Ultra Thin Organic and Polymer Films

Abstract

Preparation of ultra thin organic and polymer films could be divided into two methods. One is the wet process such as Langmuir-Blodgett (LB), spreading, dipping and casting methods. The other is dry processing, such as vapor deposition, sputtering, chemical vapor deposition, plasma polymerization and vapor deposition polymerization methods. Of these methods, the LB method has been attractive for the last decade to prepare a monolayer film, however, the vapor deposition method has also attracted attention for the preparation of well organized ultra thin films. It is important to investigate a molecular assembly in terms of the extent of aggregation, the crystalline regularity and their orientation in the thin film, since they are closely related to the physical, electrical and functional properties. This review focuses on an evaluation of the structure, molecular assembly and orientation in the thin films prepared by the LB and vapor deposition methods.     

Photo-reversible Reaction in Polymer Langmuir-Blodgett Films

Preparation of photoreactive Langmuir-Blodgett (LB) films was carried out using polymers/oligomers prepared from long-chain dialkyl esters of di-and tetra-olefins and having cyclobutane rings in the main chain. These polymers/oligomers formed stable monolayers on a water surface when mixed with arachidic acid. These monolayers could be deposited onto a substrate successfully forming Y-type films. The oligomer LB films were polymerized on irradiation. The polymer LB films showed a photo-reversible process between polymers and oligomers, depending on wavelength of the irradiating light. On the basis of spectral data and molecular weight change, this behaviour was found to be caused by cleavage and formation of cyclobutane rings.     

Langmuir and Langmuir-Blodgett Films of Polyfluorenes and Their Use in Polymer Light-Emitting Diodes

The Langmuir and Langmuir-Blodgett (LB) film properties of two polyfluorene derivatives, namely poly(2,7-9,9′-dihexylfluorene-dyil) (PDHF) and poly(9,9 dihexylfluorene-dyil-vynilene-alt-1,4-phenylene-vyninele) (PDHF-PV), are reported. Surface pressure (П-A) and surface potential (ΔV-A) isotherms indicated that PDHF-PV forms true monolayers at the air/water interface, but PDHF does not. LB films could be transferred onto various types of substrate for both PDHF and PDHF-PV. Only the LB films from PDHF-PV could withstand deposition of a layer of evaporated metal to form a light-emitting diode (PLED), which had typical rectifying characteristics and emitted blue light. It is inferred that the ability of the polymer to form true monomolecular layers at the air/water interface seems to be associated with the viability of the LB films in PLEDs.     

The electrical and optical properties of oriented Langmuir-Blodgett films of single-walled carbon nanotubes

Thin, transparent, electrically-conductive films containing single-walled carbon nanotubes have been fabricated using the Langmuir-Blodgett method. No additional surfactant was used and films up to 99 layers in thickness (300 nm) could readily be built-up. Both optical and electrical measurements revealed anisotropy in the film plane, suggesting alignment of the tubes during the deposition process. For the majority of films, DC conductivity measurements over the range 77–300 K showed an increase in the conductivity with increasing temperature, i.e. semi-conducting characteristics. However, some samples exhibited the opposite effect. Such metallic films reverted to semi-conducting behaviour following an electrical annealing process.     

Preparation of TiO2 thin films using octadecylamine Langmuir-Blodgett films and evaluation of their photocatalytic activity

A study was conducted to demonstrate that nanometer-thick titanium dioxide (TiO(2)) thin films could be prepared by the hydrolysis of titanium potassium oxalate using octadecylamine (ODA) Langmuir-Blodgett (LB) films as templates. The amount of TiO(2) generated in the LB film was found to be proportional to the number of deposited ODA layers, which enables precise control of the TiO(2) film thickness. After heat treatment of the LB films at 300-600°C, the photocatalytic activities of the resulting TiO(2) films were determined from the decomposition of stearic acid cast films when irradiated with UV light for different time periods. Higher photocatalytic activity was observed in TiO(2) films heat treated at lower temperatures.     

Molecular structure modulated properties of azobenzene-substituted polydiacetylene LB films: Chirality formation and thermal stability

Langmuir-Blodgett (LB) films of three novel azobenzene-substituted diacetylene monomers (DA1, DA2 and DA3) were fabricated and their optical and chiroptical properties were investigated in detail by ultraviolet-visible (UV-vis) spectra and circular dichroism (CD) spectra. Achiral DA1 molecules could form chiral LB films through overcrowded packing of the azobenzene moiety, while achiral DA2 and DA3 molecules not. When exposed to left-or right-handed circular polarized UV light (CPUL), striking left- or right-handed (opposite) CD signals for azobenzene chromophores and polydiacetylene chains were observed for the polymerized DA1 (PDA1) and DA2 (PDA2) LB films. However, DA3 LB films could hardly be polymerized in this case, and only striking opposite CD signals for azobenzene chromophores could be observed. It was demonstrated that the intermolecular steric hindrance and irregular arrangement of azobenzene chromophores were not favorable for the topo-polymerization and chirality formation of polydiacetylenes backbone. Further, the effects of thermal treatment on the supramolecular chirality of above three LB films were studied. Strong collective noncovalent interactions (π-π stacking) were believed to be responsible for the thermal stability of chiral supramolecular assemblies.     

Electrochemical properties of carbon nanotubes-hydrogenase conjugates Langmuir-Blodgett films

We report the preparation of Langmuir-Blodgett (LB) films composed of oxidized carbon nanotubes (CNTs) and hydrogenase (H₂ase) conjugates and their electrochemical properties. Both single-walled (SWNTs) and multi-walled CNTs (MWNTs) were used to form mixed monolayers with H₂ase on the Tris-HCl subphase surfaces. By using the LB method, the CNTs-H₂ase monolayers were transferred onto CaF₂ and indium tin oxide (ITO) electrode surfaces. The LB film modified electrodes showed a couple of waves centered at around −500 mV (versus Ag/AgCl), which corresponding to the redox reaction of [4Fe-4S]^2+/1+ clusters in the H₂ase. The current intensity was enhanced after co-assembly with CNTs. Because of the different diameters of CNTs, this current intensity was proportional to the scan rate (υ) for the electrodes modified with the LB films of pure H₂ase and SWNTs-H₂ase, but to the root of scan rate (υ^1/2) for those modified with the MWNTs-H₂ase LB film. The products of diffusion coefficient and concentration (D^1/2C) increased in the order of pure H₂ase, SWNTs-H₂ase, and MWNTs-H₂ase LB films.     

Photoinduced electron transfer in nanostructures of ultrathin polyimide films containing porphyrin moieties

Photoinduced electron transfer between porphyrin moieties and pyromellitimide fragments has been investigated in multi-layered structures of ultrathin polyimide films prepared by the Langmuir-Blodgett (LB) technique. The LB films were composed of three kinds of polyimides, which contained zinc tetraphenylporphyrin (ZnTPP) unit as an electron donor (D-layer), no chromophoric groups (S-layer), and pyromellitimide fragments as an electron acceptor (A-layer). The layered structure and orientational distribution of porphyrin moieties in the LB films were evaluated by surface plasmon measurement and absorption dichroism measurement, respectively. The thickness of monolayer was estimated to be 0.9 nm for the polyamic acid films and 0.4 nm for the polyimide films. The molecular plane of porphyrin moieties was oriented in the direction parallel to the substrate plane. In the multi-layered structures of polyimide LB films, the efficiencies of photoinduced electron transfer from porphyrin moieties to pyromellitimide fragments varied sharply with the number of spacing layers, indicating that the short-range interactions such as electron transfer could be controlled by the fabric of ultrathin films. The rate of electron transfer observed by the fluorescence quenching measurements was numerically simulated for the nanostructure using the Monte Carlo method.     

Ordered and ultrathin reduced graphene oxide LB films as hole injection layers for organic light-emitting diode

In this paper, we demonstrated the utilization of reduced graphene oxide (RGO) Langmuir-Blodgett (LB) films as high performance hole injection layer in organic light-emitting diode (OLED). By using LB technique, the well-ordered and thickness-controlled RGO sheets are incorporated between the organic active layer and the transparent conducting indium tin oxide (ITO), leading to an increase of recombination between electrons and holes. Due to the dramatic increase of hole carrier injection efficiency in RGO LB layer, the device luminance performance is greatly enhanced comparable to devices fabricated with spin-coating RGO and a commercial conducting polymer PEDOT:PSS as the hole transport layer. Furthermore, our results indicate that RGO LB films could be an excellent alternative to commercial PEDOT:PSS as the effective hole transport and electron blocking layer in light-emitting diode devices.     

Standardization of photoresponsive LB films fabricated from simple azobenzene derivative

It is believed that azobenzene amphiphiles tend to be strongly H-aggregated during pure Langmuir-Blodgett (LB) film manipulation and therefore they are unable to photoisomerize. However, we present in this article the manner for destabilizing such aggregation by means of a simple physical treatment process, obtaining finally well photoresponsive amphiphilic azobenzene in the pure LB films. Such LB films are highly suitable for regulating the orientation and photoreactivity of other surface-in touch systems such as nematic liquid crystals and photoreactive monomers to be polymerized. Therefore, we investigated the manipulation of LB films of the azobenzene derivative, 11-(4-(4-hexyl-phenylazo)-phenoxy)-undecanoic acid using different monomeric isomers, by temperature and monolayer transfer methods. The LB films were then exposed to heat treatment process and finally to photophysical processes.     

Synthesis of azopolymers with controlled structure and photoinduced birefringence in their LB films

The molecular architecture of azopolymers may be controlled via chemical synthesis and with selection of a suitable film-forming method, which is important for improving their properties for practical uses. Here we address the main challenge of combining the photoinduced birefringence features of azopolymers with the higher thermal and mechanical stabilities of poly(methyl methacrylate) (PMMA) using Atom Transfer Radical Polymerization (ATRP) to synthesize diblock- and triblock-copolymers of an azomonomer and the monomer methyl methacrylate. Langmuir-Blodgett (LB) films made with the copolymers mixed with cadmium stearate displayed essentially the same optically induced birefringence characteristics, in terms of maximum and residual birefringence and time for writing, as the mixed LB films with the homopolymer poly[4-(N-ethyl-N-(2-methacryloxyethyl))amino-2′-chloro-4′-nitroazobenzene] (HPDR13), also synthesized via ATRP. In fact, the controlled architecture of HPDR13 chains led to Langmuir films that could be more closely packed and reach higher collapse pressures than the corresponding films obtained with HPDR13-conv synthesized via conventional radicalar polymerization. This allowed LB films to be fabricated from neat HPDR13, which was not possible with HPDR13-conv. The enhanced organization in the LB films produced with controlled azopolymer chains, however, led to a smaller free volume available for isomerization of the azochromophores, thus yielding a lower photoinduced birefringence than in the HPDR13-conv films. The combination of ATRP synthesis and LB technology is then promising to obtain optical storage in films with improved thermal and mechanical processabilities, though a further degree of control must be sought to exploit film organization while maintaining the necessary free volume in the films.     

Electrochemical nitric oxide microsensors based on two-dimensional cross-linked polymeric LB films of oligo(dimethylsiloxane) copolymer

Two-dimensional cross-linked polysiloxane Langmuir-Blodgett (LB) films were prepared and applied to nitric oxide (NO)-permselective membranes in order to block other electroactive interfering species. The cross-linked siloxane LB films deposited on platinum micro-disc electrodes (10 μm in diameter) offered revealing high performances as a permselective membrane for NO sensor such as high sensitivity to NO (detection limit, 40 nM) and high selectivity (e.g., the ratio of current response for acetaminophen or uric acid on the modified electrode to that on the bare electrode, less than 10⁻³). Furthermore, the permselective membrane could be easily deposited irrespective of the size and shape of electrode.     

Aggregation in Langmuir and Langmuir-Blodgett films of azopolymers and its role for optically induced birefringence

Aggregation in azopolymers is reported to affect the Langmuir monolayer characteristics and the optically induced birefringence of Langmuir-Blodgett (LB) films from DR19 isophorone polyurethane (PIPDI) and DR19 4,4′ diphenylmethane polyurethane (PMDI). In mixed monolayers with cadmium stearate (CdSt), the folding of PMDI molecules appears to be substantially changed compared to the monolayer of the pure polymer, leading to a surface potential that is higher than observed for monolayers of pure PMDI and of pure CdSt. UV-Vis spectroscopy data of the deposited mixed LB films indicate H-type aggregation for PMDI/CdSt, in contrast to PIPDI/CdSt and other azopolymers investigated earlier. The H-type aggregation precludes photoisomerization, thus requiring a higher laser power for the maximum induced birefringence to be achieved in LB films of PMDI/CdSt.     

LB膜技术的应用研究进展

LB膜技术是在分子水平上制备有序分子超薄膜的先进技术。对LB膜技术的研究和应用进行了综述，介绍了目前LB技术在实现超微细粒子的二维有序组装，在光学，电化学器件和气体传感器中的应用以及通过LB膜技术组装生物仿生膜等方面的最新研究成果。     

Wettability of fibrous quartz with Langmuir-Blodgett films of arachidic acid and/or cellulose didecanoate

The wettability of quartz with Langmuir-Blodgett (LB) films of arachidic acid (AA) and/or cellulose didecanoate (CDD) was investigated by contact angle measurements, employing the Wilhelmy method. The advancing angles increased considerably with the film deposition, especially for the AA films, whereas the receding angles increased only slightly. A further increase in the advancing angles with time was found after the film deposition. The experimental results are discussed considering the quartz with the LB films to have a heterogeneous surface, i.e. predominantly high-energy surface with fractional low-energy regions. The increment in the advancing contact angle due to film deposition is explained by the increase in the percentage of the low-energy region. The time dependence of the advancing angle after the film deposition is considered to be caused by the increase in the difference in the intrinsic wettability between the low-energy and high-energy regions due to rearrangement of the molecules in the LB films and the migration of the AA molecules towards the air.     

Mechanical and morphological characterization of polymer-carbon nanocomposites from functionalized carbon nanotubes

Carbon nanotubes were functionalized with poly(vinyl alcohol) (PVA). The water-soluble PVA-functionalized carbon nanotubes were then embedded into PVA matrix via a wet-casting method, resulting in polymer-carbon nanocomposite films with homogeneous nanotube dispersion. Composites with pristine and functionalized nanotubes were tested in tension. It was found that the mechanical properties of these nanocomposite films were significantly improved compared to the neat polymer film. Functionalization allowed good distribution of the nanotubes in the matrix, leading to higher film strength. Scanning electron microscopy shows an apparent good wetting of the nanotubes by the PVA matrix. These results are supportive of good interfacial bonding between the functionalized carbon nanotubes and the hosting polymer matrix.     

Studies on the release of polymeric Langmuir-Blodgett multilayers from the solid supports on which they were prepared

It has been shown that polymeric Langmuir-Blodgett (LB) multilayers may be released from the supports on which they were prepared by first thermally evaporating thin films of stearic acid onto the support. The acid can subsequently be washed away, so undercutting the film and releasing it to float to the water surface. The films were redeposited onto fresh silicon wafers or onto glass microscope slides. Under the optical microscope, the films on the glass microscope slides were clear and featureless. By XRD the transferred films had the same or fewer orders of Bragg peaks and the corresponding bilayer spacings were the same or slightly larger than those of the original films. Thus, it appears that most films lose a small amount of their order in the transfer process. By second harmonic generation (SHG) the transferred alternating LB films formed from a poly(4-vinylpyridine) partially quaternised by reaction with n-docosyl bromide and from the poly(4-vinylpyridinium bromide) formed by the zwitterionic polymerisation of 4-vinylpyridine with 4(12-bromododecyloxy)-4′-trifluoromethylazobenzene displayed essentially the same SHG properties as the original films. Moreover, the SHG films could be stacked successfully to give thicker films. Several of the transferred films, but not all, contained traces of stearic acid, which appears to be present as small domains of Y-type layers. In one typical case, where the LB film consisted of 100 layers of a poly(4-vinylpyridine), it was shown that the amount of stearic acid present corresponded to an average of one monolayer.     

Interfacial Chemistry of Langmuir-Blodgett Deposited Polyimide Films on Si (100)

Using the Langmuir-Blodgett (LB) technique, ultrathin films of the octadecylammonium salt of polyamic acid (PACS) on (100) oriented silicon wafers with one, three and five monolayers were prepared. The imidization of the films was investigated with x-ray photoelectron spectroscopy (XPS) during a stepwise heating procedure in vacuum. Significant differences in the XPS spectra indicate an incomplete polymerization of the films as a function of film thickness. It is believed that the chemical interaction at the interface between Si substrate and PACS is responsible for the incomplete polymerization of the LB film in direct contact with the substrate. From ellipsometric measurements the absolute thickness of a PACS and a polyimide layer has been determined to be 1.7 nm and 0.6nm, respectively. These measurements allow us to determine the electron mean free path for the Si2p electrons (E_k=1153 eV) of λ = 4.2±0.1 nm through these films.     

Interfacial Chemistry of Langmuir-Blodgett Deposited Polyimide Films on Si (100)

Using the Langmuir-Blodgett (LB) technique, ultrathin films of the octadecylammonium salt of polyamic acid (PACS) on (100) oriented silicon wafers with one, three and five monolayers were prepared. The imidization of the films was investigated with x-ray photoelectron spectroscopy (XPS) during a stepwise heating procedure in vacuum. Significant differences in the XPS spectra indicate an incomplete polymerization of the films as a function of film thickness. It is believed that the chemical interaction at the interface between Si substrate and PACS is responsible for the incomplete polymerization of the LB film in direct contact with the substrate. From ellipsometric measurements the absolute thickness of a PACS and a polyimide layer has been determined to be 1.7 nm and 0.6nm, respectively. These measurements allow us to determine the electron mean free path for the Si2p electrons (E_k=1153 eV) of λ = 4.2±0.1 nm through these films.     

Densified aligned carbon nanotube films via vapor phase infiltration of carbon

We report a simple way to produce fully densified aligned carbon nanotube (ACNT) films. The simultaneous growth of nanotubes and densification of the ACNT films by carbon infiltration in the interstitial spaces between nanotubes are accomplished in a single step by the combination of the chemical vapor deposition and chemical vapor infiltration processes. Scanning electron microscope analysis and microbalance measurements showed that after infiltration, the diameters of nanotubes and bulk density of the ACNT films are increased by an order of magnitude (and hence the porosity of the ACNT films is decreased). Transmission electron microscope and Raman scattering analysis showed that after densification, the nanotubes are conformally coated by partially graphitized pyrolytic carbon. The compressive modulus of the densified ACNT films could be increased by three orders of magnitude compared to the pristine ACNT films. Electrical properties are also measured for the densified films showing marked differences with the ACNT films. The property enhanced densified ACNT films constitute a new form of carbon-carbon nanocomposites and could find applications as multifunctional nanocomposites.