Pulsed laser ablation and deposition of thin films

Pulsed laser ablation is a simple, but versatile, experimental method that finds use as a means of patterning a very diverse range of materials, and in wide areas of thin film deposition and multi-layer research. Superficially, at least, the technique is conceptually simple also, but this apparent simplicity hides a wealth of fascinating, and still incompletely understood, chemical physics. This overview traces our current physico-chemical understanding of the evolution of material from target ablation through to the deposited film, addressing the initial laser-target interactions by which solid material enters the gas phase, the processing and propagation of material in the plume of ejected material, and the eventual accommodation of gas phase species onto the substrate that is to be coated. It is intended that this Review be of interest both to materials scientists interested in thin film growth, and to chemical physicists whose primary interest is with more fundamental aspects of the processes of pulsed laser ablation and deposition.     

Fabrication of crystallized boron films by laser ablation

Polycrystalline β-rhombohedral boron films mixed with amorphous boron phase have been successfully fabricated on quartz substrates using pulsed laser ablation in a quartz glass tube chamber placed in an electric furnace. The crystallinity of the films strongly depended on the temperature of the furnace and the pressure of background argon gas. High temperature and high pressure in the chamber were suitable for crystallized boron film preparation. The best crystalline films (without B₂O₃ phase formation) were obtained at 1000°C, 100 Pa. XPS measurements demonstrated that the major contaminants were carbon and oxygen, and the atomic ratio of oxygen to boron was 0.05 under the preparation conditions of well-crystallized films. The surface roughness of the films decreased by lowering laser energy to 150 mJ/pulse under the same pressure and temperature conditions.     

Dicyanopyrazine-linked porphyrin Langmuir-Blodgett films

We investigated the influence of arachidic acid/cadmium dication (AA/Cd(2+)) as a transfer promoter for the deposition of dicyanopyrazine-linked porphyrin (2-DCPP) Langmuir-Blodgett (LB) films on both hydrophobic and hydrophilic substrates. In the case of LB deposition on a hydrophilic substrate, the presence of AA/Cd(2+) does not improve 2-DCPP LB deposition. The poor transfer in the case of the hydrophilic surface is believed to be due to 2-DCPP not wetting the surface during the down-stroke deposition, and this is not improved by the transfer agent. However, on a hydrophobic substrate, deposition of 2-DCPP is significantly improved by the presence of AA/Cd(2+). Comparison of the UV-visible spectrum of a 2-DCPP LB film with that of 2-DCCP dissolved in chloroform reveals that the Soret and Q bands for the 2-DCPP LB film are broadened and red-shifted due to aggregation of porphyrin rings in the LB film. UV-visible spectral changes and ellipsometry as a function of the number of deposition layers suggest continuous transfer of 2-DCPP/AA onto the hydrophobic substrate and reproducibility in the deposition process. The Soret and Q bands of the 2-DCPP LB film upon acid vapor exposure have also been investigated, and these measurements may have chemical sensor applications.     

Don't forget Langmuir-Blodgett films

Langmuir-Blodgett (LB) films have been investigated, extensively, over the past 70 years. Despite considerable efforts aimed at exploiting their nonlinear optical, piezoelectric, pyroelectric, semiconducting, sensing and barrier properties, problems associated with film quality and stability have hampered their practical development. This feature article highlights one recent advance in the LB area (i.e., the ionic cross-linking of LB films or "gluing"), which has resulted in single bilayer membranes possessing extraordinary quality and stability. The gluing of LB films provides new opportunities for an old technology that has been waning in recent years.     

Langmuir-Blodgett films of diazobenzene molecules

Langmuir-Blodgett (LB) films from diazobenzene Sudan III have been investigated using surface potential measurements as a function of number of layers and deposition pressures, with the surface potential data being related to molecular dipole moments obtained from theoretical electronic structure calculations. The surface potential increased with the number of layers for SIII LB films, and then tended to saturate. Results from density functional theory (DFT) and UV-vis spectroscopy indicated that the increase is due to addition of layers with oriented molecular dipoles, with the saturation tendency being attributed to a decrease in the amount of material deposited in each layer. The surface potential increased with the surface pressure used for deposition, probably owing to a higher contribution from the vertical component of the dipole moment as a closer molecular packing, which is associated with decreasing conformational entropy, was reached.     

Synthesis of carbon nitride films by double-pulse laser ablation

Carbon nitride films have been synthesized by double-pulse laser ablation of graphite in nitrogen plasma. The films produced in both single-and double-pulse experiments have been studied by X-ray photoelectron spectroscopy and X-ray diffraction. The degree of crystallinity and the content of sp ³-hybridized carbon atoms in the films obtained by double-pulse laser ablation turn out to be higher than in the films deposited by the conventional one-pulse method.     

Elastic theory for Langmuir-Blodgett films

An elastic theory for Langmuir-Blodgett films is presented. The expression for the free energy density of the film is obtained in terms of the deformation tensor by means of symmetry considerations and by making use of a quasi-microscopic model. The influence of a linear term in the deformation tensor in the elastic energy density is analysed. It is shown that when the elastic constant of the linear term is larger than a critical value, the ground state of the film is periodically distorted.     

Polyoxometalate monolayers in Langmuir-Blodgett films

Langmuir and Langmuir-Blodgett (LB) films of a variety of polyoxometalates of different shapes, sizes, and charges were prepared by taking advantage of the adsorption properties of these polyanions on a positively charged monolayer of an organic surfactant spread on water. Three different aspects were investigated. 1) The electrochemical and electrochromic properties of LB films containing the easily reducible polyoxoanion [P2Mo18O62]6-. Absorbance changes of these LB films deposited onto an ITO substrate have been induced by repeated switching of the applied potential. These changes are due to the formation of the colored reduced forms of the polyanion. Coloration and bleaching of the LB film occur very quickly and are reversible. 2) The preparation of LB films based on magnetic polyoxometalates, such as the Keggin anions, [CoW12O40]6- and [SiMn(OH2)W11O39]6-, or containing magnetic clusters of increasing nuclearities such as [Co4(H2O)2(PW9O34)2]10- and [Co4(H2O)2(P2W15O62)2]16- based on a Co4O16 ferromagnetic cluster, and the polyoxometalates [Co9(OH)3(H2O)6(HPO4)2(PW9O34)3]16- and [Ni9(OH)3-(H2O)6(HPO4)2(PW9O34)3]16- based on a nonanuclear M9O36 cluster. 3) The preparation of LB films of the giant heteropolyoxomolybdate, [Na3(NH4)12][Mo57Fe6(NO)6O174(OH)3-(H2O)24]76 H2O.     

Excimer laser photochemistry of lithographic systems

Laser photochemical methods are useful in the microchemical field and for microlithographic patterning of integrated circuits. For many reactions a difference in the going on and the result of the reaction is obtained at lamp or at laser initiation, respectively. For the photochemists engaged in lithography the most important properties are: intensity and collimated beam. Several excimer laser exposure systems have been developed in the last years, the importance of which is increasing. At high peak power densities of the excimer laser radiation, new phenomena in photochemical and/or lithographic behaviour are observed. The wavelength-dependent sensitivity of the positively working naphthoquinone diazide resists is caused by the change of the absorption spectrum within the pulse duration. The intensity-dependent gradation and resolution of the investigated negatively working azide resists are the result of the further excitation of the intermediately formed nitrenes.     

Phthalocyanine-based Langmuir-Blodgett films as chemical sensors

Phthalocyanines are macrocycles with an appealing diversification of characteristics of fundamental interest in contemporary advanced technologies. On the other side, the Langmuir-Blodgett method permits to deposit films with a substantial control over thickness and molecular organisation. As a natural consequence, this review deals with an actual subject of attention in up-to-date research, the employment of Langmuir-Blodgett films of phthalocyanines in chemical sensors for the revelation of analytes in both gas and liquid phases. Experimental data on the structure, morphology and surface properties of the multilayers are connected with the most relevant characteristics of sensors, in order to discover the intimate relationships between the sensor performances and the peculiarities and molecular organisation induced by the deposition technique. The integration of the unconventional electrical and optical properties of phthalocyanines with the potentialities of the Langmuir-Blodgett thin films has generated not only promising expectations, but has given also certainties about the realisation of functional sensing devices.     

Carrier gas UV laser ablation sensitizers for photopolymerized thin films

Designed carrier gas UV laser ablation sensitizers were synthesized and proved to greatly enhance the UV laser ablation of photopolymerized thin films. Polymers containing dense ester groups are reported to have better laser ablation performance because of the tendency of the ester groups to decompose into gaseous products (“carrier gases”) during the ablation process. In order to introduce this mechanism to cationic UV curable coatings for better laser ablation, a series of “carrier gas” sensitizers were synthesized by reacting hydroxyl containing reactive diluents such as oxetane and polyester polyols with monomethyl oxalyl chloride or dimethyl oxalate; the oxalyl group is considered a “carrier gas” generating moiety. Furthermore, a UV absorbing chromophore, naphthalene, is either chemically bound to the oxalyl containing molecules or blended with the synthesized oxalyl containing compounds to produce a synergistic effect. The “carrier gas” sensitizers were added into a typical cationic UV curable formulation to form sensitized coatings, which were then characterized by thermogravimetric analysis, real time FTIR and ablated by a 355 nm laser. The ablation vias were examined using optical profilometry and SEM. Compared to the control, the sensitized coatings were found to have similar thermal decomposition temperatures and higher functional group conversion during photopolymerization. All of the sensitized coatings containing the “carrier gas” sensitizers exhibited better UV laser ablation performance than the control. The combination of naphthalene derivatives and the oxalyl group gave a better ablation result, suggesting a synergistic effect. The chemical combination of the naphthalene and oxalyl group exhibited better ablation sensitization than their blends, suggesting a more efficient intramolecular laser energy utilization process.     

Polymeric Langmuir-Blodgett films containing xanthene dyes

Spectral and protolytic properties of two hydrophobic rhodamine dyes and fluorescein n-decyl ester were studied in Langmuir-Blodgett films based on a polyamido acid. The possibility of weakening the concentration quenching of rhodamine dye fluorescence with a polymeric matrix was demonstrated.     

Triplet-triplet energy transfer in Langmuir-Blodgett films

The temperature effect on the efficiency of the triplet energy transfer between different molecules included in molecular layers by the Langmuir-Blodgett (LB) procedure was studied. The efficiency of the triplet energy transfer from the LB film of the donor to the LB film of the acceptor is determined by the homogeneous broadening of the energy donor levels.     

Template-directed patterning using phase-separated Langmuir-Blodgett films

The structures of the mixed Langmuir-Blodgett (LB) films of conventional amphiphiles (CAs) and amphiphilic silane-coupling agents (SCAs) were investigated using IR spectroscopy, atomic force microscopy, and friction force microscopy. By using CAs having hydrogenated alkyl chains and SCAs having perfluorinated alkyl chains, phase-separated structures were formed with domains consisting of CAs surrounded by SCAs. The size and shape of the domains depended strongly on the mixed components, the mixing ratios, and the subphase temperature. In particular, usage of a CA having hydrogenated and perfluorinated portions in the hydrophobic group as one of the components led to the formation of nanothreads. When the phase-separated mixed LB films were heated, SCAs formed covalent bonds with the substrates having silanol groups whereas CAs did not have such ability. Rinsing the heat-treated LB films with ethanol selectively removed CAs with the SCA regions intact, resulting in the fabrication of templates. The structures of the templates reflected those of the original phase-separated LB films. LB transfer of amphiphiles on the templates led to the confinement of the amphiphiles in regions with the size and shape delineated by the templates. These results demonstrate that a variety of amphiphiles can be confined two-dimensionally in a designed manner.     

Langmuir-Blodgett films of octadecanethiol--properties and potential applications

Octadecanethiol (ODT) is known to form self-assembled monolayer on noble metal surfaces which has potential technological applications. Langmuir-Blodgett (LB) technique is another useful method of obtaining highly ordered assembly of molecules. It is of interest to find whether ODT molecules can also form a stable Langmuir monolayer which facilitates the preparation of LB films. In literature, it has been reported that ODT molecules form an unstable Langmuir monolayer. We have studied the stability of the monolayer of the ODT molecules at air-water interface using surface manometry and microscopy techniques. We find the monolayer to be stable on ultrapure water of resistivity greater than 18MOmega cm. However, the behavior changes in the presence of even small amount of additives like NaOH or CdCl2 in the subphase. Our AFM studies on the LB films of ODT deposited from ion-free ultrapure water showed streak-like bilayer domains. The LB films of ODT deposited from CdCl2 containing aqueous subphase yield dendritic domains of the complexed unit grown over ODT monolayer. These nanostructures on surfaces may have potential applications in molecular electronics.     

Photo-induced structural changes of azobenzene Langmuir-Blodgett films

Structural changes of the Langmuir-Blodgett (LB) films of azobenzene accompanied by photoisomerization are described. First, photoisomerization is explained in terms of 'free volume'. In the polyion complex monolayers of amphiphiles having two azobenzene units at the air-water interface, the area per molecule depends on the polycation species. The fraction of cis-azobenzene in the LB films at the photostationary state under the illumination with UV light increased with increasing area per molecule, which is consistent with the concept of free volume. Second, a counter example of the concept of free volume is presented. Three-dimensional cone-shaped structures developed with trans-to-cis photoisomerization in the polyion complex LB film of a water-soluble amphiphilic azobenzene. These structures appeared and disappeared reversibly by alternate illumination with UV and visible light. The results indicate that the two-dimensional LB film structure exerts significant modification by photoisomerization. This is against the concept of free volume because this concept does not consider the possibility that the two-dimensional LB film structures may change into three-dimensional ones. Finally, photo-induced J-aggregate formation of non-photochromic and photochromic dyes is described. Two cyanine dyes were each mixed with an amphiphilic azobenzene in the LB films. These cyanine dyes are known to form J-aggregates in single-component LB films. In the mixed LB films, the J-aggregate formation was suppressed to some extent. The alternate illumination of the films with UV and visible light caused the photoisomerization of azobenzene in the mixed LB films, which triggered the J-aggregate formation of the cyanine dyes. The J-aggregate formation was accompanied by the development of three-dimensional cone-shaped structures from the film surface. When an amphiphilic merocyanine was mixed with the azobenzene in the LB films, J-aggregate formation was also induced by the alternate illumination with UV and visible light. This J-aggregate formation was also accompanied by a large morphological change: circular domains changed into fractal-like ones. The J-aggregate formation of the dyes and the concomitant morphological change were irreversible. In these cases, the photoisomerization of azobenzene served as a trigger to induce self-organization of the dye molecules.     

Structure of thermally treated oxadiazoleamide Langmuir-Blodgett films

The thermal treatment of Y-type Langmuir-Blodgett (LB) films formed from the amphiphilic derivative of 2,5-diphenyl-1,3,4-oxadiazole 1 results in changes of the molecular packing. These changes have been analysed by a combination of X-ray specular reflectivity data, X-ray grazing incidence diffraction data and scanning force microscopy images. On the basis of these experimental data we have simulated possible supramolecular structures. These simulations provide insight into the intermolecular interactions giving rise to the observed structural transitions. The crystalline structure induced by thermal treatment of the LB films is chracterized by a uniaxial texture, which is correlated with the dipping direction during deposition of the LB film.     

Tribotechnical characteristics of the Langmuir-Blodgett polyvinylpyridine films

The tribological properties of the Langmuir-Blodgett poly-4-vinylpyridine monomolecular films and cationic polyelectrolytes: polydiallyldimethylammonium chloride, polyallylamine, and polyethyleneimine monolayers were studied. The highest stability toward the mechanical impact of a steel ball (indenter) was observed in the poly-4-vinylpyridine film formed at the surface pressure 20 mN m⁻¹.     

Monolayers and Langmuir-Blodgett films of crown-substituted phthalocyanines

Tetra-15-crown-5-phthalocyanine ligand and its ruthenium complex with axial CO and MeOH groups were synthesized. The properties of their monolayers and Langmuir-Blodgett films were studied. In the case of the ligand, monolayer films of molecular associates are formed. The compatibility of the ligand and stearic acid in a mixed binary monolayer was established. Stearic acid improves the ligand distribution over the water surface and results in the formation of monolayer associates immobilized in its matrix. The condensation effect of Na⁺ cations on the mixed monolayers was found. The ruthenium complex (R₄Pc)Ru(MeOH)(CO) forms stable true monolayers. The macrocycle planes in stacking are inclined relatively to the normal to the subphase surface by an angle of 25°. The Langmuir-Blodgett films of the complex were established to have redox peaks. A high electrochemical stability of the Langmuir-Blodgett films and a high electroactivity of phthalocyanine rings were demonstrated. It was shown by impedance spectroscopy that the binding of Na⁺ and K⁺ ions by Langmuir-Blodgett films of the (R₄Pc)Ru(MeOH)(CO) complex results in an increase in the impedance values in a region of medium frequencies by three and five times, respectively.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2426–2435, November, 2004.     

Side-on liquid crystal polyacrylate in Langmuir-Blodgett films

A side-on fixed liquid crystal polyacrylate has been investigated in Langmuir and Langmuir-Blodgett (LB) films. High in-plane orientation of the mesogenic groups has been observed within the LB multilayers, showing the ability of the LB technique to align a liquid crystal. The analysis of the in-plane order versus the dipping speed suggests some self-aggregation of the polymer in the monolayer. Within these aggregates, the molecular orientation (in-plane and out-plane) has been deduced from infrared dichroism experiments; the mesogenic group lies mainly parallel to the dipping direction and relatively flat on the substrate. This alignment of the polymer is however partially lost with time, leading to materials with less in-plane anisotropy.