Electroless plating is a powerful wet-chemical method for the fabrication
of metal thin films on arbitrarily shaped substrates [1]. Despite its
relative simplicity just involving the immersion of a work piece in a
deposition solution, electroless plating is suitable for the creation of
macroscopic [1] aswell as intricate nanoscale structures [2–5]. Depending
on the type of substrate and depositedmetal, the obtained materials
can be utilized in various fields, including electronics, wear and corrosion
resistance, medical technology and catalysis [1,6]. The special
properties of electrolessly plated metal nanomaterials give rise to
particularly interesting applications such as molecular separation
[4] or microreactors
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Ähnlich wie 2014 polymer activation by reducing agent absorption as a flexible tool for the creation of metal films and nanostructures by electroless plating (20)
3. 102 F. Muench et al. / Surface & Coatings Technology 242 (2014) 100–108
3.1. Influence of sensitization and activation solution composition on
seeding
3.1.1. PC-sensitization with various reducing agents
We have sensitized ion-track etched PC templateswith a pore diam-eter
of approx. 500 nm and a thickness of 30 μm with four different
methanolic solutions of reducing agents (2 M), namely (i) hydrazine,
(ii) NaBH4, (iii) formaldehyde and (iv) DMAB. In all experiments, the
composition of the activation solution remained unchanged with
59 mM AgNO3 as the metal precursor.
(i) Hydrazine sensitization led to severe embrittlement and frag-mentation
of the polymer foils and was thus not applicable. We
attribute this reactivity to the high susceptibility of PC to the
chemical attack of hydrazine [16].
(ii) With NaBH4, the templates could be stored in the sensitization
solution without significant damage, but no color change was
observed in the activation step, suggesting an insufficient up-take
of the reducing agent. Ionic species such as the reducer
tetrahydroborate have to carry counter-ions with them in
order to maintain charge neutrality, which could hinder
their diffusion into the polymer structure. Diffusion of reduc-ing
agents consisting of neutral molecules, such as DMAB or
formaldehyde, should instead be favored and facilitate their
uptake.
(iii) Accordingly, the uncharged formaldehyde which is also less
aggressive than hydrazine could be successfully implemented
as a reducing agent for the activation of PC alternatively to
DMAB. Fig. 1a,b displays TEM images of etched ion-tracks in
PC after sensitization with 2 M formaldehyde in methanol
and activation with AgNO3. Themicrotome cutting of the acti-vated
template was performed approximately perpendicular
to the long axis of the tubular pores, therefore the pore
cross-sections exhibit sometimes an elliptical shape. Because
Fig. 1. TEMimages ofmicrotome-cut ion-track etched PC templates after Ag activation (left column: survey images; right column:magnified images of individual pore cross-sections). a),
b) Sensitization with 2Mformaldehyde, activation with 59mMAgNO3. c), d) Sensitization with 2MDMAB, activation with 59mMAgNO3. e), f) Sensitization with 2MDMAB, activation
with 10 M AgNO3.
4. Fig. 2. AFM characterization of the PC samples activated with Ag (a–c) and Pt (e–g) using different amounts of DMAB in the sensitization step (0.25 M, 1 M and 2 M DMAB). The scale bar on the left refers to all AFM images. The AFM studies are
complemented by representative TEM images of the Ag (d) and Pt (h) seeds deposited after sensitization with 2 M DMAB.
F. Muench et al. / Surface & Coatings Technology 242 (2014) 100–108 103
5. 104 F. Muench et al. / Surface & Coatings Technology 242 (2014) 100–108
of the similar composition of the embedding resin and the poly-mer
matrix, the channels can only be identified by the presence
of metal NPs on their walls. It can be seen on the images that a
relatively low amount of NPs was found (size ~50 nm), which
made identifications of channel wallsmore challenging. Interest-ingly,
a halo with a contrast differing from the polymer matrix
was observed near the pores (Fig. 1a). This phenomenon was
also noted in related experiments (see Fig. 1c) and is probably
caused by a change of the polymer in the region inwhich the dif-fusion
process during sensitization takes place.
(iv) In Fig. 1c,d, the results sensitization with uncharged DMAB,
followed by activation with 59 mM AgNO3 are shown. In
this case, a higher number of Ag NPs were deposited, and
the channel walls could be identified more easily. Similar to
the formaldehyde-based activation, relatively large NPs in
the size range of some tens of nanometers were obtained.
We attribute the higher amount of deposited Ag to the higher re-ducing
efficiency of DMAB, as the complete oxidation of one mole-cule
of DMAB (Eq. (1)) yields three times more electrons than the
oxidation of one formaldehyde molecule (Eq. (2)). In addition, elec-trochemical
experiments indicate that DMAB is more easily oxidized
on Ag surfaces than formaldehyde [17], suggesting an improved con-version
of the former reducing agent on the Ag seeds evolving during
activation.
BH3
−NðCH3
Þ
2H þ 3H2O→BðOHÞ
3
þ ½NðCH3
Þ
2H2
þ þ 5H
þ þ 6e
− ð1Þ
HCHO þ H2O→½HCOO− þ 3H
þ þ 2e
− ð2Þ
Fig. 3. SEMimages of the Ag nanostructures obtained fromdifferently activated ion-track etched PC templates. a), b) Sensitization with 0.25MDMAB and activation with a) Ag and b) Pt
(b). c), d) Sensitization with 1 M DMAB and activation with c) Ag and d) Pt. e), f) Sensitization with 2 M DMAB and activation with e) Ag and f) Pt.
6. F. Muench et al. / Surface Coatings Technology 242 (2014) 100–108 105
3.1.2. Influence of the AgNO3 activation solution concentration
In an additional experiment, we significantly increased the concen-tration
of the Ag activation solution from 59 mM AgNO3 to 10 M
AgNO3, while keeping the DMAB concentration in the sensitization
step constant at 2 M. Optically, we observed that the color change of
the PC substrate after activation was stronger using the higher concen-tration
of AgNO3. Fig. 1e,f displays TEM images of cross-sections of the
activated PC membrane, evidencing that a large amount of relatively
small NPs was formed completely covering the channel walls. This be-havior
might be explained by the pronounced supersaturation of Ag
caused by the reduction of the very concentrated AgNO3 solution by
DMAB diffusing out of the polymer. While at low Ag concentration
few NPs are formed which grow during ongoing metal reduction, high
supersaturation favors a large number of nucleation events, with less
material deposited on each nucleus [18].
3.1.3. Influence of the DMAB sensitization solution concentration
The DMAB concentration in the sensitization solution affects the up-take
of the reducing agent by the polymer substrate [8] and thus should
allow modification of the amount of metal precipitated during activa-tion
in a controlled manner. We investigated this issue by applying
two different activation solutions (59 mM AgNO3 and 59 mM K2PtCl4)
on three PC templates each sensitized with a different concentration
of DMAB, namely 0.25 M, 1 M and 2 M.
The shape, size and density of the resulting seeds were studied by
TEM and AFM (Fig. 2). Fig. 2a–c shows AFM images of the Ag-activated
samples, in Fig. 2e–g the results for the Pt activation are
displayed. In each row, the DMAB concentration is rising from left to
right. In Fig. 2d and h, TEM images of Ag and Pt seeds obtained with 2
M DMAB are found.
The AFM measurements clearly evidence that the roughness of the
metallized polymer surface increases with the DMAB concentration in
the sensitization solution (Fig. 2a-c, e-g). Because the rootmean square
roughness of the bare PC surface is less than 1 nm even after sensitiza-tion
[8], the observed structures can be related to themetal NPs depos-ited
during activation. This argumentation is supported by TEM images
of NPs created during activation (Fig. 2d,h): The particle morphology
visualized by TEMresembles the surface structure of the corresponding
AFMimages.While Ag tends to form faceted, relatively large and isolat-ed
NPs (Fig. 2d), Pt activation yields aggregates consisting of smaller
NPs (Fig. 2h).
With the lowest DMAB concentration of 0.25 M, only few small NPs
were reduced on the polymer during activation with both Ag and Pt
(Fig. 2a,e). A DMAB concentration of 1 M led to a stronger uptake of
the reducing agent by the polymer and thus enabled the formation of
a much more dense layer of metal NPs (Fig. 2b,f). Compared to Pt, Ag
activation yielded a higher amount of deposited metal and larger NP
sizes. With the most concentrated sensitization solution (2 M DMAB),
even larger, but still mostly isolated particles were found in the case of
Ag (Fig. 2c), while extended clusters were obtained with Pt activation
(Fig. 2g).
3.2. Influence of the substrate activity on the electroless synthesis of metal
NTs
In this section, we demonstrate that the seed metal type and seed
density can be utilized to tailor the substrate activity to affect the
consecutive electroless plating of metal NTs. We fabricated etched ion-track
PC membranes with ~600 nm diameter channels, and activated
them using DAMB, AgNO3 and PtCl4, using identical conditions to the
experiments conducted in Section 3.1.3. Thus we obtained both Ag
and Pt seeds with three different NP loadings. After activation, all tem-plates
were subjected to electroless Ag plating for 20 h.
Fig. 4. a), b) SEM images of Cu NTs fabricated in an ion-track etched PC template sensitized with 1 M DMAB and activated with Pt seeds. c) Magnified SEM image (secondary electron
mode) of two Ag NTs (sensitization: 2 M DMAB, activation: Pt). d) SEM image of the sample shown in c) (backscattered electron mode). The Pt seeds on the outer Ag NT surface can
be clearly identified by the atomic number contrast.
7. 106 F. Muench et al. / Surface Coatings Technology 242 (2014) 100–108
Fig. 3 shows Ag nanostructures obtained sensitization with 0.25
DMAB in the case of a) Ag and b) Pt seeds. In both cases no continuous
Ag NTswere obtained due to the lowdensity of seeds created during ac-tivation
(see Fig. 2a,e). However, relatively dense Ag surface films were
formed on the outer, planar surfaces of the template foil. This result is in
agreement with previous reports [5,19,20], corroborating that the for-mation
of 2D films is easier than the homogeneous coverage of extend-ed
inner surfaces poorly accessible to the reactants.
Fig. 3c,e presents free-standing Ag NTs spanning the complete thick-ness
of the template (~30 μm). These tubes are obtained when a higher
density of Ag seeds is created by sensitization with more concentrated
DMAB solutions, namely 1 M and 2 M.
Fig. 3d,f presents Ag nanostructures obtained with increased seed
density in the case of Pt-seeded experiments. In these cases, only
short NTs are formed adjacent to the planar Ag film on the outer tem-plate
surface. To exclude the possibility that an inhomogeneous seed
distribution with low particle densities within the template channels
was responsible for this result, we performed electroless Cu plating on
an ion-track etched membrane activated with Pt seeds after sensitiza-tion
with 1 M DMAB. Fig. 4a,b evidences the formation of well-defined
Cu NTs. Because an identical amount and distribution of seeds did not
suffice to enable the formation of extended free-standing Ag NTs
(Fig. 3d), the Pt NPs initiated metal film nucleation more reliablywithin
the depth of the template pores when comparing Cu with Ag plating.
This result points out that the activation parameters of the substrates
used in the electroless fabrication of nanomaterials must be optimized
with respect to the applied plating solution.
We found that in the case of the employed electroless Ag plating re-action,
Pt seeding led to less Ag deposition within the template com-pared
to Ag seeding under identical plating conditions (Fig. 3). This
indicates a slower formation of the Ag filmin the Pt-activated template,
which can be explained by a reduced activity of the Pt seeds in the
Fig. 5. Characterization of themetal films plated on different polymers after sensitization with DMAB and activationwith Ag. a), b) SEM images of the nanostructured Ag film on ion-track
etched PET. c) SEMimage of the Ag film deposited on ABS foil. d) Photograph of a Lego® brick after electroless Ag plating. The light golden color of the work piece is often observed in the
case of Ag films roughened on the nanoscale [5,29]. e), f) SEMimages of the Au film deposited on PVA foil. (For interpretation of the references to color in this figure legend, the reader is
referred to the web version of this article.)
8. F. Muench et al. / Surface Coatings Technology 242 (2014) 100–108 107
plating reaction. Ideally, metal deposition should occur faster on the
seed particles than on the plated metal film, because in this case
substrate areas where film nucleation has not started yet are preferred
deposition sites [21]. Due to their improved activity compared to the
Pt seeds, Ag seeds are therefore preferred to obtain free-standing Ag
NTs of high aspect ratio in the reaction conditions described here.
Despite the fact that no continuous Ag NTs were obtained in the Pt
activation experiments (Fig. 3b,d,f), it is important to note that the
outlined reaction scheme can be used to create metal NTs decorated
with NPs on their outerwalls consisting of a secondmetal (Fig. 4c,d). Bi-nary
NTs represent an upcoming catalyst systembenefiting fromboth a
unique morphology and synergistic effects [22,23], thus activation with
a seed metal differing from the NT material is an interesting and
straightforward route towards metal NTs with improved functionality.
3.3. Activation protocol for different polymers
In the study introducing the swelling activation technique [8], PC
was used because of its privileged role as a template for the deposition
of high aspect ratio nanomaterials such as nanowires [24] and NTs [7].
To prove the universality of the activation scheme, it is now shown
how the process can be transferred to other polymers. Three polymer
types with significantly deviating properties were chosen, namely
(i) PET, (ii) ABS and (iii) PVA. For all three polymers, we used technical
polymer data sheets, and it was of high importance to choose a sensiti-zation
solvent which causes slight swelling of the substrate surface
without damaging themorphology of thework piece or even dissolve it.
(i) PET is a polyester like PC, but is characterized by a higher chem-ical
stability and thus can be applied undermore aggressive con-ditions
[25]. Given the stability of PET in methanol, 1,4-dioxane
was chosen as solvent for the sensitization of PET membranes.
Using DMAB as the reducing agent, Ag nuclei were deposited in
the activation step, followed by electroless Ag plating. During
activation, the PET template turned brownish, indicating the cre-ation
of Ag seeds. After electroless plating, a metallic gray luster
appeared. The creation of a homogeneous thin film composed
of the relatively large NPs typical for electroless Ag [5] was con-firmed
by SEM (Fig. 5a,b). The porous structure of the template
was fully preserved during the treatment (Fig. 5a,b). As can be
seen in Fig. 5b, Ag deposition also took place on the inner surfaces
of the PET substrate.
(ii) ABS is an industrially important polymer frequently used for elec-troless
plating [1,26]. Due to its hydrophobic nature, etching and
oxidizing steps are usually required to provide adhesion for plat-ed
metal films and to introduce polar surface functionalities for
activation procedures [26,27]. The sensitization procedure used
for PC could directly be transferred to ABS. After being sensitized
in amethanolic solution of DMAB, activation in an aqueous solu-tion
of AgNO3 yielded intensely brown-colored ABS substrates
which could be evenlymetallized by consecutive electroless plat-ing
(Fig. 5c,d). Dense Ag films were obtained, as expected from
the high seed loading indicated by the strong color shift during
activation [7]. The presence of a nanostructured Ag film was con-firmed
with SEM (Fig. 5c). Both home-made ABS foils (Fig. 5c)
and complex shaped, macroscopic work pieces such as Lego®
bricks (Fig. 5d) were successfully plated.
(iii) PVA is an extremely hydrophilic and biocompatible polymer [28].
The home-made PVA foils used for the experiments were water
soluble. Thus, all reaction steps (sensitization, activation, electro-less
plating) were performed in non-aqueous solvents. While
DMAB sensitizationwas performedwithmethanol, ethylene gly-col
was used for activation because of its improved solubility of
inorganic salts such as the AgNO3 used as metal source. After ac-tivation,
the brownish PVA foilswere placed in an ethylene glycol
based electroless Au plating bath. During the storage of the
polymer foil in the reaction solution, a color shift to blue was
observed in addition with a slight bronze-colored luster. SEM
measurements confirmed the presence of a porous nanoscale
Au film (Fig. 5e,f).
In all shown experiments, metal filmadhesionwhich displays an es-sential
issue in electroless plating [1,26] was unproblematic. No delam-ination
of the metal films was observed after plating as well as during
scotch tape tests. This is expected in the case of the ion-track etched
PC and PET templates, since the polymer foils contain a high density of
pores which reliably anchor themetal films on their surfaces. Consider-ing
the ABS substrates, a certain roughness was found after swelling
activation and plating (see Fig. 5c), which is probably the cause for the
good metal film adhesion. The bonding of the Au film to the PVA foil
probably benefited from its nanoscale structure, because it is well
known that ensuring metal adhesion is especially challenging for large
film thicknesses [1]. Consequently, in syntheses using extended plating
times and smooth PC foils not containing pores from ion-track etching,
we frequently observed metal film peeling. This is not surprising, since
the applied reaction conditions do not increase the surface roughness
of the utilized PC foils significantly [8], which is necessary to improve
mechanical bonding due to the otherwise mostly weak interactions be-tweenmetals
and polymers [1,26,27,30].While the conservation of fine
morphological features is important for template-based nanomaterial
fabrication, in such cases, surface-roughening pretreatments [1,30] are
required before sensitization.
4. Conclusion
In this study, the activation of polymer substrates sensitized by the
absorption of reducing agents in the presence of swelling solvents was
demonstrated to be a universal and highly flexible process. By choosing
appropriate solvents causing a controlled modification of the polymer
surface without destroying the substrate morphology, four polymers
with strongly differing chemical structures were successfully activated
for consecutive electroless plating. Also, the reducing agent and seed
metal could be varied.
The reaction conditions during sensitization and activation strongly
affected the formation of metal NPs. Highmetal loadings were obtained
by sensitization with concentrated solutions of the strong reducing
agent DMAB. The seed particle shape, size and distribution depended
on the composition of both the sensitization and activation solutions,
with a particularly pronounced impact of the metal precursor type.
Because the activation quality is of major relevance for the electro-less
synthesis of metal thin films and nanomaterials derived thereof,
the effect of the seeding parameters on the fabrication of free-standing
metal NTs was evaluated. To achieve this challenging prod-uctmorphology,
an appropriate seed loading proved to be necessary,
but not sufficient. Generally, an adequate density of seeds which are
active in the corresponding plating reaction and ensure reliable
nucleation is required to homogeneously cover complex shaped sub-strates
with nanoscale metal films.
Acknowledgments
We thank Prof. Dr. Christina Trautmann (GSI Helmholtzzentrumfür
Schwerionenforschung GmbH (Darmstadt, Germany)) for supportwith
the irradiation experiments and for providing access to the HRSEM of
the materials research group. The authors highly recognize the synthe-ses
performed by Sebastian Bohn.
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