Photocrosslinking of thin polymer films – materials for sensors and actuators

Polymers with temperature dependent degrees of swelling, especially polymers which exhibit lower critical solution temperature (LCST) behaviour in aqueous solutions, are of interest for applications in microsystems. For these applications it is necessary to form and pattern thin films in the μm-range. This has been achieved through photocrosslinking of linear prepolymers. Copolymers based on N-isopropylacrylamide (NIPAAm) were modified with a stilbazolium salt chromophore to yield photocrosslinkable temperature sensitive polymers. The chromophore reacts via a [2+2]-cycloaddition under irradiation, this can be used to crosslink the polymer. The photocrosslinking properties were studied by UV irradiation of thin films and measuring the changes in UV absorption spectra. Through irradiation of thin films through a mask it was possible to obtain patterned networks in the μm-range (20 μm space width and > 50 μm line width). The polymers exhibited LCST behaviour, which was measured using DSC. The resulting patterned networks had temperature dependent swelling properties in aqueous media.     

Thermorheological and glass transition properties of PNIPA/PVP and PNIPA/Carbopol blends

The miscibility of poly(N-isopropylacrylamide) (PNIPA) with poly(vinyl pyrrolidone) (PVP) and a cross-linked poly(acrylic acid) (Carbopol^® 971P) was evaluated from the rheological data of aqueous dispersions and the temperature of glass transitions of films made of binary mixtures. PNIPA has a low critical solubility temperature (LCST) of about 33°C, below which 1% dispersion behaves as a viscous system. At temperatures above LCST, the hydrophobic interactions among the isopropyl groups initially provide transient networks of greater elasticity. The LCST of PNIPA as well as its T _g (144°C, estimated by DSC and MTDSC of films) were not modified by the presence of PVP. The immiscibility of PNIPA and PVP was confirmed by the absence of interaction between both polymers as shown by FTIR analysis of the films. In contrast, PNIPA and carbopol were miscible and the behaviour of their mixtures differed significantly from that of the parent polymers; i.e. a strong synergistic effect on the viscoelasticity of the dispersions was observed below the LCST. As temperature increased, the blends showed a decrease in the loss and storage moduli, especially those with greater PNIPA proportions. The fall was smoother as the PNIPA proportion decreased. This behaviour may be explained as the result of the balance between PNIPA/carbopol hydrogen bonding interactions (as shown in the shift of C=O stretch in FTIR spectra) and PNIPA/PNIPA hydrophobic interactions. The T _g values of the films of the blends showed a positive deviation from the additivity rule; the mixtures containing more than 1:1 amide:carboxylic acid groups have a notably high Tg (up to 181°C). This increase is related to the stiffness induced in the films by the PNIPA/carbopol interactions.     

Brillouin scattering studies of polymeric nanostructures *

For a range of applications, polymers are now being patterned into nanometer‐sized features. In these applications, the robust mechanical properties of the nanostructures are critical for performance and stability. Brillouin light scattering is presented as a nondestructive, noncontact tool used to quantify the elastic constants in such nanostructures. We demonstrate this through a series of thin films and parallel ridges and spacings (gratings) with ridge widths ranging from 180 to 80 nm. For the set of films and structures presented here, the room‐temperature elastic moduli did not change with decreasing film thickness or grating ridge width, and this implied that one‐dimensional and two‐dimensional confinement‐induced changes of the mechanical properties were not significant down to feature sizes of 80 nm. Additionally, Brillouin spectra of submicrometer gratings revealed new modes not present in the spectra of thin films. The origin of these new modes remains unclear. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1106–1113, 2004     

Photomobile Polymer Materials: Photoresponsive Behavior of Cross‐Linked Liquid‐Crystalline Polymers with Mesomorphic Diarylethenes

Cross‐linked liquid‐crystalline (LC) polymers with a mesomorphic diarylethene were prepared to demonstrate a versatile strategy for cross‐linked photochromic LC polymers as photomobile materials. Upon exposure to UV light to cause photocyclization of the diarylethene chromophore, the cross‐linked polymer films bend toward an actinic light source. By irradiation with visible light to cause a closed‐ring to open‐ring isomerization, the bent films revert to the initial flat state. Without visible‐light irradiation, the bent films remain bent even at 120 °C, indicating high thermal stability of the cross‐linked diarylethene LC polymers.     

Preparation of side‐on bisazobenzene‐containing homopolymers and block copolymers via ATRP and studies on their photoisomerization and photoalignment behaviors

The preparation of a series of novel homopolymers and copolymers containing bisazobenzene chromophores with side‐on structure in the side chains via atom transfer radical polymerization (ATRP) were presented. UV–vis spectra of the thin films of these polymers under irradiation of 488 nm Ar⁺ laser suggested that the photoisomerization of the bisazobenzene chromophores happened mainly on one of the two azo groups in the bisazobenzene chromophores with similar probability due to their side‐on structure. Good photoalignment behaviors of these polymers were proved by photoinduced birefringence measurements because side‐on structure permitted the two azo groups in the bisazobenzene chromophores both participated in the trans–cis–trans photoisomerization cycles equally to induce the whole chromophore reorientation. Furthermore, the reorientation axis located at the middle of chromophore decreased the sweep volume during photoalignment. The impetus for this study was to evaluate the photoisomerization and photoalignment process of side‐on bisazobenzene‐containing polymers and to find possible applications in the photosensitive devices. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3460–3472, 2007     

Photochemical modification of the lower critical solution temperature of cinnamoylated poly(N‐2‐hydroxypropylmethacrylamide) in water

Partial modification of the nonionic polymer poly(N‐2‐hydroxy‐propylmethacrylamide) by cinnamate produces stimuli‐responsive copolymers. The hydrophobic character of the cinnamate chromophore induces not only a lower critical solution temperature (LCST) in water, but renders additionally the polymers photoresponsive. For moderate cinnamate contents of 9 mol‐%, the photoisomerization of the trans‐cinnamate to cis‐cinnamate groups allows to switch the LCST by irradiation, whereas for higher cinnamate contents of 21 mol‐%, irradiation leads to intra‐ and intermolecular photocrosslinking.     

Fluorescence “Turn‐On” Patterning With Polymers Having Pendant Triphenylmethane Groups as Fluorophore Precursors

A new methodology for creating patterned fluorescence images was developed based on acrylate polymers that have pendant triphenylmethane derivatives as precursor fluorophores. Photoinduced oxidation of the substituted nonfluorescent triphenylmethane substituents on the polymers results in the generation of fluorescent cationic species. Patterned fluorescence images were obtained when the polymer film was subjected to photomasked UV‐irradiation. The rate of formation and quality of the patterned images were found to be dependent on the nature of substituents on the methane carbon of the triphenylmethane group. Inefficient image formation takes place with the polymer derived from the H‐substituted derivative owing to the inefficient oxidation of the triphenylmethane group. In contrast, photomasked UV‐irradiation of a thin polymer film derived from the CN‐substituted triphenylmethane derivative leads to fast (1 s irradiation, 12 mW · cm⁻²) and finely resolved patterned fluorescence images.

     

Synthesis of autophotosensitive hyperbranched polyimides based on 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride and 1,3,5‐tris(4‐aminophenoxy)benzene via end capping of the terminal anhydride groups by ortho‐alkyl aniline

Benzophenone‐containing, anhydride‐terminated hyperbranched poly(amic acid)s were end‐capped by ortho‐alkyl aniline in situ and then chemically imidized, yielding autophotosensitive hyperbranched polyimides. The polyimides were soluble in strong polar solvents, such as N‐methyl‐2‐pyrrolidone, N‐dimethylformamide, dimethylacetamide, and dimethyl sulfoxide. Thermogravimetric analysis revealed their excellent thermal stability, with a 5 wt % thermal loss temperature in the range of 527–548 °C and a10 wt % thermal loss temperature in the range of 562–583 °C. The strong absorption of the polyimide films in ultraviolet–visible spectra at 365 nm indicated that the hyperbranched polyimides were patternable. Highly resolved images with a line width of 6 μm were developed by ultraviolet exposure of the polymer films. A well‐defined image with lines as thin as 3 μm was also patterned, but the lines were rounded at the edges. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2026–2035, 2003     

Temperature/Light Dual‐Responsive Inclusion Complexes of α‐Cyclodextrins and Azobenzene‐Containing Polymers

Three kinds of photoresponsive copolymers with azobenzene side chains were synthesized by radical polymerization of N‐4‐phenylazophenylacrylamide (PAPA) with N‐isopropylacrylamide (NIPAM), N,N‐diethylacrylamide (DEAM) or N,N‐dimethylacrylamide (DMAM) respectively. Their structures were characterized by FT‐IR, ¹H‐NMR and UV/Vis spectroscopy. Their reversible photoresponses were studied with or without α‐cyclodextrin (α‐CD), which showed that both the copolymers and their inclusion complexes with α‐CD underwent rapid photoisomerization. The lower critical solution temperature (LCST) of the copolymers and their inclusion complexes with α‐CD were investigated by cloud point measurement, which showed that the LCST of three kinds of copolymers increased largely after adding α‐CD. After UV irradiation on the solutions of copolymers and their inclusion complexes, the LCST of the copolymers increased slightly with the absence of α‐CD, while decreased largely with the presence of α‐CD. Furthermore, the LCST reverted to its originality after visible light irradiation. This change of LCST could be reversibly controlled by UV and visible light irradiation alternately. In particular, in the copolymer of PAPA and DMAM, the reversible water solubility of the inclusion complexes could be triggered by alternating UV and visible light irradiation.     

Water‐soluble triply‐responsive homopolymers of N,N‐dimethylaminoethyl methacrylate with a terminal azobenzene moiety

Novel water‐soluble triply‐responsive homopolymers of N,N‐dimethylaminoethyl methacrylate (DMAEMA) containing an azobenzene moiety as the terminal group were synthesized by atom transfer radical polymerization (ATRP) technique. The ATRP process of DMAEMA was initiated by an azobenzene derivative substituted with a 2‐bromoisobutyryl group (Azo‐Br) in the presence of CuCl/Me₆TREN in 1,4‐dioxane as a catalyst system. The molecular weights and their polydispersities of the resulting homopolymers (Azo‐PDMAEMA) were characterized by gel permeation chromatography (GPC). The homopolymers are soluble in aqueous solution and exhibit a lower critical solution temperature (LCST) that alternated reversibly in response to Ph and photoisomerization of the terminal azobenzene moiety. It was found that the LCST increased as pH decreased in the range of testing. Under UV light irradiation, the trans‐to‐cis photoisomerization of the azobenzene moiety resulted in a higher LCST, whereas it recovered under visible light irradiation. This kind of polymers should be particularly interesting for a variety of potential applications in some promising areas, such as drug controlled‐releasing carriers and intelligent materials because of the multistimuli responsive property. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2564–2570, 2010     

The collapse transition of poly(styrene-b-(N-isopropyl acrylamide)) diblock copolymers in aqueous solution and in thin films

The thermal behavior of a poly(styrene-b-N-isopropyl acrylamide) diblock copolymer was studied in aqueous solution as well as in thick and in thin films. The polymer was synthesized using reversible addition–fragmentation chain transfer. The critical micelle concentration in aqueous solution was determined using fluorescence correlation spectroscopy. The lower critical solution temperature (LCST) of micellar solutions was detected using microcalorimetry and turbidimetry at 31 °C. Using dynamic light scattering, the collapse of the micelles at the LCST as well as their clustering above was observed. These findings were corroborated with small-angle X-ray scattering. In thick films immersed in water, similar findings were made. In a thin film, however, the LCST is depressed and is found at 26–27 °C.     

Corrosion and tribocorrosion behaviour of super‐thick diamond‐like carbon films deposited on stainless steel in NaCl solution

Super‐thick diamond‐like carbon (DLC) film is a potential protective coating in corrosive environments. In the present work, three kinds of DLC films whose thickness and modulation periods are 4 µm and 3, 21 µm and 17 and 21 µm and 7, respectively, were fabricated on stainless steel. The effect of different thickness and modulation periods on corrosion and tribocorrosion behaviour of the DLC‐coating stainless steel was investigated in 3.5 wt% NaCl aqueous solution by a ball‐on‐flat tribometer equipped with a three‐electrode electrochemical cell. The DLC‐coating stainless steel served as a working electrode, and its OCP and potentiodynamic polarization were monitored before and during rubbing. The wear–corrosion mechanism of the DLC films was investigated by SEM. The results showed that the increasing thickness can prolong significantly lifetime of DLC films in NaCl aqueous solution. In particular, the modulation period has a significant impact on the tribocorrosion resistance of the DLC super‐thick films. The study suggested that the increasing thickness of compressive stress layer could suppress film damage by reducing crack propagation rate. Thus, the super‐thick DLC film with thickness of 21 µm and 7 periods presented the best tribocorrosion resistance among all studied films. Copyright © 2016 John Wiley & Sons, Ltd.     

Synthesis and chiroptical properties of optically active polymer liquid crystals containing azobenzene chromophores

A series of optically active methacrylic homopolymers, poly[(4‐{4′‐[(S)‐2‐methyl‐1‐butyloxycarbonyl]phenylazo}phenoxyl)x‐methylene methacrylate] (x = 0, 2, 6, or 11), were synthesized. The structures of the polymers were characterized by IR, ¹H NMR, UV, differential scanning calorimetry, and gel permeation chromatography. The chiroptical properties of the polymers in films were investigated with circular dichroism (CD) measurements. The CD and UV spectra of the films suggested that CD absorptions occurred in the films of the polymers with long spacers (x = 6 or 11) but not in the films of the polymers with short spacers (x = 0 or 2). After irradiation with linearly polarized light at 442 nm, the CD values were amplified in all the polymeric films. The amplificatory values of the CD bands in the absorption region (260–360 nm) of azobenzene chromophores suggested that the spacer length had an effect on both the transfer of chirality and photoinduced chirality in the polymeric films. The largest level of photoinduced chirality was induced in the polymer containing six methylene units. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3210–3219, 2006     

Polymers derived from N‐isopropylacrylamide and azobenzene‐containing acrylamides: Photoresponsive affinity to water

N‐Isopropylacryamide was copolymerized by free‐radical polymerization with N‐[2‐(4‐phenylazophenoxy)ethyl]acrylamide derivatives that were substituted at their 4′‐position with ethoxy, methoxyethoxy, or isopropyl units, or with N‐{2‐[4‐(pyridin‐2‐ylazo)phenoxy]ethyl}acrylamide. The polymers were soluble in cold water and possessed lower critical solution temperatures (LCSTs). The value of the LCST rose a few degrees after UV irradiation and dropped after irradiation with visible light, reversibly, in processes that corresponded to the isomerization of the azobenzene units. The polymers became increasingly hydrophobic after increasing their azobenzene content. The difference of hydrophobicity correlates with the absorption band height at about 400 nm. The structure of the substituent on the azobenzene unit affected both the transition temperature and the hydrophobicity. A change in photoinduced wettability for water was observed to occur on a prepared film at a temperature different from the LCST determined in water. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5200–5214, 2004     

Click synthesis and reversible electrochromic behaviors of novel polystyrenes bearing aromatic amine units

Novel electrochromic polymers were prepared by the click postfunctionalization of poly(4‐azidomethylstyrene) with alkyne‐containing aromatic amine units in the presence of Cu(I) catalysts. Two kinds of aromatic amine units, tris(4‐alkoxyphenyl)amine and N,N,N′,N′‐tetraphenyl‐p‐phenylenediamine, were introduced into polystyrene side chains, which were completely characterized by gel permeation chromatography–multiangle light scattering, nuclear magnetic resonance, and infrared spectroscopies, and elemental analysis. Thermal analyses demonstrated the high stability with the decomposition temperatures exceeding 300 °C even after postfunctionalization. The UV–vis absorption spectra of the polymer thin films revealed negligible absorption in the visible region, as reasonably confirmed by visual observation. The polymer thin films were prepared by spray‐coating on an indium tin oxide‐coated glass plate. Cyclic voltammograms of these films exhibited anodic peaks ascribed to the oxidation of the side‐chain aromatic amine moieties. The tris(4‐alkoxyphenyl)amine unit displayed one‐step oxidation at 0.287 V (vs. Ag/AgCl), while the N,N,N′,N′‐tetraphenyl‐p‐phenylenediamine unit showed two‐step oxidations at 0.297 and 0.641 V. These oxidation processes produced new colors of the polymer films. The former triarylamine‐based chromophore provided a blue color after the oxidation, while the latter phenylenediamine‐based chromophore showed a potentially controlled green and dark blue colors. The reversibility and switching behaviors of these color changes were also comprehensively investigated. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Novel Photobleachable Deep UV Resists Based on Single Component Nonchemically Amplified Resist System

Summary: Photobleachable deep UV resists were designed by introducing diazoketo groups in polymer side chains. The diazoketo groups undergo the Wolff rearrangement upon irradiation in the deep UV, affording ketenes that react with water to provide base‐soluble photoproducts. The polymers were synthesized by radical copolymerization of 2‐(2‐diazo‐3‐oxo‐butyryloxy)‐ethyl methacrylate, 2‐hydroxyethyl methacrylate, and γ‐butyrolacton‐2‐yl methacrylate. The single component resist showed 0.7 µm line and space patterns using a mercury‐xenon lamp in a contact printing mode.

Scanning electron micrograph of 0.7 µm line and space patterns printed with polymer B at a dose of 70 mJ · cm⁻².     

Temperature‐responsive “tadpole‐shaped” protein–polymer hybrids and their self‐assembly behavior

The temperature‐responsive poly (N, N‐diethylacrylamide) (pDEAAm) with narrower molecular weight distribution was prepared by the atom transfer radical polymerization and characterized by ¹HNMR and gel permeation chromatography. The temperature‐responsive “tadpole‐shaped” BSA–pDEAAm hybrids were fabricated via a free Cys‐34 residue of bovine serum albumin (BSA) site specifically binding to the end group disulfide bonds of pDEAAm and characterized by native‐polyacrylamide gel electrophoresis (Native‐PAGE) and matrix‐assisted laser desorption/ionization time of flight mass spectrometry. Their temperature‐responsive behaviors were measured by ultraviolet‐visible spectra (UV‐Vis). The lower critical solution temperature (LCST) of the pDEAAm was identified as 28°C, and the LCST of BSA–pDEAAm hybrids was identified as 31°C. The morphologies of BSA–pDEAAm hybrids self‐assembled in the aqueous solutions with two different temperatures at 25 °C and 40°C were investigated by transmission electron microscopy. Below the LCST of BSA–pDEAAm hybrids, the separate spherical nanoparticles were observed. In contrast, bundles and clusters were observed above the LCST of BSA–pDEAAm hybrids. The results suggested that the self‐assembly morphology of BSA–pDEAAm hybrids depended upon the pDEAAm block in BSA–pDEAAm hybrids, and the morphology transitions were effected by the LCST of BSA–pDEAAm hybrids. It would be expected to be used in biomedicine and materials science. Copyright © 2016 John Wiley & Sons, Ltd.     

Synthesis and characterization of novel degradable photocrosslinked poly(ether‐anhydride) networks

New degradable poly(ether‐anhydride) networks were synthesized by UV photopolymerization. Dicarboxylated poly(ethylene glycol) (PEG) or poly(tetramethylene glycol) (PTMG) was reacted with an excess of methacrylic anhydride to form dimethacrylated macromers containing anhydride linkages. The percent of conversion for the macromer formation was more than 80% at 60 °C after 24 h. ¹H NMR and IR spectroscopies show the presence of anhydride linkages in the macromer. In vitro degradation studies were carried out at 37 °C in PBS with crosslinked polymer networks formed by UV irradiation. All PEG‐based polymers degraded within 2 days, while PTMG‐based polymers degraded by 50% of the initial weight after 14 days. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1277–1282, 2000     

Lowering the dielectric constant of polyimide thin films by swelling with supercritical carbon dioxide

The swelling with supercritical carbon dioxide (sc‐CO₂) of thin films of polyimides having various structures was investigated. It was shown that the degree of swelling is significantly influenced by the solvent which was used for the synthesis of those polyimides, by the solvent which was used for the preparation of thin films and by the conformational rigidity of the polymers. The presence of hexafluoroisopropylidene groups in the main chain of a polymer prevents its swelling with sc‐CO₂. The best results were obtained for polyimide film ULTEM, based on m‐phenylene‐diamine and isopropylidene‐diphenoxy‐bis(phthalic anhydride), synthesized in benzoic acid, whose free volume increased twice and its dielectric constant decreased from 3.15 to 2.45 by swelling with sc‐CO₂. Copyright © 2013 John Wiley & Sons, Ltd.     

Fine Patterning of Transparent, Conductive SnO2 Thin Films by UV-Irradiation

Finely patterned transparent, conductive SnO₂ thin films have been prepared. UV-light from a high-pressure mercury lamp was irradiated through a mask on the precursor films prepared from SnCl₂ with acetyl acetone in the ambient atmosphere, and this irradiation led to the change of solubility of the films in alkaline solution. Patterns with a width of about 3 to 50 m and thickness of about 0.1 m were formed with a pitch of about 2 to 20 m. The resistivity of the films heat-treated at 500°C after UV irradiation was about 1 × 10^–2 cm, which was almost the same resisitivity for the films heat-treated at 500°C without UV irradiation.