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Article
Electronic Structure of Core/shell Metal/oxide Aluminium Nanoparticles
Giulia Maidecchi, Chinh Duc Vu, Renato Buzio, Andrea Gerbi,
Gianluca Gemme, Maurizio Canepa, and Francesco Bisio
J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.5b07678 • Publication Date (Web): 04 Nov 2015
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The Journal of Physical Chemistry C is published by the American Chemical Society.

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8 Electronic Structure of Core/Shell Metal/Oxide
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12 Aluminium Nanoparticles
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16 Giulia Maidecchi,†,⊥ Chinh Vu Duc,‡,† Renato Buzio,¶ Andrea Gerbi,¶ Gianluca
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18 Gemme,§ Maurizio Canepa,k,§ and Francesco Bisio∗,¶
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21 †Dipartimento di Fisica, Università di Genova, via Dodecaneso 33, I-16146 Genova, Italy
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23 ‡Institute of Materials Science - Vietnam Academy of Science and Technology, 18 Hoang
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25 Quoc Viet Road, Cau Giay District, Ha Noi, Viet Nam
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27 ¶CNR-SPIN, C.so Perrone 24, I-16152 Genova, Italy
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§INFN, Sezione di Genova, via Dodecaneso 33, I-16146 Genova, Italy
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kDipartimento di Fisica, Università di Genova and CNISM, Sede Consorziata di Genova,
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via Dodecaneso 33, I-16146 Genova, Italy
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36 ⊥Present address: Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy
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39 E-mail: francesco.bisio@spin.cnr.it
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Abstract
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6 We report a combined X-ray photoelectron spectroscopy and atomic-force microscopy
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8 study of ultrafine (< 30 nm) Al/Al-oxide core/shell nanoparticles. A complex fine
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10 structure is observed within O1s and Al2p core-level electronic spectra of the particles,
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12 indicative of a corresponding complex system morphology. The photoemission spectra
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14 of the Al metallic core exhibited a low-binding-energy component, ascribed to strongly
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16 undercoordinated metallic Al atoms in the particle core. Such a fraction of underco-
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18 ordinated metallic atoms grows larger in relative weight as the particles get smaller,
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finally becoming completely dominant for nanoparticle size below 20 nm. This fea-
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21 ture is interpreted as the fingerprint of vacancy-cluster formation within the metallic
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23 core as an effect of oxidation. For the smallest particle size investigated (< 10 nm),
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25 vacancy clusters coalesce leading to the core disruption, with a heavy impact on the
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27 corresponding electronic and plasmonic response.
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32 1 Introduction
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35 Aluminum nanoparticles (NPs) and nanostructures are extremely appealing due to their po-
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37 tential application as low-cost plasmonic systems endowed with broadband plasmonic func-
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39 tionality extending from the visible to the deep-ultraviolet (DUV) photon-energy range. 1–26
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41 The plasmonic response of aluminium NPs is extremely sensitive to the NP size and shape, 2,3,6,8,17
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43 much more than the conventional plasmonic metals Au and Ag. This implies that the control
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45 over the NP morphology and composition is of paramount importance, the more so when
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47 DUV plasmonics, calling for NP size around or below the 20-nm mark, is involved.
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49 Aluminum undergoes a fast surface oxidation in atmosphere, leading to the quick for-
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51 mation of a 2-3 nm thick oxide layer. 27 Such a native oxide has a strong influence on the
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53 plasmonic response, leading to a significant redshift of the plasmon resonances, that can be
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55 also positively exploited to extend the application range of Al NPs towards the visible-light
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regime. 1–3,6–9,11 The impact of oxidation clearly becomes increasingly relevant for smaller NP
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size, where the mass transport associated with the anion/cation migration and their different
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6 migration velocity may strongly affect the morphology of the metallic core. 27,28 Understand-
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8 ing the morphology and composition of ultrafine metal/oxide Al core-shell NPs is therefore
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10 relevant for harnessing the fabrication procedures of Al nanostructures, and understanding
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12 their chemical and physical response for all the applications in atmosphere. Despite the
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14 relevance of the subject and the growing interest in Al NPs, however, the objective difficulty
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16 of fabricating very fine Al particles and of addressing this system have strongly limited the
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18 studies of Al NPs morphology and composition in the <20 nm size regime. 28
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20 In this paper, we report a combined X-ray photoelectron spectroscopy (XPS) and atomic-
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22 force microscopy (AFM) study of ordered arrays of metal/oxide Al core-shell NPs with
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24 diameter in the 10 − 30 nm range. XPS is indeed extremely powerful for exploring the
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26 growth of Al oxide and the resulting chemico-physical properties of oxidised Al, 29–39 and can
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28 be efficiently applied to characterize core-shell NPs. The XPS data are interpreted by means
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30 of a simple model relying on an ancillary atomic force microscopy (AFM) characterization
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32 that gives insights in the morphology of such systems. 8,40 The deconvolution of XPS spectra
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34 demonstrates the existence of O and Al atoms in different ionization states in the NPs. In
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36 particular, we observed a characteristic low-binding-energy (BE) metallic-Al subcomponent
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38 that gradually became completely dominant for the smallest NP size investigated. Such
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a feature was interpreted as the spectroscopic fingerprint of vacancy-cluster formation in
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the metallic NP core during the oxidation process, suggesting a major modification of the
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morphology and electronic structure of the metallic core below a critical NP size with respect
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47 to the ideal ”compact-core” situation, with a strong impact on Al-NP electronic and optical
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49 response.
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2 Results and discussion
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7 2.1 Experimental
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10 The systems consist of ultrafine Al NPs, arranged in 2-dimensional (2D) densely-packed
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12 arrays supported on an insulating single-crystal substrate. The arrays are fabricated by
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14 a template-deposition approach, depositing Al on LiF(110) substrates previously nanopat-
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16 terned by self-organization. The samples were fabricated in a high-vacuum vessel (chamber
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18 base pressure pbase = 5 · 10−9 mbar) according to a procedure which is described in detail
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20 in previous work. 8,41 First, self-organized nanopatterns are realized on the surface of a flat
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22 LiF(110) crystal by homoepitaxial deposition (LiF(110) crystals, 10 × 10 × 1 mm3 , Crystec
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24 Gmbh). The nanopatterns consist of aligned nanoridges formed by evenly-spaced [100] and
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26 [010] exposed facets with a periodicity Λ ≈ 25 nm. 41–43 Thereafter aluminium is deposited
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28 at grazing incidence (60◦ from the normal) on the nanopatterned LiF(110) by molecular
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30 beam epitaxy at a pressure p < 2.5 · 10−8 mbar, thus preventing the inclusion of impu-
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32 rities within the metallic core. 44 The grazing-angle deposition promotes the formation of
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34 Al nanowires, thanks to the shadow effect of the nanoridges. An annealing treatment at
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T=670 K in vacuum for five minutes promotes the nanowire dewetting and consequent for-
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mation of disconnected Al NPs. 8,41 After the annealing, the samples are exposed to a flux
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of research-grade oxygen (p = 1 · 10−5 mbar × 200 s) at a temperature T≈ 350 K.
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43 The NPs are then briefly exposed to atmosphere (typ. few minutes) prior to their inser-
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45 tion in the XPS apparatus, again under HV conditions. The AFM characterization, involving
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47 longer permanence in atmosphere, which may affect the oxide composition, was performed
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49 on sacrificial samples, nominally identical to the ones used for XPS. In this work, we ad-
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51 dressed Al NPs characterized by a different mean size, that were obtained simply depositing
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53 a different amount of Al onto the nanopatterned substrate. 8 In order to minimize any spuri-
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55 ous substrate effect, NPs with different mean size were realized depositing different amounts
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57 of Al on different zones of the same nanopatterned substrate. These zones are thus labelled,
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in order of increasing Al coverage, as ”zone” 0, 1, 2 and 3 (z0, z1, z2, z3), corresponding
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6 to an Al effective coverage (defined as the thickness of the deposited material assuming a
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8 uniform substrate coverage) of 0.8 nm, 1.7 nm, 2.5 nm and 3.4 nm, respectively.
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10 The sample characterization has been performed within 24 hours from their fabrication.
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12 AFM imaging was realized by meas of a Solver P47H-PRO by NT-MDT. The XPS spectra
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14 were collected using a PHI ESCA 5600 system, equipped with a monochromatized Al source
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16 Kα (1486.7 eV photon energy). Due to the insulating properties of the LiF substrates, it was
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18 necessary to use a neutralizer electron gun to compensate for the sample charging effects.
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20 The neutralizer was applied extremely carefully in order to avoid the deformation of the
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22 peaks due to the inhomogeneous charge-up of the substrates.
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26 2.2 Morphology of Al nanoparticle arrays
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29 In Fig. 1a-d we report representative AFM images for each of the four different zones (z0
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31 to z3). A graphical sketch of the array morphology is reported in the figure center. The
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33 nanopatterned LiF surface that supports the NPs exhibits coherently-aligned nanogrooves,
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35 that effectively induce the formation of Al particles with small size and a reduced size
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37 dispersion that are aligned along the substrate grooves. 8 The images clearly show these Al
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39 NPs, with circular in-plane aspect and with a mean size that increases with increasing Al
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41 coverage. The areal density ρ of the NPs in the arrays was assessed by carefully applying a
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43 digital recognition algorithm of the ”watershed” type to the images. The algorithm identifies
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45 each isolated ”bump” above a critical pixel size in the images and assigns it to an individual
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47 NP. The few coalesced structures, or features that could not be resolved as multiple closely-
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49 spaced NPs were treated as a single NP. The reliability of the algorithm and its robustness
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51 were carefully checked by manual inspection of the results. The so-obtained ρ reads 2000±60,
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53 1750 ± 40, 1300 ± 30, 950 ± 30 NP/µm2 for z0 to z3. Knowing the amount of deposited Al
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55 for each zone, it is then straightforward to calculate the average number of Al atoms per
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57 particle NAl for each zone, which reads: NAl =2.5 × 104 , 6 × 104 , 1.2 × 105 and 2.2 × 105 atoms
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from z0 to z3, respectively (Table 2). It can be clearly seen that the degree of alignment of
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6 the NPs with the substrate grooves tend to decrease with increasing Al coverage, as possible
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8 cross-groove NP coalescence sets in, decreasing the overall order of the NP arrays.
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8 nm
a b 26 nm

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15 e [1
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[0
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[001]
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26 nm 26 nm
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19 Λ

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24 0 nm c d 0 nm
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26 Figure 1: (a-d) AFM images of the Al/Al-oxide NPs systems obtained following the deposition of
27 different equivalent thickness of Al: (a) z0: 0.8 nm, (b) z1: 1.7 nm, (b) z2: 2.5 nm, (d)
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29 z3: 3.4 nm. The area of the images is 1000 x 1000 nm2 . (e) Schematic representation
30 of the nanostructured LiF substrate and the supported Al NPs.
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33 .
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37 2.3 X-ray Photoeletron Spectroscopy
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40 In Fig. 2 we report XPS spectra of the Al-NP system. Fig. 2b (c) shows the O1s (Al2p)
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42 energy region of the XPS spectra measured on the Al NP arrays (z3 to z0 from top to
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44 bottom). The spectra have been recorded in the geometry depicted in Fig. 3. The cor-
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46 responding spectra recorded on a flat and continuous 20-nm-thick Al film, measured for
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48 reference purposes, are reported in Fig. 2a. At a first glance, all the Al2p spectra show two
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50 main peaks, while the O1s spectra are composed by a single broad feature. In the case of Al,
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52 the two peaks respectively correspond to atoms in metallic (lower BE) or oxidized (higher
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54 BE) state. 29,30,32,34,35,39,40 The intensity of the metallic-Al peak monotonously decreases as
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56 the mean NP size decreases, whereas the Al-oxide peak and the O1s peak almost seem un-
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58 affected. We believe this effect can be rationalized based on the fact that the volume of
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7 Metal
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II core
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I III
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12 Oxide
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34 of the reference flat-Al film. panels b (c): experimental spectra of O1s (Al2p) for z3,
35 z2, z1, z0 (top to bottom). Experimental data (markers), best fit (solid black line) and
36 deconvolved subcomponents (colored areas) are reported. The roman numbers (I to III)
37 are used to label the various subcomponents. OI (light gray), OII (gray), OIII (black),
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AlIox , AlII III
ox , Alox (shades of gray), Alinterf (blue), Alcore (light blue).
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X-Rays ] [0
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D
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55 Figure 3: (a) Schematic representation of the XPS measurement configuration (a) and scheme of a
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the oxide-shell, responsible for the XPS oxide contributions, scales more slowly for changing
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6 Al effective thickness with respect to the metallic counterpart. However, the analysis per-
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8 formed in the following will rely on relative intensities and XPS-peak BE, and is unaffected
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10 by absolute-intensity issues.
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12 More detailed information can be however obtained deconvolving these peaks into their
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14 subcomponents. The Al2p spectra were thus fitted as a superposition of Doniach-Sunjic
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16 doublets with branching ratio of 0.5 and a spin-orbit splitting of 0.42 eV. 30,32 The O1s
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18 peaks were instead fitted as a superposition of Lorentian-Voigt components. A Shirley-type
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20 background was employed in all cases. In the NP case, the width of the various subcompo-
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22 nents of the Al-oxide peaks were constrained to be equal among themselves, thus effectively
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24 limiting the number of independent degrees of freedom in the fit, and the same was done
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26 for the metallic-Al subcomponents and for the O1s subcomponents. This because the peak
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28 width/shape is mainly determined by the core-hole lifetime, that is expected to be equal
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30 within each specific atomic environment (metallic or oxide). In the reference flat-Al case,
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32 the same constraints were applied, although these peaks are narrower with respect to the
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34 NP case. Indeed, the core-hole screening and lifetime in insulated NPs or in a continuous
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36 metal film are different, leading to different peak width between the two cases (so-called final
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38 state effect). 45 While measuring NP spectra, an external charge neutralizer was employed to
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prevent the buildup of sample charge arising due to the insulating nature of the substrate.
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The deconvolution of the spectra was initially performed for the flat-Al case, where the
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smaller peak width allowed to better disentangle the various subcomponents. In doing so, we
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47 adapted the approach of well-established photoemission studies. 30,32 In the Al2p core-level,
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49 we identified three oxide subcomponents, AlIox (73.4 eV, light-gray area), AlII
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51 and AlIII
ox (75.2 eV, dark gray), that can be assigned to different ionization states of Al bound
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53 to O. 30,32,35 The metal peak was instead fitted as the superimposition of two doublets spaced
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55 in energy by 0.3 eV, christened Alcore (72.7eV, light blue) and Alinterf (72.4 eV, deep blue). 32
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57 Please notice that the energy alignment of the BEs was performed setting Alinterf at 72.4
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Alox
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43 Figure 4: Binding energy and peak area of each component of the spectra shown in panel c and
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45 b for Al2p (top) and O1s (bottom). The stick height is proportional to the peak area,
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eV, also for the NP systems. 32
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6 The main contribution to each Al2p spectrum is represented by AlIII
ox , corresponding
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8 to the amorphous bulk aluminium oxide resulting from the low temperature oxidation of
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10 the metal. 28,34,39 The two minor contributions to the oxide peak, AlII I
ox and Alox , correspond
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12 instead to sub-oxide components. The dominance of the AlIII
ox peak is a typical fingerprint of
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14 the advanced state of oxide formation that is witnessed after atmospheric exposure. 30 The
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16 two metallic subcomponents have a more intriguing origin: indeed, while the Alcore peak is
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18 assigned to bulk metallic Al, the Alinterf state arises upon oxidation, and has been assigned
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20 to undercoordinated metallic Al atoms within the metallic state. It will be discussed in more
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22 depth in the following.
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24 The O1s peak has been fitted as the superposition of three subcomponents, OI (530.6 eV,
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26 light gray), OII (531.8 eV, gray) and OIII (533.1 eV, dark gray), corresponding to aluminium
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28 oxide, aluminium hydroxide and water, respectively. 31,37,38
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30 Table 1: Energy of the subcomponents of the Al2p (top) and O1s (bottom) spectra for the reference
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flat film and the four nanoparticle arrays. The BEs are expressed in electronvolts.
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34 AlIII
ox AlII
ox AlIox Alcore Alinterf
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36 Flat 75.2 74.5 73.4 72.7 72.4
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38 z0 75.4 74.6 73.8 – 72.4
39 z1 75.4 74.8 73.65 – 72.4
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41 z2 75.5 74.75 73.75 72.9 72.4
42 z3 75.35 74.6 73.7 72.7 72.4
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44 OIII OII OI
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46 Flat 533.1 531.8 530.6
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48 z0 532.8 531.9 530.6
49 z1 532.8 531.7 530.4
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51 z2 533.0 531.9 530.4
52 z3 533.0 531.9 530.7
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56 The NP spectra were fitted in strict analogy with the reference ”flat-Al” case. However,
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the metallic-Al case, we effectively constrained the energies of the various NP-spectrum
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6 subcomponents to lie within ±0.4 eV (Al oxide), ±0.2 eV (metallic Al) ±0.3 eV (O1s) with
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8 respect to the reference values. This was done to prevent the achievement of good fits with
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10 unphysical energy shifts of the fit subcomponents. The best-fit BEs for each subcomponent
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12 are reported in Table 1, and graphically represented in Fig. 4. In Fig. 4 it can be clearly seen
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14 that the energy spread in the subcomponent BEs, which naturally arises from the presence
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16 of noise in the spectra, and gets larger upon the broadening of the spectral features, is much
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18 smaller than the energy separation between the different subcomponents, meaning that the
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20 subcomponent assignment performed for the flat-Al reference still holds for the Al NPs.
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22 Incidentally, this implies that fitting the metallic peak with a single component would yield
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24 an unphysical result in comparison with the reference case, supporting the evidence that
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26 both ”interface” and ”bulk” subcomponents can be observed in NPs.
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28 Looking at the NP spectra, we notice some clear trends of subcomponent intensity as a
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30 function of the NP size for both the O1s and the Al2p peaks. For O1s, we witness a gradual
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32 increase in the relative weight of Al-oxide (OI ) with respect to hydroxide (OII ) for decreasing
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34 NP size, and the disappearance of the water component. In the smallest-NP case (z0), a
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36 broad feature (systematically observed) appears at BE lower than the O1s main peak, for
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38 which however, no clear interpretation can be found in the current literature.
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Speaking of Al2p, whereas its oxide subcomponents show no well-defined trends in in-
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tensity or BE upon NP size, an interesting trend emerges for the intensity of the metallic
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counterpart. Indeed, it appears that the Al2p metallic peak can be fitted by the two estab-
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47 lished Alcore and Alinterf components only in the case of larger NP size (z2 and z3), whereas
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49 for the smallest size (z0 and z1) the metal peak is compatible with the exclusive presence of
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51 the ”interface” subcomponent Alinterf . In retrospect, this justifies the choice of referring the
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53 BE to this peak, since the other obvious choice (Alcore ) is not observable for all the spectra.
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2.4 Discussion
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6 The NP size, crucial for discussing the data, cannot be extracted from AFM data alone.
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8 However, combining XPS and AFM data, the mean NP size can be successfully extracted
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10 applying the model thoroughly described in Ref. 8. To this end, the NPs were modelled
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12 as semiellipsoids laid onto the (010) facet of the LiF ripples (Fig. 3a), having circular
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cross-section parallel to the (010) facet and composed by a metallic core surrounded on the
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atmosphere side by an oxide shell of thickness D = 2 nm, as appropriate for brief exposure
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to atmosphere. 3 Fixing the total number of Al atoms per NP at the experimental NAl , the
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21 ratio between the oxide and metallic XPS contributions depends on the NP-core in-plane
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23 radius (xmet ) and its out-of-plane aspect ratio (zmet /xmet ) only (Fig. 3b). 8 Thus, comparing
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25 the experimental metal/oxide ratio in Al2p with the ones calculated by the model of Ref.
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27 8, the mean values of zmet and xmet can be deduced. The mean NP dimensions so obtained
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29 are reported in table 2. The total NP diameter (core & shell) in the (010)-facet plane reads
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31 (10 ± 4) nm, (17 ± 5) nm, (22± 8) nm, (29 ± 10) nm for z0 through z3 respectively, with
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33 particles that tend to get flatter for increasing size. The uncertainty in NP size is mostly to
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35 be ascribed to the size dispersion of the NPs. 8 The high out-of-plane aspect ratio calculated
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37 for z0 clearly hints at the breakdown of the model’s assumptions for such a small NP size,
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39 that will be addressed in detail further on.
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41 Table 2: Geometrical parameters of the NP arrays: Nanoparticle density ρ and mean in-plane and
42 out-of-plane semiaxis of the ellipsoidal core).
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45 Zone ρ xmet zmet
46 N P s/µm2 nm
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0 2000 ± 60 3.2 ± 1.6 7.7 ± 3.9
49 1 1750 ± 40 6.3 ± 2.6 5.7 ± 2.2
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2 1300 ± 30 9.1 ± 3.9 6.4 ± 2.8
52 3 950 ± 30 12.3 ± 5.1 7.4 ± 3.1
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56 Having assessed the NP size, we can now discuss the XPS data in more depth. For the O1s
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very similar oxide composition in the two cases. The two main O1s subcomponents (OI
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6 and OII ) correspond to the O2− anions in non-crystalline alumina and to surface OH−
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8 groups, respectively, 31,37,38 though the OH− peak may bear a contribution from adventitious
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10 species. 38,46 The hydroxilation of the NP occurs upon interaction with atmospheric humidity,
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12 which is also responsible for the relatively weak undissociated-water peak, OIII . 37
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14 The water-related oxygen subcomponents are simply due to the interaction of the system
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16 with water vapour during the short exposure to atmosphere during the transfer from the
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18 preparation chamber to the XPS setup. The small intensity of the OIII peak demonstrates
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20 that only a very small fraction of adsorbed water is present, while most molecules quickly
21
22 dissociate leading to surface hydroxilation. The OII peak can bear a contribution from
23
24 the Al-related OH− groups and from adventitious molecules adsorbed on the sample during
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26 the transit in atmosphere. The OH− contribution can be thus calculated subtracting from
27
28 the OII peak the component due to adventitious molecules that can be extracted from the
29
30 deconvolution of the high-resolution C1s core-level spectra (not shown). Such a contribution
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32 reads between 28−33% in all zones. After this subtraction, the OH− component exceeds
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34 that of O2− for all the four zones, thus demonstrating a significant hydroxilation of the
35
36 nanoparticle surface. The oxide stoichiometry, calculated through the intensity ratio between
37
38 the oxide-related O1s and Al2p components (XPS intensity yield 4:1), reads ≈ 2 for all the
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40
four zones, a value that corresponds to an oxyhydroxide stoichiometry, indicating that the
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42
exposure to atmosphere might induce the formation of AlO(OH), as previously observed in
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the case of air-formed Al films. 37
46
47 More intriguing is the analysis of the Al2p line. The oxide-related components, as pre-
48
49 viously mentioned, are dominated by AlIII
ox subcomponent, as expected for the advanced
50
51 degree of oxidation of the systems. We notice that the intensity of the oxide subcomponents
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53 remains almost unchanged as a function of decreasing NP size. This is mainly a consequence
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55 of the limited probing depth of XPS and an indication that the oxide thickness does not sig-
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57 nificantly vary as a function of NP size. Coming to the metallic subcomponents, the crucial
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point is the Alinterf contribution. Previous XPS studies on oxidation of single-crystal sys-
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6 tems had already detected it and vaguely ascribed it to metallic Al atoms in proximity of the
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8 metal/oxide interface. 32,35 Its origin remains however unclear; in particular, the energy shift
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10 towards lower BE cannot be rationalized in terms of oxygen-induced electron depletion but
11
12 instead suggest the formation of open and undercoordinated structures within the metallic
13
14 Al. 47 The association of the Alinterf component with phenomena occurring at the metal/oxide
15
16 interface is consistent with its intensity trend vs NP size, that sees the Alinterf contribution
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18 become dominant as the NP size is reduced. In very fine NPs (diameter<20 nm), our XPS
19
20 analysis assigns the totality of the metallic atoms to such an interface electronic state.
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22 In order to understand its origin and its implications for ultrafine Al NPs, the microscopic
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24 dynamics of Al oxidation has to be recalled. According to the Cabrera-Mott theory, indeed,
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26 Al oxidation is characterized by a faster outward migration of the Al cations with respect
27
28 to the oxygen anions through the forming oxide layer. 27 Such a different diffusion velocity
29
30 induces the formation of vacancies in the metal at the metal-oxide interface that coalesce to
31
32 form vacancy clusters leading to the formation of open, undercoordinated metallic structures
33
34 near the interface. We remark that such Al-interface state, originally observed upon con-
35
36 trolled oxidation in ultra-high vacuum of Al single crystal, appears as a remarkably general
37
38 effect, observable also under the less-ideal conditions in which we performed the oxidation,
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40
and therefore of wide impact in all the atmospheric applications of Al NPs.
41
42
In NPs, these microscopic effects migth have a potentially disruptive impact on the metal
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44
45
core, as indeed shown in a recent transmission-electron microscopy study where metallic Al
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47 NPs with diameter below a critical value (d <8 nm) were so heavily affected by oxidation
48
49 to completely lose their metallic core (Kirkendall effect), giving rise to hollow-core NP mor-
50
51 phologies. 28,48 Based on this, we therefore suggest that the Alinterf is the spectral fingerprint
52
53 of vacancy clusters at the metal/oxide interface. This phenomenon is clearly associated with
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55 an alteration of the electronic properties of the NP core with respect to its idealized bulk
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57 counterpart. Its increasing relevance for smaller NP surely implies a substantial difference of
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the overall electronic (hence plasmonic) response of the these systems with respect to expec-
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6 tations based on oversimplified NP-oxidation models. This incidentally promotes XPS as an
7
8 effective method for assessing nanometric characteristics of NPs having a complex chemical
9
10 structure.
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12 In this respect, we have to mention that recent measurements of DUV plasmonic response
13
14 of Al core/shell NPs revealed that NPs as small as those of z1 still support a clearly-detectable
15
16 localized-surface plasmon resonance, 8 whereas for smaller NPs (z0) no such response was
17
18 observed. This sets the threshold for plasmonic functionality in between the pertinent mean
19
20 NP size for z0 and z1 systems, where z0 NPs, while still retaining a fraction of metallic
21
22 atoms, are likely characterized by a disrupted core morphology unable to sustain detectable
23
24 free-electron plasma oscillations.
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26
27
28
29 3 Conclusions
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31
32 We reported a combined AFM and XPS study of the electronic properties of ultrafine Al/Al-
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34 oxide core/shell NPs supported on nanopatterned insulating substrates. The photoemission
35
36 spectra of Al NPs are deconvolved as the superposition of several chemically-shifted sub-
37
38 components, indicative of a complex chemistry of the oxidized shell and the metallic core.
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40 We identified a characteristic low-binding-energy valence state of metallic Al, that could
41
42 be ascribed to undercoordinated metallic atoms within the core. For decreasing NP size,
43
44 the undercoordinated metallic structures coalesce in vacancy clusters within the NP inner
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46 metallic core, possibly leading to the disruption of the homogeneous Al metallic core for NP
47
48 diameters below 10 nm, with heavy implications for the electronic and plasmonic response
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50 of ultrafine Al particles.
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4 Acknowledgments
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7 Financial support from the Fondazione Carige, from Sincrotrone Elettra SCpA (PIK Ex.Pro.Rel.)
8
9 and from the Ministero dell’Istruzione, dell’Università e della Ricerca (Project no. PRIN
10
11 2008AKZSXY 002) is acknowledged. The image analysis was performed using the open-
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13 source software Gwyddion. 49
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15
16
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