Surface-Grafted Polymer-Assisted Electroless Deposition of Metals for Flexible and Stretchable Electronics

Surface-grafted polymers, that is, ultrathin layers of polymer coating covalently tethered to a surface, can serve as a particularly promising nanoplatform for electroless deposition (ELD) of metal thin films and patterned structures. Such polymers consist of a large number of well-defined binding sites for highly efficient and selective uptake of ELD catalysts. Moreover, the polymer chains provide flexible 3D network structures to trap the electrolessly deposited metal particles, leading to strong metal–substrate adhesion. In the past decade, surface-grafted polymers have been demonstrated as efficient nanoplatforms for fabricating durable and high-performance metal coatings by ELD on plastic substrates for applications in flexible and stretchable electronics. This focus review summarizes these recent advances, with a particular focus on applications in polymeric flexible and stretchable substrates. An outlook on the future challenges and opportunities in this field is given at the end of this paper.     

Correlation between structure and stress-strain characteristics of metallic coatings deposited onto a polymer by the method of ionic plasma sputtering

Data on the strength of coatings based on noble metals (Pt, Au) deposited onto PET films by the method of ionic plasma sputtering are analyzed. In addition to precipitation of the metal, this mode of deposition is accompanied by modification of the surface polymer layer due to its interaction with plasma. As a result, a complex three-layered structure near the polymer surface forms. A new method for estimating the strength of coatings deposited onto polymer supports is advanced. This method makes it possible to analyze stress-strain characteristics of the three-layered systems that emerge owing to deposition of nanoscale layers of noble metals on polymer films via ionic plasma sputtering. The proposed relationships are in fair agreement with the experimental data.     

Structure and properties of nanosized coatings deposited onto polymers

Results of studies aimed at developing a new approach to measuring stress-strain properties of nanosized solids (strength, yield stress, and the value of plastic deformation at uniaxial tension) are generalized. This approach is based on the analysis of the parameters of microrelief arising upon the deformation of polymer films with thin coatings. It is demonstrated for the first time that the stress-strain properties of aluminum coatings deposited onto Lavsan substrates depend on the level of stresses in the substrate, the value of its deformation, and the thickness of the coating. The evolution of these parameters is related to the strain hardening of metal and the effect of nanostructuring of crystalline materials in the range of small thicknesses. When precious metal (Au, Pt) nanosized films are deposited onto polymers by ion-plasma sputtering, in the course of metal deposition, polymer surface layers interact with cold plasma. Stress-strain properties of polymer surface layers modified by plasma are quantitatively estimated for the first time. The model is proposed that makes it possible to take into account the contribution of the properties of precious metal and plasma-modified polymer surface layer to the strength of the coating.     

Electrochemical deposition of copper in polyaniline films — number density and spatial distribution of deposited metal clusters

The electrochemical deposition of copper in reduced polyaniline (PAN) films is studied at different polymer layer thicknesses. A saturation in the number density, n₀, of active sites for metal deposition is found at 0.5 μm PAN thickness (n₀=10⁸ cm⁻²). The surface spatial distribution of the deposited copper crystals is analysed in two cases. It is found that nucleation exclusion zones play an appreciable role in the course of the deposition process in thin PAN films. In contrast, a random distribution and a larger number of deposited crystals are obtained in thicker PAN layers.     

Silver particles-modified polysulfonic acid-doped polyaniline layers: electroless deposition of silver in slightly acidic and neutral solutions

Polyaniline layers are produced by electrochemical polymerisation of aniline in the presence of small amounts of poly(2-acryalamido-2-methyl-propane-sulfonic acid) in an inorganic acid solution. Electroactivity and in situ conductance of the obtained polysulfonic acid-doped layers are studied in slightly acidic and neutral solutions. Electroless deposition of silver particles is carried out in silver-EDTA complex ion solutions at pH????.2 and pH????.6 by using the polyaniline layers as reductant. The amount of electroless-deposited silver is studied depending on: polymerisation charge used to synthesize the polymer layer, pH of the plating solution, metal ion concentration and dipping time. SEM shows in all cases a highly non-homogeneous distribution of the metallic phase over the surface, the most protruding fibrillar polymer structures favouring the electroless silver deposition. A linear dependence between amount of the polyaniline material and amount of deposited silver is found for the silver plating solutions with the highest investigated concentration (10?mmol?l^??). At lower concentrations (2.0 and 0.4?mmol?l^??), the same amount of silver becomes deposited on polymer layers with markedly different charges. The electroless deposition of silver in the solutions with lower acidity results in lower amounts of deposited silver at otherwise identical conditions. Effects such as charge transfer within the polymer phase and mass transport in the solution are addressed to explain the observed dependencies of the amount of deposited silver on concentration and pH in the different plating solutions.     

PEDOT-supported Pd nanoparticles as a catalyst for hydrazine oxidation

Composite poly-3,4-ethylenedioxythiophene (PEDOT)/palladium (Pd) films were obtained by chemical deposition of dispersed palladium nanoparticles into PEDOT conducting polymer matrix. The amounts of palladium particles incorporated into PEDOT films were estimated by electrochemical quartz crystal microbalance measurements. It was shown that palladium loading depends on the time a PEDOT film is exposed in the solution, containing Pd(II)-ions, on the concentration of Pd(II) ions and the film thickness. X-ray photoelectron spectroscopy data have confirmed the presence of metallic palladium in the polymer. The morphology of pristine and composite films as well as the size of Pd nanoparticles and their distribution were characterized using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). From SEM images, it was found that Pd particles decorated PEDOT globular structures as quasi-spherical particles, and their mean size was dependent on synthesis conditions. The nanoparticles were non-uniformly dispersed on the polymer surface. The comparison of TEM images of composite PEDOT/Pd films obtained for different times of metal loading was made. The remarkable effect of loading time on the size of particles has been established: the mean size of dominating palladium particles was close to 6–10 nm for 30 s of metal deposition, and it was getting larger with the increase of deposition time (close to 15–30 nm for 120 s). It is most likely that with prolongation of synthesis time, the deposition of palladium predominantly proceeds on the already deposited palladium clusters, resulting in the extension growth of their size. Catalytic properties of PEDOT/Pd composite films were studied in respect to hydrazine oxidation by cyclic voltammetry and voltammetry on rotating disk electrode. The obtained data allow to conclude that the process of hydrazine oxidation on PEDOT/Pd composites takes place predominantly on palladium particles, located on the surface or in the near-surface layers of the polymer. The diffusion nature of the limiting current of hydrazine oxidation on composite PEDOT/Pd film in phosphate buffer solution рН = 6.86 was confirmed, and hydrazine diffusion coefficient was calculated. The increase of the limiting currents of hydrazine oxidation with the increase of Pd deposition time was observed, resulting from the increase of the active surface area of palladium particles, acting as microelectrodes. The electroanalytical applications of these nanocomposite materials for the determination of hydrazine were demonstrated.     

Silver particles-modified polysulfonic acid-doped polyaniline layers: electroless deposition of silver in slightly acidic and neutral solutions

Polyaniline layers are produced by electrochemical polymerisation of aniline in the presence of small amounts of poly(2-acryalamido-2-methyl-propane-sulfonic acid) in an inorganic acid solution. Electroactivity and in situ conductance of the obtained polysulfonic acid-doped layers are studied in slightly acidic and neutral solutions. Electroless deposition of silver particles is carried out in silver-EDTA complex ion solutions at pH = 4.2 and pH = 6.6 by using the polyaniline layers as reductant. The amount of electroless-deposited silver is studied depending on: polymerisation charge used to synthesize the polymer layer, pH of the plating solution, metal ion concentration and dipping time. SEM shows in all cases a highly non-homogeneous distribution of the metallic phase over the surface, the most protruding fibrillar polymer structures favouring the electroless silver deposition. A linear dependence between amount of the polyaniline material and amount of deposited silver is found for the silver plating solutions with the highest investigated concentration (10 mmol l⁻¹). At lower concentrations (2.0 and 0.4 mmol l⁻¹), the same amount of silver becomes deposited on polymer layers with markedly different charges. The electroless deposition of silver in the solutions with lower acidity results in lower amounts of deposited silver at otherwise identical conditions. Effects such as charge transfer within the polymer phase and mass transport in the solution are addressed to explain the observed dependencies of the amount of deposited silver on concentration and pH in the different plating solutions.

     

Polymer/montmorillonite nanocomposites with improved thermal properties: Part I. Factors influencing thermal stability and mechanisms of thermal stability improvement

The results of recent research indicate that the introduction of layered silicate - montmorillonite - into polymer matrix results in increase of thermal stability of a number of polymer nanocomposites. Due to characteristic structure of layers in polymer matrix and nanoscopic dimensions of filler particles, several effects have been observed that can explain the changes in thermal properties. The level of surface activity may be directly influenced by the mechanical interfacial adhesion or thermal stability of organic compound used to modify montmorillonite. Thus, increasing the thermal stability of montmorillonite and resultant nanocomposites is one of the key points in the successful technical application of polymer-clay nanocomposites on the industrial scale. Basing on most recent research, this work presents a detailed examination of factors influencing thermal stability, including the role of chemical constitution of organic modifier, composition and structure of nanocomposites, and mechanisms of improvement of thermal stability in polymer/montmorillonite nanocomposites.     

Electrochemistry of conductive polymers 39. Contacts between conducting polymers and noble metal nanoparticles studied by current-sensing atomic force microscopy

Electrical properties of contacts formed between conducting polymers and noble metal nanoparticles have been examined using current-sensing atomic force microscopy (CS-AFM). Contacts formed between electrochemically prepared pi-conjugated polymer films such as polypyrrole (PPy), poly(3-methylthiophene) (P3MeT), as well as poly(3,4-ethylenedioxythiophene) (PEDOT) and noble metal nanoparticles including platinum (Pt), gold (Au), and silver (Ag) have been examined. The Pt nanoparticles were electrochemically deposited on a pre-coated PPy film surface by reducing a platinum precursor (PtCl62-) at a constant potential. Both current and scanning electron microscopic images of the film showed the presence of Pt islands. The Au and Ag nanoparticles were dispersed on the P3MeT and PEDOT film surfaces simply by dipping the polymer films into colloid solutions containing Au or Ag particles for specified periods (5 to approximately 10 min). The deposition of Au or Ag particles resulted from either their physical adsorption or chemical bonding between particles and the polymer surface depending on the polymer. When compared with PPy, P3MeT and PEDOT showed a stronger binding to Au or Ag nanoparticles when dipped in their colloidal solutions for the same period. This indicates that Au and Ag particles are predominantly linked with the sulfur atoms via chemical bonding. Of the two, PEDOT was more conductive at the sites where the particles are connected to the polymer. It appears that PEDOT has better aligned sulfur atoms on the surface and is strongly bonded to Au and Ag nanoparticles due to their strong affinity to gold and silver. The current-voltage curves obtained at the metal islands demonstrate that the contacts between these metal islands and polymers are ohmic.     

Annealing sequence dependent open-circuit voltage of inverted polymer solar cells attributable to interfacial chemical reaction between top electrodes and photoactive layers

The ability to laminate and delaminate top metal contacts during the processing and testing of inverted polymer solar cells has led us to uncover the peculiar dependence of their open-circuit voltage (V(oc)) on the annealing sequence. Specifically, thermally annealing inverted polymer solar cells having bulk-heterojunction photoactive layers after top electrode deposition above 100 °C leads to lower V(oc) compared to analogous devices with unannealed photoactive layers or photoactive layers that have been annealed prior to metal electrode deposition. This reduction in V(oc), however, can be reversed when the top electrodes are replaced. This observation is thus a strong indication that such changes in V(oc) with annealing sequence are manifestations of changes at the top electrode-photoactive layer interface, and not structural changes in the bulk of the photoactive layer. Electronic characterization conducted on the photoactive layers and metal contacts after dissection of the polymer solar cells via delamination suggests the reduction of V(oc) on thermal annealing in the presence of the metal top contacts to stem from an interfacial chemical reaction between the photoactive layers and the metal electrodes. This chemically generated interfacial layer is removed upon electrode delamination, effectively reverting the V(oc) to its original value prior to thermal annealing when the top electrodes are replaced.     

Graphitic encapsulation of catalyst particles in carbon nanotube production

A new model is proposed for the encapsulation of catalyst metal particles by graphite layers that are obtained, for example, in low-temperature chemical vapor deposition production of carbon nanotubes (CNTs). In this model graphite layers are primarily formed from the dissolved carbon atoms in the metal-carbide particle when the particle cools. This mechanism is in good agreement with molecular dynamics simulations (which show that precipitated carbon atoms preferentially form graphite sheets instead of CNTs at low temperatures) and experimental results (e.g., encapsulated metal particles are found in low-temperature zones and CNTs in high-temperature regions of production apparatus, very small catalyst particles are generally not encapsulated, and the ratio of the number of graphitic layers to the diameter of the catalyst particle is typically 0.25 nm(-1)).     

Synthesis and characterization of nanostructural polymer-silica composite: positron annihilation lifetime spectroscopy study

The swelling of poly(TRIM) spherical particles in TEOS is assessed as a potential way for obtaining polymer-silica nanocomposite materials. Silica deposition was achieved by simply stirring of swollen polymer particles in acidic hydrochloric-water solution. This procedure leads to spherical composite particles with dispersed silica gel within the polymer matrix. The resulting material exhibits the same morphology as the initial polymer. Nanocomposite particles are silica rich (about 17 wt.%). Characterization of the nanocomposites was performed using scanning electron microscopy, FT-IR spectroscopy, (29)Si CP MAS NMR spectroscopy and thermogravimetry. Moreover, the use of positron annihilation lifetime spectroscopy PALS to characterize the structural properties of the nanocomposites is presented. This technique gave more realistic pieces of information about the pore structure of the investigated samples in contrast to nitrogen adsorption studies.     

Defect-free polymer multilayers prepared via chemoselective immobilization

In this paper, we investigated electrochemical properties of polymer multilayers on gold substrates using impedance spectroscopy. The multilayer was prepared by chemoselective ligation between aldehyde- and oxyamine-functionalized polymers via a layer-by-layer approach. The impedance spectra in a buffer solution in the absence of redox species revealed the formation of highly impermeable and defect-free films. The dielectric thickness of the polymer film, which is proportional to the reciprocal of capacitance, linearly increased as the number of deposition layer increased. The defect area of the polymer multilayer was obtained using the faradaic impedance with redox species. The surface coverage of eight polymer layers was determined to be 99.99%. Thus, the layer-by-layer deposition via chemoselective ligation offers a new way to prepare a highly insulating and defect-free polymer layer with finely tunable capacitance as a function of the number of deposition layers.     

Packing density control in P(NIPAM-co-AAc) microgel monolayers: effect of surface charge, pH, and preparation technique

In the present paper, thermosensitive coatings are prepared by deposition of P(NIPAM-co-AAc) microgel particles on precoated silicon wafers. The effect of pH, substrate precoating, and preparation technique is studied. The pH value is found to significantly influence the adsorption density, while the substrate surface charge is less important. Hence, the electrostatic contribution of the particle-particle interaction seems to play a more pronounced role for the adsorption density than at least the electrostatic part of the particle-surface interaction. For the latter, also nonelectrostatic contributions like hydrogen bonding and surface roughness play an important role. Immersion of the prepared polyelectrolyte/microgel layers in buffers leads to a reorganization of the adsorbed particles at the surface.     

聚合物表面自组装电极的制备

采用在聚合物表面制备选择性化学镀电极的方法, 将具有电极结构的模板置于聚萘二甲酸乙二醇酯(PEN)基片表面上, 用紫外光进行照射, 使辐照区域表面形成羧基, 然后通过配位作用使银离子附着到表面上, 再经过紫外光照射还原出金属银颗粒, 最后以表面的金属银颗粒为催化剂进行特定区域化学镀铜形成电极. 利用四探针法测得电极的电阻率为5.063×10-2 Ω·mm2/m, 与纯金属铜的电阻率的数量级相同.     

Poly(methyl methacrylate) composites with size‐selected silver nanoparticles fabricated using cluster beam technique

An embedment of metal nanoparticles of well‐defined sizes in thin polymer films is of significant interest for a number of practical applications, in particular, for preparing materials with tunable plasmonic properties. In this article, we present a fabrication route for metal–polymer composites based on cluster beam technique allowing the formation of monocrystalline size‐selected silver nanoparticles with a ±5–7% precision of diameter and controllable embedment into poly (methyl methacrylate). It is shown that the soft‐landed silver clusters preserve almost spherical shape with a slight tendency to flattening upon impact. By controlling the polymer hardness (from viscous to soft state) prior the cluster deposition and annealing conditions after the deposition the degree of immersion of the nanoparticles into polymer can be tuned, thus, making it possible to create composites with either particles partly or fully embedded into the film. Good size selection and rather homogeneous dispersion of nanoparticles in the thin polymer film lead to excellent plasmonic properties characterized by the narrow band and high quality factor of localized surface plasmon resonance. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1152–1159     

Determination of aluminium in natural water samples

The atmospheric deposition of terrestrial dust into the ocean is an important factor in controlling Earth's climate. Aluminium can be used as a tracer for the magnitude and location of dust transported from the land to surface ocean. The element is ideal for this purpose since its primary input is via aeolian dust deposition and it has a short surface water residence time. The accurate determination of dissolved aluminium in seawater is difficult due to the complexity of the matrix and the trace (nanomolar) concentrations at which the metal exists. This paper presents a critical review of the different sampling and analytical methods for the determination of the concentration of aluminium in natural waters, with particular focus on techniques successfully applied to shipboard analysis of seawater.     

Nucleation of gold nanoparticles on latex particle surfaces

Gold particles were nucleated on functionalized (i.e., sulfonate or imidazole groups) latex particle surfaces. Gold ions were associated with the functional groups present on the surface of the latex particles by metal‐ligand formation and were then reduced to nucleate gold particles on the particle surface. The use of imidazole groups favored the metal‐ligand formation more effectively compared with sulfonic acid groups, so gold nucleation was investigated on the surface of imidazole‐functionalized model latex particles. The desorption of gold atoms or their surface migration first occurred during the reduction process and then gold nanoparticles were nucleated. The utilization of strong reductants, such as NaBH₄ and dimethylamine borane (DMAB) under mildly acidic conditions (i.e., pH 4) led to the deprotonation of imidazole‐rich polymer chains present on the surface of the model latex particles followed by deswelling of hydrophilic polymer surface layers. As a result, well‐dispersed gold nanoparticles were embedded in the hydrophilic polymer surface. On the other hand, the use of weak reductants led to the formation of localized gold aggregates on the surface of the latex particles. The removal of residual styrene monomer is very important because gold ions can be coordinated with the vinyl groups present in styrene monomer and would then be reduced by nucleophilic water addition. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 912–925, 2008     

Ultrastable Au nanocatalyst supported on surface-modified TiO2 nanocrystals

The surfaces of TiO2 nanocrystals were modified with amorphous aluminum-oxide layers using a surface sol-gel process to control the interaction between supports and metal particles. Ultrastable Au nanocatalysts were prepared by the deposition of Au nanoparticles on the surface-modified TiO2 nanocrystals using a deposition-precipitation (DP) method. The TEM analysis showed that the Au nanoparticles on the surface-modified nanocrystal supports were highly stable with a sinter-resistant capability during high-temperature calcination. The HRTEM analysis revealed that the surface of the TiO2 nanocrystals was covered by an amorphous aluminum-oxide layer and the Au nanoparticles were primarily anchored to this amorphous layer. This amorphous aluminum-oxide layer played an extremely important role in the stabilization of the supported Au nanoparticles without affecting catalytic activities. The surface modification of nanocrystal supports highlights new opportunities in tailoring the stability and activity of supported nanocatalyst systems.     

On the interfacial chemistry of aryl diazonium compounds in polymer science

This review emphasises the role of aryl diazonium compounds as a new class of coupling agents for grafting polymer thin layers onto carbon, diamond, metals, metal oxides, alloys, semi-conductors, ceramics, and polymers. Physical and chemical methods are first reported for anchoring aryl layers to the surfaces, then the review concentrates on the modification of the above substrates by thin polymer films via a range of the “grafting from” and “grafting onto” strategies. Some applications are described which highlight the important role that diazonium salts will continue to play in the near future in the polymer and surface sciences.