Materials 2015, 8, 1027-1042; doi:10.

3390/ma8031027
OPEN ACCESS

materials
ISSN 1996-1944
[Link]/journal/materials
Article

Precursor-Less Coating of Nanoparticles in the Gas Phase

Tobias V. Pfeiffer 1,*, Puneet Kedia 1, Maria E. Messing 2, Mario Valvo 3 and
Andreas Schmidt-Ott 1,*

1
Faculty of Applied Sciences, Delft University of Technology, Julianalaan 136, Delft 2628 BL,
The Netherlands; E-Mail: [Link]@[Link]
2
Solid State Physics, Lund University, Box 118, Lund 221 00,
Sweden; E-Mail: [Link]@[Link]
3
Department of Chemistry–Ångström Laboratory, Uppsala University, Box 538, Uppsala 751 21,
Sweden; E-Mail: [Link]@[Link]

* Authors to whom correspondence should be addressed;

E-Mails: [Link]@[Link] (T.V.P.); [Link]-ott@[Link] (A.S.-O.);
Tel.: +31-15-278-3995 (T.V.P.); +31-15-278-3577 (A.S.-O.).

Academic Editor: Maryam Tabrizian

Received: 17 January 2015 / Accepted: 28 February 2015 / Published: 11 March 2015

Abstract: This article introduces a continuous, gas-phase method for depositing thin
metallic coatings onto (nano)particles using a type of physical vapor deposition (PVD) at
ambient pressure and temperature. An aerosol of core particles is mixed with a metal vapor
cloud formed by spark ablation by passing the aerosol through the spark zone using a
hollow electrode configuration. The mixing process rapidly quenches the vapor, which
condenses onto the core particles at a timescale of several tens of milliseconds in a manner
that can be modeled as bimodal coagulation. Gold was deposited onto core nanoparticles
consisting of silver or polystyrene latex, and silver was deposited onto gold nanoparticles.
The coating morphology depends on the relative surface energies of the core and coating
materials, similar to the growth mechanisms known for thin films: a coating made of a
substance having a high surface energy typically results in a patchy coverage, while a
coating material with a low surface energy will normally “wet” the surface of a core
particle. The coated particles remain gas-borne, allowing further processing.

Keywords: spark ablation; nanoparticles; coating; gas phase; continuous process

Materials 2015, 1028
8
1. Introduction

Gas phase production of nanomaterials offers high purity and high throughput. Absolute impurity
levels in gas phase systems are orders of magnitudes lower than those in liquids, in part because of
convenient purification methods and in part because of the lower specific gravity of gases compared to
liquids. Moreover, the solvents and surfactants necessary in liquid phase methods should by
themselves be considered impurities. Contrary to a vacuum, the presence of a gaseous carrier allows
continuous processing with sequential unit operations. A commonly mentioned drawback of gas phase
processing is that one inevitably ends up with an agglomerated product, rather than individual
spherical particles. This poses some practical challenges if one wants to functionalize the individual
particles, as the coating must be applied before the particles agglomerate further. This requires either
lowering the coagulation rate by working at low particle concentrations or working on very short
(∼ms) timescales.
When an aerosol of substrate particles of the desired size and concentration is obtained, the coating
material can be added using either chemical or physical methods. In chemical vapor deposition (CVD),
gaseous precursor molecules are decomposed to form condensing species. Carbon-encapsulated
particles can be made by decomposition of hydrocarbons [1]. Inorganic coatings are obtained by
decomposition of organometallic complexes, forming oxides such as SiO2 [2], Fe2O3 [3] and Bi2O3 [4],
or noble metals such as Pt [5]. The decomposition requires elevated temperatures, so that typically
metal oxides, such as SiO2 and TiO2, are used as substrate materials. A disadvantage of the CVD
approach is that the required precursors tend to be highly reactive and are often toxic.
Physical vapor deposition (PVD) is a cleaner alternative, eliminating both precursor and
decomposition products from the process. In PVD, the coating material is first evaporated and
subsequently condensed onto the substrate. Evaporation furnaces are suitable if the melting point of
the substrate particle is significantly higher than that of the coating material, such as for the deposition
of Ga on Au [6] or L-leucine on NaCl or lactose [7]. Organic molecules can be deposited on silver
nanoparticles, with lower melting point materials having the tendency to form more uniform coatings
[8]. Methods that apply focused heating, such as the axial hot wire used to decorate 10- to 50-nm SiO 2
particles with 1- to 3-nm Au domains [9], can in theory be used with low melting point substrates.
Spark ablation is a versatile method for the production of nanoparticles ranging from several atoms
up to about 20 nm [10]. Each spark is a ∼10 µs electric discharge that rapidly heats the electrode
surface to temperatures on the order of 20,000 K, resulting in the ablation of part of the electrode
material. The formed vapor rapidly expands into a flow of quenched gas, resulting in quench rates on
the order of −107 K·s−1. As the gas cools, the vapor condenses to form nanoparticles. Here, we
present a simple, flexible and continuous gas phase method for the physical deposition of an arbitrary
electrically conductive material onto nanoparticles of any shape, size and composition, at ambient
pressure and temperature using spark ablation as a convenient vapor source.

2. Theory

In short, substrate particles are mixed with the coating vapor, resulting in a bimodal coagulation
process (Figure 1). Homogeneous nucleation of the coating material occurs in parallel, resulting in the
growth of coating clusters. However, scavenging [11] results in the preferential deposition of coating
Materials 2015, 1029
8
vapor and coating clusters on the substrate particles. Substrate-substrate collisions can be neglected due
to their lower diffusivity and concentration (appendix A).

He nanoparticles
subs
.
spark

>
γ
coa decoration
γt
cluster
s
bimodal γcoat≈γsubs.
N2 coagulation
substrat
e intermediate
particle
s γcoa
t

<
γ subs
hollow .
electrode core/shell
s

Figure 1. Schematic cross-section of the coating process in a hollow-electrode spark.

Below a certain critical size a deposited vapor cluster is unstable, allowing the cluster to migrate
across the substrate surface and enabling epitaxial growth of a coating layer [12]. The deposited
clusters rearrange to form a coating according to one of three well-studied growth mechanisms,
depending on the relative surface free energies of substrate and adsorbate, σsubs and σads, respectively,
and their interface energy σint. Two-dimensional Frank–van der Merwe (FW) growth occurs if the
surface energy of the substrate exceeds that of the adsorbate (σsubs > σads + σint), resulting in a smooth,
conformal coating. On a low surface energy surface (σsubs < σads + σint), a metal-island film grows
according to three-dimensional Volmer–Weber (VW) growth. The intermediate case, σsubs ≈ σads +
σint, can lead to mixed 2D/3D Stranski–Krastanov (SK) growth. These growth methods can also be
understood in terms of the physical-chemical interpretations of wetting and non-wetting liquids on
surfaces. The above description of film growth is based on thermodynamic equilibrium, valid for
single crystalline surfaces, in absence of strain or lattice mismatches. Kinetic effects, such as
interdiffusion and strain relief by interfacial alloying, play an equally important role. While
thermodynamic arguments alone are clearly insufficient to describe nanoparticles, which have multiple
facets that are often strained due to the stress of the large surface curvature, they do present a clear
starting point for studying the growth of coatings on unsupported nanoparticles.
Materials 2015, 1030
8 Here, we use two metals of similar surface energies: gold (σads, Au = 1.54 J·m−2 [13]) and silver
(σsubs, Ag = 1.32 J·m−2 [13]), as well as gold on gold, to study the intermediate domain. Both Ag and Au
have an fcc structure, with similar lattice constants of 408.53 pm and Au 407.82 pm, respectively.
Both FW- and SK-type growth modes are known for Ag/Au systems, and interfacial alloying is
known to
Materials 2015, 1031
8
occur [14]. Polystyrene (PSL, σads,PSL = 0.04 J·m−2 [15]) nanoparticles were used as low surface energy
core particles. Spark ablation is used to evaporate the coating material. This provides three advantages:
(1) the coating material is selectively heated, reducing the co-evaporation of contaminants [16]; (2)
only a small fraction of the gas is heated, so that the overall gas temperature stays close to room
temperature; and (3) the substrate particles can be brought into close proximity of the evaporation
source, ensuring that the coating clusters stay below the critical size.

3. Experimental Section

Au-coated Ag (Au-on-Ag) nanoparticles and Ag-coated Au (Ag-on-Au) nanoparticles were

generated in a setup consisting of a particle source for the core particles, a coating zone consisting of a
hollow electrode spark, a differential mobility analyzer to isolate the coated particles and a collection
zone (Figure 2). The setup was operated at slightly above atmospheric pressure. Ag and Au core
particles were formed by spark ablation [10] (20 nF, 30 mA, 1.1 kV–1.2 kV) in a flow of 1.6 L·min−1
N2 (room temperature, 1 atm), followed by reshaping of the formed agglomerates to ∼40-nm
spheroids using a sintering furnace (42 cm hot zone, Tfurnace ∼ 90% of the melting point) [17].
Diluted suspensions of polystyrene-latex (PSL) spheres (80 nm ± 18%, Duke Scientific, 5008A, Palo
Alto, CA, USA) in demineralized water were nebulized in an atomizer (TSI 3076) and dried in a
diffusion drier loaded with silica gel [18]. The combination of the atomizer and the diffusion drier
replaces the first spark and the sintering furnace in Figure 2, and no differential mobility analyzer
(DMA) was used with PSL cores.
Core particles Coating

isolato viewpo
N2 r rt

+
spark V hollow
He electrode

Collection
DMA

Size selection

+
V
Figure 2. Coating setup comprising a particle source, coating zone, differential mobility
analyzer (DMA) and an electrostatic precipitator (ESP).

The concentration of core particles measured with a condensation nucleation particle counter
(TSI 3776, TSI Inc., Shoreview, MN, USA) downstream of the size selection step ranged from
0.5·1013 m−3 to 1.5·1013 m−3. All flow lines consisted of 6-mm stainless steel tubing with Swagelok
Materials 2015, 1032
8
fittings, and sufficient length (∼30 cm) was provided to ensure the core particle aerosol had cooled to
room temperature before entering the coating zone.
The coating zone (schematically represented in Figure 1) consisted of two axially-aligned hollow
electrodes (Ag or Au, inner diameter 4 mm, outer diameter 6 mm) spaced ∼0.5 mm apart, contained
within a stainless steel housing with NW35CF flanges. The coating metal was ablated using low
energy sparks (2 nF, 15 mA, 0.3 kV (Ag), 0.7 kV (Au)) to avoid the formation of large particles. A
sheath flow of the low breakdown strength gas helium (2 L·min−1) was used to both allow a lower
spark energy in the gap [10] and to introduce a forced mixing of the metal vapor with the core
particles, taking advantage of the high diffusion coefficient in He. The vapor condensed on the core
particles, until the coating process was stopped by removing the fine fraction in the aerosol using
electrical mobility separation in a DMA [19] with a 2:1 sheath-to-aerosol ratio. This was possible due
to the self-charging that occurs in spark discharge [10]. Finally, the coated particles were deposited
during 20 min on various substrates (TEM grids, Si wafer, glass) using an electrostatic precipitator
(ESP) before further characterization.
Transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDX) were
performed on a JEOL 300F microscope (JEOL, Akishima, Tokyo, Japan) with a field emission gun
(FEG) at 300 kV. Additional TEM was performed using an FEI monochromated Tecnai 200STEM-
FEG (FEI, Hillsboro, OR, USA) at 200 kV and a JEOL JEM 1400 at 100 kV. Raman spectra were
recorded by a inVia Raman microscope (Renishaw, Wotton-under-Edge, UK) using laser excitation
wavelengths of 532 and 633 nm and applying a nominal power of 0.5 and 0.05 mW, respectively. The
lens used in the optical microscope during the measurements provided a 50× magnification, in order to
easily focus the laser beam onto the mesh wires of the various coated TEM grids. All of the spectra
were calibrated on the basis of the peak at
520.6 cm−1 obtained from a preceding measurement on a (100)Si wafer. Twenty cumulative
acquisitions were run in order to improve the S/N ratio in the ultimate spectra, which had a measuring
time of 20 s for all of the specimens.

4. Results and Discussion

4.1. Coagulation Model

The coating process can be described adequately by a simple bimodal coagulation model
(appendix A). Large particles (the cores) are known to preferentially scavenge smaller ones (the
clusters) [18], and for 10–100 nm nanoparticles, the coagulation kernel K of cluster-core collisions
exceeds the cluster-cluster coagulation kernel by up to four orders of magnitude (Equation 2).
Simulations performed for core particle concentrations of 1.5·1013 m-3 and core particle sizes of 10,
20, 40 and 80 nm show that the coating process occurs on a sub-second timescale (Figure 3). The rate
at which the available clusters N1 disappear and the size d1 to which they grow are weakly dependent
on the core size d2. The rate at which clusters deposit on the core particles scales with d22, i.e., the
available surface area. The coating thickness dc grows faster for smaller particles despite this constant
flux, because they need less mass (∝ d3) to achieve the same growth in diameter.
Materials 2015, 1033
8

-8
10
N1 20
10
Diameter or thickness, m

-9 10 nm

Concentration, m-3
10 d1 10
19

80 nm

18
dc 10
-10
10
17
10

-11
10 16
-5 -4 -3 -2 - 10
10 10 10 10 10
1
Time, s
Figure 3. Simulation results for cluster concentration (N1, blue), cluster size (d1, red) and
coating thickness (dc, black), using core particle sizes of 10 nm (solid), 20 nm (dash), 40
nm (dash-dot) and 80 nm (dots).

While collisions between core particles can be neglected, a non-negligible growth of the clusters
occurs. This is because the cluster concentration is much larger than that of the core particles,
compensating for the lower K of cluster-cluster collisions. Smooth coatings can only be obtained
when the deposited clusters have not yet reached their critical size. Below ∼3 nm, both Ag and
Au nanoparticles are essentially liquid-like at room temperature [20], and we assume that this size
corresponds to the critical size. To allow the growth of smooth layers, we stop the coating process
by filtering out the clusters when they have reached the critical size after a residence time of 40 ms
(Figure 3). At this stage, the coating thickness has grown to 0.6–0.8 nm, while the cluster size d1 has
grown to 3.5–3.7 nm.

4.2. Au on Au

Figure 4a shows a 0.45- µm sphere of Au, collected during deposition of Au on PSL with a high
spark energy. The microsphere is a solidified droplet. Such droplets are occasionally ejected in spark
ablation apart from the vapor [10]. They are usually undesired, but here this event gives us the
opportunity to observe the coating of Au particles with Au nanoparticles and clusters. Vapor and
clusters rapidly attach to the large gold cores in the vicinity of the spark. As we do not separate the
coating particles from the core particles in this experiment, we allow the coating particles to grow to a
size around 10 nm, and they can still attach to the core particles at that stage.
The TEM micrographs (Figure 4a) show dome-like structures that have evidently been formed by
the attachment of particles between 5 and 10 nm in diameter. As we know that in the vicinity of the
spark a rapid attachment of much smaller particles occurs, the absence of smaller domes tells us that
Materials 2015, 1034
8
these smaller particles form a smooth coating, not leaving any visible traces for the case of Au on
Au. This observation is in agreement with the fact that small particles are liquid-like below a certain
size [20] as a consequence of reduced binding energies of surface atoms due to the surface curvature.
In independent experiments, we have frequently observed that Au particles exhibit complete
coalescence into a spheroidal shape if they are smaller than 5 nm [21]. The reduction of surface
curvature by the dome formation or wetting process leads to solidification. We conclude that for the
case of equal surface free energies of the core and the coating particles, smooth coatings can be formed
if the latter are smaller than this liquefaction size. In contrast, island structures form if larger particles
are deposited. The complete coalescence of <5 nm Au particles is confirmed by the single, round
clusters deposited on the holey carbon film of the TEM grid having a modal size of 2–4 nm, while
non-spherical agglomerates start appearing above 3 nm. The wetting droplets and the single round
clusters validate the assumption of fast coalescence of <3 nm particles, i.e., liquid-like particles,
allowing the clusters in this size range to be modeled as simple spheres.

(a) (b)

Figure 4. Au clusters deposited on an Au microsphere. (a) Au microsphere with Au clusters;

(b) detail of the microsphere, with Au [111] lattice fringes indicated by the arrow. Scale
bars are 100 nm and 10 nm, respectively.

4.3. Au Clusters on PSL Cores

The Au clusters (dark) deposited on the PSL core particles (bright) decorate the surface of the
spheres (Figure 5a). The PSL spheres had diameters of 66 ± 7 nm and were deposited as singlets,
doublets and multiplets. The size of the clusters ranges from 1 to 10 nm, and the dark spots are
confirmed to be gold from lattice spacings of 0.23–0.24 nm (Au [111]). Figure 5b shows the size
distribution of 105 clusters deposited on PSL spheres, with circular (primary) particles and non-
circular particles (agglomerates) shown separately. The shape of surface equivalent diameters below
1.3 nm cannot be
Materials 2015, 1035
8
resolved sufficiently to distinguish spherical particles from agglomerates, but non-circular particles are
categorized as agglomerates for consistency. Only clusters overhanging the holes in the carbon film are
taken into account, to avoid counting clusters that arrived on the TEM grid independently of the PSL
cores. The size distribution normalized to a single PSL sphere corresponds to a deposited volume of
4.8·103–6.9·103 nm3, or 1·105 Au atoms per PSL particle. The model for 80-nm PSL spheres
overpredicts at 7·105 atoms per particle, although the modal size of the clusters, 2–5 nm (Figure 4b),
fits rather well. The discrepancy in deposited gold can be explained by the presence of dimer and
oligomer PSL particles, resulting in a larger PSL surface area at the measured particle number
concentration.

20 Primary p.

Count 15

10

5
Agglom.

0
1 10
-9
Surface equivalent diameter, 10 m

(a) (b)

Figure 5. Au clusters deposited on polystyrene (PSL) nanospheres. (a) TEM micrograph,

20-nm scale bar; and (b) size distribution of primary (round) and agglomerated cluster
domains, 105 in total.

4.4. Au Clusters on Ag Cores

The Au-on-Ag particles appear as light cores with a single dark cap (Figures 6 and 7a). The Au-on-
Ag particles size has a broad distribution, with a modal size of 21 nm (Figure 6b). The broadness of
the size distribution has three causes: (1) the core particle source was not optimized for
monodispersity; (2) the DMA was operated with a broad transfer function to allow high transmission;
and (3) doublets of smaller particles were also collected. These doublets either formed between the
sintering oven and the cluster source or downstream of the cluster source. Because the residence time
prior to the cluster source (∼400 ms) was much larger than that downstream of the source (40 ms),
most of these doublets were likely formed before the cluster source. From the limited number of
doublets observed, we conclude that core-core particle collisions can indeed be neglected in the
coating process. Starting with a monodisperse aerosol source, e.g., by size selection with an additional
DMA, is thus expected to result in equally monodisperse bimetallic particles.
Materials 2015, 1036
8

40

30

Count
20

10

0
1 10
-9
Particle size, 10 m

(a) (b)

Figure 6. (a) TEM micrograph of Au-on-Ag particles with s 50-nm scale bar; (b) particle
size distribution of 116 particles.

(a) (b)

Figure 7. TEM micrograph of Au-on-Ag particles. (a) Two patchy particles and two
clusters; (b) HRTEM image with lattice fringes of Ag 2S (0.334 nm) and Au (0.231 nm).
Note the different scale bars of 20 nm in (a) and 5 nm in (b).

Each core particle had a dark patch of at least 7 nm in diameter (Figure 7). The majority of the cores
has exactly one spot, although some non-spherical particles with two dark patches were also observed.
Lattice spacings of the dark patches match Au (Figure 7b), but due to the similar lattice constants,
could
Materials 2015, 1037
8
also originate from Ag or an Ag-Au alloy. The light zones do not show lattice spacings consistent with
Ag. Instead, lattice spacings of 0.167 nm (Figure 7b) are attributed to Ag2S, a well-known silver
tarnish that forms upon exposure to ambient air [22,23]. The relative abundances of Au, Ag and S in
energy dispersive X-ray spectroscopy (EDX) are consistent with the light zones being sulfidated Ag
and the dark zones being Au. Ten individual particles had a Au content of 17% ± 13% on a metal
basis, with the remainder being Ag. This is equivalent to a conformal coating thickness of 1.1 to 1.3
nm, which is somewhat larger than the 0.6 to 0.8 nm obtained from the coagulation model.
Au clusters with a mean diameter of 3.6 nm were observed in TEM micrographs alongside Au-on-
Ag particles (Figure 7a). The high diffusivity of the 3.6-nm clusters allowed a fraction of these
clusters to pass through the DMA. The size of these clusters is again consistent with the cluster size
obtained from the simulations. In particles where the dark spot is on the edge of the particle, the Au
appears to envelop the Ag core (e.g., Figure 7a) or to be partially embedded. This is consistent with the
mechanism of Au forming a patch covering the lighter Ag core, rather than a doublet of odd-sized
particles aligned parallel to the electron beam. Burrowing of the Au domain into the Ag particle by
interdiffusion, such as observed for thin films [14], could neither be confirmed nor excluded.

4.5. Ag Clusters on Au Cores

The Ag-on-Au particles have a broad distribution of particle sizes ranging from 27 to 130 nm and
consist of a mixture of sintered spheres (Figure 8a) and agglomerates (Figure 8b). The extent of neck
formation implies that the agglomerates formed by coagulation in the sintering oven, as a result of
a higher initial Au core particle concentration. The particles are identified as gold from EDX and
Fourier transform lattice spacings of 0.23–0.24 nm (Au [111]). Ag could not be detected by EDX on
30-nm particles, where a 1-nm coating would correspond to molar content of ∼10% Ag. No distinct
layer of any Ag compound was visible on any of the Ag-on-Au particles under HRTEM. Due to their
similar lattice spacings, Ag and Au cannot be distinguished within the resolution of the lattice spacing
measurements. The 0.6 to 1.0 nm coating thickness predicted by the coagulation model corresponds to
3–5 monolayers. Even in absence of interfacial alloying [14], the high density of the gold core
combined with the similar lattice parameters of the two metals would make it difficult to see a silver
shell of only several monolayers thick.
To test for Ag-based tarnish compounds, Raman spectroscopy was used to probe the particle
surface of both Ag-on-Au and Au-on-Ag nanoparticles (Figure 9). The assumption is that surface-
enhanced Raman scattering (SERS) [24] occurs for, e.g., Ag2S domains sitting on the noble metal core
particles undergoing their characteristic surface plasmon resonance. The particles of both
configurations show strong Raman signals under both excitation wavelengths (Figure 9). Under 532-
nm excitation, a strong mode appears at 1575 cm−1 for Au-on-Ag particles and at 1540 cm−1 for Au-on-
Ag particles (Figure 9a). Under excitation by a 633-nm laser, vibrational modes appear at 111, 146,
539, 635, 1243, ∼1396 and 1529–1550 cm−1 for Ag-on-Au particles (Figure 9b). The stronger of these
features also appears for Au-on-Ag particles at lower wavenumbers with a shift of about 5 cm−1. The
Ag-on-Au particles show a broad band in the 1800–3000 cm−1 range at both wavelengths, which likely
is the result of fluorescence. The strong Raman signals indicate that SERS indeed occurs. However, it
should be noted that most of
Materials 2015, 1038
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