Electroless deposition of copper on polyimide films modified by surface graft copolymerization with nitrogen-containing vinyl monomers

Surface modification of Ar-plasma-pretreated polyimide (PI) films (Kapton® HN films) via UV-induced graft copolymerization with 1-vinylimidazole (VIDz), 4-vinylpyridine (4VP), and 2-vinylpyridine (2VP) under atmospheric conditions was carried out to improve their adhesion with the electrolessly deposited Cu. The surface compositions of the graft-copolymerized PI films were characterized by X-ray photoelectron spectroscopy. The adhesion strength of the electrolessly deposited Cu on the surface-graft-copolymerized PI film was affected by the type of monomers used for graft copolymerization and the graft concentration. T-peel adhesion strengths of about 15, 10, and 6?N/cm were obtained for the Cu/graft-modified PI assemblies involving, respectively, the VIDz, 4VP, and 2VP graft-copolymerized PI films. These adhesion strengths are much higher than those obtained for assemblies involving electrolessly deposited Cu on pristine or on Ar-plasma-treated PI films. The adhesion strengths involving the VIDz and 4VP surface-graft-copolymerized PI films are also higher than those involving PI films modified by chemical etching. The cohesive failure inside the PI substrate of the Cu/graft-modified PI assemblies during delamination suggested that not only were the grafted polymer chains covalently tethered on the PI film, they were also incorporated into the metal matrix during the electroless plating process.     

Electroless Deposition of Copper on Poly(tetrafluoroethylene) Films Modified by Plasma-Induced Surface Grafting of Poly(4-vinylpyridine)

Argon plasma-pretreated poly(tetrafluoroethylene) (PTFE) films were solution coated with a thin layer of poly(4-vinyl pyridine) (P4VP). Subsequent exposure of the films to argon plasma resulted in the grafting of P4VP on the PTFE films. Electroless plating of copper could be carried out effectively on the P4VP-grafted PTFE (P4VP-g-PTFE) surface after PdCl₂ activation and in the absence of SnCl₂ sensitization (the Sn-free process). The catalytic processes of the electroless plating of copper in the presence and absence of sensitization by SnCl₂ were also compared. The effect of glow discharge conditions on the P4VP concentration and the adhesion strength of the electrolessly deposited copper was investigated. The T-peel adhesion strength of the electrolessly deposited copper with the graft-modified PTFE film was improved in the absence of SnCl₂ sensitization and could reach about 3 N/cm. PdCl₂ activation and electroless deposition of copper could not be carried out on the pristine or the Ar plasma-treated PTFE surface in the absence of prior sensitization by SnCl₂. X-ray photoelectron spectroscopic (XPS) analysis revealed that the electrolessly deposited copper delaminated from the P4VP-g-PTFE film by cohesive failure inside the PTFE film.     

Surface modification of polytetrafluoroethylene films via graft copolymerization for auto-adhesion

The surfaces of Ar plasma-pretreated polytetrafluoroethylene (PTFE) films are further functionalized via UV-induced graft copolymerization with amphoteric N,N′-dimethyl(methacryloylethyl)ammonium propansulfonate (DMAPS) either in Ar atmosphere, or under atmospheric conditions and in the absence of a polymerization initiator. The so-modified PTFE films from either process are capable of exhibiting adhesive-free adhesion or auto-adhesion with one another when brought into intimate contact in the presence of a small quantity of water. The lap shear adhesion strength increases with increasing graft concentration and can readily exceed the yield strength of the PTFE substrate. Two plasma-pretreated PTFE films also readily undergo thermal graft copolymerization with concurrent lamination when lapped together in the presence of a small quantity of the DMAPS monomer solution at elevated temperature in the atmosphere. The surface compositions of the graft-copolymerized PTFE films and the delaminated surfaces were characterized by X-ray photoelectron spectroscopy (XPS). In most cases, adhesional failure occurred near the graft-substrate interphase. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 3107–3114, 1998     

Surface modification of poly(tetrafluoroethylene) films by plasma polymerization of glycidyl methacrylate and its relevance to the electroless deposition of copper

Surface modification of poly(tetrafluoroethylene) films by plasma polymerization and deposition of glycidyl methacrylate (GMA) was carried out. The effects of glow‐discharge conditions on the chemical structure and composition of the deposited GMA polymer were analyzed by X‐ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy. XPS and FTIR results revealed that the epoxide groups in the plasma‐polymerized GMA (pp‐GMA) layer had been preserved to various extents, depending on the plasma deposition conditions. The morphology of the modified PTFE surface was investigated by atomic force microscopy (AFM). The pp‐GMA film with well‐preserved epoxide groups was used as an adhesion promotion layer to enhance the adhesion of the electrolessly deposited copper on the PTFE film. The T‐peel adhesion test results showed that the adhesion strength between the electrolessly deposited copper and the pp‐GMA‐modified PTFE (pp‐GMA‐PTFE) film was much higher than that between the electrolessly deposited copper and the pristine or the Ar plasma‐treated PTFE film. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3498–3509, 2000     

Reflective and conductive surface‐silvered polyimide films prepared by surface graft copolymerization and electroless plating

Argon plasma‐pretreated polyimide (PI) films were subjected to UV‐induced surface graft copolymerization with 4‐vinylpyridine(4VP) under atmospheric conditions. Electroless plating of silver was carried out effectively on the 4VP graft copolymerized PI (PI‐g‐P4VP) surface after PdCl₂ activation and in the absence of SnCl₂ sensitization (the Sn‐free process). The surface compositions of the modified PI films were studied by X‐ray photoelectron spectroscopy (XPS). XPS results showed that the PI‐g‐P4VP surface is ready for electroless deposition of silver via the Sn‐free process. The grafted 4VP layer with well‐preserved pyridine groups was used not only as the chemisorption sites for the palladium complexes (without the need for prior sensitization by SnCl₂) during the electroless plating of silver, but also as an adhesion promotion layer for the electrolessly deposited silver. The silver metallized PI films show high reflectivity and conductivity with a surface resistance of 1.5 Ω and a reflectivity of 91.3%, respectively. Copyright © 2007 John Wiley & Sons, Ltd.     

Electroless plating of copper on Si(100) surfaces modified by surface‐initiated atom‐transfer radical polymerization of 4‐vinylpyridine

Surface‐initiated atom‐transfer radical polymerization (ATRP) of 4‐vinylpyridine (4VP) on a pretreated Si(100) surface was carried out. The composition and topography of the Si(100) surface modified by poly(4‐vinylpyridine) (P4VP) were characterized by XPS and atomic force microscopy (AFM), respectively. The P4VP layer on the Si(100) surface was used not only as chemisorption sites for the palladium complexes without prior sensitization by SnCl₂ solution during the electroless plating, but also as an adhesion promotion layer for the electrolessly deposited copper. The electrolessly deposited copper on the Si–P4VP surface exhibited a 180° peel adhesion strength above 6 N/cm. The adhesion strength was much higher than that of the electrolessly deposited copper to the pristine silicon surface. Copyright © 2008 John Wiley & Sons, Ltd.     

Nanowear studies in chemically heterogeneous responsive polymeric brushes by surface force microscopy

In this study, we present nanowear studies using surface force microscopy (SFM), on nanoscopic thin films of reversibly switchable binary polymer brushes [polystyrene (PS) + poly(2-vinylpyridine) (P2VP)] and respective monobrushes [polystyrene and poly(2-vinylpyridine)] synthesized via “grafting to” method. The aim was to tune the wear in nanothin polymer brush surfaces. Therefore, the effect of conformational switching of PS + P2VP brush on treatment with selective solvents for PS and P2VP chains on the wear process was investigated. Wear process on thick spin-coated films of PS and P2VP was also investigated for comparison. Nanowear experiments were performed using SFM tip by repeating scans over the surface to follow the wear process closely. The wear process on different surfaces was explained on the basis of molecular entanglement as well as adhesion and friction on the sample surface. For spin-coated PS film as well as PS and PS + P2VP brush surfaces (treated with toluene) with molecular entanglements at surface, wear mechanism involved formation of ripples. However, in case of spin-coated P2VP films as well as P2VP and PS + P2VP brush surfaces (treated with ethanol) with no molecular entanglements at surface, wear occurred via removal of polymer chains and their accumulation at the rim. For PS + P2VP surface treated with acidic water, wear mechanism was complex and inhomogeneous ripple formation was followed by formation of heaps of polymeric material in the center of scanned area. The extent of wear as measured either by root mean square roughness of the surface or spacing between the ripples, increased with the number of scans for all the surfaces. Our study shows that wear mode of polymer brush surfaces is different for different polymers and can be controlled/tuned by the use of binary polymer brushes.     

Fluoride ions at the Cu–fluoropolymer interface

Nanometer thick films of sputtered and evaporated Cu were deposited on the surfaces of the fluoropolymers poly(tetrafluoroethylene) (PTFE), poly(tetrafluoroethylene‐co‐hexafluoropropylene) (FEP) and poly(tetrafluoroethylene‐co‐perfluoropropyl vinyl ether) (PFA) and studied by both angle‐resolved XPS at takeoff angles of 10°, 45° and 80° and in situ argon ion etching. Higher yields of the fluoride ion to fluoropolymer ratio were detected for sputtered than evaporated Cu. PFA and FEP show enhanced interaction with sputtered Cu to produce fluoride ions relative to the more polycrystalline PTFE. At intermediate depths (takeoff angle of 45°), PFA and FEP exhibit the strongest fluoride F 1s signals compared with the fluoropolymer peaks. The amount of fluoride ion detected reaches a maximum after brief Ar ion etching and then decreases with prolonged etching. Compared with untreated fluoropolymers, improved adhesion of evaporated Cu was observed on the fluoropolymer surfaces that were argon ion etched to expose fluoride ions. Copyright © 2013 John Wiley & Sons, Ltd.     

Thermal imidization of poly(pyromellitic dianhydride-4,4′-oxydianiline) precursors on fluoropolymers modified by surface graft-copolymerization with glycidyl methacrylate

Composite films of polyimide (PI) and poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP) or of PI and poly(tetrafluoroethylene) (PTFE) were prepared by thermal imidization of the poly(amic acid) (PAA) precursors of poly(pyromellitic dianhydride-4,4′-oxydianiline) (PMPA-ODA) on glycidyl methacrylate (GMA) graft-copolymerized FEP and PTFE films. The resulting PI/GMA-g-FEP and PI/GMA-g-PTFE composites exhibited T-peel adhesion strength of approximately 7.0 and 6.5 N/cm, respectively, compared to negligible adhesion strength for the laminates prepared from thermal imidization of the PAA on the pristine and the Ar plasma-treated FEP and PTFE films. X-ray photoelectron spectroscopy (XPS) results revealed that both the PI/GMA-g-FEP and PI/FEP-g-PTFE composite films delaminated by cohesive failure inside the FEP and PTFE films, respectively. The so-delaminated PI films with a covalently tethered FEP or PTFE surface layer were highly hydrophobic, having static water contact angles above 140°. The highly hydrophobic property depends on both the composition and roughness of the delaminated surface.     

Effects of polymer architecture and composition on the adhesion of poly(tetrafluoroethylene).

Poly(glycidyl methacrylate), PGMA, chains in linear and arborescent structures were incorporated onto surfaces of poly(tetrafluoroethylene), PTFE, films by hydrogen plasma and ozone treatment and atom transfer radical polymerization. The epoxide groups of the PGMA chains were further reacted with acetic acid (AAc), oxalic acid (XAc), allyl amine (AA), and ethylenediamine (EDN) to introduce hydroxyl and amine groups to the surfaces of the PTFE films. Surface characterizations performed by Fourier Transform infrared attenuated total reflectance (FTIR-ATR) spectroscopy and X-ray photoelectron spectroscopy (XPS) confirmed the surface modification and the chemical structure. The PGMA chains in arborescent structures show a high effectiveness for the enhancement of the adhesion of PTFE films. The adhesion of PTFE films was also significantly enhanced by ring-opening reactions of the PGMA epoxide groups with acetic acid and amine compounds. A high value of 9.5 N cm(-1) in the optimum 180 degrees peel strength test was observed with PTFE/copper assemblies.     

Functional and surface-active membranes from poly(vinylidene fluoride)-graft-poly(acrylic acid) prepared via RAFT-mediated graft copolymerization

Poly (vinylidene fluoride) (PVDF) with "living" poly (acrylic acid) (PAAc) side chains (PVDF-g-PAAc) was prepared by reversible addition-fragmentation chain transfer (RAFT)-mediated graft copolymerization of acrylic acid (AAc) with the ozone-pretreated PVDF. The chemical composition and structure of the copolymers were characterized by elemental analysis, Fourier transform infrared spectroscopy, and thermogravimetric analysis. The copolymer could be readily cast into pH-sensitive microfiltration (MF) membranes with enriched living PAAc graft chains on the surface (including the pore surfaces) by phase inversion in an aqueous medium. The surface composition of the membranes was determined by X-ray photoelectron spectroscopy. The morphology of the membranes was characterized by scanning electron microscopy. The pore size distribution of the membranes was found to be much more uniform than that of the corresponding membranes cast from PVDF-g-PAAc prepared by the "conventional" free-radical graft copolymerization process. Most important of all, the MF membranes with surface-tethered PAAc macro chain transfer agents, or the living membrane surfaces, could be further functionalized via surface-initiated block copolymerization with N-isopropylacrylamide (NIPAAM) to obtain the PVDF-g-PAAc-b-PNIPAAM MF membranes, which exhibited both pH- and temperature-dependent permeability to aqueous media.     

Adsorption thermodynamics of short-chain peptides on charged and uncharged nanothin polymer films

The present work describes experimental measurements of submolecular-level interaction energies involved in the process of peptide adsorption on polymer films using surface plasmon resonance spectroscopy. Gibbs energy change on adsorption (DeltaG(ad)) for tyrosine, phenylalanine, and glycine homopeptides were measured at 25 degrees C and pH 7 on highly uniform, nanothin polymer films, and the results were used to predict DeltaG(ad) for homologous homopeptides with a larger number of residue units. Nanothin poly(2-vinylpyridine), poly(styrene), and poly(1-benzyl-2-vinylpyridinium bromide) films were used for the adsorption studies; they were prepared using a graft polymerization methodology. In-situ swelling experiments were done with ellipsometry to examine the uniformity of the surfaces and to ensure that the graft densities of the different polymer films were similar to facilitate the comparison of adsorption results on these surfaces. The swelling experiments showed that the films were uniform, and the grafting densities were found to be 0.14-0.17 chains/nm(2). For uncharged surfaces, predicted and measured DeltaG(ads) values for homopeptides deviated by < or =4.9%. To extend this approach to a mixed-residue peptide, measurements were made for glycine, phenylalanine, and tyrosine-leucine subunits found in leucine enkephalin. The predicted DeltaG(ads) values for leucine enkephalin deviated by 3.0% and -9.1% for poly(2-vinylpyridine) and poly(styrene) films, respectively. Deviations between measured and predicted adsorption energies were larger for the charged poly(1-benzyl-2-vinylpyridinium bromide) surface relative to uncharged surfaces. While the adsorption energies were found to be additive within experimental uncertainties for the charged surface, generally speaking, measured uncertainty values were also larger for the charged surface.     

Reactive adsorption of aminosilane onto the glycidyl methacrylate graft‐copolymerized poly(tetrafluoroethylene) film surface for adhesion enhancement with evaporated copper

Surface modification of argon‐plasma‐pretreated poly(tetrafluoroethylene) (PTFE) film via UV‐induced graft copolymerization with glycidyl methacrylate (GMA) was carried out first. Reactive adsorption of γ‐aminopropyltriethoxysilane (APS) onto the GMA graft‐copolymerized PTFE (GMA‐g‐PTFE) film surface was performed by the simple immersion of the film in the APS solution. The adsorption process was studied as a function of the APS concentration, the immersion time of the graft‐modified PTFE film in the APS solution, and the washing protocol. The chemical composition and morphology of the silane‐modified surfaces were characterized by X‐ray photoelectron spectroscopy and atomic force microscopy, respectively. The performance of the silane‐modified PTFE surface in adhesion promotion was investigated. The T‐peel adhesion strength of the evaporated Cu on the PTFE film with the reactively adsorbed organosilane increased significantly to about 12.5 N/cm. This adhesion strength was more than twice that of the assembly involving evaporated Cu on the GMA‐g‐PTFE film and about 10 times that of the assembly involving evaporated Cu on the Ar‐plasma‐treated PTFE film. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 80–89, 2000     

Conductive thin film formation onto radiation grafted polymeric surfaces using electroless plating technique

Surface modification of polypropylene films (PP) was carried out via radiation induced graft copolymerization of 4‐vinyl pyridine (4VP) and acrylamide (AAm) to enhance the adhesion ability of the PP surface for electroless deposition of copper. Factors affecting the grafting process such as suitable solvent, comonomer composition and concentration and irradiation dose were optimized. The grafted films produced were characterized by studying their Fourier‐transform infrared (FTIR) spectra and thermal stability. The grafted films were copper‐plated by electroless deposition using Pd as the catalyst to initiate the redox reaction. The influence of catalytic activation method parameters on the plating rate were studied. Scanning electron microscopy revealed a dense and void‐free copper deposited film. The adhesion of the deposited copper film to the modified PP films was determined by measuring the tensile strength of the copper plated films. The electrical characteristics of the copper plated films in comparison with grafted films were studied. The results showed the high adhesion of the deposited copper film to the grafted PP film as well as the high electrical conductivity. Copyright © 2008 John Wiley & Sons, Ltd.     

Atom transfer radical polymerization directly from poly(vinylidene fluoride): Surface and antifouling properties

The direct preparation of grafting polymer brushes from commercial poly (vinylidene fluoride) (PVDF) films with surface‐initiated atom transfer radical polymerization (ATRP) is demonstrated. The direct initiation of the secondary fluorinated site of PVDF facilitated grafting of the hydrophilic monomers from the PVDF surface. Homopolymer brushes of 2‐(N,N‐dimethylamino)ethyl methacrylate (DMAEMA) and poly (ethylene glycol) monomethacrylate (PEGMA) were prepared by ATRP from the PVDF surface. The chemical composition and surface topography of the graft‐functionalized PVDF surfaces were characterized by X‐ray photoelectron spectroscopy, attenuated total reflectance/Fourier transform infrared spectroscopy, and atomic force microscopy. A kinetic study revealed a linear increase in the graft concentration of poly[2‐(N,N‐dimethylamino)ethyl methacrylate] (PDMAEMA) and poly[poly(ethylene glycol) monomethacrylate] (PPEGMA) with the reaction time, indicating that the chain growth from the surface was consistent with a controlled or living process. The living chain ends were used as macroinitiators for the synthesis of diblock copolymer brushes. The water contact angles on PVDF films were reduced by the surface grafting of DMAEMA and PEGMA. Protein adsorption experiments revealed a substantial antifouling property of PPEGMA‐grafted PVDF films and PDMAEMA‐grafted PVDF films in comparison with the pristine PVDF surface. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3434–3443, 2006     

Controlled grafting from poly(vinylidene fluoride) films by surface‐initiated reversible addition–fragmentation chain transfer polymerization

A reversible addition–fragmentation chain transfer (RAFT) polymerization technique was applied to graft polymerize brushes of poly(methyl methacrylate) (PMMA) and poly(poly(ethylene glycol) monomethacrylate) (PPEGMA) from poly(vinylidene fluoride) (PVDF) surfaces. PVDF surfaces were exposed to aqueous LiOH, followed by successive reductions with NaBH₄ and DIBAL‐H to obtain hydroxyl functionality. Azo‐functionalities, as surface initiators for grafting, were immobilized on the PVDF surfaces by esterification of 4,4′‐azobis(4‐cyanopentanoic acid) and the surface hydroxyl groups. The chemical composition and surface topography of the graft‐functionalized PVDF surfaces were characterized by X‐ray photoelectron spectroscopy, attenuated total reflectance‐FTIR spectroscopy, and atomic force microscopy. Kinetics studies revealed a linear increase in the graft concentration of PMMA and PPEGMA with the reaction time, indicating that the chain growth from the surface was consistent with a “controlled” or “living” process. The living chain ends were used as the macroinitiator for the synthesis of diblock copolymer brushes. Water contact angles on PVDF films were reduced by surface grafting of PEGMA and MMA. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3071–3082, 2006     

Surface‐initiated atom transfer radical polymerization from porous poly(tetrafluoroethylene) membranes using the C?F groups as initiators

This work reports the surface‐initiated atom transfer radical polymerization (ATRP) from hydrogen plasma‐treated porous poly(tetrafluoroethylene) (PTFE) membranes using the C? F groups as initiators. Hydrogen plasma treatment on PTFE membrane surfaces changes their chemical environment through defluorination and hydrogenation reactions. With the hydrogen plasma treatment, the C? F groups of the modified PTFE membrane surface become effective initiators of ATRP. Surface‐initiated ATRP of poly(ethylene glycol) methacrylate (PEGMA) is carried out to graft PPEGMA chains to PTFE membrane surfaces. The chain lengths of poly(PEGMA) (PPEGMA) grafted on PTFE surfaces increase with increasing the reaction time of ATRP. Furthermore, the chain ends of PPEGMA grown on PTFE membrane surfaces then serve as macroinitiators for the ATRP of N‐isopropylacrylamide (NIPAAm) to build up the PPEGMA‐b‐PNIPAAm block copolymer chains on the PTFE membrane surfaces. The chemical structures of the modified PTFE membranes are characterized using X‐ray photoelectron spectroscopy. The modification increases the surface hydrophilicity of the PTFE membranes with reductions in their water‐contact angles from 120° to 60°. The modified PTFE membranes also show temperature‐responsive properties and protein repulsion features owing to the presence of PNIPAAM and PPEGMA chains. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2076–2083, 2010     

Annealing-free adhesive electroless deposition of a nickel/phosphorous layer on a silane-compound-modified Si wafer

In this study, a post-annealing-free, adhesive nickel/phosphorous (Ni/P) layer was deposited on a 3-[2-(2-aminoethylamino)ethylamino] propyl-trimethoxysilane-modified (ETAS-modified) silicon (Si) surface through an electroless deposition process catalyzed by a novel polyvinylpyrrolidone-capped palladium nanocluster (PVP-nPd). ETAS was covalently bonded on the Si surface, whereas the amino groups on ETAS bridged with the palladium core in the PVP-nPd clusters. Because of the mentioned two effects, the deposited Ni/P layer showed superior adhesion on the Si wafer without the requirement of conventional annealing treatment. Compared with the Ni/P films deposited on bare and ETAS-modified Si surfaces by using commercial Sn/Pd colloids, the adhesion of the Ni/P film catalyzed by PVP-nPd on the ETAS-modified Si wafer improved 4- and 2-fold, respectively.     

Surface characteristics of a self-polymerized dopamine coating deposited on hydrophobic polymer films

This study aims to explore the fundamental surface characteristics of polydopamine (pDA)-coated hydrophobic polymer films. A poly(vinylidene fluoride) (PVDF) film was surface modified by dip coating in an aqueous solution of dopamine on the basis of its self-polymerization and strong adhesion feature. The self-polymerization and deposition rates of dopamine on film surfaces increased with increasing temperature as evaluated by both spectroscopic ellipsometry and scanning electronic microscopy (SEM). Changes in the surface morphologies of pDA-coated films as well as the size and shape of pDA particles in the solution were also investigated by SEM, atomic force microscopy (AFM), and transmission electron microscopy (TEM). The surface roughness and surface free energy of pDA-modified films were mainly affected by the reaction temperature and showed only a slight dependence on the reaction time and concentration of the dopamine solution. Additionally, three other typical hydrophobic polymer films of polytetrafluoroethylene (PTFE), poly(ethylene terephthalate) (PET), and polyimide (PI) were also modified by the same procedure. The lyophilicity (liquid affinity) and surface free energy of these polymer films were enhanced significantly after being coated with pDA, as were those of PVDF films. It is indicated that the deposition behavior of pDA is not strongly dependent on the nature of the substrates. This information provides us with not only a better understanding of biologically inspired surface chemistry for pDA coatings but also effective strategies for exploiting the properties of dopamine to create novel functional polymer materials.     

Block copolymer micelles as switchable templates for nanofabrication

Block copolymer inverse micelles from polystyrene-block-poly-2-vinylpyridine (PS-b-P2VP) deposited as monolayer films onto surfaces show responsive behavior and are reversibly switchable between two states of different topography and surface chemistry. The as-coated films are in the form of arrays of nanoscale bumps, which can be transformed into arrays of nanoscale holes by switching through exposure to methanol. The use of these micellar films to act as switchable etch masks for the structuring of the underlying material to form either pillars or holes depending on the switching state is demonstrated.