Matrix assisted pulsed laser evaporation: the surface cluster problem

The unexpected presence of agglomerates in polymer films deposited by the Matrix Assisted Pulsed Laser Evaporation (MAPLE) technique is discussed. Many experimental and theoretical works suggest that the simple model of individual molecule evaporation must be abandoned. Solute concentration, boiling temperature and vapor pressure of solvents, laser pulse number, and laser light penetration depth are important parameters to be considered to explain the morphology of the MAPLE deposited films. Nanorods films, which can be efficiently deposited on rough surfaces using the MAPLE technique, present more or less large surface droplets, also. Here, the reduced melting temperature of nanostructured materials can explain agglomeration even at low laser fluences.     

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.     

Solvent effects on the electrical and optical properties of composite carbon nanotube/MEH-PPV films

Optical signals were used to modulate the resistance of single-walled carbon nanotube–polymer composite films for development of optical switching devices. Films were fabricated from nanotubes dispersed in poly(2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV) solutions in either tetrahydrofuran (THF) or toluene. MEH-PPV was affected by the solvent choice, with THF causing an absorbance shift to shorter wavelengths. Composite films formed from THF dispersions showed 1–4% resistance decreases when illuminated with a green diode laser. Illumination of toluene-based films showed up to 5.4% resistance decreases, smaller than expected based on the polymer solution absorbance. Fluorescent emission from the polymer in toluene appears to inhibit charge transfer from the polymer to the nanotubes. THF films were unaffected by illumination with a red diode laser, while toluene dispersion films showed resistance decreases up to 1%. Nanotube dispersion and film formation reproducibility, evaluated for both the solvents, showed that the solvent affected film resistance and dispersion stability.     

Study of temperature dependence and angular distribution of poly(9,9-dioctylfluorene) polymer films deposited by matrix-assisted pulsed laser evaporation (MAPLE)

Poly(9,9-dioctylfluorene) (PFO) polymer films were deposited by matrix-assisted pulsed laser evaporation (MAPLE) technique. The polymer was diluted (0.5 wt%) in tetrahydrofuran and, once cooled to liquid nitrogen temperature, it was irradiated with a KrF excimer laser. 10,000 laser pulses were used to deposit PFO films on 〈1 0 0〉 Si substrates at different temperatures (−16, 30, 50 and 70 °C). One PFO film was deposited with 16,000 laser pulses at a substrate temperature of 50 °C. The morphology, optical and structural properties of the films were investigated by SEM, AFM, PL and FTIR spectroscopy. SEM inspection showed different characteristic features on the film surface, like deflated balloons, droplets and entangled polymer filaments. The roughness of the films was, at least partially, controlled by substrate heating, which however had the effect to reduce the deposition rate. The increase of the laser pulse number modified the target composition and increased the surface roughness. The angular distribution of the material ejected from the target confirmed the forward ejection of the target material. PFO films presented negligible modification of the chemical structure respect to the bulk material.     

An experimental investigation of inhomogeneities in resonant infrared matrix-assisted pulsed-laser deposited thin polymer films

Thin polymer films are deposited using matrix-assisted pulsed-laser evaporation and subsequently are characterized by scanning electron and atomic force microscopies. An Er : YAG laser (2937 nm, 350 μs) is used as a light source and the effect of the energy density supplied by the laser on the morphology of the deposited films is investigated. It is found that the appearance of undesirable non-uniform morphological features arises from either poor solubility of the guest molecules or insufficient energy density provided by the laser to vaporize the entire ejected volume. In addition, the surface roughness of two guest–host systems is found to depend linearly on the polymer concentration. These results allow us to better understand earlier work in the field and to establish a framework by which MAPLE films may be improved.     

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.     

Effect of substrate temperature on MAPLE deposition of synthetic eumelanin films

Eumelanin is an important pigment almost ubiquitous in animals and plants exhibiting interesting charge transport capabilities. Its poor solubility in common solvents represents a severe limitation for preparing thin films. It was recently demonstrated that eumelanin films can be successfully deposited with the MAPLE (Matrix Assisted Pulsed Laser Evaporation) technique starting from a frozen water suspension, using infrared laser radiation. The low laser absorption of ice together with the high absorption of eumelanin suggests that the target ablation is due to laser energy absorbed by the eumelanin molecules, followed by thermal energy transfer, and ejection of ice/water/vapor containing undamaged eumelanin molecules and supramolecular structures.     

不同沉积参量下ZrO2薄膜的微结构和激光损伤阈值

ZrO2采用X射线衍射(XRD)技术分析了不同充氧条件和沉积温度对ZrO2溥膜组成结构的影响,并对不同工艺下制备的薄膜的表面粗糙度和激光损伤阈值进行了测量。结果发现随着氧压的升高,ZrO2溥膜将由单斜相多晶态逐渐转变为非晶态结构,而随着基片温度的增加,溥膜将由非晶态逐渐转变为单斜相多晶态。同时发现随着氧压升高晶粒尺寸减小,而随着沉积温度增加,晶粒尺寸增大。氧压增加时工艺对表面粗糙度有一定程度的改善,而沉积温度升高,工艺对表面粗糙度的改善不明显。晶粒尺寸大小变化与表面粗糙度变化存在对应关系。激光损伤测量表明,氧压条件和沉积温度对ZrO2薄膜的抗激光损伤能力有着较大影响。     

Pulsed laser thin film growth of di-octyl substituted polyfluorene and its co-polymers

Matrix-assisted pulsed laser deposition (PLD) allows a controlled layer-by-layer growth of polymer films. Di-octyl substituted polyfluorene (PF8) and its copolymers were deposited as thin films using matrix-assisted PLD by employing a KrF excimer laser with a fluence of 125 mJ/pulses. The optical and structural properties of these films are compared with spincoated films via Raman spectroscopy, absorption and photoluminescence. The Raman spectra of both PLD and spincoated films are similar indicating that the polymer films deposited via PLD maintain their molecular structure. Both the spincoated and the PLD grown PF8 films that were cast from toluene show the presence of the β phase. Benzothiadiazole substituted PF8 (F8BT) and butyl phenyl-substituted PF8 (PFB) PLD grown films show a slightly broader emission compared to the spincoated films, which is attributed to an enhanced intermolecular interaction in the PLD grown thin films.     

Structural characterization and optoelectronic properties of GaN thin films on Si(111) substrates using pulsed laser deposition assisted by gas discharge

GaN films have been grown on Si(111) substrates with a thin AlN buffer layer using pulsed laser deposition (PLD) assisted by gas discharge. The crystalline quality, surface morphology and optoelectronic properties of the deposited films were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), photoluminescence (PL) spectroscopy, and room-temperature Van der Pauw–Hall measurements. The influence of the deposition temperature in the range 637–1037 K on the crystallinity of GaN films, the laser incident energy in the range 150–250 mJ/pulse on the surface morphology and the optoelectronic properties were systematically studied. The XRD analysis shows that the crystalline quality of the GaN films improves with increasing deposition temperature to 937 K, but further increase of the deposition temperature to 1037 K leads to the degradation of the crystalline quality. AFM results show that the surface roughness of the GaN films can be decreased with increasing laser incident energy to 220 mJ/pulse. Further increase of the laser incident energy to 250 mJ/pulse leads to an increase in the surface roughness. The optoelectronic properties of GaN films were also improved by increasing the laser incident energy to 220 mJ/pulse. GaN films which have a n-type carrier concentration of 1.26×10¹⁷ cm^-3 and a mobility of 158.1 cm²/Vs can be deposited at a substrate temperature of 937 K, a deposition pressure of 20 Pa and a laser incident energy of 220 mJ/pulse. Their room-temperature PL spectra exhibit a strong band-edge emission at 365 nm. PACS 81.15.Fg; 81.05.Ea; 78.20.-e; 73.61.Ey; 78.66.Fd     

衬底温度对PLD制备的Mo薄膜结构及表面形貌的影响

 运用脉冲激光沉积(PLD)技术在Si(100)基片上沉积了金属Mo薄膜。在激光重复频率2 Hz,能量密度5.2 J/cm²,本底真空10^－6 Pa的条件下,研究Mo薄膜的结构和表面形貌,讨论了衬底温度对薄膜形貌与结构的影响。原子力显微镜(AFM)图像和X射线小角衍射(XRD)分析表明,薄膜表面平整、光滑,均方根粗糙度小于2 nm。沉积温度对Mo薄膜结构和表面形貌影响较大,在373~573 K范围内随着温度升高,薄膜粗糙度变小,结晶程度变好。     

Surface foaming of collagen, chitosan and other biopolymer films by KrF excimer laser ablation in the photomechanical regime

Collagen, an important material made of a protein of the extracellular matrix, was extracted from rat tail tendons by acetic acid dissolution, and dry glassy films (15% water content) with smooth surfaces were casted from the solution with a thickness of ∼25 μm. Collagen and similar biopolymer films surface were exposed to single pulses of radiation of the KrF laser with increasing fluence. A white damaged area appears on the treated surface at a threshold of 0.5 J/cm² with a single pulse and becomes more visible for higher fluence. SEM and profilometry of the ablated surface displays an important swelling (∼5–7 μm) and a microscopic foam structure indicative of the laser induced expansion of the excited material. This process is due to the explosive ablation (a critical phenomenon also called explosive boiling or phase explosion) of the irradiated material and produces upon laser heating a high concentration of bubbles within the polymer because of the relatively large absorption depth (20 μm) and the presence of a large amount of water in the material. Further bubble colliding and bursting produces a three-dimensional polymer micro-foam with interconnected pores. This is the first this result has been reported. The laser induced micro-foam may display some interesting properties for new applications. PACS 42.62; 61.82; 42.70-aThis revised version was published online in June 2005 with corrections to equations 7, 9 and 10.     

Effect of crystalline microstructure on the photophysical performance of polymer／perylene composite films

To obtain high carrier mobility, better charge injection capability, and high photovoltaic device conversion efficiency, a powerful strategy is to improve the morphology of the polymer/dye composite films. Conjugated conducting polymer (CP) thin films doped with perylene derivative (PV) of various concentrations were prepared by spin-casting method, and their morphology and photovoltaic characteristics were examined. The change in morphology and molecular reorientation occurring in CP-PV composite films upon annealing at different temperatures was investigated using scanning electron microscopy, x-ray diffraction, Fourier transform infrared and UV-vis absorption. By changing the annealing temperature, PV microcrystallines of 8－10μm in size lying parallel to the substrate surface can be obtained. Annealing effect improved the photovoltaic performance of ITO/CP-PV/Al Schottky-type solar cells, which can be attributed to the formation of an electron conducting PV crystal network. Preliminary studies indicate that the morphological structure in CP-PV composite films has an important influence to their photovoltaic properties.     

Substrate temperature influence on the properties of nanostructured ZnO transparent ultrathin films grown by PLD

Zinc oxide films of 40 nm thickness have been deposited on glass substrates by pulsed laser deposition using an excimer XeCl laser (308 nm) at different substrate temperatures ranging from room temperature to 650 °C. Surface investigations carried out by using atomic force microscopy have shown a strong influence of temperature on the films surface topography. UV-VIS transmittance measurements have shown that our ZnO films are highly transparent in the visible wavelength region, having an average transmittance of ∼90%. The optical band gap of the films was found to be 3.26 eV, which is lower than the theoretical value of 3.37 eV. Besides the normal absorption edge related to the transition between the valence and the conduction band, an additional absorption band was also recorded in the wavelength region around 364 nm (∼3.4 eV). This additional absorption band may be due to excitonic, impurity, and/or quantum size effects. Photoreduction/oxidation in ozone of the ZnO films lead to larger conductivity changes for higher deposition temperature. In conclusion, the ozone sensing characteristics as well as the optical properties of the ZnO thin films deposited by pulsed laser deposition are strongly influenced by the substrate temperature during growth. The sensitivity of the films towards ozone might be enhanced significantly by the control of the films deposition parameters and surface characteristics.     

溶剂对溶胶-凝胶法制备的掺铝氧化锌透明导电薄膜性质的影响

采用溶胶-凝胶法在玻璃基底上制备得到了高透光率,高导电性的掺铝氧化锌薄膜。研究了溶剂对薄膜晶体结构,薄膜厚度,表面形貌,光学性质和电学性质的影响,结果表明:在相同的制备条件下,薄膜的厚度随溶剂沸点的升高而降低;低沸点溶剂制备的薄膜由c轴择优取向的六角纤锌矿结构的晶体构成,且比较致密;所有薄膜可见光区的透光率在85%以上;乙二醇独甲醚为溶剂制备的薄膜电阻率最低,为3.0×1-0 4Ωm。     

Surface Modification of Poly (ether ether ketone) with a Medlite C6 (ND-YAG Q-Switched) Skin Treatment Laser

Poly ether ether ketone (PEEK), a synthetic polymer, is expected to be useful as a biomaterial due to its appropriate mechanical, chemical, and biocompatibility properties. However, this polymer is biologically inert, requiring surface modification to improve its adhesion to bone cells for use as a bone substrate. Surface properties, such as roughness and hydrophilicity, are important factors in the adhesion of biomaterials to the surrounding tissue; therefore, in this study, laser treatment was performed for surface modification. The aim of the research described here was to investigate the effect of two laser parameters, fluency and wavelength, on the surface roughness and hydrophilicity to determine the optimum parameters for improving surface adhesion. The surface topography and average roughness (R_a) were investigated by atomic force microscopy (AFM). Surface morphology was also observed with an optical microscope, and the hydrophilicity of the surfaces was investigated with static contact angle tests. The results obtained showed that the samples treated at the wavelength of 532?nm with fluency of 8?J/cm², compared to fluencies of 4 and 12?J/cm², showed improved surface properties. However, in terms of radiation wavelength, the wavelength of 1064?nm at these three fluencies showed the most promising results for enhancing the surface properties of PEEK for bone implant applications.     

Optical properties of amorphous HF–In–Zn–O thin films estimated from transmission spectra

Amorphous and flat (<1 nm roughness) Hf–In–Zn–O thin films were prepared by radio frequency (rf) magnetron sputtering method at room temperature (RT) and at 300 °C substrate temperature. The crystal structure and surface morphology were investigated by high resolution X-ray diffraction (HR-XRD) and atomic force microscopy (AFM), respectively. Optical properties of these films were obtained from the UV–VIS–NIR transmission spectra, at normal incidence, over the 200–2000 nm spectral range. Swanepoel's method was used to calculate the thickness and the refractive index of the films. The dispersion of refractive index was obtained in terms of the single-oscillator Wemple–DiDomenico model. The optical absorption edge was described using the direct transition model proposed by Tauc. The film deposited at higher substrate temperature had lower optical band gap, higher refractive index, higher oscillator strength and energy of the effective dispersion oscillator. Optical characterization shows that films become more stable, relaxed and rigid at higher substrate temperature.     

Thin films of polyaniline deposited by MAPLE technique

Polyaniline (PAni) has important electro-conductive properties, high absorbance in microwave range and it is also frequently used in gas sensors because of its capability to convert chemical interactions into electrical signals. The methods of obtaining polyaniline in the form of thin films and/or nanostructures are complicated and request special physical and chemical treatments, both on the substrate surface and for the polymer itself.In this paper we applied matrix assisted pulsed lased evaporation (MAPLE) for obtaining thin films and nanostructures of polyaniline. In MAPLE, the target consisting of the material (usually 0.2-3 wt%) dissolved in a solvent is frozen and it is evaporated using a laser. In our case polyaniline-emeraldine salt (PAni-ES) was dissolved in xylene or toluene, frozen in liquid nitrogen and was used as target. The third and the fourth harmonics of a Nd-YAG laser (λ = 355 nm and 266 nm) were used as laser sources. The obtained films have been characterized by atomic force microscopy, dielectric spectroscopy and Fourier transform infrared spectroscopy. The influence of the solvent type and of the laser parameters (wavelengths and fluence) on the polyaniline structures composition and properties has been investigated.     

The role of the temperature and laser fluence on the properties of PLD bioactive glass films

The effect of the deposition temperature and laser fluence on the bonding configuration, morphology and mechanical properties of the PLD bioactive glass thin films in the system SiO₂P₂O₅CaONa₂OK₂OMgO is presented.Information on the IR active Si-O groups was obtained by Fourier Transform Infrared (FTIR) spectroscopy. Surface morphology changes were followed by Atomic Force Microscopy (AFM) and the film thickness was measured by profilometry. Hardness and elastic modulus were determined by nano-indentation.The frequency shifting and intensity variations of the IR absorption bands indicate that the substrate temperature plays an important role on the bonding configuration of the films. This effect is associated with a network rearrangement and the surface chemistry that occurs during the film growth.The main effects of the laser fluence on the film properties are the linear dependence on it of the growth rate and the changes induced on the surface morphology. Both results are discussed in terms of beam–matter interaction and plume–substrate interaction in the PLD process. Finally, the hardness and the elastic modulus of the films are in agreement with the values reported in the literature for the bulk material. PACS 81.15.Fg; 87.68.+z; 68.60.Bs; 68.37.Ps; 61.43.F1; 67.70.+n     

RIR-MAPLE deposition of conjugated polymers for application to optoelectronic devices

Resonant-infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE) is a promising deposition technology for the fabrication of conjugated polymer-based optoelectronic devices for two primary reasons: (i) the ability to control film morphology, and (ii) the ability to deposit multi-layered heterostructures. This article reviews a variation of RIR-MAPLE that uses emulsified targets of organic solvents and water such that the incident laser wavelength (Er:YAG at 2.9 μm) is resonant with hydroxyl (O–H) bonds in the host matrix, which are absent from the guest material. The novelty of the approach lies in the fact that while most polymers of interest and many compatible solvents do not resonantly absorb the laser energy at 2.9 μm, the emulsion with water enables high-quality, thin-film deposition with minimal photochemical and structural degradation for almost any polymer of interest. In addition, the advantages of emulsion-based RIR-MAPLE for conjugated polymer-based optoelectronic devices are demonstrated by two important studies. First, conjugated polymer films deposited by RIR-MAPLE are shown to have higher hole drift mobilities than films deposited using traditional drop-casting and spin-casting techniques. Second, the unique capability of RIR-MAPLE to enable conjugated polymer-based optical heterostructures is demonstrated by the fabrication and characterization of a multi-layer, polymer distributed Bragg reflector.