
References
1.
2.
3.
4.
5.
6.
7.
L.Pasteur, Ann.Chim. Phys. III, 24, 442(1848).
I. Agranat, H. Caner, and J. Caldwell, Nat. Rev. Drug. Discov. 1, 753 (2002); T. P. Yoon and E. N.
Jacobsen, Science 299, 1691 (2003).
H. B. Fang, L. C. Giancarlo, and G. W. Flynn, J. Phys. Chem. B 102, 7311 (1998); R.Fasel, M. Parschau,
and K.-H. Ernst, Angew. Chem. Int. Ed. 42, 5177 (2003).
J. W. Kim, M. Carbone, J. H. Dil, M. Tallarida, R. Flammini, M. P. Casaletto, K. Horn, and M. N.
Piancastelli, Phys.Rev. Lett., 95, 107601(2005).
M. Lastapis, M. Martin, D. Riedel, L. Hellner, G. Comtet, G. Dujardin, Science 308,1000(2005).
M. Parschau, T. U. Kampen, and K.-H. Ernst, Chem. Phys. Lett. 407, 433-437 (2005).
W. Fuß, C. Kosmidis, W.E. Schmid, and S. A. Trushin, Angew. Chemie Int.Ed. 43, 4178(2004).
IP4 – B2
CRP Acronym: MOL-VIC
IP Nr:
must be consistent with the rules set by
the relevant national funding agencies
Duration
where
appropriate
in month,
including start
date
YEAR 1 Funding
YEAR 2
Funding
YEAR 3
Funding
TOTAL Funding
(in Euros) [other
currencies]
(in Euros) [other
currencies]
(in Euros) [other
currencies]
(in Euros) [other
currencies]
56.000
56.000
Short Description
of each budget item where
appropriate
Fritz-Haber-Institut
DFG
Funding Agency:
Outline Proposal Nr(s).:
BUDGET ITEMS
K.Horn
PI Name & Institution:
4
Salary position
Ph.D. student
Post-doc. researcher
Scientific experiments on
senior researcher
supramolecular structures on
Technician
surfaces
56.000
168.000
student stipend / student assistant
Equipment per item
item 1
item 2
item …
Travel
conferences, workshops, travel to
fieldwork, visits
(including networking within the CRP)
Consumables / Running Costs
including analysis costs
Publication, Dissemination Costs
Overheads
if applicable
Others
including access to large infrastructures,
shiptime, etc. (please specify)
TOTAL
56.000
56.000
56.000
168.000
29
IP4 – B3 RELATED PROJECTS
The group of the Principal Investigator has conducted, over the last six years,, a number of research
projects aimed at understanding the electronic structure of low-dimensional systems, as well as
complex metallic alloys. There are no related projects in this sense which are funded from national or
international agencies. The PI is partner of the EU Network of Excellence "Complex Metallic Alloys" in
which crystalline alloys with hundreds and thousands of atoms in the unit cell as well as
quasicrystalline materials are investigated.
IP 4 – B4 OTHER SCIENTIFIC COLLABORATIONS
The principal investigator maintains a number of informal collaborations with German and EU groups
in the field of adsorbed layers and low-dimensional systems, which do not, however, collide with the
activities proposed in the continuation project.
30
IP5-B1 PI: Rainer Herges, Universität Kiel
One-dimensional polymerization and attachment
a) Aims and objectives
“IP Herges” aims at the design and synthesis of compounds for the preparation of linear polymeric structures, such as
polydiacetylenes and unfolded poteins, on a surface. Polydiacetylenes are fully conjugated molecules that exhibit interesting
electronic properties such as conductivity and thus have the potential to be used as molecular wires. The polymerization of
suitable precursors preorganized in a linear array leads to protein chains in a non-natural unfolded conformation providing
the opportunity to study the biochemically important folding process.
b) Methodologies / Experiments
Chemistry and particularly chemical synthesis on metal surfaces is different from the traditional “wet chemistry”. To
synthesize isolated linear polymers on surfaces, the monomers have to be designed in such a way that a self-propagating
chain reaction in one or two dimensions can be initiated. E. g. diynes with an alkane spacer and a thiol end group and a long
alkane substituent are forming self assembled monolayers suitable for photochemically induced polymerization. Oxazolinediones and malonic acid monoazides are suitable precursors for the protein formation under above conditions. One- or twodimensional arrangements of C60 will be used as templates for protein synthesis. To attach the amino acid lysine on C 60 the
amino group in the side chain has to be converted to an azide. More functionalized fullerenes will be prepared by
cyclopropanation via the Bingel reaction. The amino acid monomers and photoswitchable compounds have to be modified
with thiol or dithiocarbamate groups to be attached to a gold surface. These compounds are not commercially available and
have to be synthesized and optimized in our laboratory. Moreover, surface polymer chemistry is a relatively new field and
has to be developed in specific areas by our group. Our compounds will be tested in close collaboration with the surface
physicists “IP’s Bernd, Greber, Horn and Michel.
c) Workplan
(1) Polymerisation of amino acid derivatives on surfaces.
In nature proteins are sequentially synthesized in the ribosome. Immediately after the protein chain leaves the ribosome
it starts folding to the native structure. The folding process is difficult to study because so far there is virtually no way
to prepare the linear starting structure and because the folding cannot be stopped and investigated in intermediary
stages. A linear array of amino acid precursors on a surface polymerized to an isolated non-solvated protein chain
would be a prototype starting configuration for the investigation of the folding process. Studies of the (electronic)
structure of the unfolded protein would be inherently interesting.
Unfortunately, the well established “wet chemistry” methods for protein synthesis are not suitable under the ultra
high vacuum conditions necessary for the present study. New methods have to be developed that avoid additional
reagents and polar solvents. Oxazolidine-2,5-diones have been shown to polymerize in solution[8] or even in the solid
state[9,10] to form proteins when initiated with a base in a self-propagating chain reaction. Oxazoline diones can be
prepared from various amino acids and phosgene[11] or the less hazardous triphosgene.[12] It should be possible to
initiate the polymerization at the surface using the STM tip.
Other protein precursors that can be initiated by heat or irradiation are salts of carboxy-hydroxamic acids[13,14] or
substituted malonic acid mono azides.[15]
Two different approaches will be pursued to prepare linear arrays of amino acid precursors
[8] K. Heyns, R. Brockmann, Z. Naturforschg 1954, 9b, 21-26.
[9] H. Kanazawa, Polymer 1992, 33, 2557-66.
[10] B. M. Abo-El Khair, T. Komoto, T. Kawai, Makromol. Chem. 1976, 177, 2481-2489.
[11] J. Grimshaw, S. D. Perera, J. Chem. Soc., Perkin Trans 2 1989, 1771-18.
[12] I. A. Rivero, S. Heredia, A. Ochoa, Synth. Commun. 2001, 31, 2169-76.
[13] C. D. Hurd, C. M. Buess, J. Am. Chem. Soc. 1951, 73, 2409.
[14] C. D. Hurd, C. M. Buess, L. Bauer, J. Org. Chem. 1952, 17, 865.
[15] T. Curtius, W. Sieber, Ber. Dtsch. Chem. Ges. 1922, 55, 1543.
31
(1.1) Unfolded protein on C60 meshes and wires
C60 islands and stripes prepared by IP Berndt will be functionalized with lysine derivatives which subsequently will be
polymerized to form unfolded protein chains. The amino acid lysine, therefore, will be converted to the corresponding
oxazolidine-2,5- dione with triphosgene and the amino end group to an azide with azidotris(diethylamino)phosphonium
bromide[16] or sodium azide and triflic anhydride.[17] The azide reacts with C60 by elimination[18] of N2 connecting the
lysine side chain to C60. Polymerization will be initiated by irradiation or with the STM tip.
Further substituted fullerenes will be synthesized by cyclopropanation of C60 using the Bingel-reaction with 2-bromoindan-1,3-dione. The C60 derivatives will be used by IP Ortega.
(1.2) Unfolded “stretched protein“
We will prepare various oxazolidin-2,5-diones from amino acids, as well as carboxy-hydroxamic acids[19,20] and
substituted malonic acid mono azides. IP Berndt will adsorb the “protein monomers” on metal sufaces and initiate the
polymerizations using the STM tip, heat or light. Horn and Michel will characterize the electronic structure of these
proteins.
(2) Polydiacetylenes
Self-assembled monolayers of diacetylenes polymerize upon irradiation or by application of an electric stimulus using a
STM microprobe. The method can be used to create one-dimensional molecular nanowires[21] at desired positions with
controlled termination by making artificial defects in the monolayer.[22] Applications range from sensors, non-linear
optical materials to the realization of nanodevices.[23] The starting material will be synthesized by the IP5, Herges and
the surface experiments are performed by IP Berndt.
[16] S. P. Klump, H. Shechter, Tetrahedron Lett. 2002, 43, 8421-24.
[17] C. J. Cavender, Shiner, V. J., J. Org. Chem. 1972, 37, 3567-69.
[18] M. Prato, Q. Li, F. Wudl, V. Lucchini J. Am. Chem. Soc. 1993, 115, 1148.
[19] C. D. Hurd, C. M. Buess, J. Am. Chem. Soc. 1951, 73, 2409.
[20] C. D. Hurd, C. M. Buess, L. Bauer, J. Org. Chem. 1952, 17, 865.
[21] M. kai-Kasaya, K. Shimizu, Y.Watanabe, A. Saito, M. Aono, Y. Kuwahara, Phys. Rev. Lett. 2003, 91(25) 255501/1255501/4.
[22]Y. Okawa,. M. Aono, e-Journal of Surface Science and Nanotechnology (2004), 2 99-105.
[23] H. Matsuda, H. Nakanishi, J. Mat. Chem. 2000, 10, 819-28
32
(3) Retinal adsoption on Au
Switching processes of molecules at surfaces are of particular interest in view of the construction of nanodevices.
Retinal is one of the biologically most important photoswitchable molecules. The cis-trans isomerization of retinal is
the pivotal process for the visual perception and for the membrane transport in halophilic bacteria. To attach retinal to a
gold surface the molecule has to be functionalized in such a way that the isomerization process is not hindered. There
are several ways to attach a thiol or a dithiocarbamate group at the aldehyde function of Retinal. (a) Reaction of 2mercaptoethylamine with retinal, (b) functionalization of the surface with 2-mercaptoethylamine and addition of the
retinal in a second independent step or (c) preparation of the imine with formaldehyde and simultaneous reaction with
CS2 at the Au surface forming dithiocarbamate link. The surface chemisty will be performed in close collaboration with
“IP6” (Gerber).
The project will be started immediately after approval.
For the time schedule and organization see d) Deliverables
d) Deliverables/Milestones
First year: report on the progress of the synthesis of the oxazolidine-2,5-diones from gylcine, alanine and cysteine and
functionalization of lysine.
First year: synthesis of diynes with a hydrocarbon backbone.
First year: functionalization of retinal with 2-mercaptoethylamine
Second year: synthesis of oxazolidine-2,5-diones from basic and acidic amino acids, such as aspartic acid, tryptophan
and histidin and unnatural amino acids, such as D-alanine
Second year: functionalization of retinal with formaldehyde, metalo-phthalocyanines as platforms.
Third year: synthesis of molecular tripods for the attachment of retinal and other photoswitchable molecules.
e) Justification for budget items
The budget is mainly needed for the salary of a postdoc (36 months), chemicals, and equipment. For the photochemical
polymerizations and the cis-trans isomerization of the surface bound retinal we need a tunable high-intensity light
source e.g. the Model SID-201 from Photon Technology International. Standard equipment and the usual infrastructure
(NMR, IR, UV, fluorescence MS etc.) for preparative chemistry is available in our institute. The travel budget should
cover the expenses for mutual visits and for attending international meetings to present our results.
.
33
Requested budget for IP5 – B3 Herges
CRP Acronym: MOL-VIC
IP Nr:
must be consistent with the rules set by
the relevant national funding agencies
Rainer Herges, Unibersität Kiel
Funding Agency:
Outline Proposal Nr(s).:
BUDGET ITEMS
PI Name & Institution:
Duration
where
appropriate
in month,
including
start date
YEAR 1
Funding
YEAR 2
Funding
YEAR 3
Funding
TOTAL
Funding
(in Euros)
[other
currencies]
(in Euros)
[other
currencies]
(in Euros)
[other
currencies]
(in Euros)
[other
currencies]
Short description/
justification of each budget item **
Salary position
Ph.D. student
Post-doc. Researcher
48.000
48.000
48.000
144.000
Design, synthesis and characterization of
compounds
High intensity light source SID-201, fiber optic coupler
lamps , for photopolymerization and isomerization
HPLC software and columns (accessories to existing
instrument)
senior researcher
Technician
student stipend / student assistant
Equipment per item
Item 1
21.000
21.000
Item 2
8.000
8.000
Item …
Travel
conferences, workshops, travel to
fieldwork, visits
(including networking within the CRP)
Consumables / Running Costs
4.000
5.000
5.000
14.000
10.000
12.000
10.000
32.000
including analysis costs
Publication, Dissemination
Costs
Overheads
if applicable
Others
including access to large
infrastructures, shiptime, etc. (please
specify)
T O T A L
91.000
65.000
63.000
219.000
chemicals, glassware, analytics
34
IP5.– B3 RELATED PROJECTS

HE 1530/11-1 „Synthese Möbius-aromatischer
-Seite“
supported by the Deutsche Forschungsgemeinschaft.

“Rational synthesis of carbon nanotubes”. We are aiming at the chemical synthesis of nanotubes
with uniform geometries and thus well defined physical properties for the use in molecular
electronics.

“Design and synthesis of a light-driven proton pump”. Final goal is the uphill transport of
protons through an artificial membrane or through a layer on a metal surface using
photoswitchable molecules as carriers.

Design and synthesis of “molecular plates and tripods” for the orthogonal orientation of
photoswitchable molecules on Au surfaces.
IP5. – B4 OTHER SCIENTIFIC COLLABORATIONS
There is a close collaboration with the surface physicists Prof. Berndt and Prof. Magnussen in the
Department of Physics of our University. We are preparing various photoswitchable molecules which are
suitable for the preparation of functional surfaces. The monolayers are investigated using STM, AFM
and electrochemistry.
In collaboration with Prof. Faupel from Materials Department we are developing functional polymers.
Properties such as shape, conductivity, and transparency can be reversibly switched.
Prof. Kuzmany in Vienna and Prof. Thomsen (TU Berlin) are measuring Raman spectra of our nanotube
structures.
35
IP6-B1 PI: Thomas Greber, University of Zürich (UZH)
Endofullerene chains and switching isomers
a) IP AIMS AND OBJECTIVES
IP6 shall investigate molecular nano-structures, which spontaneously form on vicinal surface-templates. Besides
stepped surfaces which provide 1D structures, we will also use kinked (chiral surfaces), which may pin single
molecules on the kinks, i.e. form 0D structures and flat (111) surfaces, which provide 2D structures. We start with
metal vicinal surfaces where we will profit from the knowledge of the whole MOL-VIC consortium on how to
prepare them. In a second step, where functionality shall be demonstrated, it might become important to form
structures in two steps, i.e. to pre-cover the metal substrate with molecules of type A, which will then allow to grow
structures with molecules of type B on top of this less reactive and less metallic substrate. This has the purpose that
molecules, as e.g. retinal will not lay flat on the surface and not loose their functionality as it is the conformational
change (cis-trans isomerisation) upon light absorption. It has to be noted in brackets that UZH is currently
investigating such a system, where hexagonal boron nitride layers play the role of molecules of type A (STREP
Nanomesh).
IP6 will investigate two types of self organized nano-structures on vicinal surfaces: Endofullerenes and cis-trans
isomer reactions.
A) Endofullerenes
Molecular chain structures shall be built from endofullerenes. In this field N@C60 is a particularly interesting
candidate. It is a unique molecule with one nitrogen atom enclosed in a cage of 60 carbon atoms. This conceptually
simple atomic system has a 4S3/2 ground state with spin 3/2. The spin is chemically isolated from the surrounding
and the molecule is thus considered as a candidate material for spintronic applications or quantum computers
[Harneit, PRA, 65 (2002) 032322]. We would also like to use N@C60 as a “magnetic spy” on the surface.
Therefore the behavior in its condensed form has to be studied. So far the molecules have been investigated with
electron spin resonance in toluene solutions or in powder samples [Waiblinger et al. PRB, 64 (2001) 159901]. It has
to be stressed that N@C60 chain formation is a very difficult task. This is mainly given by the fact that the nitrogen
atoms tend to leave the carbon cage at about the same temperature as the C60 molecules evaporate. Furthermore, it is
not clear whether N@C60 maintains its pure spin structure on a surface where the C60 cage is charged up by
electron transfer from the substrate. Therefore this subproject will start with other endofullerenes as e.g. noble gas
containing C60, which are known to be more stable and easier to handle. The production of endofullerenes strongly
progressed recently [Komatsu et al. Science, 307 (2005) 238.] and we are confident to produce self-organized
nanostructures from endofullerenes.
36
B) Switching Isomers
Isomerisation changes the molecular conformation and is thus considered to become functional
as a nanomechanical switch. This is e.g. beautifully realized in retinal, the molecule where the
human perception process of light starts. There, an absorbed photon triggers the cis-trans
isomerisation. We want to mimick this process at surfaces and form nano-structures from retinallike molecules which undergo conformational changes upon light absorption. We will consider
two possible routes to form free-standing retinal molecules on surfaces: Either by substitution of
the CHO-end group with e.g. a thiol group, or by the pre-coverage of the surface by a molecular
carpet on which the original retinal molecules shall bind. This project will be in close
collaboration with IP5 (Herges), which will provide the molecules and the chemical background.
Furthermore it is related to IP4 (Horn) on stilben, which also undergoes isomerisation reactions.
We expect that XPD experiments will demonstrate conformational changes as it occurs in an
isomerisation reaction.
Scheme of the isomerisation of retinal.
Free standing retinal structures, bound
with the CHO end to a surface shall be
built and investigated with respect to
switchability with light. The
conformational changes will be
monitored with XPD.
Synergies:
We expect from the existing CRP significant synergies with respect to the preparation of suitable molecules
(Gourdon, Herges), techniques as low temperature scanning tunneling microscopy (Berndt), discussion and
understanding of electronic effects as revealed by photoemission (Ortega, Horn, Michel) magnetism and chirality
XRCD (Horn), and insight in functionalisation of such structures on the nanometer scale (theory in San Sebastian).
IP6 will contribute precise XPD determinations of molecular conformations and their functionalisation change upon
polymerization magnetization. IP6 will also supply on site support to all IP’s on MOL-VIC at the Swiss synchrotron
Light Source.
b) METHODOLOGY/EXPERIMENTS
General:
The Surface Physics Group of Prof. Dr. Jürg Osterwalder and Prof. Dr. Thomas Greber has a worldwide reputation
in the field of photoemission spectroscopy, especially for new developments and its application to investigating
structural, electronic and magnetic properties of surfaces. The laboratory features excellent experimental facilities,
including a system that allows efficient preparation of surfaces and nanostructures and in-situ analysis by both STM
and photoemission, a femtosecond laser system for time-resolved photoemission and electron diffraction
experiments, as well as a spin-resolved photoemission experiment based at the nearby Swiss Light Source
synchrotron radiation facility. The main expertise in the group is angle-resolved photoemission, and in particular
photoelectron diffraction, holography, and Fermi surface mapping, as well as the preparation and characterization of
atomic and molecular monolayers and of nanostructures based on vicinal crystal surfaces. It has the expertise and the
equipment to contribute to the understanding of the atomic structure and self-assembly processes of molecules with
up to 100 atoms on vicinal surfaces. 2π-X-ray photoelectron diffraction (XPD) is particularly well suited in order to
directly determine the conformation of molecules at surfaces.
37
Related work on Self organized Nano-Structures at UZH:
The system of one monolayer of C60 on vicinal Cu(665) is found to exhibit a one-dimensional molecular double
chain structure, with a much stronger electron hopping rate parallel to the chains than perpendicular to the chains.
STM picture from C60 molecular
chains on a B-type Cu vicinal
surface. Two chain types with two
different contrasts and defect
densities are seen. [Tamai et al.
Surf. Sci. 566-568 (2004) 63]
By means of X-ray photoelectron diffraction (XPD) it was demonstrated that the C60 molecules bind with two
orientations, i.e. pentagon and hexagon bonds to the (111) terraces. Furthermore, the observed electron dispersion
along the chains and the comparison with density functional theory (DFT) calculations emphasizes the two C60
orientations to constitute the two molecular chains.
2π-XPD maps from C60 on Cu(665).
Top experiment, bottom Single
Scattering Cluster (SSC) calculation
with 50% pentagon and two
equivalent hexagon orientations
(each 25% weight). The agreement
between experiment and theory is
perfect. [Tamai et al. submitted]
c) WORK PLAN
The project will start after appointment with a qualified postdoc.
The work will be organized according to the deliverables.
d) DELIVERABLES/MILESTONES
D6.1
month 12 IP6 reports on progress in preparation and characterization of low
dimensional endofullerene structures on metallic surfaces.
D6.2
month 12 IP6 reports on progress in preparation and characterization of low
dimensional retinal structures on metallic surfaces.
D6.3
month 24 IP6 reports on N@C60 endofullerene structures on surfaces and
38
whether the spin on the N atoms may be detected.
D6.4
month 24 IP6 reports on retinal structures on surfaces and whether the
molecules may be switched by light.
D6.5
month 36 IP6 reports on the whole project.
e) JUSTIFICATION OF BUDGET
The budget mainly consists in salaries, running costs for the experiment, travel and publication money.
We ask for salaries of a postdoc (36 month) and a technician (6 month) and for the expenses of a guest professor (5
month). The postdoc position is necessary in order to run the above mentioned XPD experiment at the Swiss Light
Source, and to train students on the PhD and the graduate level. The technician position is necessary in order to
further develop the difficult task to evaporate large molecules of which nanogram quantities were available, only.
The money for a guest is important in order to fertilize the research, in particular in view of the theoretical
understanding of the results. We furthermore expect from this guest to help to maximize synergies inside and outside
MOL-VIC and to develop new opportunities and views in the field of self organized nano-structures. The surface
physics group at UZH will contribute the salary of the PI, who will work about 30% on MOL-VIC, and potential
PhD students on the project.
A contribution to the running costs for the experiments is expected. E.g. the consumable “channeltrons” has to be
covered from inside MOL-VIC. The surface physics group of Prof. Dr. Jürg Osterwalder and the physics institute at
UZH will add about an equal amount to the running costs and the infrastructure of IP6.
Travel and publication money is important for the networking inside MOL-VIC and the dissemination of the results
to the world-wide community. Again, the outside contribution from the surface physics group and the physics
institute at UZH will be about an equal amount to travel and publication money of IP6.
.
39
Overall budget of the CRP (A9 f):
CRP Acronym: MOL-VIC
IP Nr:6
Funding Agency solicited:
Outline Proposal Nr(s).:
BUDGET ITEMS
must be consistent with the rules set by
the relevant national funding agencies
PI Name & Institution:
GREBER, UZH
Duration
where
appropriate
in month,
including
start date
YEAR 1
Funding
YEAR 2
Funding
YEAR 3
Funding
TOTAL
Funding
(in Euros)
[other
currencies]
(in Euros)
[other
currencies]
(in Euros)
[other
currencies]
(in Euros)
[other
currencies]
Short description/
justification of each budget item **
Salary position
Ph.D. student
Post-doc. Researcher
36/1
senior researcher
5/13
Technician
6/6
79’584
16’123
79’584
20’000
16’123
79’584
238’753
20’000
32’246
Guest Professor
6’000
Evaporator components
Runs the Project at the Synchrotron
Technician for special evaporator development
student stipend / student assistant
Equipment per item
Item 1
6’000
Item 2
Item …
Travel
conferences, workshops, travel to
fieldwork, visits
(including networking within the CRP)
2’100
2’100
2’100
6’300
7’000
500
5’000
8’000
1’000
8’000
1’500
5’000
23’000
3’000
21’061
27’561
18’237
66’860
500
500
1’000
2’000
Consumables / Running Costs
including analysis costs
Publication, Dissemination
Costs
Overheads
if applicable
Others
including access to large
infrastructures, shiptime, etc. (please
specify)
T O T A L
126’866
165’868
110’423
403’159
Channeltrons
40
IP6 – B3 RELATED PROJECTS
Author SNF und PSI “Direct determination of adsorption induced structural changes in large molecules by
Near Node Photoelectron Holography”
(0.1 MEuro/2 years) ends 2006.
Coauthor CERC3 “Time-resolved low energy electron diffraction from large molecules on surfaces”
(0.03 MEuro/5 years) ends 2006.
Coauthor of the SNF fundings of the group of J. Osterwalder 2005
(0.5 Meuro/2 years), ends 2007.
Coauthor of STREP EU project “Boron Nitride Nanomesh as a Scaffold for Nanocatalysts and Functional
Surfaces”
(2 MEuro/3 years) ends 2008.
SNF
Swiss National Science Fundation
PSI
Paul Scherrer Institut
IP6 – B4 OTHER SCIENTIFIC COLLABORATIONS
Ari Seitsonen, Paris, DFT Theory,
ZX Shen, Stanford, Photoemission,
Wolfgang Harneit, FU Berlin, Endofullerenes,
Koichi Komatsu, Kyoto, Endofullerenes,
Abdelkader Kara, Manhattan, DFT Theory,
CERC3 “Time-resolved low energy electron diffraction from large molecules on surfaces”:
Herbert Over, Giessen,
STREP EU project “Boron Nitride Nanomesh as a Scaffold for Nanocatalysts and Functional Surfaces”:
Herrmann Sachdev, Saarbrücken, precursor molecules
Matthias Schreck, Würzburg, crystalline thin film samples
Neil Campness, Nottingham, large molecules synthesis
Peter Beton Nottingham, large molecules, STM
Herbert Over, Giessen, LEED
Peter Blahe, Wien, DFT theory
Joost Frenken, Leiden, High temperature STM
David Williams, Hitachi Cambridge, Nanotechnolgy.
41
Section C - Associated Project (AP)
AP1-C1 PI: André Gourdon, CEMES-CNRS, Toulouse
1 Associated Project aims & objectives
"AP1 Gourdon" general objective is to provide dedicated new molecules or molecular systems to understand the 1D
supramolecular organisation on vicinal surfaces.
2 Methodologies/experiments
The supramolecular organisation of molecules on a surface is function of a subtle balance of various parameters such as
the molecule-substrate Van der Waals forces, the molecular rigidity towards these forces, the inter-molecular interactions
(through space or mediated by the substrate), the chemical reactivity, the mobility on the surface, etc.. Therefore
molecules design will be adapted in function of the first results obtained on the benzodiguanamie and the pyrazolecarboxylic molecules in the project first year.
3 Work plan
Two of the main problems encountered in the study of supramolecular ordering of somehow fragile large organic
molecules on a substrate are 1) the difficulty to transfer the molecule to the substrate by sublimation in UHV 2) the lack of
mobility of the molecules at rather low temperature which prevents a clean 2D "recrystallisation" to give well ordered
structures. In order to improve the mobility of the molecule at not-too high temperatures, and to reduce the sublimation
point of large aromatic molecules, it is necessary to equip these molecules with bulky substituants which reduces the
intermolecular interactions in the solid state and the aromatic part-substrate interaction (and then the annealing
temperature) after transfer on a clean metallic surface. We have recently shown that molecules of the type: Hexa-tertButylphenylbenzene allow nice supramolecular ordering on Cu(111) (Phys. Rev. B (2005) B71, 165428.). We propose to
extend this type of structure to functionalized molecules able to show 1D ordering from a general structure of tetra-tertButyl-(functionalised)diaromatic-benzene 1. A first synthetic target will be the dipyridyl tertar-tert-butylbenzene 2 using
synthetic methodologies we have just developed. It should give interesting 1D structures by coadsorption with organic
diacids like terephthalic acid.
R X
X R
1
N
N
2
The next synthetic objectives will be to add various X-R fragments to this design to increase the intermolecular
interactions eventually by co-adsorption experiments for instance with 4 + 5.
42
H2N
N
N
NH2
N
N
N
N
N
N
H2N
NH2
4
3
O
OH
HO
O
5
Depending on the observation done by the project partners, new molecules will be proposed used the synthetic
methodology that will be developed for molecules 2 to 5
4 Deliverables and/or milestones
See work plan
AP1-C2 - Information on funding
No specific external funding; the expenses will be paid by the group budget.
43
Annexes to the Proposal
MOL-VIC
IP1.- ANNEX I----------- CV ORTEGA
Birth date: 7th January, 1963 in San Sebastián (Spain).
Address: Dept. Física Aplicada I, Universidad del País Vasco, Plaza de Oñate 2, 20018-San Sebastián.
Phone number: +34 943 018289; e-mail: ortega@sq.ehu.es
UNIVERSITY EDUCATION:
Bachelor in Physical Sciences, Universidad Autonoma de Madrid, June 1986.
Ph.D., Universidad Autonoma de Madrid, September 1990.
EMPLOYMENT RECORD:
Researcher as graduate student at Univ. Autonoma de Madrid (1986 - 1990).
Full-time Associate Professor at Univ. Autonoma de Madrid (1990-1991).
Post-doc at the IBM T. J. Watson Research Center, New York (USA) (1991-1993).
Researcher at Univ. Autonoma de Madrid (1993-1995).
Visiting professor Univ. del País Vasco San Sebastián (1995 - 1996).
Full-time Associate Professor at Univ. del País Vasco San Sebastián (1996 - 1998).
Full Assistant Professor at Univ. del País Vasco San Sebastián since 1998.
Full Professor at Univ. del País Vasco San Sebastián since 2003.
RESEARCH:
Areas of research include: epitaxial growth of metal on metal, electronic structure of metallic interfaces, electronic
and geometric structure of metal-semiconductor interfaces, nanotechnology and nanofabrication, electronic and
geometric structure thin films, vicinal surfaces and lateral nanostructures.
Experimental Techniques used: Inverse Photoemission Spectroscopy (IPS), Photoemission with synchrotron
radiation, comprising Ultraviolet Photoemission Spectroscopy (UPS) (both angle-integrated and angle-resolved) and
X-Ray Photoemission Spectroscopy (XPS), Auger Electron Spectroscopy (AES), Low Energy Electron Diffraction
(LEED), Scanning Tunneling Microscopy (STM).
PUBLICATIONS:
About 75 articles in refereed international journal. The 10 most relevant for this proposal are the following
1. "Magnetic Nanostructures", F. J. Himpsel, J. E. Ortega, G. J. Mankey, and R. F. Willis, Advances in Phys. 47,
511 (1998). (Review article)
2. “The electron wave function at a vicinal surface: Switch from terrace to step modulation”, J. E. Ortega, S. Speller,
A. Bachmann, A. Mascaraque, E. G. Michel, A. Mugarza, A. Närmann, A. Rubio, and F. J. Himpsel, Phys. Rev.
Lett. 84, 6110 (2000).
3. “One-dimensional Ag-Cu superlattices on vicinal Cu(111)”, A. R. Bachmann, A. Mugarza, S. Speller, and J. E.
Ortega, Phys. Rev. B 64, 153409 (2001).
4. “Electron confinement in Surface States on a Stepped Gold Surface Revealed by Angle-Resolved
Photoemission”, A. Mugarza, A. Mascaraque, V. Pérez-Dieste, V. Repain, S. Rousset, F. J. García de Abajo, and
J. E. Ortega, Phys. Rev. Lett 87, 107601 (2001).
5. “Ag-induced zero- and one-dimensional nanostructures on vicinal Si(111), J. Kuntze, A. Mugarza, y J. E. Ortega,
Appl. Phys. Lett. 81, 2463 (2002).
6. “Driving forces for Ag-induced nanostructuration on vicinal Cu(111)”, A. R. Bachmann, S. Speller, A. Mugarza,
and J. E. Ortega, Surf. Sci. 526, L143 (2003).
7. “Electronic States at Vicinal Surfaces”, A. Mugarza y J. E. Ortega, J. Phys. Cond. Mat. 15, S3281 (2003).
8. “Tuning surface state dimensionality in Cu nanostripes”, J. Lobo, E. G. Michel, A. Bachmann, S. Speller, J.
Kuntze, and J. E. Ortega, Phys. Rev. Lett. 93, 137602 (2004).
9. “Fermi gap stabilization of an incommensurate two-dimensional superstructure”, F. Schiller, J. Cordón, D.
Vyalikh, A. Rubio, and J. E. Ortega, Phys. Rev. Lett. 94, 016103 (2005).
10. “Scattering of surface states at step edges in nanostripe arrays”, F. Schiller, J. Cordón, M. Ruiz-Osés, and J. E.
Ortega, Phys. Rev. Lett 95, 066805 (2005).
MOL-VIC
IP2.- ANNEX I----------- CV BERNDT
1962
1982-1984
1984-1987
1985-1987
1987-1988
1988-1992
18.2.1992
1992-1996
1996-1999
Aug. 1996
Jul. 1999
Oct. 2000
28.3.2001
Mar. 2002
22.11.2003
Born in Gladbeck, Germany
Student of physics and ''Vordiplom'' at the University of Osnabrück
Student of physics at the University of Göttingen, Germany
Diploma project at the Max-Planck-Institut für Strömungsforschung in
Göttingen with Prof. J.P. Toennies on surface phonons.
Scientist at the Max-Planck-Institut für Strömungsforschung.
Scientist with the IBM Research Division, Zurich Research Laboratory in
Rüeschlikon, Switzerland
Awarded PhD summa cum laude from the University of Basel.
Supervisors: Prof. H.-J. Güntherodt and Dr. H. Rohrer.
“Premier assistant'' at the Institut de Physique Expérimentale of the
University of Lausanne with Prof. W.-D. Schneider
Associate professor at the RWTH Aachen, Germany
Visiting scientist at the National Research Institute for Metals, Tsukuba, Japan
Full professor at the University of Kiel, Germany
Managing Director of the IEAP
Received Nanoscience Price 2001”
”professeur invité'' at the Université Paul Sabatier, Toulouse
Received Joachim Jungius-Price
Selected publications:
[1] J. Kuntze, R. Berndt, P. Jiang, H. Tang, A. Gourdon, C. Joachim, Conformations of a molecular
wire adsorbed on a metal surface, Phys. Rev B 65, 233405 (2002)
[2] G. Hoffmann, L. Libioulle, R. Berndt, Tunneling induced luminescence from adsorbed organic
molecules with submolecular lateral resolution, Phys. Rev. B 65, 212107 (2002)
[3] G. Hoffmann, R. Berndt, P. Johansson, Two-Electron Photon Emission from Metallic Quantum
Wells, Phys. Rev. Lett. 90, 046803 (2003)
[4] L. Limot, T. Maroutian, P. Johansson, R. Berndt, Surface State Stark Shift in a Scanning
Tunneling Microscope, Phys. Rev. Lett. 91, 196801 (2003)
[5] J. Kuntze, X. Ge, R. Berndt, Chiral structures of lander molecules on Cu(100), Nanotechnology
15, S337-S340 (2004)
[6] G. Hoffmann, Th. Maroutian, R. Berndt, Color View of Atomic Highs and Lows in Tunneling
Induced Light Emission, Phys. Rev. Lett. 93, 076102 (2004)
[7] L. Limot, E. Pehlke, J. Kröger, R. Berndt, Surface-State Localization at Adatoms, Phys. Rev. Lett.
94, 036805 (2005)
[8] L. Limot, J. Kröger, R. Berndt, A. Garcia-Lekue, W.A. Hofer, Atom Transfer and Single-Adatom
Contacts, Phys. Rev. Lett. 94, 126102 (2005)
[9] N. Néel, J. Kröger, R. Berndt, Highly Periodic Fullerene Nanomesh, subm. to Advanced Materials
[10] J. Kröger, H. Jensen, R. Berndt, R. Rurali, N. Lorente, Molecular Orbital Shift of
Perylenetetracarboxylic-Dianhydride, subm. to Phys. Rev. Lett., see also cond-mat/0506025.
MOL-VIC
IP3.- ANNEX I----------- CV MICHEL
Birth date: 3rd May, 1962 in Madrid (Spain).
Address: Dept. de Física Materia Condensada, Universidad Autónoma de Madrid, 28049-Madrid.
Phone number: +34 91 397 4759; e-mail: enrique.garcia.michel@uam.es
UNIVERSITY EDUCATION:
Bachelor in Physical Sciences, Universidad Autónoma de Madrid, June 1985.
M.Sc. (Surface Physics), Universidad Autónoma de Madrid, June 1986.
Ph.D., Universidad Autónoma de Madrid, October 1988. Faculty prize for best thesis.
EMPLOYMENT RECORD:
Researcher as graduate student at Univ. Autónoma de Madrid (1986 - 1988).
Researcher at the Fritz Haber Institut of the MPG in Berlin (September 1987 - December 1987).
Full-time Associate Professor at Univ. Autónoma de Madrid (1988 until February 1997).
Researcher at the Hamburg Synchrotron Radiation Laboratory (HASYLAB) (1989 - 1990).
Research Fellow of the Alexander von Humboldt Foundation (Germany) (1990).
Full Professor at the Universidad Autónoma de Madrid (February 1997 until now).
Director of the Department of Condensed Matter Physics (since March 2005).
RESEARCH:
My areas of research have include: epitaxial growth of metal on metal, electronic structure of metallic interfaces,
electronic and crystallographic structure of metal-semiconductor interfaces, electronic Structure of High-Tc
superconductors, nanotechnology and nanofabrication, electronic and crystallographic structure of halogensemiconductor interfaces, epitaxial growth of silicides on silicon, surface phase transitions, surface charge density
waves, electronic confinement at surfaces.
Experimental Techniques used: Inverse Photoemission Spectroscopy (IPS), Ultraviolet Photoemission Spectroscopy
(UPS) (both angle-integrated and angle-resolved), X-Ray Photoemission Spectroscopy (XPS), Ion Scattering
Spectroscopy (ISS), Auger Electron Spectroscopy (AES), Thermal Desorption Spectroscopy (TDS), Low Energy
Electron Diffraction (LEED), Surface X-ray diffraction (SXRD), Scanning Tunneling Microscopy (STM), Near-Edge
X-ray Extended Fine Structure (NEXAFS), Photoemission of Adsorbed Xenon (PAX), X-Ray Photoelectron and
Auger Electron Diffraction (XPD, AED), X-Ray Standing Waves (XSW), X-Ray Fluorescence with Synchrotron
Radiation. I have supervised six PhD thesis, two other are to be finished in 2006, plus many Diploma Thesis.
PUBLICATIONS:
I have published approx. 100 articles in refereed international journal. The 10 most relevant papers from last 5 years are listed in
Annex 2.
OTHER R+D ACTIVITIES
I have served in several international and national editorial and evaluation committees as:
International Programme Committee of synchrotron LURE in Orsay (France), since 1991.
Spanish delegate in the Scientific Committee of the European synchrotron ESRF (1993-94) and Scientific activity
evaluator for the beamline BL32 of ESRF (1999).
Spanish delegate in the EU panel “New applications of accelerators: free electron laser” (1994-95) and expert in the
EU Growth Programme (2000)
Editor of “Journal of Physics Condensed Matter” (since 2000) and Chairman of the Surface Science Editorial Board
(since January 2005).
Fellow of the Institute of Physics (London).
Programme Committee of SLS (Swiss Light Source) of the PSI (Switzerland), since January 2002
I have organized several scientific meetings, the most important being the 19th European Conference on Surface
Science, held in Madrid in September 2000 (700 participants).
I am referee of many scientific journals and regularly participate in the evaluation of scientific and technological grants at national
and international level.
MOL-VIC
IP3.- ANNEX I----------- CV HORN
December 17th, 1946
Date of birth. Parents: Kurt Horn, accountant, and Erika Horn
1953 -1966
Primary and secondary school in Düsseldorf, Germany
1966 -1968
Military service in Borken/West Germany. Final rank: Second Lieutenant
1968 -1973
Undergraduate education in physics at Rheinisch-Westfälische Technische
Hochschule Aachen. Diploma thesis (with Prof. H.Ibach ) on "Oxidation of
Si(111) single crystal surfaces"
1973 - 1976
Graduate studies at Queen Mary College, University of London, Great Britain,
with Prof, J.Pritchard. Ph.D. thesis: "A study of adsorption on metal single
crystals by IR absorption spectroscopy"
June 1976
Awarded degree of Doctor of Philosophy (University of London)
August 1976
Post-doctoral position at the Fritz-Haber-Institut of the Max-PlanckGesellschaft, with Prof. A.M.Bradshaw. First work in photoelectron
spectroscopy.
from 1978 onwards
Staff scientist at the Fritz-Haber-Institut, with an independent research group
1979 and 1981
work at University of Wisconsin Synchrotron Radiation Center, with Prof.
E.W.Plummer, Univ. of Pennsylvania, and Dr.D.E.Eastman, IBM Research
1984
named "Privatdozent" in the Freie Universität Berlin
from 1992
Editor of "Handbook of Surfaces Vol. II - Electronic Structure" with Prof.
Matthias Scheffler
1993
Chairman of Symposium "Electronic Structure of Surfaces", with Prof. Matthias
Scheffler
1995
awarded the rank of Adjunct Professor in the Department of Physics of the Freie
Universität Berlin
1997
elected Fellow of the American Vacuum Society
1998 ....
Chairman of Proposal Review Committee of the ELETTRA Synchrotron
radiation facility in Trieste, Italy
2000
Co-Organizer of a Symposium on Surface and Thin Films at the MRS Fall
Meeting in Boston, Mass. (USA)
 Author and co-author of about 165 papers in refereed scientific journals
 Adviser for about 20 Ph.D. and Diploma students
 Frequent teaching assignments at the Freie Universität Berlin
 Member of Deutsche Physikalische Gesellschaft, European Physical Society,
Member of the American Vacuum Society.
 Frequent activities as External Referee for Ph.D. theses, proposals and vacant
positions in research institutes and departments both in Germany and abroad
MOL-VIC
IP5.- ANNEX I----------- CV HERGES
Study
Oct.1975 - March 1981, Study of chemistry at the University of the Saarland, Saarbrücken (a city close to the French
border) - 10 Semester.
Diplom
March 1981, Saarbrücken
Diplom thesis
Title: "Valence Isiomerisation and Ring inversion of Cycloheptatrienenes" with Prof. Dr. H. Dürr.
Graduation
July 1981 - July 1984; Scholarship of the "Fonds der Chemischen Industrie"; Department of Organic Chemistry Technical
University Munich. Title: "Computer Aided, Deductive Search for Novel Reactions and their Experimental Verification" with
Prof. I. Ugi.
Post-Doc.
Sept. 1984 - Sept. 1985; Feodor-Lynen-Scholarship of Alexander von Humboldt-Stiftung; University of Southern California,
Los Angeles with Prof. G. A. Olah. Synthesis of Carbocations and Dications.
Habilitation
Dec. 1985 - July 1992; Liebig-Scholarship of the Fonds der Chemischen Industrie; Institute f. Organic Chemistry,
Universität Erlangen-Nürnberg with Prof. P. v. R. Schleyer. Title: "Reaction Planning: Rational Planning of Chemical
Reactions".
Visiting Prof.
15. Sept -15. Okt. 1995 at the École Normale Supérieure, Paris.
Professor (C3)
since 1. Feb. 1996, Institut für Organische Chemie, Technische Universität Braunschweig.
Visiting Prof.
Okt. 1998 - Dez. 1998 at the Stanford University.
Professor (C4)
since 1. March 2001, Institut für Organische Chemie, Christian-Albrechts-Universität Kiel.
Awards
Dissertation Award of the Technical Universitiy Munich, July 1986
Chemical Structure Association Trust Award 1993
Habilitation Award: ADUC Jahrespreis für Habilitanden 1993
Fields of Research
Synthetic Chemistry
Quantum Chemistry
Computational Chemistry
MOL-VIC
IP6.- ANNEX I----------- CV GREBER
Born on February 23rd 1960 in Solothurn, Switzerland.
Son of Hedwig Maria Greber - Renggli and Josef Alois Greber.
Single, no children.
Finals:
1966-1979
School in Zofingen up to Matura (Typus C).
1980-1986
Studies on Physics at ETH Zürich.
1986
Diploma "Wasser auf Cer", in the group of Prof. Dr. H.-C. Siegmann with Dr. L. Schlapbach.
1990
Promotion " Two aspects concerning 4f impurities on metals", ETH
Diss No 9092 in
Zürich and Fribourg with Prof. Dr. H.-C. Siegmann and Prof. Dr. L. Schlapbach.
1997
Habilitation "Charge-transfer induced particle emission in gas surface reactions", Universität
Zürich.
Jobs:
1986-1988
Assistant in the Laboratorium für Festkörperphysik at ETHZ.
1988-1991
Assistant at the Université de Fribourg, Schweiz.
1990
Guest at the Universiity of Kogaquin, Tokyo, with Prof. Dr. S. Suda.
1991-1994
Postdoc at the Fritz-Haber-Institute, Berlin, with Prof. Dr. G. Ertl with
scholarships from
the Schweizerischen Nationalfonds and the
Alexander von Humboldt Stiftung. Work on
"Electron emission in
nonadiabatic gas surface reactions".
since 1995
Oberassistant in the group of Prof. Dr. J. Osterwalder at the Universität Zürich. Set up of a
new surface physics lab. Teaching courses: Surface Physics, Electron Spectroscopy, Math.
Methods in Physics, Solid State Physics, Nano- and Interface Physics.
1997
Guest of Prof. Dr. U. Heinzmann at ZIF Bielefeld within the "Interactions of oriented
molecules" project.
1997
Privatdozent (PD)/Oberass. habil. mbA.
2000
Referee in the program committee “surfaces” of LURE.
Awards:
1991
"SPG Preis gestiftet von der Firma IBM für hervorragende Arbeiten auf dem Gebiet der
kondensierten Materie 1991" with A. Stuck and Dr. J. Osterwalder .
2004
Titularprofessor
Own projects:
1997,2004
"Near Node Photoelectron Holography", SNF.
1997
Collaboration in the Advanced Photoemission Experiment (APE) at the Synchrotrone Trieste
(ELETTRA).
2000
“Time-resolved low energy electron diffraction from large molecules on surfaces”, SNF,
DFG, CERC3.
MOL-VIC
AP1.- ANNEX I----------- CV GOURDON
Dr. André Gourdon is Research Director at CNRS. After a post-doc in 1980-1981 at the Inorganic Chemistry
Laboratory (Oxford) in the group of Prof. M. L. H Green, he joined the CNRS (Paris, Université P. & M. Curie)
in 1981 to work on organometallic chemistry and crystallography of iron clusters as models of metallic
nanoparticules. He joined Prof. J.-P. Launay's Molecular Electronics group in 1988 to study intramolecular
electron transfer and moved with his group to Toulouse in 1990. Dr Gourdon is interested in the design, synthesis
and structural studies of organic and inorganic molecular devices for nanoscience and molecular electronics.
Groupe Electronique Moléculaire, CEMES-CNRS, 29, Rue J. Marvig BP 4347, 31055 Toulouse Cedex,
France, Phone: (33) 562 25 78 59; Fax: (33) 562 25 79 99, Email: gourdon@cemes.fr
Selected recent publications
Synthesis of Molecular Landers
André Gourdon
EurJOC (1998) 2797-2801.
Conformational Changes of Single Molecules Induced by Scanning Tunneling Microscopy Manipulation: A
Route to Molecular Switching
F. Moresco, G. Meyer, K.-H. Rieder, H. Tang, A. Gourdon and C. Joachim
Phys. Rev. Letters (2001) 86:4, 672-675.
Low temperature manipulation of big molecules in a constant height mode
F. Moresco, G. Meyer, K.H. Rieder, H. Tang, A. Gourdon et C. Joachim
Applied Physics Letter (2001) 78, 306-308.
Recording Intramolecular Mechanics during the Manipulation of a Large
F. Moresco, G. Meyer, K. H. Rieder, H. Tang, A. Gourdon and C. Joachim
Phys. Rev. Letters (2001) 87, 088302
Molecule
Conformations of a long molecular wire with legs on a Cu(100) surface
T. Zambelli, H. Tang; J. Lagoute, S. Gauthier, A. Gourdon and C. Joachim
Chem. Phys. Letters (2001) 348, 1-6
Conformations of a molecular wire adsorbed on a metal surface
J. Kuntze, R. Berndt, J. Ping, H. Tang, A. Gourdon and C. Joachim
Phys. Rev. B (2002), 233405, 1-4
Organic molecules acting as templates on metal surfaces
F. Rosei, M. Schunack, P. Jiang, A. Gourdon, E. Laegsgaard, I. Stensgaard, C. Joachim and F. Besenbacher
Science (2002), 296:5566, 328-331.
Probing the Different Stages in Contacting a Single Molecular Wire
Francesca Moresco, Leo Gross, Micol Alemani, Karl-Heinz Rieder, Hao Tang, André Gourdon, and Christian
Joachim
Phys. Rev. Lett. 91, 036601 (2003)
Molecules on Insulating Films: Scanning-Tunneling Microscopy Imaging of Individual Molecular Orbitals
Jascha Repp, Gerhard Meyer, Sladjana M. Stojkovi , André Gourdon, and Christian Joachim
Phys. Rev. Lett. 94, 026803 (2005).
MOL-VIC
IP1.-ORTEGA ANNEX II: MOST RELEVANT PUBLICATIONS (last 5 years)
1. “The electron wave function at a vicinal surface: Switch from terrace to step modulation”, J. E.
Ortega, S. Speller, A. Bachmann, A. Mascaraque, E. G. Michel, A. Mugarza, A. Närmann, A. Rubio,
and F. J. Himpsel, Phys. Rev. Lett. 84, 6110 (2000).
2. “One-dimensional Ag-Cu superlattices on vicinal Cu(111)”, A. R. Bachmann, A. Mugarza, S. Speller,
and J. E. Ortega, Phys. Rev. B 64, 153409 (2001).
3. “Electron confinement in Surface States on a Stepped Gold Surface Revealed by Angle-Resolved
Photoemission”, A. Mugarza, A. Mascaraque, V. Pérez-Dieste, V. Repain, S. Rousset, F. J. García de
Abajo, and J. E. Ortega, Phys. Rev. Lett 87, 107601 (2001).
4. “Ag-induced zero- and one-dimensional nanostructures on vicinal Si(111)”, J. Kuntze, A. Mugarza,
and J. E. Ortega, Appl. Phys. Lett. 81, 2463 (2002).
5. “Driving forces for Ag-induced nanostructuration on vicinal Cu(111)”, A. R. Bachmann, S. Speller, A.
Mugarza, and J. E. Ortega, Surf. Sci. 526, L143 (2003).
6. “Measurement of electron wave functions and confining potentials via photoemission”, A. Mugarza, J.
E. Ortega , F. J. Himpsel, and F. J. García de Abajo, Phys. Rev. B 67, 081404 (2003)
7. “Tuning surface state dimensionality in Cu nanostripes”, J. Lobo, E. G. Michel, A. Bachmann, S.
Speller, J. Kuntze, and J. E. Ortega, Phys. Rev. Lett. 93, 137602 (2004).
8. “Fermi gap stabilization of an incommensurate two-dimensional superstructure”, F. Schiller, J.
Cordón, D. Vyalikh, A. Rubio, and J. E. Ortega, Phys. Rev. Lett. 94, 016103 (2005).
9. “Scattering of surface states at step edges in nanostripe arrays”, F. Schiller, J. Cordón, M. Ruiz-Osés,
and J. E. Ortega, Phys. Rev. Lett 95, 066805 (2005).
10. “Surface state scattering at a buried interface”, F. Schiller, R. Keyling, E. V. Chulkov, and J. E.
Ortega, Phys. Rev. Lett. 95, 126402 (2005).
MOL-VIC
IP2.-BERNDT ANNEX II: MOST RELEVANT PUBLICATIONS (last 5 years)
J. Kuntze, X. Ge, R. Berndt, Chiral structures of lander molecules on Cu(100), Nanotechnology 15, S337
(2004)
L. Limot, E. Pehlke, J. Kröger, R. Berndt, Surface-State Localization at Adatoms, Phys. Rev. Lett. 94, 036805
(2005).
L. Limot, J. Kröger, R. Berndt, A. Garcia-Lekue, W. A. Hofer, Atom Transfer and Single-Adatom Contacts,
Phys. Rev. Lett. 94, 126102 (2005).
N. Neel, J. Kröger, R. Berndt, Highly Periodic Fullerene Nanomesh, Advanced Materials (in press)
J. Kröger, H. Jensen, R. Berndt, R. Rurali, N. Lorente, Molecular Orbital Shift of PerylenetetracarboxylicDianhydride, submitted to Phys. Rev. Lett.
IP3.-MICHEL ANNEX II: MOST RELEVANT PUBLICATIONS (last 5 years)
1-“The electron wave function at a vicinal surface: Switch from terrace to step modulation”
J. E. Ortega, S. Speller, A. Bachmann, A. Mascaraque, E. G. Michel, A. Mugarza, A. Närmann, A. Rubio, and F. J.
Himpsel.
Physical Review Letters 84 (2000) 6110.
2-“Periodicity and thickness effects in the cross section of quantum well states”
A. Mugarza, J.E. Ortega, A. Mascaraque, E.G. Michel, K.N. Altmann, and F.J.
Himpsel
Physical Review B 62 (2000) 12672.
3-“Reversible structural phase transitions in semiconductor and metal/semiconductor surfaces”
A. Mascaraque and E.G. Michel
Journal of Physics: Condensed Matter 14, 6005 (2002).
4- “Phonon Softening, Chaotic Motion, and Order-Disorder Transition in Sn/Ge(111)''
D. Farías, W. Kaminski, J. Lobo, J. Ortega, E. Hulpke, R. Pérez, F. Flores, and E.G. Michel
Physical Review Letters 91 (2003) 016103.
5-“Electronic structure of Sn/Si(111)-(p3 £ p3)R30± as a function of Sn coverage”
J. Lobo, A. Tejeda, A. Mugarza, and E.G. Michel
Physical Review B 68, 235332 (2003).
6-“Tuning surface state dimensionality in Cu nanostripes”
J. Lobo, E.G. Michel, A.R. Bachmann, S. Speller, J. Kuntze, and J.E. Ortega
Physical Review Letters 93 (2004) 137602.
7-“Photoelectron diffraction study of the Si-rich 3C-SiC(001)-(3 £ 2) structure”
A. Tejeda, D. Dunham, F.J. García de Abajo, J.D. Denlinger, E. Rotenberg, E.G.
Michel, and P. Soukiassian
Physical Review B 70, 045317 (2004).
8-“Accurate band mapping via photoemission from thin films”
A. Mugarza, A. Marini, T. Strasser, W. Schattke, A. Rubio, F. J. García de Abajo,
J. Lobo, E. G. Michel, J. Kuntze, and J. E. Ortega
Physical Review B 69, 115422 (2004).
9-“Structural phase transitions in two-dimensional systems: Pb/Ge(111) and Sn/Ge(111)”
A. Cano, A.P. Levanyuk, and E.G. Michel
Zeitschrift für Kristallographie 220 (2005) 663.
10-“Fermi surface gapping and nesting in the surface phase transition of Sn/Cu(100)”
J. Martínez-Blanco, V. Joco, H. Ascolani, A. Tejeda, C. Quirós, G. Panaccione, T.
Balasubramanian, P. Segovia, and E.G. Michel
Physical Review B 72 (2005) 041401(R)
MOL-VIC
IP4.-HORN ANNEX II: MOST RELEVANT PUBLICATIONS (last 5 years)
1. S.R.Barman, P.Häberle, K.Horn, J.Maytorena und A.Liebsch
Quantum well behavior without confining barrier observed via dynamically screened
photon field
Phys.Rev. Lett. 86, 5108 (2001).
2. L. Aballe, C. Rogero, S. Gokhale, S. Kulkarni und K. Horn
Quantum-well states in ultrathin aluminium films on Si(111)
Surface Science 482 - 485, 488(2001).
3.
M.P.Casaletto, R.Zanoni, M.Carbone, M.N.Piancastelli, K.Weiss, L.Aballe, und K.Horn
Methanol adsorption on Si(100)-(2 x 1) investigated by high resolution photoemission
Surface Science 505, 251(2002)
4. L.Aballe, C.Rogero, und K.Horn
Quantum well states in Mg films on Si(111)
Phys.Rev. B 65, 125319 (2002)
5.
J.Schaefer, S.C.Erwin, M.Hansmann, Z.Song, E.Rotenberg, S.D.Kevan, C.S.Hellberg, und K.Horn
Random Registry shifts in Quasi-one-dimensional Adsorbate Systems
Phys.Rev. B 67, 085411(2003).
6. J.H. Dil, J.W. Kim, S. Gokhale, M. Tallarida and K. Horn
Self-organization of Pb thin films on Cu(111) induced by quantum size effects: An
angle-resolved photoemission study
Phys.Rev. B70, 045405 (2004).
7. J. I. Pascual, G. Bihlmayer, Yu.M. Koroteev, H.-P. Rust, G. Ceballos, M. Hansmann,
K. Horn, E.V. Chulkov, S. Blügel, P.M. Echenique, and Ph. Hofmann
Role of Spin in quasiparticle interference
Phys.Rev.Lett. 93, 196802(2004).
8. J. W. Kim, M. Carbone, J. H. Dil, M. Tallarida, R. Flammini, M. P. Casaletto, K.
Horn, and M. N. Piancastelli
Atom-specific identification of adsorbed chiral molecules by photoemission
Phys.Rev.Lett. 95, 107601 (2005).
MOL-VIC
IP5.-HERGES ANNEX II: MOST RELEVANT PUBLICATIONS (last 5 years)
Delocalization of Electrons in Molecules
R. Herges, D. Geuenich
J. Phys. Chem. A 2001, 105, 3214-3220
Homoaromaticity in tris(ethylene)nickel(0) and tris(ethyne)nickel(0)
R. Herges, A. Papafilippoulos
Angew. Chem. 2001, 113, 4809-4813
Angew. Chem. Int. Ed. Engl. 2001, 40, 4671-4674
Two Unusual, Competitive Mechanisms for (2-Ethynylphenyl)triazene Cyclization; Pseudocoarctate versus Pericyclic
Reactivity
D. B. Kimball, R. Herges, M. M. Haley,
J. Am. Chem. Soc. 2002, 124, 1572-1573
Diciphering the Mechanistic Dichotomy in the Cyclization of 1-(2-Ethynylphenyl)-3,3-dialkyltriazenes: Competition
Between Pericyclic and Pseudocoarctate Pathways.
B. Kimball, T. J. R. Weakley, R. Herges, M. M. Haley
J. Am. Chem. Soc. 2002, 124, 13463-13473
Synthesis of a Chiral Tube
R. Herges, M. Deichmann, T. Wakita, Y. Okamoto
Angew. Chem. 2003, 115, 1202-1204.
Angew. Chem. Int. Ed. Engl. 2003, 42, 1170-1172.
Picotube Tetraanion: a Novel Lithiated Tubular System
N. Treidel, M. Deichmann, T. Sternfeld, T. Sheradsky, R. Herges, M. Rabinowitz
Angew. Chem. 2003, 115, 1204-1208.
Angew. Chem. Int. Ed. Engl. 2003, 42, 1172-1176
Synthesis, Structure and Complexation Properties of Amide Substituted Norbornadiene and Quadricyclane Derivatives
T. Winkler, Ina Dix, P. G. Jones, R. Herges
Angew. Chem. 2003, 115, 3665-3668.
Angew. Chem. Int. Ed. Engl. 2003, 42, 3541-3544
Synthesis of a Möbius aromatic hydrocarbon
D. Ajami, O. Oeckler, A. Simon, R. Herges
Nature 2003, 426, 819-821.
Arsenic- Interactions Stabilize a Self-Assembled As2L3 Supramolecular Complex
W. Winkler, R. Herges
Angew. Chem 2004, 116, 5955-5957
Angew. Chem. Int. Ed. Engl. 2004, 43, 5831-5833.
cis-Bromination of Alkynes without Cationic Intermediates.
R. Herges, A. Papafilippopoulos, K. Hess, C. Chiappe, D. Lenoir, H. Detert
Angew. Chem. 2004, 117, 1437-1441.
Angew. Chem. Int. Ed. Engl. 2004, 44, 1412-1416.
MOL-VIC
IP6.-GREBER ANNEX II: MOST RELEVANT PUBLICATIONS (last 5 years)
1. C. Cepek, R. Fasel, M. Sancrotti, T. Greber and J. Osterwalder:
Coexisting inequivalent orientations of C60 molecules adsorbed on Ag(100)
Phys. Rev. B, 63, 125406 (2001).
2. J. Wider, F. Baumberger, M. Sambi, R. Gotter, A. Verdini, F. Bruno, D. Cvetko, A. Morgante, T. Greber and J.
Osterwalder:
Atomically resolved images from near node photoelectron holography experiments on Al(111)
Phys. Rev. Lett. 86, 2337 (2001).
3. F. Baumberger, Th. Herrmann, A. Kara, S. Stolbov, N. Esser, T.S. Rahman, J.Osterwalder, W. Richter and T.
Greber:
Optical recognition of atomic steps on surfaces
Phys. Rev. Lett. 90, 177402 (2003).
4. A. Tamai, W. Auwärter, C. Cepek, F. Baumberger, T. Greber and J. Osterwalder:
One dimensional chains of C60 molecules on Cu(221)
Surf. Sci. 566-568, 633 (2004).
5. F. Baumberger, M. Hengsberger, M. Muntwiler, M. Shi, J. Krempasky, L. Patthey, J. Osterwalder and T. Greber:
Step lattice induced band gap opening at the Fermi level
Phys. Rev. Lett. 92, 016803 (2004).
6. M. Muntwiler, W. Auwärter, A.P. Seitsonen, J. Osterwalder and T. Greber:
Rocking motion induced charging of C60:C60 on h-BN/Ni(111)
Phys. Rev. B, 71, 121402(R) (2005).
7. M. Corso, W. Auwärter, A. Tamai, T. Greber and J. Osterwalder:
Boron Nitride Nanomesh
Science, 303, 217 (2004).
8. R. Fasel, J. Wider, C. Quitmann, K.-H. Ernst and T. Greber:
Determination of the absolute chirality of adsorbed molecules
Angew. Chem. Int. Ed. 43, 2853 (2004).
9. F. Baumberger, M. Hengsberger, M. Muntwiler, M. Shi, J. Krempasky, L. Patthey, J. Osterwalder and T. Greber:
Localization of surface states in disordered step lattices
Phys. Rev. Lett. 92, 196805 (2004).
10. F. Baumberger, W. Auwärter, T. Greber and J. Osterwalder:
Electron. coherence in a melting lead monolayer
Science, 306, 2221 (2004).
MOL-VIC
AP1.-GOURDON ANNEX II: MOST RELEVANT PUBLICATIONS (last 5 years)
1.Grll, L. et al. Controlling the electronic interaction between a molecular wire and its atomic scale contacting pad. Nano
Letters 5, 859-863 (2005).
2.Gross, L. et al. Scattering of surface state electrons at large organic molecules. Physical Review Letters 93 (2004).
3.Moresco, F. & Gourdon, A. Scanning tunneling microscopy experiments on single molecular landers. Proceedings Of
The National Academy Of Sciences Of The United States Of America 102, 8809-8814 (2005).
4.Moresco, F. et al. Probing the different stages in contacting a single molecular wire. Physical Review Letters 91 (2003).
5.Moresco, F. et al. Conformational changes of single molecules induced by scanning tunneling microscopy manipulation:
A route to molecular switching. Physical Review Letters 86, 672-675 (2001).
6.Otero, R. et al. One-dimensional assembly and selective orientation of lander molecules on an O-Cu template.
Angewandte Chemie-International Edition 43, 2092-2095 (2004).
7.Repp, J., Meyer, G., Stojkovic, S. M., Gourdon, A. & Joachim, C. Molecules on insulating films: Scanning-tunneling
microscopy imaging of individual molecular orbitals. Physical Review Letters 94 (2005).
8.Rosei, F. et al. Organic molecules acting as templates on metal surfaces. Science 296, 328-331 (2002).
9.Rosei, F. et al. Properties of large organic molecules on metal surfaces. Progress In Surface Science 71, 95-146 (2003).
10.Sadhukhan, S. K., Viala, C. & Gourdon, A. Syntheses of hexabenzocoronene derivatives. Synthesis-Stuttgart, 15211525 (2003).
11.Viala, C., Seechi, A. & Gourdon, A. Synthesis of polyaromatic hydrocarbons with a central rotor. European Journal Of
Organic Chemistry, 4185-4189 (2002).
MOL-VIC
IP1-ORTEGA.- ANNEX III: APPLICATIONS ON RELATED SUBJECTS (last 5 years)
1.
“ Autoensamblado de nanoestructuras laterales y estudio de estados electrónicos”
Funding agency: Spanish Ministry of Education
Reference: MAT2002-03427
Total: 90.000 EURO
2.
“One-dimensional molecular self-assembly on vicinal surfaces”
Funding agencies: European Science Foundation, Spanish Ministry of Education
Reference: MAT2002-12241-E
Total: 81.650 EURO
3.
“Caracterización experimental de la respuesta electrónica y óptica de nanoestructuras y sistemas de baja
dimensionalidad”.
Funding agency: Spanish Ministry of Education
Reference: FIS2004-06490-C03-03
Total: 48.400 EURO
MOL-VIC
IP2-BERNDT.- ANNEX III: APPLICATIONS ON RELATED SUBJECTS (last 5 years)
“Rastertunnelmikroskopie von Metallchalkogeniden und organischen Molekülen“ within FOR 353 „ChalkogenidSchichtstrukturen: Wachstum und Grenzfl¨achenph¨anomene“, 3 year postdoc position (BAT IIa), approx. 28 000 Euro
consumables etc.
MOL-VIC
IP3-MICHEL.- ANNEX III: APPLICATIONS ON RELATED SUBJECTS (last 5 years)
Requested (R)
and obtained
Title of the project
Principal researcher
(O) funding
Funding agency and
reference
EURO
Electron spectroscopies Enrique García Michel 120.000 (O)
Dirección General de
with high energetic
Enseñanza Superior e
(ARUPS) and spatial
Investigación Científica
(STM) resolution in low
PB97-0031
dimensional systems
Electronic localization Enrique García Michel 58.058 (O)
Comunidad de Madrid
and correlation effects
07N/0031/1998
in metal/semiconductor
interfaces
Development of UHV Enrique García Michel 124.950,41 (O) Dirección General de
Technology and
Enseñanza Superior e
Instrumentation for
Investigación Científica
Synchrotron Radiation
FPA2000-0026-P4-01
end-stations
Growth of
Enrique García Michel 33.176 (O)
Comunidad de Madrid
nanostructures by self07N/0056/2001
organization in stepped
surfaces
Electronic structure of Enrique García Michel 270.936,26 (O) Ministerio de Ciencia y
quantum confined
Tecnología
systems
BFM2001-0244
Electronic structure of Enrique García Michel 60.835 (O)
Comunidad de Madrid
self-assembled lateral
07N/0022/2002
nanostructures
Electronic and
Enrique García Michel 9.400 (O)
Ministerio de Educación
crystallographic
y Ciencia
structure of low
FIS2001-00049
dimensional systems
with high momentum
resolution
Electronic structure of Pilar Segovia Cabrero 40.825 (O)
Comunidad de Madrid,
self-organized molecular
GR/MAT/0022/2004
systems at surfaces
One-dimensional
Enrique García Michel 51,300 (O)
molecular self-assembly
on vicinal surfaces
(corresponds to the
current MOL-VIC
project)
Collective phenomena Enrique García Michel 278,579(R)
and quantum
confinement in low
dimensional systems
Period
1/10/19981/10/2001
14/12/199814/12/2000
7/11/20016/11/2004
1/01/200231/12/2002
27/12/200126/12/2004
1/01/200331/12/2004
1/01/2005
31/12/2005
1/01/2005
31/12/2005
Ministerio de Ciencia y
Tecnología
07/04/2004
MAT2002-11975-E
06/04/2007
Ministerio de Educación 2006-2008
y Ciencia
FIS2005-00747
MOL-VIC
IP4-HORN.- ANNEX III: APPLICATIONS ON RELATED SUBJECTS (last 5 years)
No applications.
MOL-VIC
IP5-HERGES- ANNEX III: APPLICATIONS ON RELATED SUBJECTS (last 5 years)

HE 1530/11-1 „Synthese Möbius-aromatischer Annulene; Moleküle mit nur einer -Seite“ (Synthesis of Moebius
aromatic annulenes, molecules with a single  side). The project is supported by the Deutsche
Forschungsgemeinschaft.

“Rational synthesis of carbon nanotubes”. We are aiming at the chemical synthesis of nanotubes with uniform
geometries and thus well defined physical properties for the use in molecular electronics.

“Design and synthesis of a light-driven proton pump”. Final goal is the uphill transport of protons through an
artificial membrane or through a layer on a metal surface using photoswitchable molecules as carriers.

Design and synthesis of “molecular plates and tripods” for the orthogonal orientation of photoswitchable
molecules on Au surfaces.
MOL-VIC
IP6-GREBER- ANNEX III: APPLICATIONS ON RELATED SUBJECTS (last 5 years)
Author SNF und PSI “Direct determination of adsorption induced structural changes in large molecules by
Near Node Photoelectron Holography”
(0.1 MEuro/2 years) ends 2006.
Coauthor CERC3 “Time-resolved low energy electron diffraction from large molecules on surfaces”
(0.03 MEuro/5 years) ends 2006.
Coauthor of the SNF fundings of the group of J. Osterwalder 2005
(0.5 Meuro/2 years), ends 2007.
Coauthor of STREP EU project “Boron Nitride Nanomesh as a Scaffold for Nanocatalysts and Functional
Surfaces”
(2 MEuro/3 years) ends 2008.
SNF
Swiss National Science Fundation
PSI
Paul Scherrer Institut
MOL-VIC
MOL-VIC
Annex 4
Budget summary
[Template]
Please prepare this Annex by adding the separate budgets under A 9 (overall budget) and B7 of
each IP (budget of each IP) together.
MOL-VIC
Overall budget of the CRP (A9 f):
BUDGET
ITEMS
EUROCORES
Funding
Agency (EFA)
Estimate of Funding
PI 1 Ortega
Ministerio de
Educación y Ciencia
(Spain)
(in Euros)
Salary costs
Ph.D.
student(s)
Post-doc.
Researcher(s)
Senior
researcher (s)
Technician(s)
Estimate of Funding
PI 2 Berndt
Deutsche
Forshungsgemeinshaft
(Germany)
(in Euros)
Estimate of Funding
PI 3 Michel
Ministerio de
Educación y Ciencia
(Spain)
(in Euros)
3 x 56000 = 168000
2x35360=70720
Estimate of Funding
PI 4 Horn
Deutsche
Forshungsgemeinshaft
(Germany))
(in Euros)
Estimate of Funding
PI 5 Herges
Deutsche
Forshungsgemeinshaft
(Germany))
(in Euros)
3 x 56000 = 168000
3 x 48000 = 144000
Estimate of Funding
PI 6 Greber
Swiss National Science
Foundation
(Switzerland)
(in Euros)
Estimate of
TOTAL Funding
(in Euros)
238753
789473
Guest Prof:
20000
32246
20000
32246
Equipment per
item
item 1
UV source + optics
19700
item 2
item 3
Item 4
Item 5
Travel
conferences,
worksh.,visits
Consumables
/ Runn. Costs
Including
analysis costs
Publication,
Dissem. Cost
Overheads
if applicable
Electron analyzer
133400
Quad. mass spectrom.
12000
UHV chamb. and gaug.
20000
Ion, turbo and rotary
pumps, gate valves
20000
High Intens. Light
sourc., fiber optic lamp
21000
Evaporator comp.
6000
HPLC software
8000
245100
Transfer rod: 5000
12000
12000
6000
14000
6300
50300
12000
15000
6000
32000
93000
2000
0
Channeltrons 5000
23 000
3000
19%
26927
0
20%
66860
19%
29906
5000
123693
Others
Travel to synchrcotron
3000
187306
T O T A L
214700
171647
168000
0
administrative coordin.
2000
219000
403159
5000
1363812
MOL-VIC
Requested budget for IP1 (IP1 – B1)
(The budget items have to be consistent with the rules of your national funding agency; Please contact them if you have questions about this matter):
CRP Acronym: MOL-VIC
PI Name & Institution: Enrique Ortega, Universidad del País Vasco
IP Nr:1
Funding Agency: Ministerio Educación y Ciencia (Spain)
Outline Proposal Nr(s).:
BUDGET ITEMS
must be consistent with the rules set by
the relevant national funding agencies
Duration
where
appropriate
in month,
including start
date
YEAR 1 Funding
YEAR 2
Funding
YEAR 3
Funding
TOTAL Funding
(in Euros) [other
currencies]
(in Euros) [other
currencies]
(in Euros) [other
currencies]
(in Euros) [other
currencies]
Short Description
of each budget item where
appropriate
Salary position
Ph.D. student
Post-doc. researcher
senior researcher
Technician
student stipend / student assistant
Equipment per item
item 1
Electron analizer
133400
item 2
133400
item …
Travel
conferences, workshops, travel to
fieldwork, visits
(including networking within the CRP)
Consumables / Running Costs
Conferences, workshops
4000
4000
4000
12000
Small parts, samples,
evaporation material
4000
4000
4000
12000
26866
1520
1520
29906
including analysis costs
Publication, Dissemination Costs
Overheads
19%
if applicable
Others
including access to large infrastructures,
shiptime, etc. (please specify)
T O T A L
168266
9520
** If necessary, please also use the text box on the next page for additional description/justification of each budget item.
9520
187306
MOL-VIC
Additional description/justification of budget items of IP1 (1 page maximum)
High Resolution angular photoemission equipment:
Self-assambled supramolecular structures exhibit an inherent degree of complexity, namely large, complex building-blocks (unit cells) and small interaction
energies. In practice, systems are difficult to characterize with standard electron diffraction techniques, and hence the combination of powerful, sensitive
techniques in both real (STM) and reciprocal space (photoemission) is necessary. The current proposal is intended to incorporate state-of-the-art high
resolution, angular Photoemission (HR-ARPES) to the current set-up in San Sebastian, which includes Variable Temperature STM and standard electron
diffraction techniques. The HR-ARPES equipment consists on a display-type electron analyzer that allowing simultaneous measurement of angle-resolved
spectra within a  5º range, a plasma-discharge lamp and a monochromator. Only the full equipment ensures energy resolution below 10 meV and angular
resolution down to 0.1º. The former is necessary for the small interacting energies (narrow bands and gaps), whereas the latter is critical to resolve band
structures for extended states in large unit cells (for instance, to explore substrate mediated interactions): in fact, with the standard photon energy of 21 eV, the
angular resolution becomes 0.005 Å-1, and hence assuming 10 points per Brillouin zone, the equivalent spatial resolution goes beyond 10 nm.
MOL-VIC
Requested budget for IP2 (IP2 – B1)
(The budget items have to be consistent with the rules of your national funding agency; Please contact them if you have questions about this matter):
CRP Acronym: MOL-VIC
PI 2 Berndt, Kiel University:
IP Nr: 2
Funding Agency:
Outline Proposal Nr(s).:
BUDGET ITEMS
must be consistent with the rules set by
the relevant national funding agencies
Duration
where
appropriate
in month,
including
start date
YEAR 1
Funding
YEAR 2
Funding
YEAR 3
Funding
TOTAL Funding
Short Description
of each budget item where appropriate
(in Euros) [other
currencies]
(in Euros) [other
currencies]
(in Euros) [other
currencies]
(in Euros) [other
currencies]
Complex experiments with
interdisciplinary aspects
56000
56000
56000
UV-lamp setup for polymerisation
experiments
19700
Salary position
Ph.D. student
Post-doc. researcher
168000
senior researcher
Technician
student stipend / student assistant
Equipment per item
item 1
19700
item 2
item …
Travel
conferences, workshops, travel to
fieldwork, visits
(including networking within the CRP)
4000
4000
4000
12000
5000
5000
5000
15000
Consumables / Running Costs
including analysis costs
Publication, Dissemination Costs
Overheads
if applicable
Others
including access to large infrastructures,
shiptime, etc. (please specify)
T O T A L
84700
65000
** If necessary, please also use the text box on the next page for additional description/justification of each budget item.
65000
214700
MOL-VIC
Additional description/justification of budget items of IP2 (1 page maximum)
Staff: The complexity of the planned experiments along with the interdisciplinary aspect of the work requires a post doctoral researcher.
Equipment: To induce polymerisation an UV lamp (Lot-Oriel, 160-370 nm, 0.1 W/cm2) is required along with a power supply. The light will be focussed onto
the sample in ultra-high vacuum using UV-grade lenses (Melles Griot), which can be approached to the sample by a translation stage (MDC).
MOL-VIC
Requested budget for IP1 (IP3 – B.2)
(The budget items have to be consistent with the rules of your national funding agency; Please contact them if you have questions about this matter):
CRP Acronym:
Outline Proposal Nr(s).: 05SONS-OP-014
BUDGET ITEMS
must be consistent with the rules set
by the relevant national funding
agencies
Salary position
Post-doc. Researcher
IP Nr: 3
Duration
where
appropriate
in month,
including start
date
PI Name & Institution:
Enrique Garcia Michel, Universidad Autonoma de Madrid
Funding Agency solicited:
Ministerio de Educación y Ciencia (Spain)
YEAR 1
Funding
YEAR 2
Funding
YEAR 3
Funding
TOTAL
Funding
(in Euros)
[other
currencies]
(in Euros)
[other
currencies]
(in Euros)
[other
currencies]
(in Euros)
[other
currencies]
24,1.1.2008
35360
Equipment per item
Item 1
Item 2
35360
12000
20000
20000
5000
Item 3
Item 4
Travel
conferences, workshops, travel
to fieldwork, visits
Short description/
justification of each budget item **
70720
Salary of post-doc researcher
12000
20000
20000
5000
Quadrupole Mass Spectrometer
UHV chamber and UHV gauge
Turbo and rotary pumps, gate valve
Transfer rod
2000
2000
2000
6000
Conferences, workshops,
2000
0
2000
1000
2000
1000
6000
2000
Small parts, samples, evaporation material
Publication costs
(including networking within the
CRP)
Consumables / Running Costs
including analysis costs
Publication, Dissemination
Costs
Overheads
if applicable
19%
9310
9948
7668
26927
1000
1000
1000
3000
Others
including access to large
infrastructures, shiptime, etc. (please
specify)
T O T A L
59310
63308
49028
Travel to synchrotron radiation facilities
171647
** If necessary, please also use the text box on the next page for additional description/justification of each budget item.
MOL-VIC
Additional description/justification of budget items of IP3 (1 page maximum)
The main budget item is related to scientific equipment needed to build a new sample preparation chamber adapted for the exposure to organic molecules,
This includes pumps and accessories for sample cleaning (ion gun), and transfer (transfer rod). A QMS is also required to guarantee the quality and
cleanliness of the molecular evaporations.
Smaller budget items are required for consumables and travel to conferences and mutual visits.
An important budget item is the application for the salary of a postdoctoral researcher during two years. The development of the activities described in the
project, represent a significant increase of the work load, which cannot be undertaken without additional manpower. The postdoctoral researcher hired
within this IP will take care of the operation of the SPALEED, data acquisition and analysis, with support from the rest of group. He/she will also be
involved in the whole research activities related to this IP.
MOL-VIC
Requested budget for IP4 (IP4 –B2)
(The budget items have to be consistent with the rules of your national funding agency; Please contact them if you have questions about this matter):
CRP Acronym: MOL-VIC
IP Nr:
must be consistent with the rules set by
the relevant national funding agencies
Duration
where
appropriate
in month,
including start
date
YEAR 1 Funding
YEAR 2
Funding
YEAR 3
Funding
TOTAL Funding
(in Euros) [other
currencies]
(in Euros) [other
currencies]
(in Euros) [other
currencies]
(in Euros) [other
currencies]
56.000
56.000
Short Description
of each budget item where
appropriate
Fritz-Haber-Institut
DFG
Funding Agency:
Outline Proposal Nr(s).:
BUDGET ITEMS
K.Horn
PI Name & Institution:
4
Salary position
Ph.D. student
Post-doc. researcher
Scientific experiments on
senior researcher
supramolecular structures on
Technician
surfaces
56.000
168.000
student stipend / student assistant
Equipment per item
item 1
item 2
item …
Travel
conferences, workshops, travel to
fieldwork, visits
(including networking within the CRP)
Consumables / Running Costs
including analysis costs
Publication, Dissemination Costs
Overheads
if applicable
Others
including access to large infrastructures,
shiptime, etc. (please specify)
TOTAL
56.000
56.000
** If necessary, please also use the text box on the next page for additional description/justification of each budget item.
56.000
168.000
MOL-VIC
Additional description/justification of budget items of IP4 (1 page maximum)
This work needs a fully dedicated postdoctoral researcher to tackle the complexity of the experiments involved, and the command of the different experimental efforts and
interpretation methods.
MOL-VIC
Requested budget for IP5 (IP5–B2)
(The budget items have to be consistent with the rules of your national funding agency; Please contact them if you have questions about this matter):
CRP Acronym: MOL-VIC
IP Nr:
must be consistent with the rules set by
the relevant national funding agencies
Rainer Herges, Unibersität Kiel
Funding Agency:
Outline Proposal Nr(s).:
BUDGET ITEMS
PI Name & Institution:
Duration
where
appropriate
in month,
including
start date
YEAR 1
Funding
YEAR 2
Funding
YEAR 3
Funding
TOTAL
Funding
(in Euros)
[other
currencies]
(in Euros)
[other
currencies]
(in Euros)
[other
currencies]
(in Euros)
[other
currencies]
Short description/
justification of each budget item **
Salary position
Ph.D. student
Post-doc. Researcher
48.000
48.000
48.000
144.000
Design, synthesis and characterization of
compounds
High intensity light source SID-201, fiber optic coupler
lamps , for photopolymerization and isomerization
HPLC software and columns (accessories to existing
instrument)
senior researcher
Technician
student stipend / student assistant
Equipment per item
Item 1
21.000
21.000
Item 2
8.000
8.000
Item …
Travel
conferences, workshops, travel to
fieldwork, visits
(including networking within the CRP)
Consumables / Running Costs
4.000
5.000
5.000
14.000
10.000
12.000
10.000
32.000
including analysis costs
Publication, Dissemination
Costs
Overheads
if applicable
Others
including access to large
infrastructures, shiptime, etc. (please
specify)
T O T A L
91.000
65.000
63.000
219.000
chemicals, glassware, analytics
MOL-VIC
Additional description/justification of budget items of IP5 (1 page maximum)
The budget is mainly needed for the salary of a postdoc (36 months), chemicals, and equipment. For the photochemical polymerizations and the cis-trans
isomerization of the surface bound retinal we need a tunable high-intensity light source e.g. the Model SID-201 from Photon Technology International.
Standard equipment and the usual infrastructure (NMR, IR, UV, fluorescence MS etc.) for preparative chemistry is available in our institute. The travel budget
should cover the expenses for mutual visits and for attending international meetings to present our results.
MOL-VIC
Requested budget for IP6 (IP6–B2)
(The budget items have to be consistent with the rules of your national funding agency; Please contact them if you have questions about this matter):
CRP Acronym: MOL-VIC
IP Nr:6
Funding Agency solicited:
Outline Proposal Nr(s).:
BUDGET ITEMS
must be consistent with the rules set by
the relevant national funding agencies
PI Name & Institution:
GREBER, UZH
Duration
where
appropriate
in month,
including
start date
YEAR 1
Funding
YEAR 2
Funding
YEAR 3
Funding
TOTAL
Funding
(in Euros)
[other
currencies]
(in Euros)
[other
currencies]
(in Euros)
[other
currencies]
(in Euros)
[other
currencies]
Short description/
justification of each budget item **
Salary position
Ph.D. student
Post-doc. Researcher
36/1
senior researcher
5/13
Technician
6/6
79’584
16’123
79’584
20’000
16’123
79’584
238’753
20’000
32’246
Guest Professor
6’000
Evaporator components
Runs the Project at the Synchrotron
Technician for special evaporator development
student stipend / student assistant
Equipment per item
Item 1
6’000
Item 2
Item …
Travel
conferences, workshops, travel to
fieldwork, visits
(including networking within the CRP)
2’100
2’100
2’100
6’300
7’000
500
5’000
8’000
1’000
8’000
1’500
5’000
23’000
3’000
21’061
27’561
18’237
66’860
500
500
1’000
2’000
Consumables / Running Costs
including analysis costs
Publication, Dissemination
Costs
Overheads
if applicable
Others
including access to large
infrastructures, shiptime, etc. (please
specify)
T O T A L
126’866
165’868
110’423
403’159
Channeltrons
MOL-VIC
Additional description/justification of budget items of IP6 (1 page maximum)
The budget mainly consists in salaries, running costs for the experiment, travel and publication money.
We ask for salaries of a postdoc (36 month) and a technician (6 month) and for the expenses of a guest professor (5 month). The postdoc position is necessary in order to run the
above mentioned XPD experiment at the Swiss Light Source, and to train students on the PhD and the graduate level. The technician position is necessary in order to further
develop the difficult task to evaporate large molecules of which nanogram quantities were available, only. The money for a guest is important in order to fertilize the research, in
particular in view of the theoretical understanding of the results. We furthermore expect from this guest to help to maximize synergies inside and outside MOL-VIC and to
develop new opportunities and views in the field of self organized nano-structures. The surface physics group at UZH will contribute the salary of the PI, who will work about
30% on MOL-VIC, and potential PhD students on the project.
A contribution to the running costs for the experiments is expected. E.g. the consumable “channeltrons” has to be covered from inside MOL-VIC. The surface physics group of
Prof. Dr. Jürg Osterwalder and the physics institute at UZH will add about an equal amount to the running costs and the infrastructure of IP6.
Travel and publication money is important for the networking inside MOL-VIC and the dissemination of the results to the world-wide community. Again, the outside
contribution from the surface physics group and the physics institute at UZH will be about an equal amount to travel and publication money of IP6.