Facile measurement of polymer film thickness ranging from nanometer to micrometer scale using atomic force microscopy

As many properties of polymer thin films critically depend on their thickness, a convenient and cost‐effective method for precise measurement of film thickness in a wide range is highly desirable. Here, we present a method which enables polymer film thickness, ranging from nanometer to micrometer scale, to be facilely determined by measuring the height of an artificially created film step on smooth substrates with atomic force microscopy (AFM). Three polymeric films (polystyrene, poly(methyl methacrylate) and poly(styrene–ethylene/butylene–styrene) films), spin‐coated on either mica or quartz substrate with thickness ranging from 5.7 nm to 4.4 µm, were employed to demonstrate the procedure and feasibility of our method. The proposed method is particularly suitable for thicker polymer films, thus complementing the traditional AFM ‘tip‐scratch’ method which is generally limited to polymer films of no more than 100 nm thickness. Copyright © 2010 John Wiley & Sons, Ltd.     

Polyelectrolytes bearing azobenzenes for the functionalization of multilayers

Thin polymeric films are assembled by the alternating adsorption of oppositely charged polyelectrolytes. The polyions are functionalized by azobenzenes, typically carrying donor-acceptor substituents. The azobenzene chromophores are exploited as versatile analytical tools, to study the assembling process, and to control the film quality. A high concentration of ionic groups does not seem to be advantageous per se for good film growth, but rather the matching of the charge densities of the polyelectrolyte pair used seems to be important. Also, the influence of the strongly interacting, form-anisotropic character of the azobenzenes on the internal film structure was investigated. Although even high concentrations of azobenzenes and of other mesogens do not induce particular ordering, a few polymer pairs allowed the construction of real multilayer films, exhibiting e.g. Bragg peaks.     

Integrated surface modification of fully polymeric microfluidic devices using living radical photopolymerization chemistry

Surface modification using living radical polymerization (LRP) chemistry is a powerful technique for surface modification of polymeric substrates. This research demonstrates the ability to use LRP as a polymer substrate surface‐modification platform for covalently grafting polymer chains in a spatially and temporally controlled fashion. Specifically, dithiocarbamate functionalities are introduced onto polymer surfaces using tetraethylthiuram disulfide. This technique enables integration of LRP‐based grafting for the development of an integrated, covalent surface‐modification method for microfluidic device construction. The unique photolithographic method enables construction of devices that are not substrate‐limited. To demonstrate the utility of this approach, both controlled fluid flow and cell patterning applications were demonstrated upon modification with various chemical functionalities. Specifically, poly(ethylene glycol) (375) monoacrylate and trifluoroethyl acrylate were grafted to control fluidic flow on a microfluidic device. Before patterning, surface‐functionalized samples were characterized with both goniometric and infrared spectroscopy to ensure that photografting was occurring through pendant dithiocarbamate functionalities. Near‐infrared results demonstrated conversion of grafted monomers when dithiocarbamate‐functionalized surfaces were used, as compared to dormant control surfaces. Furthermore, attenuated total reflectance/infrared spectroscopy results verified the presence of dithiocarbamate functionalities on the substrate surfaces, which were useful in grafting chains of various functionalities whose contact angles ranged from 7 to 86°. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1404–1413, 2006     

Biocompatible "click" wafer bonding for microfluidic devices

We introduce a novel dry wafer bonding concept designed for permanent attachment of micromolded polymer structures to surface functionalized silicon substrates. The method, designed for simultaneous fabrication of many lab-on-chip devices, utilizes a chemically reactive polymer microfluidic structure, which rapidly bonds to a functionalized substrate via"click" chemistry reactions. The microfluidic structure consists of an off-stoichiometry thiol-ene (OSTE) polymer with a very high density of surface bound thiol groups and the substrate is a silicon wafer that has been functionalized with common bio-linker molecules. We demonstrate here void free, and low temperature (< 37 °C) bonding of a batch of OSTE microfluidic layers to a silane functionalized silicon wafer.     

Introducing NH2 onto polymeric films via photo-induced C—H bond transformation with phenol derivatives as building blocks

A one-step process to introduce both the aromatic and aliphatic primary amino groups with high chemoselectivity was developed.Triplet state acetone abstracts the hydrogen atoms from both the C-H bond of the polymeric film substrate and the O-H bond of phenol which is the building block and the amino group carrier.As a result,two kinds of free radicals, confined carbon-centered chain radicals of the polymer substrate and mobile oxygen-centered phenoxy radicals,were generated.Then the C-O bonds were formed by the coupling reaction between these two kinds of free radicals.p-Tyramine and p-aminophenol were used as amino carriers.The successful introduction of amino groups onto LDPE,BOPP and PET film substrates was demonstrated by measurements of water contract angle（CA）,ultraviolet spectra（UV）,X-ray photoelectron spectroscopy（XPS） and fluorescent microscopy.The processing factors,such as the UV-light intensity and irradiation time,concentrations of p-tyramine and p-aminophenol,and the ratio of acetone/water were investigated.The optimized process parameters are as follows:UV light intensity 9500μW/cm²;irradiation time 18 min for BOPP and LDPE, 22 min for PET;the ratio of acetone/water = 1;and concentration of p-tyramine and p-aminophenol 15%for BOPP and LDPE,1%for PET.Based on the UV absorbance,the amino groups on the polymeric substrates were estimated to be in the range of 6.3×10^-6-9.5×10^-6 mmol/mm².     

光响应性超疏水偶氮苯自组装多层膜的制备及性质研究

近年来,偶氮苯类化合物的光学顺反异构现象已引起人们的广泛关注[1~7].在紫外光照射下,偶氮苯由反式结构转变为顺式结构,引起分子的偶极矩发生变化,导致分子的吸收光谱、尺寸及表面能等均发生变化[7].偶氮苯表面能的改变可引起其表面浸润性发生变化.据文献[1~4]报道,偶氮苯膜在紫外光照射前后接触角最大改变了11°.浸润性是固体表面的一个重要特性,主要受固体表面的化学组成和微观几何结构(粗糙度)影响[8~11].通常,与水的接触角大于150°的表面称为超疏水表面;而与水的接触角小于5°的表面称为超亲水表面.本文以2-(4-偶氮苯基苯氧基)丙烯酸…     

A Novel pH/Light‐Triggered Surface for DNA Adsorption and Release

A simple strategy for the immobilization of Cy3‐labeled single strand DNA (Cy3‐ssDNA) on a Si(001) surface and its release under control of both light and pH stimuli is presented. In order to prepare a dual pH/light‐triggered surface, positively chargeable azobenzene molecules are self‐assembled on the Si(001) surface. The surface wettability of this substrate can be changed under influence of both light and pH conditions. The substrates can be positively charged under mildly acidic conditions. The pH‐sensitive behavior of the film allows binding of Cy3‐ssDNA on the functionalized Si(001) surface through e?ective electrostatic interactions with the negatively charged polynucleotide backbone. Moreover, irradiation of the film with UVA light induces trans–cis isomerization of the azobenzene units on the surface. As a result, the binding a?nity for DNA decreases due to the changing surface hydrophilicity. In order to understand and control the reversible photoswitchable mechanism of this surface, water contact angles are measured after UVA and visible light irradiation. The release of DNA from a dual pH/light‐sensitive sample is performed using fluorescence microscopy. The results show that irradiation of the film with UVA light induces trans–cis isomerization of the photoresponsive azobenzene units; this leads to significant changes in the surface hydrophilicity and reduces the binding affinity for DNA.     

Depth-resolved molecular structure and orientation of polymer thin films by synchrotron X-ray diffraction

An exemplary system suitable for optoelectronics applications, i.e. poly(3-hexylthiophene), hereinafter P3HT, deposited by spin casting onto silicon substrates functionalised by three selected molecules and then properly annealed, has been examined. Grazing Incidence X-ray Scattering (GIXS) measurements have been performed with 4-circle diffractometer, allowing for a fine control of sample axes movement.By choosing different grazing incident angles, diffraction patterns from different layers of polymeric thin films have been recorded. Both in-plane and out-of-plane geometries have been combined in order to obtain complementary structural information. In this way structural and orientational differences of the polymer along with the film thickness (?50 nm) have been highlighted. For all P3HT films spun on functionalized Si wafer, macromolecular layers close to the substrate surface give some evidence of higher order and orientation than those outmost the surface, and this behaviour is pronounced to a different extent depending on the functionalized molecules used. Contrariwise P3HT layers deposited onto bare Si wafer display reduced orientation and decreased crystallite size, especially at buried interface.     

Micropatterning of functional conductive polymers with multiple surface chemistries in register

A versatile procedure is presented for fast and efficient micropatterning of multiple types of covalently bound surface chemistry in perfect register on and between conductive polymer microcircuits. The micropatterning principle is applied to several types of native and functionalized PEDOT (poly(3,4-ethylenedioxythiophene)) thin films. The method is based on contacting PEDOT-type thin films with a micropatterned agarose stamp containing an oxidant (aqueous hypochlorite) and applying a nonionic detergent. Where contacted, PEDOT not only loses its conductance but is entirely removed, thereby locally revealing the underlying substrate. Surface analysis showed that the substrate surface chemistry was fully exposed and not affected by the treatment. Click chemistry could thus be applied to selectively modify re-exposed alkyne and azide functional groups of functionalized polystyrene substrates. The versatility of the method is illustrated by micropatterning cell-binding RGD-functionalized PEDOT on low cell-binding PMOXA (poly(2-methyl-2-oxazoline)) to produce cell-capturing microelectrodes on a cell nonadhesive background in a few simple steps. The method should be applicable to a wide range of native and chemically functionalized conjugated polymer systems.     

Wetting-dewetting transition line in thin polymer films

Thin polymeric films are increasingly being utilized in diverse technological applications, and it is crucial to have a reliable method to characterize the stability of these films against dewetting. The parameter space that influences the dewetting of thin polymer films is wide (molecular mass, temperature, film thickness, substrate interaction) and a combinatorial method of investigation is suitable. We thus construct a combinatorial library of observations for polystyrene (PS) films cast on substrates having orthogonal temperature and surface energy gradients and perform a series of measurements for a range of molecular masses (1800 g/mol < M < 35 000 g/mol) and film thicknesses h (30 nm < h < 40 nm) to explore these primary parameter axes. We were able to obtain a near-universal scaling curve describing a wetting-dewetting transition line for polystyrene films of fixed thickness by introducing reduced temperature and surface energy variables dependent on M. Our observations also indicate that the apparent polymer surface tension gamma(p) becomes appreciably modified in thin polymer films from its bulk counterpart for films thinner than about 100-200 nm, so that bulk gamma(p) measurements cannot be used to estimate the stability of ultrathin films. Both of these observations are potentially fundamental for the control of thin film stability in applications where film dewetting can compromise film function.     

Surface Initiated Polymerization on Pulsed Plasma Deposited Polyallylamine: A Polymer Substrate‐Independent Strategy to Soft Surfaces with Polymer Brushes

The deposition of polyallylamine (PAA) adlayers by pulsed plasma polymerization on various types of polymeric substrates has been explored as a general route to amino functionalized polymeric surfaces. These amino groups are highly suitable for anchoring an atom transfer radical polymerization (ATRP) initiator via a robust amide linkage. Subsequent surface initiated ATRP (SI‐ATRP) of monomethoxy oligo(ethylene glycol) methacrylate (MeOEGMA) resulted in polyMeOEGMA brush grafted polymer surfaces. This combined strategy of pulsed plasma polymerization with SI‐ATRP was demonstrated for five different polymeric substrates namely polyether ether ketone (PEEK), polyethylene terephthalate (PET), polyimide (PI), polypropylene (PP), and polytetrafluoroethylene (PTFE). Analysis of brush layers by attenuated total reflection infrared (ATR‐IR) spectroscopy as well as X‐ray photoelectron spectroscopy (XPS) fully corroborated the success of the proposed strategy for all substrate types.

     

Strategies toward biocompatible artificial implants: Grafting of functionalized poly(ethylene glycol)s to poly(ethylene terephthalate) surfaces

Epoxide and aldehyde end‐functionalized poly(ethylene glycol)s (PEGs) (M_w = 400, 1000, 3400, 5000, and 20,000) were grafted to poly(ethylene terephthalate) (PET) film substrates that contained amine or alcohol groups. PET‐PAH and PET‐PEI were prepared by reacting poly(allylamine) (PAH) and polyethylenimine (PEI) with PET substrates, respectively; PET‐PVOH was prepared by the adsorption of poly(vinyl alcohol) (PVOH) to PET substrates. Grafting was characterized and quantified by the increase of the intensity of the PEG carbon peak in the X‐ray photoelectron spectra. Grafting yield was optimized by controlling reaction parameters and was found to be substrate‐independent in general. Graft density consistently decreased as PEG chain length was increased. This is likely due to the higher steric requirement of higher molecular weight PEG molecules. Water contact angles of surfaces containing long PEG chains (3400, 5000, and 20,000) are much lower than those containing shorter PEG chains (400 and 1000). This indicates that longer PEG chains are more effective in rendering surfaces hydrophilic. Protein adsorption experiments were carried out on PET‐ and PEG‐modified derivatives using collagen, lysozyme, and albumin. After PEG grafting, the amount of protein adsorbed was reduced in all cases. Trends in surface requirements for protein resistance are: surfaces with longer PEG chains and higher chain density, especially the former, are more protein resistant; PEG grafted to surfaces containing branched or network polymers is not effective at covering the underlying substrate, and thus does not protect the entire surface from protein adsorption; and substrates containing surface charge are less protein‐resistant. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5389–5400, 2004     

The effect of light intensity,film thickness,and monomer composition in styrene-based bioinspired polymers

Abstract

The effect of irradiation light intensity, film thickness, and polymer composition upon photo-irradiation of water-soluble polymers containing thymine was studied by ultraviolet (UV)-vis spectroscopy. Coatings of aqueous solution of the polymer on PET substrates were exposed to UV light at 254 nm through a standard mask. The effect of irradiation dose is similar to the typical behavior of photo-resists: the degree of crosslink increases over the time until it reaches saturation. The polymer composition effect shows an expected trend on the curing process, the more vinylbenzylthymine (VBT) content in the copolymer the higher the degree of crosslinking, a situation that agrees with the fact the VBT is the monomer playing the main role in the photo-reaction. It was observed that the effect of film thickness was as expected, the thicker the film the slower the immobilization of the polymer on the substrate. It was demonstrated that by varying these parameters one could control the crosslinking rate of the polymer.     

Unique molecular orientation in a smectic liquid crystalline polymer film attained by surface-initiated graft polymerization

Liquid crystalline (LC) polymer brushes containing a mesogenic azobenzene (Az) moiety are synthesized on a quartz or silicon substrate by surface-initiated atom transfer radical polymerization. The molecular orientation of the Az units and the LC properties in the grafted chains are evaluated by UV-vis spectroscopy, polarized optical microscopy, and grazing incidence X-ray diffraction measurements. The Az side chains of the grafted chains exhibited a smectic LC phase in which the smectic layers are oriented perpendicular to the substrate with a parallel orientation of the mesogens. In contrast, a spincast film of the identical LC polymer without grafting to the surface shows layer structures parallel to the substrate. A drastic effect of tethering one end to the substrate on the LC orientation is demonstrated.     

基于银纳米线复合透明电极的可弯折柔性聚合物太阳能电池

本文设计了一种可以通过刮涂方法制备的基于银纳米线(AgNWs)的柔性复合透明电极,并以此为基础实现了高性能柔性聚合物太阳能电池的制备。 基于银纳米线的柔性复合薄膜(APA)由银纳米线(AgNWs),聚乙烯醇缩丁醛(PVB)和铝掺杂氧化锌(AZO)纳米粒子在低温下通过多层刮涂的方法制备。 APA透明复合薄膜在550 nm处透光率达到90.90%,面电阻低至13.01 Ω/sq,在柔性基底上具有很高的粘附性。 在透明的APA/聚对苯二甲酸乙二醇酯(PET)基底上制备的柔性聚合物太阳能电池(PSCs),能量转换效率达到5.47%。 而且以5 mm为曲率半径,经过1000次循环弯曲实验,电池的能量转换效率仅下降了14%。     

A Rapidly Self‐Healing Supramolecular Polymer Hydrogel with Photostimulated Room‐Temperature Phosphorescence Responsiveness

Development of self‐healing and photostimulated luminescent supramolecular polymeric materials is important for artificial soft materials. A supramolecular polymeric hydrogel is reported based on the host–guest recognition between a β‐cyclodextrin (β‐CD) host polymer (poly‐β‐CD) and an α‐bromonaphthalene (α‐BrNp) polymer (poly‐BrNp) without any additional gelator, which can self‐heal within only about one minute under ambient atmosphere without any additive. This supramolecular polymer system can be excited to engender room‐temperature phosphorescence (RTP) signals based on the fact that the inclusion of β‐CD macrocycle with α‐BrNp moiety is able to induce RTP emission (CD‐RTP). The RTP signal can be adjusted reversibly by competitive complexation of β‐CD with azobenzene moiety under specific irradiation by introducing another azobenzene guest polymer (poly‐Azo).     

Preparation and characterization of thin films of monomeric and polymeric octacyanophthalocyanines

Thin films were prepared on substrates, cleavage surface of KCl single crystal, and metallic copper, by reaction of 1,2,4,5-tetracyanobenzene with the substrate at various temperatures. The films were characterized by elemental analysis, IR, and UV/VIS spectroscopies. The films were observed by scanning electron microscopy. The films produced on copper at temperatures between 300 and 400°C consisted of copper octacyanophthalocyanine and its polymer with ladder structure. The ratio of polymer to monomer increased with elevating the reaction temperature. The films were composed of ribbon-like crystals. The film produced on copper above 450°C was composed of an amorphous and continuous layer of polymeric copper phthalocyanine. The film produced on KCl at temperatures between 250 and 350°C consisted of potassium octacyanophthalocyanine and its polymer with ladder structure. The film produced on KCl above 450°C was polymeric potassium phthalocyanine. Those films contained more metal content than that required stoichiometrical.     

Electrophysical and photophysical properties of films made from an azobenzene-functionalized polymeric cobalt complex

Electric conductivity, photoconductivity, and electro-and magneto-optical properties of films from a novel polymeric complex of 4-methacryloyloxy-(4′-carboxy-3′-hydroxy)azobenzene with cobalt were studied. Electric conductivity and visible photoconductivity are determined by the orientation effects of azobenzene groups and by charge-carrier generation and transport in the polymer films. A change in the spatial orientation of the photoinduced dipole moments of azobenzene groups in an external electric or magnetic field is accounted for by the appearance of forces acting on charged magnetic metal ions that are rigidly bound to these fragments.     

Micropatterning of copper on a poly(ethylene terephthalate) substrate modified with a self-assembled monolayer

We have developed a technique for the site-selective electroless deposition of Cu on poly(ethylene terephthalate) (PET) substrate modified with an organic self-assembled monolayer (SAM). The PET substrate was first modified with a silica-like layer by being dip-coated in an acetone solution of 3-aminopropyltrimethoxysilane and treated with UV light. The PET substrate was further modified with thiol groups using a 3-mercaptopropyltrimethoxysilane-SAM and then irradiated by UV light through a photomask to prepare thiol-group regions and OH-group regions. Cu was then deposited on only the thiol-group regions of the substrate by electroless deposition in a neutral solution with no catalysts by using dimethylamineborane as a reducing reagent. This site-selective deposition process can control the deposition conditions by an organic thin film fabricated on a surface-modified PET substrate, and thus can be applied to other low heat-resistant substrates.     

Inactivation of Food-borne Spoilage and Pathogenic Micro-organisms on the Surface of a Photoactive Polymer

The photodynamic action of a novel photoactive polymer comprising covalently bound anthraquinone (AQ) moieties was evaluated after developing a methodology to reliably immobilize viable micro-organisms onto polymer film surfaces. The survival of Escherichia coli, Bacillus cereus (vegetative cells and spores), Fusarium oxysporum and Saccharomyces cerevisiae microbes inoculated on the surface of inert polymeric substrates was assessed to determine the effect of inoculum composition, drying rate and exposure to ultraviolet (UV-A) radiation. Their survival was highly dependent on microbial genus, with E. coli consistently displaying markedly shorter survival times than the other microbes, and B. cereus spores being the most resistant. Inoculation of the microbes onto the surface of the photoactive polymer films, followed by exposure to UV-A radiation, dramatically accelerated the inactivation of all microbial types studied compared with their survival on the surface of inert polymer substrates. Simultaneous exposure to both oxygen and UV-A radiation is required to affect cell survival, which is consistent with this effect most likely originating from the photoinduced production of singlet oxygen by the photoactive polymer. These results provide further compelling evidence that singlet oxygen produced exogenously by this photoactive polymeric substrate can successfully inactivate a broad spectrum of microbes on the substrate’s surface.