Resonant infrared matrix-assisted pulsed laser evaporation of TiO2 nanoparticle films

The successful development of flexible, high performance thin films that are competitive with silicon-based technology will likely require fabricating films of hybrid materials that incorporate nanomaterials, glasses, ceramics, polymers, and thin films. Resonant infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE) is an ideal method for depositing organic materials and nanoparticles with minimal photochemical or photothermal damage to the deposited material. Furthermore, there are many nonhazardous solvents containing chemical functional groups with infrared absorption bands that are accessible using IR lasers. We report here results of recent work in which RIR-MAPLE has been employed successfully to deposit thin films of TiO₂ nanoparticles on Si substrates. Using an Er:YAG laser (λ=2.94 μm), we investigated a variety of MAPLE matrices containing –OH moieties, including water and all four isomers of butyl alcohol. The alcohol isomers are shown to provide effective and relatively nontoxic solvents for use in the RIR-MAPLE process. In addition, we examine the effects of varying concentration and laser fluence on film roughness and surface coverage.     

Optical properties of hybrid polymers as barrier materials

The development of high barrier films for the encapsulation of organic electronics devices onto flexible polymeric substrates is attracting a considerable scientific interest, since it is important to protect the organic semiconductor layers of these devices from corrosion due to atmospheric gas molecule permeation. The barrier layers for encapsulation consist of a sequence of inorganic and hybrid polymer thin films that are deposited onto flexible polymeric substrates, such as polyethylene terephthalate (PET). In addition to their barrier response, these multilayer systems should also exhibit high transparency and good adhesion between the hybrid polymer and inorganic layers. The knowledge of their optical properties and the correlation of the optical response with their structure and the final barrier response are of major importance since it will contribute towards the optimization of their functionality. In this work, the optical properties of hybrid polymers deposited onto silicon oxide inorganic thin films that were grown onto flexible polymeric substrates, have been investigated by the use of spectroscopic ellipsometry in a wide spectral region from the infrared to the visible-ultra violet. As it has been found, the increase of the solid content in the hybrid polymers is associated with a reduction in the refractive index values. This behavior can be correlated to a lower density of the hybrid polymer, and furthermore to a poor barrier response, due to the less cohesive inorganic-organic bonding network. Finally, from the investigation of the optical response of the hybrid polymers in the IR spectral region has revealed information on their bonding structure that has been discussed together with their barrier response.     

MAPLE deposition of PEG:PLGA thin films

We report on MAPLE deposition of thin films of PEG:PLGA blends. The films were analyzed in terms of morphology, chemical composition, wettability, and optical constants. These properties were particularly discussed in correlation with film thickness. The film thickness was increased by increasing the deposition rate (i.e., laser fluence). This method was effective for fluences up to 1 J/cm², above which the efficiency of the deposition leveled off. Moreover, with increasing fluence above 1 J/cm², important changes in the polymeric films were noticed: the surface roughness increased abruptly (up to ∼200 nm), the polymers lost their chemical integrity and their optical constants underwent significant changes. In addition, surface wettability decreased considerably, water contact angle reaching ∼90°; this was attributed to increased surface roughness and to orientation of the hydrophobic groups toward the surfaces of the films. An alternative method for obtaining thicker films was employed, by prolonging the deposition time while maintaining a constant, relatively low, deposition rate (i.e., fluence). In this case, the properties of the films were significantly less affected.     

MAPLE deposition of methoxy Ge triphenylcorrole thin films

Methoxy Ge Triphenylcorrole [Ge(TPC)OCH₃] has been recently synthesized and deposited as thin film by the Matrix Assisted Pulsed Laser Evaporation (MAPLE) technique. In the last few years, corroles have been the object of an increasing number of studies and MAPLE technique seems to be a very promising deposition method for organic and polymeric films, producing good results for applications in chemical gas sensing layers production. In this work Ge(TPC)OCH₃ thin films were deposited by both spin coating and MAPLE techniques for comparison. The morphology of the films was investigated by Atomic Force Microscopy (AFM), while their optical properties were analyzed by photoluminescence (PL) and UV-vis absorption measurements and were compared with the ones of the starting solution. The film absorption spectrum presented the same peaks with the same relative intensities of that recorded in solution. The luminescence spectra were acquired periodically to evaluate the aging effects and no detectable variations were recorded over a period of 1 month.     

Matrix-assisted pulsed laser evaporation of polyfluorene thin films

Poly(9,9-dioctylfluorene) (PF8) thin films have been deposited by matrix-assisted pulsed laser evaporation (MAPLE) using a KrF excimer laser. The influence of the laser fluence (50-500 mJ/cm²) and the nature of the solvent (chloroform, toluene, tetrahydrofuran) on the films properties have been studied. The chemical composition of the deposited films was investigated by Fourier transform infrared (FTIR) spectroscopy and compared with the one of spin coated films. To investigate the effect of the deposition parameters on the optical properties of the films, photoluminescence (PL) measurements were performed. Poor structural and optical properties were observed for films deposited starting from chloroform solutions. When using toluene as solvent, the spectra characteristics improved with increasing laser fluence, while wide PL spectra were observed. The characteristic emission bands of the PF8 polymer were nicely detected for films deposited starting from a tetrahydrofuran (THF) solution. Moreover, in this last case, the PF8 structure is preserved at high laser fluences, too.     

Deposition of antibacterial of poly(1,3-bis-(p-carboxyphenoxy propane)-co-(sebacic anhydride)) 20:80/gentamicin sulfate composite coatings by MAPLE

We report on thin film deposition of poly(1,3-bis-(p-carboxyphenoxy propane)-co-sebacic anhydride)) 20:80 thin films containing several gentamicin concentrations by matrix assisted pulsed laser evaporation (MAPLE). A pulsed KrF* excimer laser was used to deposit the polymer-drug composite thin films. Release of gentamicin from these MAPLE-deposited polymer conjugate structures was assessed. Fourier transform infrared spectroscopy was used to demonstrate that the functional groups of the MAPLE-transferred materials were not changed by the deposition process nor were new functional groups formed. Scanning electron microscopy confirmed that MAPLE may be used to fabricate thin films of good morphological quality. The activity of gentamicin-doped films against Escherichia coli and Staphylococcus aureus bacteria was demonstrated using disk diffusion and antibacterial drop test. Our studies indicate that deposition of polymer-drug composite thin films prepared by MAPLE is a suitable technique for performing controlled drug delivery. Antimicrobial thin film coatings have several medical applications, including use for indwelling catheters and implanted medical devices.     

Thin films of Cu(II)-o,o′-dihydroxy azobenzene nanoparticle-embedded polyacrylic acid (PAA) for nonlinear optical applications developed by matrix assisted pulsed laser evaporation (MAPLE)

Thin films based on two different metal-organic systems are developed by MAPLE and their nonlinear optical applications are explored. A complex of o,o′-dihydroxy azobenzene with Cu²⁺ cation is found to organize as a non-central symmetric crystallite. A simple protocol is developed for the in situ fabrication of highly monodisperse copper-complex nanoparticles in a polymer film matrix of polyacrylic acid. The thin films were deposited on quartz substrates by MAPLE (matrix assisted pulsed laser evaporation) using a Nd:YAG laser working at 355 nm. Atomic force microscopy (AFM), Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), and optical second harmonic generation (SHG) were performed on the samples. The optical limiting capability of the nanoparticle-embedded polymer film is investigated.     

Vapor deposition of intact polyethylene glycol thin films

Thin films of polyethylene glycol (PEG) of average molecular weight, 1400 amu, were deposited by both matrix-assisted pulsed laser evaporation (MAPLE) and pulsed laser deposition (PLD). The deposition was carried out in vacuum (∼10^-6 Torr) with an ArF (λ=193 nm) laser at a fluence between 150 and 300 mJ/cm². Films were deposited on NaCl plates, Si(111) wafers, and glass slides. The physiochemical properties of the films are compared via Fourier transform infrared spectroscopy (FTIR), electrospray ionization (ESI) mass spectrometry, and matrix-assisted laser desorption and ionization (MALDI) time-of-flight mass spectrometry. The results show that the MAPLE films nearly identically resemble the starting material, whereas the PLD films do not. These results are discussed within the context of biomedical applications such as drug delivery coatings and in vivo applications where there is a need for transfer of polymeric coatings of PEG without significant chemical modification. Received: 2 March 2001 / Accepted: 5 March 2001 / Published online: 23 May 2001     

非线性光学中的新型有机和聚合分子材料

近年来的研究成果表明在非线性光学中一些有机和聚合分子材料与相应的无机晶体、半导体如LiNbO₃、GaAs等相比较,具有许多优越性。本文介绍了一些有机和聚合分子材料的非线性光学效应,包括模拟,离散和双稳现象及其潜在的应用。然后描述了几种这类晶体与薄膜材料的制备技术,其中LB膜沉积是制备超薄有机聚合膜的有效方法。     

MAPLE-deposited polymer films for improved organic device performance

Matrix-assisted pulsed-laser evaporation (MAPLE) provides a mechanism for layer-by-layer growth to control the polymer–dielectric interface in organic metal–insulator–semiconductor (MIS) diodes and field-effect transistors (FETs). MAPLE-deposited copolymers of polyfluorene (PF) and polythiophene maintain their structural and optical properties, as determined by Raman spectroscopy, absorption, and photoluminescence. These films are further utilized in MIS and FET structures with SiO₂ and other polymer dielectrics. Since common polymer dielectrics prevent spin coating of solution processable polymers due to solubility effects, MAPLE is one of the only deposition techniques for investigating all polymer semiconductor-insulator interfaces. In this paper we present optical and electrical studies of MAPLE-deposited PF and polythiophene films in FETs and MIS structures. The FET carrier mobilities of these devices compare well with spin-coated devices. Capacitance–voltage and conductance–voltage from MIS structures with MAPLE-deposited PF copolymer films yield interface trap densities in the low 10¹² eV⁻¹ cm⁻² range.     

Applications of the matrix-assisted pulsed laser evaporation method for the deposition of organic,biological and nanoparticle thin films: a review

The matrix-assisted pulsed laser evaporation (MAPLE) technique offers an efficient mechanism to transfer soft materials from the condensed to the vapor phase, preserving the versatility, ease of use and high deposition rates of the pulsed laser deposition (PLD) technique. The materials of interest (polymers, biological cells, proteins, …) are diluted in a volatile solvent. Then the solution is frozen and irradiated with a pulsed laser beam. Here, important results of MAPLE deposition of polymer, biomaterials and nanoparticle films are summarized. Finally, the MAPLE mechanism is discussed. A review of experimental and theoretical works points out that the simple model of individual molecule evaporation must be abandoned. Solute concentration, solubility, evaporation temperature of solvents, laser pulse power density and laser penetration depth emerge as important parameters to explain the morphology of the MAPLE-deposited films.     

The Matrix-Assisted Pulsed Laser Evaporation (MAPLE) process: origins and future directions

This review discusses the origins and evolution of the MAPLE technique as it started as an alternative to spray coating of thin films for chemical vapor sensors. It describes its numerous applications for the deposition of thin films of polymeric, organic and biomaterials for various applications. This is followed by an overview of several new variations of the MAPLE technique. This review concludes with an outlook on the future of this highly versatile and successful vapor deposition process.     

The influence of oxygen on the optical properties of RF-sputtered zinc oxide thin films

In this article, we investigate the effects of oxygen partial pressure in the deposition chamber on the optical properties of zinc oxide (ZnO) thin films; in particular, we examine the variation of the refractive index with oxygen flux.ZnO thin films were deposited by radio-frequency (RF) magnetron sputtering and studied by means of X-ray diffraction (XRD) and spectroscopic ellipsometry (SE). We have found a preferential c-axis growth of ZnO films, with slightly variable deposition rates from 2.6 to 3.8 Å/s. Conversely, the refractive index exhibits, from ultraviolet (UV) to near infrared (IR), a considerable and almost linear variation when the oxygen flux value in the deposition chamber varies from 0 to 10 sccm.     

脉冲等离子体推力器羽流沉积薄膜的结构与光学性质研究

为了研究脉冲等离子体推力器羽流污染特性,把握脉冲等离子体推力器羽流沉积薄膜性质,利用质谱仪对推力器羽流残余气体成分进行了分析,利用红外傅里叶光谱、光电子能谱及紫外可见光分光光度计对推力器羽流区阴极侧不同方位角处沉积薄膜的结构及光学性质进行了诊断研究结果表明,推力器羽流中主要存在C,F,CF,CF2和CF3气体分子;在各方位角处脉冲等离子体推力器羽流沉积生成了低氟碳比碳氟薄膜;沉积薄膜微观结构以30°角为界在羽流不同区域中具有不同的变化趋势;羽流沉积薄膜具有对波长小于500 nm的光低透射率及增强反射率的光学特性,受薄膜性质的影响,其光学特性具有极大的角度依赖性.     

CdS thin films obtained by thermal treatment of cadmium(II) complex precursor deposited by MAPLE technique

Thin films of [Cd{SSi(O-Bu^t)₃}(S₂CNEt₂)]₂, precursor for semiconducting CdS layers, were deposited on silicon substrates by Matrix-Assisted Pulsed Laser Evaporation (MAPLE) technique. Structural analysis of the obtained films by Fourier transform infrared spectroscopy (FTIR) confirmed the viability of the procedure. After the deposition of the coordination complex, the layers are manufactured by appropriate thermal treatment of the system (thin film and substrate), according to the thermal analysis of the compound. Surface morphology of the thin films was investigated by atomic force microscopy (AFM) and spectroscopic-ellipsometry (SE) measurements.     

Structural and optical properties study of nanocrystalline Si (nc-Si) thin films deposited on porous aluminum by plasma enhanced chemical vapor deposition

In this paper we report detail investigation and correlation between micro-structural and optical properties of nanocrystalline silicon (nc-Si) deposited by plasma enhancement chemical vapor deposition (PECVD) on porous aluminum structure. The influence of the microstructure of the nc-Si thin films on their optical properties was investigated through an extensive characterization. The effect of anodisation currents on the microstructure of aluminum surface layer and nc-Si films was systematically studied by atomic force microscopy (AFM) and transmission electron microscopy (TEM), Raman spectroscopy and X-ray diffraction (XRD). The optical constants (n and k as a function of wavelength) of the films were obtained using variable angle spectroscopic ellipsometry (SE) in the UV-vis-NIR regions. The silicon layer (SL) was modeled as a mixture of void, crystalline silicon and aluminum using the Bruggeman approximation. Based on this full characterization, it is demonstrated that the optical characteristics of the films are directly correlated to their micro-structural properties. A very bright photoluminescence (PL) was obtained and find to depend on anodisation current.     

衬底温度对HfO_2薄膜结构和光学性能的影响

采用直流磁控反应溅射法,分别在室温,200,300,400和500℃下制备了HfO2薄膜。利用X射线衍射(XRD)、椭圆偏振光谱(SE)和紫外可见光谱(UVvis)研究了衬底温度对HfO2薄膜的晶体结构和光学性能的影响。XRD研究结果显示:不同衬底温度下制备的HfO2薄膜均为单斜多晶结构;随衬底温度的升高,(-111)面择优生长更加明显,薄膜中晶粒尺寸增大。SE和UVvis研究结果表明:随衬底温度升高,薄膜折射率增加,光学带隙变小;制备的HfO2薄膜在250～850nm范围内有良好的透过性能,透过率在80%以上。     

Temperature dependence of low loss polymeric AWG

We investigate on the variation of loss and temperature dependence of a polymeric arrayed waveguide grating (AWG) depending on its substrate, by fabricating 16-channel polymeric AWGs with various substrate conditions. Insertion loss for a polymeric AWG on a silicon substrate is measured as low as 3.1 dB. The temperature-dependent wavelength shift for a polymeric AWG detached from the substrate is maintained within 0.1 nm from 20 to 80 °C. But we observe a degradation of insertion loss and a little instability in wavelength characteristics both for the detached polymeric AWG and for a polymeric AWG on a polymer substrate. We investigate on those optical properties of the polymeric AWGs based on measured thermal expansion properties of the polymers.     

Physical and dispersive optical characteristics of ZrON/Si thin-film system

To date, the complex evaluation of physical and dispersive optical characteristics of the ZrON/Si film system has yet been reported. Hence, ZrON thin films have been formed on Si(100) substrates through oxidation/nitridation of sputtered metallic Zr in N₂O environment at 500, 700, and 900 ^°C. Physical properties of the deposited films have been characterized by X-ray diffractometry (XRD), Fourier transform infrared (FTIR) spectroscopy, reflection high-energy electron diffraction (RHEED), and spectroscopic ellipsometry (SE). It has been shown that ZrON/Si thin films without optical absorption can be prepared by oxidation/nitridation reaction in N₂O environment at 700–900 ^°C.     

Studying polymer thin films with hybrid optical microcavities

Organic and inorganic polymeric thin films have numerous applications, including solar cells, biodetection, and nanocomposites. Improving our understanding of the fundamental material behavior is critical to designing polymers with ideal behavior and increased lifetime. However, there are limited nondestructive characterization methods that are able to perform these high-resolution measurements. In this Letter, we demonstrate a method that is able to detect temperature-induced changes in the refractive index of polystyrene polymer thin films as small as 10(-7). This approach is based on optical microcavity resonators. The experimental results agree well with the theoretical simulations.