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Materials Chemistry C
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On the origin of the ferromagnetic signature

in silver nanoparticles and thin films†
Cite this: J. Mater. Chem. C, 2017,
5, 4899
Armando J. Marenco,a David B. Pedersen*b and Simon Trudel *a

The unconventional ferromagnetism of Ag as been studied in highly pure nanomaterials. Gas-phase

Received 27th February 2017,
Accepted 27th April 2017
DOI: 10.1039/c7tc00879a
rsc.li/materials-c
synthesis of nanoparticles and thin films allow for the independent study of size and ligand-free surface
effects. No size correlation to magnetism in Ag nanoparticles ranging from 3.3  0.9 to 7.8  1.3 nm
was determined by superconducting quantum interference device (SQUID) magnetometry. Additionally,
magnetic quartz crystal microbalance (MQCM) under vacuum conditions of 3.3  0.9 nm Ag NPs shows
magnetic behaviour only after the onset of oxidation. SQUID magnetometry shows a higher magnetization
for samples exposed to O2 compared to inert atmospheres. This indicates non-stoichiometric oxidation at
the surface as the reason for the observed magnetism as supported by an B8 : 1 Ag : O ratio from MQCM
measurements. Additionally, heat-treated Ag thin films present a lower saturation magnetization compared
to those kept in O2 without heating. This latter observation could be the result of driving the oxidation to
stoichiometric surface oxides AgO and Ag2O which are known to be diamagnetic.

1 Introduction poly-N-vinyl-2-pyrrolidone have been shown to induced ferro-

In recent years, nanoscaled materials displayed new physical
properties not observed in their bulk counterparts; a striking
example is the observation of ferromagnetic-like behaviour in
nanomaterials that are diamagnetic (i.e., non-magnetic) in the
bulk.1–3 The elements subject to such studies are, for the most
part, the coinage metals (i.e., Cu, Ag, and Au).4–6 The electronic
valence configuration of all coinage metals is d10s1 resulting in
an overall magnetic moment in unbound individual atoms – the
result of the unpaired s electron. However, as atoms form bulk
materials, delocalization of the electronic states results in their
well-known conductive and diamagnetic characteristics.7–9
Ferromagnetism in nanoscale coinage and noble metals has
been achieved through chemical surface modifications (i.e., capping
ligands), as well as in uncapped (and undoped) nanomaterials and
clusters. For instance, hysteretic magnetization loops have been
reported for coinage and noble-metal nanoparticles (NPs) of 2.3 
0.3 nm Cu;4 2.3  0.3 nm Ag;4 and, 1.4 nm10 and 1.9  0.2 nm4 Au
modified at the surface with self-assembled monolayers (SAMs)
of sulfur-containing ligands. Non-sulfur containing SAMs of
a
Department of Chemistry and Institute for Quantum Science and Technology,
University of Calgary, 2500 University Dr NW, Calgary, AB, Canada.
E-mail: trudels@ucalgary.ca; Fax: +1-403-289-9488; Tel: +1-403-210-7078
b
Directorate K&T for Security, Defence R&D Canada – Centre for Security Science,
222 Nepean St, 11 floor, Ottawa, ON, K1A 0K2, Canada.
E-mail: david.pedersen@drdc-rddc.gc.ca
† Electronic supplementary information (ESI) available: Ag NP synthesis para-
meters and mass spectrometry peak deconvolution; SQUID, SEM, XPS of Ag thin
films; Ag : O ratio calculations. See DOI: 10.1039/c7tc00879a
magnetism in B3 nm Au and Pd NPs.11 Au thin films also show
ferromagnetic behaviour when modified at the surface with
alkanethiols (e.g., C2- and C8-alkanethiols, and C22-polyalanine)12
and azobenzene disulfide13 SAMs.
Conversely, nanomaterials with unmodified surfaces such
as Au thin films have been found to display paramagnetism14
and ferromagnetism.15 In the paramagnetic case, 27 nm thick
Au films deposited onto cylindrical Pyrex substrates (i.e., ring-
shaped films), exhibited strong magnetism at 5 K but not at
300 K.14 The different magnetic responses were attributed to
the Wigner radius rs (defined as the radius of the sphere
occupied by an electron) which in a thin film would result in
a large dipole layer when positioned at the surface aided by an
almost-featureless textured Au films.14 In the ferromagnetic
case, the Au film was prepared by deposition of B2.6  0.6 nm
diameter clusters.15 The source of ferromagnetism is attributed
to the existence of a core–shell nanostructure constituted of a
bulk-like diamagnetic core and a magnetically active shell
caused by the reduced coordination of surface atoms helped
by a strong spin–orbit coupling in Au.15
Furthermore, predicted magnetic states have been theorized
for nanoclusters of Ag16,17 and Au16 – interestingly, these
nanoclusters studies found the icosahedral 13-atom cluster
(diameter of 0.548 nm for Ag18 and of 0.7 nm for Au19) to be
the most magnetic with a moment of B5 mB per cluster.16,17 In
the Ag case, the 4d orbital of the central atom in Ag13 overlaps
with those of its 12 outer-shell neighbouring atoms resulting in
a charge transfer favouring the outer-shell atoms.17 Calculations
for highly symmetrical Ag and Au clusters up to a maximum of

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147 atoms (equivalent to 1.664 nm radius for Ag18) has been
reported with several degrees of magnetism.16 Since both Ag and
Au atoms are d10s1 metals, it is claimed that the origin of this
magnetism in these larger clusters is due to spin alignment of
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the s-electrons from atoms in the outer shell in a ‘‘superatom’’.16
Additionally, experimental measurements for icosahedral Pt13
(diameter of 0.7  0.1 nm) supported in zeolite resulted in a
magnetic moment of 3.7  0.4 mB per cluster with only 15–20%
of Pt atoms in this configuration contributing to the overall
magnetic signal.20
However, extrinsic sources of magnetism (e.g., impurities,21
or surface species differing from the nominal composition of
the material22) should not be dismissed. Surface oxidation has
been found to be another process inducing ferromagnetism in
otherwise diamagnetic materials when the formation of non-
stoichiometric structures is favoured such as in mixed oxides
where interfaces are prevalent or in nanomaterials where the
percentage of surface atoms is high. For instance, Cu oxides in
the form of B26 nm CuO NPs,23 Cu/Cu2O composites,24 and
Cu/Cu2O microspheres25 can behave ferromagnetically. Nano-
crystalline powders of 10–100 nm size composed of Cu2O1+x
where x 4 0, also behave ferromagnetically.26 Theoretical
studies of defect formation in a 48-atom Cu2O supercell have
shown that interstitial O surrounded by six (i.e., octahedral site)
and four (i.e., tetrahedral site) Cu atoms27 induce ferromag-
netic behaviour. Although this latter study was performed on a
stoichiometric Cu2O supercell, their proposed Cu/O atomic
ratios resulting in ferromagnetism are non-stoichiometric in
nature (i.e., 6 : 1 Cu/O for octahedral and 4 : 1 for tetrahedral).
Experimentally, we have recently shown that Cu NPs and thin
films behave ferromagnetically through non-stoichiometric
oxidation of the surface with a calculated atomic ratio of
B3–5 : 1 Cu/O.22 In our Cu study we conclusively showed that
slight surface oxidation leading to an optimum partial oxidation
state resulted in ferromagnetism, while overoxidation or under-
oxidation both lead to the expected diamagnetic behaviour.
The computational work of Kasai et al.28 shows that Ag
surfaces exposed to O2 can result in metastable ferromagnetic
interactions. Specifically, Ag(111) surfaces are able to dissociate
O2 only under certain conditions (e.g., vertical trajectory of O2
molecule as it approaches the Ag surface; and, the molecular
interaction with certain Ag atomic sites – for example, the top of
an atom or fcc-hollow site). Once dissociated onto Ag, O atoms
(at a 0.5 monolayer coverage in their studies, equivalent to a
2 : 1 Ag : O ratio) create magnetic states at the surface due to a
combination of superexchange interactions between neighbour-
ing O atoms via the Ag atom; and, direct exchange interactions
between the 4d orbitals of Ag and its nearest O 2p states.28
Moreover, these particular direct exchange interactions result in
ferromagnetic behaviour, while interactions between the 2px
orbital of the O atom and the 5s orbital of the nearest Ag atom
result in antiferromagnetic direct exchange interactions, although
their contributions are a small compared to the former.28 The
same group studied oxygen diffusion (at a 0.5 monolayer cover-
age) on Ag(111).29 They found that in-plane diffusion (i.e., parallel
to Ag surface) reduces the distance between O atoms which could
4900 | J. Mater. Chem. C, 2017, 5, 4899--4908
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Journal of Materials Chemistry C
induce associate desorption as O2. Similarly, perpendicular diffu-
sion (i.e., sub-surface O atoms) which results in O atoms gaining
more electrons from the Ag surface inducing quenching of the
ferromagnetic behaviour.29 It is important to note that adsorbed
O2 without dissociating (i.e., as a molecule) at the Ag surface does
not induce a magnetic response but the event does occur.28
In the current manuscript, we extend our studies to Ag in
both NP and thin-film forms. Ag is diamagnetic in the bulk with a
molar susceptibility, wm, of 19.5  10 6 cm3 mol 1,7 where the
negative sign indicates diamagnetic behaviour. For comparison,
the most common Ag oxides Ag2O and AgO are both diamagnetic
in the bulk with wm of 134 and 19.6  10 6 cm3 mol 1,
respectively.7 NPs and thin-film synthesis was conducted by
sputtering in the gas-phase thus avoiding capping ligands and
allowing for pristine surfaces to be analyzed. Our main findings
are that (1) metallic silver NPs as-prepared are non-magnetic; (2)
magnetism is indeed a surface phenomenon, governed by surface
oxidation; and, (3) we find no strong size dependence on the
magnetic properties. This is a significant finding that may yield
insight into the wide scatter of reported magnetic properties, e.g.,
saturation magnetization.2,3
2 Experimental section
2.1 Sample preparation
In order to avoid surface capping ligands during synthesis,
nanomaterials were prepared in the gas-phase allowing for
pristine surface formation. All samples were synthesized under
vacuum using a Mantis NanoGen sputtering system described
elsewhere22,30 and schematically illustrated in Fig. 1. During
standard use, NPs initially generated in the aggregation chamber
are swept out to adjacent chambers due to interchamber pressure
differential. As the Ag NPs produced are negatively charged,31 a
quadrupole mass spectrometer within the adjacent chamber is
used for size analysis and filtering. NPs leaving the mass spectro-
meter enter the collection chamber where they are deposited onto
substrates (site a in Fig. 1). To increase particle flux and yield
during sample preparation experiments, the mass spectrometer
was removed. It is important to note that NP sizing is wholly
determined within the aggregation chamber and this modification
Fig. 1 Schematic of deposition system showing only its major compo-
nents. In the aggregation chamber, the red holder represents the dc
magnetron, on which the Ag metal target sits. Sampling location are as
follows: site a for NPs, site b for ON-target thin films, and site c for
OFF-target thin films. See text for full description.
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to the apparatus does not impact size.32 Different size Ag NPs were
prepared by modifying source conditions to generate NPs with
modal diameters of 3.3  0.9, 5.0  0.9, and 7.8  1.3 nm
(see Table S1 for conditions, ESI†).
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In addition to collecting NP samples in the collection
chamber, thin films of Ag were also collected at two different
locations within the aggregation chamber. Thin films were
prepared by placing a substrate directly onto the metal target
away from the plasma etching location (site b in Fig. 1). At this
position (referred to as ON-target sample herein) Ag thin films
form on the substrate in the presence of a 250 mT magnetic
field. The magnetic field is due to the presence of a dc
magnetron behind the target as required for sputtering. Ag
thin films were also collected on substrates placed inside the
aggregation chamber but away from the metal target (site c in
Fig. 1). At this position, metal atoms from the plume land onto
substrates as in atomic vapour deposition. These OFF-target
samples were collected in the absence of any significant
magnetic field; thus, the two film types were synthesized under
different conditions. Si wafers (B5  5 mm in size) and NaCl
crystals (B10  7 mm in size) were used as substrates. Once
synthesized, NPs and thin films were stored in sealed containers
under either Ar or O2 atmospheres until analysis was performed.
Finally, all depositions were performed in 5 min intervals
(i.e., 5 min of deposition followed by 5 min of rest) to avoid
overheating of the metal target.
2.2 Sample characterization
Magnetometry. Magnetic properties of the prepared samples
were studied using superconducting quantum interference
device (SQUID) magnetometry. Measurements were carried
out using a Quantum Design MPMS XL-7S system. Samples
were either tested together with their Si substrate onto which
they were originally deposited or were exfoliated from their
substrate (either Si or NaCl) with diamagnetic Kapton tape.
Mass values were acquired by mass difference. In both cases,
samples were inserted in a clear diamagnetic plastic straw for
measurements. Isothermal magnetization as a function of field
strength measurements were carried out at 300 K by cycling the
applied magnetic field between 1 and 1 T. Diamagnetic
corrections were performed to all resulting M versus m0H loops
to remove contributions from the holder and substrate.22
In situ magnetic measurements. All nanomaterials studied
initially comprised pristine surfaces as a result of synthesis by
sputtering under vacuum. A challenge was to keep these
surfaces from reacting with ambient air when retrieving samples
from the instrument; e.g., some exposure to air is unavoidable
during magnetometry sample preparation and loading. The reac-
tive nature of nanomaterials is well known and oxidation from
ambient air is expected (although it was minimized by storing
these materials under Ar gas, for instance). In situ magnetic
measurements were made using a magnetic quartz crystal micro-
balance (MQCM) method33,34 we implemented inside the Nano-
Gen sputtering system. This technique was successfully applied to
our previous study regarding the role of oxidation on the magnetic
behaviour of Cu NPs.22 Briefly, a QCM crystal was placed in the
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collection chamber as a collecting substrate for Ag NPs. Then,
a bar magnet was brought in proximity of the crystal until a
magnetic field of 0.1 T was exerted onto it (i.e., MQCM). This
initial step essentially asserts the presence of magnetic proper-
ties (if any) of surface-pristine NPs. Subsequently, air was slowly
bled into the apparatus and more MQCM measurements were
made. Further oxidation was achieved with mild ex situ heat
treatments. The MQCM technique has the advantage that in
addition to affording opportunity to measure the response of
Ag NP films to the 0.1 T field, in the absence of the field the
mass of oxygen uptake by samples can be measured using
standard QCM methodology.
Surface analysis. Oxidation states and sample purity were
analyzed using X-ray photoelectron spectroscopy (XPS). A Physical
Electronics PHI VersaProbe 5000-XPS instrument with a mono-
chromatic Al Ka source (1486.6 eV) and a 200.0 mm beam
diameter was used to record XPS spectra. All spectra were
analyzed using CasaXPS software.35 Spectra were corrected by
calibrating all peaks to the adventitious C 1s peak signal at
284.8 eV. A Shirley-type background was used, and curve fitting
was performed using a combination of Gaussian and Lorentzian
[GL(85)] profiles. The analysis of the O 1s region followed a
methodology presented elsewhere.36
Imaging and composition. Scanning electron microscopy
(SEM) images were collected using a Zeiss Sigma VP field-
emission scanning electron microscope equipped with an
Oxford INCA X-Act unit for energy-dispersive X-ray spectroscopy
(EDXS) analysis. Atomic force microscopy (AFM) images were
collected using a Veeco Innova AFM mounted on an acoustic-
vibration isolation system. A silicon cantilever with a spring
constant of B50 N m 1 in tapping mode was used to collect the
AFM images.
3 Results
3.1 Ag NPs
Ag NPs of varying diameters were prepared by modifying
chamber conditions (see Table S1 for parameters, ESI†) while
generating NPs. NPs with modal diameters of 3.3  0.9, 5.0  0.9,
and 7.8  1.3 nm were obtained as determined from in situ mass
spectrometry (Fig. 2a and Fig. S1, ESI†). These three source
conditions were used to generate all the NPs studied in this work.
Ag NPs were deposited for 10 min onto Si wafers in the collection
chamber. For clarity, it must be stated that the NP samples consist
of NP thin films, as magnetic measurements on monolayers of
well-separated NPs were beyond the sensitivity of our measure-
ment techniques. This means effects such as the presence of grain
boundaries are present as well. However, we do not believe this
changes the main conclusions of our work, namely that it is the
high surface area and non-stoichiometric nature of the materials
that make them magnetic (vide infra). Following preparation,
samples were stored in sealed containers under Ar gas until
SQUID measurements were performed. Fig. 2b shows SQUID
magnetometry measurements on these NPs supported on their
original Si wafer substrate. A clear magnetic response is observed
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3.2 Ag films
In Fig. 3, magnetization loops are shown for an ON-target film
exfoliated from its substrate using Kapton tape. Similar to the
Ag NPs, the film collected ON-target shows a clear magnetic
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response. Moreover, closer inspection of the M vs. H loop near

the origin (Fig. 3 inset) shows a weak coercivity (m0Hc = 1.28 mT)
and reduced remanent magnetization (Mr/M1T = 0.012), an
indication that the Ag film behaves as a soft ferromagnet at
room temperature. By exfoliating the film off its substrate, any
possible role played by the substrate on the magnetic response
of the film is negated (see also Fig. S2, ESI†). Also shown in Fig. 3
are analogous data for a film collected OFF-target. In sharp
contrast to the NPs and ON-target film, the OFF-target sample
shows no obvious hysteresis and the film is thus considered
diamagnetic.
To gain some insight into the dramatic different magnetic
behaviours observed for OFF-target vs. ON-target films, AFM
and SEM microscopies were used to study the morphologies of
the samples. In Fig. 4, the topographies of the ON-target and
OFF-target samples are shown. The two samples were prepared
simultaneously (eliminating extrinsic impurities) during a 5 min
deposition onto Si. Despite the identical source conditions, the SEM
and AFM images show a drastic morphology difference. As seen, the
film collected OFF-target is relatively flat containing B65 nm
diameter islands and a relatively homogeneous size distribution,
typical of vapour deposition of atomic Ag species onto the Si
substrate which produces mirror surfaces (Fig. 4a and b). On the
contrary, the film collected ON-target shows features of B1 mm in
size in both SEM and AFM (Fig. 4c and d). Moreover, both Fig. 4c
and d show the presence of small structures of a few nanometers in
size dispersed on the surface of the 1 mm structures not present in
the other film (Fig. S3, ESI† shows the presence of NPs is character-
istic of ON-target deposition, irrespective of deposition time).

Fig. 2 (a) Ag NP sizes determined by in situ mass spectrometry. The

responses have been shifted vertically, and the response for the smaller
NPs has been multiplied by a factor of 2 for ease of visualization. Mean
diameters are (m) 3.3  0.9 nm, () 5.0  0.9 nm, and (’) 7.8  1.3 nm.
Lines are Gaussian fits to the data. For the two bigger NPs, two Gaussian
fits per peak were utilized (see Fig. S1, ESI†). (b) SQUID measurements of
Ag NPs at room temperature (300 K). Inset is closeup of the origin. Lines
are guides to the eyes.

in the M versus m0H loops for all NPs. Specifically, a ferromagnetic

signature is observed as seen in the inset on Fig. 2b which
corresponds to a closeup of the origin showing weak coercivity
m0Hc and remanent magnetization, which are indicative of the Ag
NPs behaving as soft ferromagnets at room temperature (300 K).
Based solely on the M versus m0H loops, there is no clear size
dependency to the magnetic signal as all loops show a similar –
albeit noisy – magnetic saturation Ms of B0.93  10 3 emu g 1,
coercivity m0Hc of B24 mT and reduced remanent magnetization Fig. 3 Room-temperature (300 K) M vs. H loops for Ag thin films collected
Mr/Ms of B0.16. ON- and OFF-target. Inset shows the zoomed section near the origin.

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Fig. 4 SEM (top) and AFM topography (bottom) images of Ag thin films
collected OFF-(a and b) and ON-target (c and d). All scale bars measure
200 nm.
The difference in topographies does suggest that the presence
of nano-dimensioned structures is pre-requisite for ferro-
magnetism to be observed. This hypothesis is consistent
with the fact that the NP films also exhibited ferromagnetic
behaviour, although varying the size of the nanoparticles in
the 3 to 8 nm diameter range had no apparent effect. We also
note that throughout imaging, we did not see any evidence of
impurities that could account for the magnetic properties
observed.
3.3 Ag NPs: in Situ oxidation effects
In previous work, ferromagnetism of Cu NPs and nanostruc-
tured films was associated with non-stoichiometric oxidation.22
To explore this possibility, in situ MQCM magnetic measure-
ments of nascent Ag NPs were made as a function of their
exposure to oxygen. Representative data are presented in Fig. 5.
We have previously shown the responses of different magnetic
materials during MQCM experiments.22 The general trends in
MQCM experiments are as follows: ferromagnetic materials
result in a frequency increase (i.e., positive DfMQCM) when
exposed to a magnetic field, while diamagnetic and weakly-
paramagnetic materials result in a negative frequency change.
As seen in Fig. 5, when the mass of oxygen adsorbed to the NPs
is zero (i.e. nascent NPs), a small negative frequency change
when exposed to a magnetic field of 0.1 T is observed; this is
indicative of a non-magnetic species.22 As oxygen is adsorbed,
there is a rapid increase in magnetic response that abruptly
stops and proceeds to slightly diminish with further oxidation.
This magnetic response is persistent even with heat treatments
of the samples in air. Clearly, there is a correlation between the
magnetic properties of the Ag NPs and oxidation.
To explore the role of oxidation, 3.3  0.9 nm Ag NPs and
ON-target thin films were deposited onto NaCl surfaces.
Samples were prepared by depositing nanomaterial for 30 min
followed by their immediate storage in either Ar or O2 atmospheres
for a period of 5–6 days. It is important to note that all samples
were exposed to air for a short period of time during sample
retrieval for storage, and during sample preparation and mounting
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Fig. 5 MQCM experiment using (’) nascent Ag NPs with subsequent (K)
oxidation with ambient air and (J) heat treatment. All measurements
performed at room temperature. Line is a guide to the eye.
for magnetometry measurements. Thus minor oxidation is
expected even for samples kept in Ar. To perform SQUID
magnetometry measurements, NP and ON-target films were
exfoliated from the NaCl surfaces with Kapton tape. SQUID
magnetometry data for NP samples are shown in Fig. 6a. As
seen, the sample stored in O2 had a higher saturation magne-
tization Ms than the sample stored in Ar gas. In addition, the
remanent magnetization Mr/Ms and coercivity m0Hc (lower inset
of Fig. 6a), show higher values for the Ar-kept sample compared
to O2-kept NPs. This data is found in Table 1. Data for the
analogous SQUID measurements for ON-target Ag films are
shown in Fig. 6b and Table 1. The effect of oxidation on the
ON-target Ag film samples was analogous to the NP samples
with those stored in oxygen having higher saturation magneti-
zation Ms that those stored in Ar. In addition, Fig. 6 suggests
the presence of a weak magnetic field during Ag deposition
(as in the case for ON-target films but not NPs), does not play a
significant role in the occurrence of magnetism.
To further explore the effect of oxidation, three Ag films
collected ON-target and deposited onto Si were heat-treated
in air (i.e., 75 and 150 1C for 2 h each) with one of them
tested as-prepared. The series of SQUID measurements of
heat treated films is shown in Fig. 7. As seen, heating
in air results in a decrease in saturation magnetization Ms;
however, subsequent heating (e.g., 150 1C) causes less of a
decrease than the prior heating (e.g., 75 1C). In this context,
the SQUID data are completely consistent with the MQCM
data presented above with oxidation resulting in a higher
magnetic response than that observed in more fully oxidized
samples. Another notable change in these samples is their
coercivity m0Hc and remanent magnetization Mr/Ms values
(see Table 1).
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Table 1 Magnetic properties of Ag nanomaterials

3
Ms (10 emu g 1) Mr/Ms m0Hc (mT)
NPs
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Kept in O2 4.28 0.20 12.62

Kept in Ar 1.40 0.25 28.56

ON-target thin films

Kept in O2 1.45 0.03 0.95
Kept in Ar 0.81 0.08 8.64

Heat-treated
ON-target thin films
As prepared kept in O2 1.29 0.02 1.15
75 1C for 2 h 1.06 0.05 7.73
150 1C for 2 h 0.94 0.10 12.39

Fig. 7 Room-temperature (300 K) SQUID magnetometry measurements

of heat-treated Ag films. Films were heat-treated in air at 75 1C (’) and
150 1C (m). An as-prepared sample stored at room temperature under O2
(K) is also shown.

Fig. 6 Room-temperature (300 K) SQUID magnetometry measurements

of (a) Ag NPs and (b) thin films stored in either Ar (K) or O2 (m) atmo-
spheres. Bottom insets in both (a) and (b) show a close up of the origin.
Lines are a guide to the eye. Top insets show SEM images with a (a) 100 nm
and (b) 500 nm bars.
3.4 Surface analysis
To determine the impact of any surface contamination on the
magnetic properties observed, EDXS analysis was performed on
an ON-target Ag film resulting from a 15 minute deposition
onto a NaCl substrate. The ferromagnetic behaviour of the film
is clear from the M versus m0H loop presented in Fig. S2 (ESI†).
Fig. 8 shows EDXS elemental analysis, using two excitation
beam energies (15 and 30 keV) that penetrate the film to
different extents (estimated at B500 nm and B1250 nm,
respectively, using the CASINO simulation software37). Except
for a trace level peak observed at 1.24 keV for the spectrum
collected with 30 keV excitation (identified as Mg – a diamagnetic
element), only transitions assigned to Ag are observed. This would
indicate that the film does not contain any magnetic impurities
(i.e., Fe, Co, or Ni) that could induce the observed ferromagnetic
behaviour.38 The noticeable absence of oxygen shows the bulk of
the material consists of metallic silver. This result is consistent
with the MQCM results of NPs behaving ferromagnetically only
after exposure to ambient air with subsequent oxidation (Fig. 5).
As EDXS has limited surface sensitivity, XPS was used to analyze
the surface of the deposited Ag material.
To gain insight into oxidation states of Ag species that might
contribute to the ferromagnetism observed, XPS analysis was
performed on all samples presented in Fig. 7. A sample XPS
survey spectrum of the Ag thin film kept in O2 is shown in Fig. 9
(all other surveys can be found in Fig. S4, ESI†). Fig. 9 supports
the lack of magnetic impurities shown by EDXS. Furthermore,
XPS data showing the Ag 3d region of Ag films kept in O2 before

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Fig. 8 EDXS analysis of a Ag thin film transferred to Kapton tape after
deposition onto NaCl substrate. Main graph shows an energy beam of
30 keV while inset shows a value of 15 keV energy beam.
Fig. 9 XPS survey spectrum of the Ag film kept under an O2 atmosphere.
Spectrum shows Ag as the major component with common atmospheric
elements such as C and O.
and after sputtering, and heat-treated at 75 and 150 1C are
presented in Fig. 10a with their corresponding O 1s region in
Fig. 10b.
4 Discussion
4.1 Surface species characterization
Oxygen interacting with metal silver surfaces forms silver oxide
overlayers.42 The two most common Ag oxides are Ag2O and AgO.
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Fig. 10 XPS data showing the (a) Ag 3d and the (b) O 1s regions of Ag films
kept in O2 before and after sputtering, and heat-treated at 75 and 150 1C.
Raw data are shown as scattered plots. All amplitudes are maximized for
ease of visualization, thus are not comparable. (a) Peak fitting and Shirley
background are shown for the 3d5/2 and 3d3/2 peaks. The appearance of
the plasmon peaks are indicative of Ag metallic interior. (b) Peak fitting
(solid and dotted lines) and Shirley background are shown for the O 1s
region. C–O and CQO peak areas in the O 1s region match those
corresponding to the C 1s region (latter data not shown).
Thermodynamically, Ag2O is the most stable oxide in air at
room temperature among the possible Ag oxides.43,44 Both of
these oxides are diamagnetic in the bulk.44,45 Accordingly
ferromagnetism observed in our Ag films must be associated
with non-stoichiometric oxides, consistent with the observation
that magnetic susceptibility is maximum when the Ag films are
partially oxidized as indicated by the MQCM data in Fig. 5 and
the SQUID data in Fig. 6 and 7.
QCM data allow us to calculate the average stoichiometry
of Ag oxides present on the surface of the films at the peak of
J. Mater. Chem. C, 2017, 5, 4899--4908 | 4905

Paper
magnetic susceptibility in the MQCM data (Fig. 5). This peak
corresponds to an uptake of 0.7993 mg of oxygen by B97 mg Ag
NPs deposited onto the QCM crystal. This leads to a Ag : O
atomic ratio of B8 : 1 (for calculations, see ESI†). It must be
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noted that this is an overestimated value as the calculation
assumes a film of NPs in monolayer arrangement in which all
Ag atoms are surface atoms and available for oxidation. MQCM
analysis during extended heat treatments with increasing
oxygen uptake do not seem to induce an effect (either a positive
or negative DfMQCM) and the signal intensity remains stable. As
seen in Fig. 5, the greatest change in MQCM response by the
Ag NPs is with initial exposure to oxygen and initial heat
treatments. The lack of additional change in magnetic response
with additional heating likely indicates that the additional
mass being adsorbed is not manifesting itself in the formation
of non-stoichiometric oxides but rather that the increase in
temperature affords possibility of oxidation of interstitial Ag
surface available in the film interior thus forming stoichio-
metric, non-magnetic oxides as expected within the framework
of a ‘‘normal’’ Ag lattice. In previous work, the accessibility of
oxygen to the interior of Cu NPs (a more readily oxidizing metal
compared to Ag) was modeled and experimentally validated.46
That work is consistent with only the outer 1–2 layers of exposed
Cu atoms being available for oxidation at room temperature.
The XPS data shown in Fig. 10a reveal a shift of the Ag 3d5/2
peak to higher binding energy upon exposure to O2 (relative to
the sputtered surface which is effectively pure Ag). These data are
also presented in Fig. 11c. At its simplest, this shift is consistent
with an oxidation process forming Ag+, where shielding electron
density (e.g., s electrons) have been decreased. From the literature,
both Ag2O and the Ag+ contribution of AgO are shown by Fig. 11b
to have 3d5/2 binding energies shifted to higher energy compared
to the binding energy of Ag. With high temperatures (150 1C)
heating, however, the peak in Fig. 10a (top frame) is seen to shift
back to lower binding energy (also presented in Fig. 11c). This
shift is consistent with the formation of AgO species as can be
seen in Fig. 11a and b. In this context, higher temperatures drive
conversion of the Ag nanostructures to non-magnetic AgO species,
while lower temperatures favour formation of Ag(I)-oxide species,
Fig. 11 XPS literature comparison to our Ag 3d5/3 peak positioning. (a) Literature average from the NIST database.39,40 (b) XPS values from ref. 41. Labels
marked with an * represent deconvoluted peak values. (c) Our experimental XPS values. Each panel consists of metallic Ag (bottom of ordinate) and
several oxide species. Broken lines represent the binding energy division (i.e., higher or lower) compared to metallic Ag.
4906 | J. Mater. Chem. C, 2017, 5, 4899--4908
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Journal of Materials Chemistry C
some of which contribute to the ferromagnetism observed. This is
supported by Fig. 10b where AgO is clearly seen at 150 1C but
under no other condition. The O 1s spectra in Fig. 10b also show
clearly that Ag2O is the dominant species at O2, 75 and 150 1C
conditions. However, peak fitting clearly shows that Ag2O and AgO
cannot by themselves be responsible for the spectra observed and
at least two other chemically distinct species must be present in
order to fit the shape of the spectra observed. These are most
likely attributable to surface contamination species, but non-
stoichiometric silver oxides cannot be ruled out.
A useful characteristic of Ag XPS spectra is the presence of
loss peaks due to plasmons, which result from the collective
excitation of the valence band electrons by the photoelectron
and are indicative of a clean surface. For Ag, plasmon loss
peaks are expected at binding energies of B372 and B378 for
the Ag 3d5/2 and 3d3/2 peaks, respectively, B4 eV higher than
their corresponding photoelectron peak.47 All of our XPS spectra
(Fig. 10) contain plasmon peaks at ca. 370.6 and 376.6 eV
indicative of Ag(0) most likely present in the interior of the sample
(taking into account that XPS analysis probes at a depth of
B10 nm) as we expect the oxidation to be a surface effect.22
Furthermore, the plasmon peak position is 3.6 eV on average from
their respective 3d5/2 peak (see Table 2), as expected. The presence
of such peaks in all of our XPS spectra are indicative of a thin-layer
surface oxidation since plasmon peaks are indicative of a clean
surface. The same chemical species, albeit with different contents,
are also present in the sample heat-treated at 75 1C.
4.2 Origin of ferromagnetism in Ag NPs
In this work, three types of Ag samples were produced: NPs, and
ON- and OFF-target films. As revealed by SEM and AFM, the
former two of these included nanodimensioned structures
(i.e., inset in Fig. 6a for NPs; and, Fig. 4c, d and 6b inset,
Fig. S3a and d, ESI† for ON-target films) and these were found
to be ferromagnetic when partially oxidized. The OFF-target
films, although chemically identical (prepared under identical
conditions), formed a near-mirror like surface at 5 minute
deposition with a very smooth morphology (i.e., Fig. 4a and b);
these OFF-target samples were diamagnetic (Fig. 3) and therefore
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Journal of Materials Chemistry C
Table 2 3d5/2 XPS fitting analysis for Ag thin films from Fig. 10
Sputtered Kept in O2 75 1C 150 1C
3d5/2 position (eV) 368.2 368.4 368.4
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3d spin–orbit split (eV) 6.00 6.05 6.00
3d5/2 FWHM (eV) 0.665 0.694 0.696
Percent Ag(0) present (%) 100.0 81.5 88.5
Percent Ag oxide present (%) 0.0 18.5 11.5
D plasmon – 3d5/2 position (eV) 3.70 3.55 3.60
nanostructure is important for ferromagnetism to be present.
However, it is also clear that oxidation is prerequisite for the
magnetism observed in these Ag samples.
MQCM measurements of freshly-synthesized 3.3  0.9 nm
Ag NPs, for example, did not yield a ferromagnetic signal
(Fig. 5). This result indicates that nanodimensionality alone
is not sufficient to impart a magnetic behaviour to Ag, indicating
magnetism is an extrinsic property of the material. Magnetism
can be activated upon exposure to trace amounts of oxygen to
form non-stoichiometric Ag-oxides AgnO with n o 8. Further
oxidation is not conducive to forming a more magnetic material
since higher temperatures yield non-magnetic AgO as evidenced
by the XPS data. The combined data suggest that partial oxida-
tion of nanodimensioned structures is key to the observed
ferromagnetism while additional oxidation leads to a reduced
saturation magnetization.
Consistent with these findings, we propose the following
process by which Ag can become magnetic when exposed to
oxygen as illustrated in Fig. 12. Pristine Ag nanostructures are
diamagnetic. When the surface of these Ag nanomaterials is
exposed to a low-O2 atmosphere, a non-stoichiometric oxide
layer is formed at the surface. Such surface oxidation has been
predicted to lead to ferromagnetic centres,28,29 which from our
experiments are characterized by low saturation magnetization
and higher coercivity. Initially, further oxidation leads to a
higher magnetization presumably due to the further formation
of magnetic centres. At a certain point, however, further oxida-
tion starts to reduce the magnetization of the material as clearly
shown in the SQUID data in Fig. 6 and 7. This may occur due to
Fig. 12 Proposed oxidation stages of Ag from a fcc unit cell to cubic
Ag2O. Both metallic Ag and Ag2O are non-magnetic. Intermediate steps
include exposure to low O2 concentrations with a potential single type of
magnetic centre, and high O2 exposure with two potential magnetic
centre types.
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Paper
the increased antiferromagnetic interactions with distant
surface sites,28 or the formation of the diamagnetic stoichiometric
silver oxides. We also observe a decrease in the coercivity as the
367.8 magnetization decreases. Assuming a common (and yet-to-be-
6.00
0.670 determined) magnetization reversal process in all samples, this
70.7 can be due to the larger moment which makes reversal easier upon
29.3 applying a magnetic field, or a decrease in the effective anisotropy
3.60
constant. The latter can be due to the increasingly symmetric
environment as the sample is further oxidized.
5 Conclusion
We have shown the synthesis of highly pure Ag nanoscale
materials. Both Ag NPs and thin films behave ferromagnetically
at 300 K. The ferromagnetic behaviour is extrinsic to the
material and is linked to the non-stoichiometric oxidation near
the surface. The ferromagnetism exhibited does not show size
dependency. This study sheds insight into the origin of the
unexpected ferromagnetic characteristics of nanoscaled coinage
metal materials.
Acknowledgements
The authors thank the Natural Sciences and Engineering Research
Council of Canada (Discovery Grant), Defence R&D Canada, and
the University of Calgary for funding. This research uses infra-
structure funded by the Canadian Foundation for Innovation.
References
1 S. Trudel, Gold Bull., 2011, 44, 3–13.
2 G. L. Nealon, B. Donnio, R. Greget, J.-P. Kappler, E. Terazzi
and J.-L. Gallani, Nanoscale, 2012, 4, 5244–5258.
3 A. Sundaresan, R. Bhargavi, N. Rangarajan, U. Siddesh and
C. N. R. Rao, Phys. Rev. B: Condens. Matter Mater. Phys., 2006,
74, 161306.
4 J. S. Garitaonandia, M. Insausti, E. Goikolea, M. Suzuki,
J. D. Cashion, N. Kawamura, H. Ohsawa, I. Gil de Muro,
K. Suzuki, F. Plazaola and T. Rojo, Nano Lett., 2008, 8,
661–667.
5 L. Armelao, D. Barreca, G. Bottaro, A. Gasparotto, S. Gross,
C. Maragno and E. Tondello, Coord. Chem. Rev., 2006, 250,
1294–1314.
6 M. Sargolzaei and N. Lotfizadeh, Phys. Rev. B: Condens.
Matter Mater. Phys., 2011, 83, 155404.
7 W. M. Haynes, D. R. Lide and T. J. Bruno, CRC Handbook of
Chemistry and Physics, CRC Press, Boca Raton, FL, 96th edn,
2015–2016.
8 G. A. Landrum and R. Dronskowski, Angew. Chem., Int. Ed.,
2000, 39, 1560–1585.
9 N. E. Christensen, J. Phys. F: Met. Phys., 1978, 8, L51.
10 P. Crespo, R. Litrán, T. C. Rojas, M. Multigner, J. M. de la
Fuente, J. C. Sánchez-López, M. A. Garcı́a, A. Hernando,
S. Penadés and A. Fernández, Phys. Rev. Lett., 2004,
93, 087204.
J. Mater. Chem. C, 2017, 5, 4899--4908 | 4907

Paper
11 H. Hori, T. Teranishi, Y. Nakae, Y. Seino, M. Miyake and
S. Yamada, Phys. Lett. A, 1999, 263, 406–410.
12 I. Carmeli, G. Leitus, R. Naaman, S. Reich and Z. Vager,
J. Chem. Phys., 2003, 118, 10372–10375.
Published on 05 May 2017. Downloaded by Central Glass & Ceramic Research Institute (CGCRI) on 7/4/2022 7:30:48 AM.
13 M. Suda, N. Kameyama, A. Ikegami and Y. Einaga, J. Am.
Chem. Soc., 2009, 131, 865–870.
14 S. Reich, G. Leitus and Y. Feldman, Appl. Phys. Lett., 2006,
88, 222502.
15 V. Tuboltsev, A. Savin, A. Pirojenko and J. Räisänen,
ACS Nano, 2013, 7, 6691–6699.
16 W. Luo, S. J. Pennycook and S. T. Pantelides, Nano Lett.,
2007, 7, 3134–3137.
17 M. Pereiro, D. Baldomir and J. E. Arias, Phys. Rev. A: At.,
Mol., Opt. Phys., 2007, 75, 063204.
18 V. I. Kuzmin, D. L. Tytik, D. K. Belashchenko and
A. N. Sirenko, Colloid J., 2008, 70, 284–296.
19 G. Schmid, Chem. Soc. Rev., 2008, 37, 1909–1930.
20 J. Bartolomé, F. Bartolomé, L. M. Garcı́a, E. Roduner,
Y. Akdogan, F. Wilhelm and A. Rogalev, Phys. Rev. B:
Condens. Matter Mater. Phys., 2009, 80, 014404.
21 S. Ramachandran, R. Latsuzbaia, K. N. K. Kowlgi,
H. Geerlings, L. Zhang, U. Lafont, B. Norder, S. Picken
and G. Koper, Langmuir, 2015, 31, 651–653.
22 A. J. Marenco, D. B. Pedersen and S. Trudel, J. Phys. Chem. C,
2016, 120, 7388–7396.
23 D. Gao, J. Zhang, J. Zhu, J. Qi, Z. Zhang, W. Sui, H. Shi and
D. Xue, Nanoscale Res. Lett., 2010, 5, 769–772.
24 D. Gao, Z. Zhang, Z. Yang and D. Xue, Appl. Phys. Lett., 2012,
101, 132416.
25 D. Gao, Z. Zhang, Q. Xu, J. Zhang, Z. Yan, J. Yao and D. Xue,
Appl. Phys. Lett., 2014, 104, 022406.
26 A. Yermakov, M. Uimin, A. Mysik, V. Vykhodets, T. Kurennykh,
V. Sokolov, V. Gaviko, N. Schegoleva and N. Gruzdev, J. Magn.
Magn. Mater., 2007, 310, 2102–2104.
27 A. Soon, X.-Y. Cui, B. Delley, S.-H. Wei and C. Stampfl,
Phys. Rev. B: Condens. Matter Mater. Phys., 2009, 79, 035205.
28 Y. Kunisada, M. C. Escaño and H. Kasai, J. Phys.: Condens.
Matter, 2011, 23, 394207.
29 Y. Kunisada, H. Nakanishi, W. A. Diño and H. Kasai,
Int. J. Pharm. Chem. Sci., 2012, 379, 012013.
30 D. B. Pedersen and S. Wang, J. Phys. Chem. C, 2007, 111, 1261–1267.
31 J. Tang, E. Verrelli and D. Tsoukalas, Microelectron. Eng.,
2009, 86, 898–901.
32 M. Gracia-Pinilla, E. Martı́nez, G. Vidaurri and E. Pérez-
Tijerina, Nanoscale Res. Lett., 2010, 5, 180–188.
33 G. Y. Yu, W. D. Hunt, M. Josowicz and J. Janata, Rev. Sci.
Instrum., 2007, 78, 065111.
4908 | J. Mater. Chem. C, 2017, 5, 4899--4908
View Article Online
Journal of Materials Chemistry C
34 G. Y. Yu and J. Janata, Anal. Chem., 2008, 80, 2751–2755.
35 CasaXPS: Processing Software for XPS, AES, SIMS and More,
Teignmouth, UK, 2016.
36 L. Trotochaud, J. K. Ranney, K. N. Williams and S. W.
Boettcher, J. Am. Chem. Soc., 2012, 134, 17253–17261.
37 D. Drouin, A. R. Couture, D. Joly, X. Tastet, V. Aimez and
R. Gauvin, Scanning, 2007, 29, 92–101.
38 The question of adventitious magnetic impurities will
always naturally and rightfully arise when dealing with very
weakly magnetic species, as is the case here. Care was taken
to always handle samples and sample holders with only
fresh gloves, in a designated clean area, and only non-
magnetic tweezers or scissors were used during sample
handling. When NPs were deposited onto the QCM crystal
and measured under vacuum there was no signal that could
be interpreted as magnetic. It was only after air was intro-
duced in the system (in the process oxidizing the surface of
NPs) that a magnetic signal was observed. This is strong
evidence that the magnetic species is not present in the as-
deposited material. We also never observed physical impu-
rities during SEM or AFM imaging. Finally, the saturation
magnetizations are all comparable with one another, and
comparable to literature values, including our own previous
study of Cu nanostructures (see ref. 22). A spurious impurity
would be expected to yield widely differing results from
sample to sample, which is not what we observed.
39 M. C. Biesinger, X-ray Photoelectron Spectroscopy (XPS)
Reference Pages, 2016, http://www.xpsfitting.com/2013/04/
silver.html.
40 A. V. Naumkin, A. Kraut-Vass, S. W. Gaarenstroom and
C. J. Powell, NIST X-ray Photoelectron Spectroscopy Database,
2016, https://srdata.nist.gov/xps/.
41 A. M. Ferraria, A. P. Carapeto and A. M. B. do Rego, Vacuum,
2012, 86, 1988–1991.
42 E. V. Trushin and I. L. Zilberberg, Chem. Phys. Lett., 2013,
560, 37–41.
43 T. Shinagawa, Y. Ida, K. Mizuno, S. Watase, M. Watanabe,
M. Inaba, A. Tasaka and M. Izaki, Cryst. Growth Des., 2013,
13, 52–58.
44 T. C. Kaspar, T. Droubay, S. A. Chambers and P. S. Bagus,
J. Phys. Chem. C, 2010, 114, 21562–21571.
45 V. Scatturin, P. L. Bellon and A. J. Salkind, J. Electrochem.
Soc., 1961, 108, 819–822.
46 D. B. Pedersen, S. Wang and S. H. Liang, J. Phys. Chem. C,
2008, 112, 8819–8826.
47 R. Pollak, L. Ley, F. McFeely, S. Kowalczyk and D. Shirley,
J. Electron Spectrosc. Relat. Phenom., 1974, 3, 381–398.
This journal is © The Royal Society of Chemistry 2017