Surface modification of polymers by ion-assisted reaction

This paper deals with a new surface modification technique of polymers, the so-called ion-assisted reaction (IAR) to improve the surface properties of polymers and provides outstanding experimental results regarding wettability and adhesion of various polymers. In the IAR, polymer surfaces were subjected to low energy ion irradiation at different dosage in reactive gas environment. Dramatic improvements in wettability and surface energy are observed for the IAR-treated polymer surfaces and can be explained by the addition of functional groups, responsible for the increase of polar component in surface energy. The formation of functional groups results from the interaction among ion, reactive gas and polymer chain involved in IAR treatment, depending on the reactive ion species, the flow rate of the reactive gas and the irradiating ion fluence. The improvement in adhesion between the IAR-treated polymers and coating materials was explained in terms of the increased surface energy as well as surface roughness in the polymers modified by the IAR and possible adhesion enhancement mechanism is to be discussed.     

Chemical surface modification of poly (ethylene terephthalate) by excimer irradiation of high and low intensities

Poly (ethylene terephthalate) (PET) was modified by a KrF 248 nm excimer laser with high- (above ablation threshold) and low- (below ablation threshold) fluence. The PET surface develops usually a periodic roughness or ripples with high fluence. The roughness size is in the micron range and the surface shows signs of global melting. However, the ripple size can be reduced to sub-micron level by an irradiation of the sample below the ablation threshold with a polarized beam. The morphology of the irradiated surfaces was examined by scanning electron microscopy (SEM). Chemical surface changes of the materials were characterized by X-ray photoelectron spectroscopy (XPS). The PET modification by high fluence will normally results in the deposition of some yellow to black materials (debris), on the treated surface. The debris are ionized and from carbon rich materials which finally condense forming higher aggregates, resulting in a reduction of O/C ratio. By contrast, modification of PET surfaces by low fluence leads to an oxidation and almost no ablation is detected. The increase of oxygen concentration on low fluence modified surfaces is probably due to a subsequent reaction with atmospheric O₂ during irradiation. Our work suggests that a careful selection of laser parameters for the surface modification of polymer is of primary importance. Received: 06 November 2000 / Reviewed and accepted: 07 November 2000     

Surface morphology of steel and titanium induced by ion beam bombardment – Comprehensive analysis

It is well known that ion bombardment of solid surface modifies its physical and chemical properties, among others, surface morphology. In this paper we try to concentrate on four aspects of ion beam induced surface morphology, i.e.: (a) surface topography, (b) surface roughness, (c) rate of profile shape variability, and (d) surface morphology arrangement. Surface topographies (in micro- and nanometre range) were observed by means of scanning electron and near-field microscopes. High quality profilograph and atomic force microscope were utilised to measure surface roughness parameters. To do that, surface profiles must be well known. To detect any profile shape alteration during ion beam bombardment we used fractal analysis, and especially fractal dimension D that can give information about rate of profile shape variability. Surface morphology arrangement, i.e. a question whether it is random or determined, was studied with the use of frequency plots resulting from harmonic analysis of profiles.We studied surface topographies, selected roughness parameters, fractal dimensions and frequency plots relating to stainless steel and polycrystalline 99.5% titanium bombarded with perpendicular low energy (800 eV) broad argon ion beam as well as neutralized narrow argon or krypton ion beam (up to 6 keV).     

在120 keV质子辐照下环氧树脂的质损效应

对AG-80环氧树脂浇注体进行了120 keV质子辐照试验,测试了质子辐照前后AG-80的质损率,借助AFM、XPS对环氧树脂表面的形貌、化学成分和化学结构进行了分析.试验结果表明,随质子辐照剂量增加,质损率首先增加,随后变化趋于平缓;表面粗糙度先增加后减小.在质子辐照的作用下,AG-80环氧树脂表面离子碎片逸出和表面层发生炭化是其质损和表面粗糙度发生变化的原因.     

Monte Carlo simulation of intermixed layer formed by ion beam enhanced deposition

A Monte Carlo simulation code SIBL has been used to simulate the intermixed layer formed during ion beam enhanced deposition (IBED). Depending on the simple collision cascade mixing model, the relations between the shape of the intermixed layer and the ion energy, the atomic arrival ratio and the incident angle have been investigated. A semi-empirical expression has been established, which is in agreement with Sigmund's analytical expression, indicating a quadratic dependence of the thickness of the intermixed layer on the ion fluence and the total elastic energy deposited in the interface region.     

Energetic ion irradiation induced crystallization of Ni–Mn–Sn ferromagnetic shape memory alloy thin film

The ion irradiation induced crystallization of Ni–Mn–Sn ferromagnetic shape memory alloy (FSMA) thin film is investigated. Thin films of Ni–Mn–Sn FSMA synthesized by DC magnetron sputtering on Si substrate at 200 °C are irradiated by a beam of 120 MeV Ag ions at different fluence varying from 1 × 10¹² to 6 × 10¹² ions/cm². X-ray diffraction pattern reveals that the pristine film grows in L2₁ cubic austenite phase with poor crystallinity and crystallinity of the film improves with increasing ion fluence, which is attributed to the strain relaxation by the energy deposited by incoming ions and promotes the grain growth. Grain growth is further confirmed by Atomic force microscopy. The temperature dependent magnetization measurements show improvement in the magnetic and shape memory properties of the films with increasing fluence, which is ascribed to the ordering of austenite phase. Nanoindentation measurements show that with increasing fluence of 120 MeV Ag ions, films exhibit a greater stiffness and smaller tendency towards plastic deformation.     

Influence of SHI irradiation on the structure and surface topography of CdTe thin films on flexible substrate

Impact of ion irradiation on thin films is an emerging area for materials modification. CdTe thin films grown by thermal evaporation on flexible molybdenum (Mo) substrate were irradiated with Swift (100 MeV) Ag⁺⁷ ions for various ion fluence in the range 10¹²–10¹³ ions/cm². The modifications in the composition, structure and surface morphology have been studied as a function of ion fluence. The Energy Dispersive X-ray Analysis (EDS) shows slightly Te-rich composition for both as-grown and irradiated films with no significant change after irradiation. X-ray diffraction (XRD) analysis indicates a consistent shift in the (111) peak position towards higher diffraction angle and an increase in the full width at half maximum (FWHM) with increase in ion fluence. The change in the residual stress during irradiation has been evaluated and is related to the corresponding microstructural changes in the films. The initial tensile stress is found to be relaxed after irradiation. Atomic Force Microscopy (AFM) studies revealed significant grain splitting after irradiation and formation of hillocks at higher ion fluence. The surface roughness was significantly increased at higher ion fluence.     

Radio frequency source power-induced ion energy impact on SiN films deposited using a room temperature SiH4-N2 plasma

Using a SiH4-N2 plasma, silicon nitride films were deposited at room temperature. The impact of source power ranging from 500 to 900 W and ion energy are investigated. The film properties examined include a deposition rate, a refractive index, and a surface roughness. Ion energy diagnostics was conducted to explore the relationships between ion energy and film properties. A variation in ion energy with source power was quite complex. By contrast, a decrease in ion energy flux was observed for a decrease in the source power. An increase in the deposition rate with the decrease in source power was attributed to enhanced ion energy. The refractive index strongly correlated with low ion energy flux. A decrease in surface roughness in the range of 500-700 W was related to larger ion energy. The deposition rate, refractive index, and surface roughness were varied in the range of 0.27-0.35 nm/sec, 1.690-1.739, and 6.7-52.5 nm, respectively.     

Adhesion and proliferation of keratinocytes on ion beam modified polyethylene

Polyethylene (PE) foils were modified by irradiation with ArE ⁺ and XeE ⁺ ions to different fluences and different physico-chemical properties of the irradiated PE were studied in relation to adhesion and proliferation of keratinocytes on the modified surface. Changes in the PE surface roughness were examined using the AFM technique, the production of conjugated double bonds and oxidized structures by UV-VIS and FTIR techniques respectively. The surface polarity was determined by measuring surface contact angle and two-point technique was used for the determination of PE sheet resistance. Adhesion and proliferation of keratinocytes was characterized using the MTT-test. The ion irradiation leads to creation of conjugated double bonds which, together with progressive carbonization, contribute to the observed decrease of sheet resistance. Oxidation of the irradiated PE surface layer during the ion implantation is observed. Besides oxidation, the PE surface polarity is affected by other factors. The observed increase of the PE surface roughness due to the ion irradiation is inversely proportional to the ion size. The adhesion and proliferation of keratinocytes on the ion irradiated PE is significantly higher than on the pristine PE. Distribution of results in keratinocyte cultivation and the number of cells is related to the ion fluence applied and to ion species as well.     

Analysis of organometallics dispersed polymer composite irradiated with oxygen ions

Thin films of polymethyl methacrylate (PMMA) were synthesized. Ferric oxalate was dispersed in PMMA films. These films were irradiated with 80 MeV O⁶⁺ ions at a fluence of 1×10¹¹ ions/cm². The radiation induced changes in electrical conductivity, Mössbauer parameter, microhardness and surface roughness were investigated. It is observed that hardness and electrical conductivity of the film increases with the concentration of dispersed ferric oxalate and also with the fluence. It indicates that ion beam irradiation promotes (i) the metal to polymer bonding and (ii) convert the polymeric structure into hydrogen depleted carbon network. Thus irradiation makes the polymer harder and more conductive. Before irradiation, no Mössbauer absorption was observed. The irradiated sample showed Mössbauer absorption, which seems to indicate that there is significant interaction between the metalion and polymer matrix. Atomic force microscopy shows that the average roughness (R _a) of the irradiated film is lower than the unirradiated one.     

Low energy Ar+ ion beam irradiation effects on Si ripple pattern

Etching of surfaces by ion beam sputtering is widely used to pattern surfaces. Recent studies using the high-spatial-resolution capability of the scanning tunneling microscope, atomic force microscope and SEM (Scanning Electron Microscopy) disclose in fact that ion bombardment creates repetitive structures at micro-nanometre scale, waves (ripples), checkerboards or pyramids. The phenomenon is related to the interaction between ion erosion and diffusion of adatoms (vacancies), which causes surface re-organization. In this paper we investigated the ripple pattern formation on Si substrates by low energy Ar+ ion bombardment and the dose effect on ripple size. We also briefly discussed the irradiation effects (at normal incidence) on ripple pattern for different irradiation time. Finally, based on Bradley and Harper (BH) theory we proposed a model to understand the mechanism of ripple pattern change due to Ar+ ion beam irradiation.     

Optical properties and instrumental performance of thin gold films near the surface plasmon resonance

The optical properties of very thin gold films have been evaluated by Fresnel analysis, with optical boundary conditions pertaining to the surface plasmon resonance (SPR) at the gold-water interface. The experimental SPR characteristic was evaluated in the angular interrogation mode. Film morphology was characterized by high resolution transmission electron microscopy. The magnitude of the resonance, i.e., the SPR signal, sensitively depends on, and is affected by film thickness and morphology. A sharply defined thickness of 55 ± 5 nm is required, to achieve optimum SPR excitation conditions, and instrumental sensitivity. With decreasing film thickness, below 40 nm, the resonance angle starts to shift to larger values. A substantial increase of the intrinsic resonance broadening parameter is observed below 70 nm, associated with an increasingly asymmetric SPR line shape. A similar effect occurs in the presence of a very thin chromium adhesion layer. Surface roughness and film thickness modulations determine the experimentally observed line broadening parameter. Instrumental noise levels largely depend on accuracy and quality at which the resonance angle can be determined. Substantial improvement and instrumental sub-pixel resolution is achievable by optimum fitting routines, accounting for drastic noise reduction and improved instrumental sensitivity, up to two orders of magnitude over the inherent geometric sensor pixel resolution.     

Effect of SHI irradiation on the morphology of SnO2 thin film prepared by reactive thermal evaporation

SnO₂ thin films prepared by reactive thermal evaporation on glass substrates were subjected to 120 MeV Ag⁹⁺ ion irradiation. The surface topography progression using the swift heavy ion irradiation was studied. It shows creation of unique surface morphologies and regular structures on the surface of the SnO₂ thin film at particular fluences. Field Emission Scanning electron microscopy (FE-SEM) and Atomic force microscopy (AFM) are used for investigating the effect of Ag ions at different fluences on the surface of SnO₂. The morphological changes suggest that ion assisted/induced diffusion process play a significant role in the evolution of nanostructures on SnO₂ surface. The roughness increases from 9.4 to 14.9 with fluence upto 1 × 10¹² ions/cm² and beyond this fluence, the roughness decreases. Ion-beam induced recrystallization at lower fluences and amorphization or disordering of crystals at higher fluences are understood based on the thermal spike model.     

Magnetic Resonance Line Shape for Small Clusters with Exchange and Quadrupole Interactions

Magnetic resonance line shape for small clusters in manganites with super-exchange and quadrupole interactions is studied by means of numerical analysis. It is shown that the line is Lorentzian for clusters with number of spins more than three. The half-width of line is approximately proportional to quadrupole interaction energy in clusters with number of spins less than tens, while for larger clusters the half-width is approximately proportional to square of quadrupole energy, as predicted by the theory of exchange narrowing.     

Impact of duty ratio-controlled ion energy on surface roughness of silicon nitride films deposited using a SiH4-NH3 plasma

The impact of duty ratio-controlled ion energy on the surface roughness of silicon nitride (SiN) films is examined as a function of the bias power and the duty ratio. Experimental ranges are 30-90 W and 20-80% for the bias power and the duty ratio, respectively. SiN films were deposited at room temperature using a SiH4-NH3 pulsed plasma. Atomic force microscopy was used to measure surface roughness. Investigation is detailed in view of a mean-surface roughness, a non-uniformity of surface height distribution, and using a prediction model. The prediction model was constructed using a neural network and a genetic algorithm. A decrease in the duty ratio results in an increase in the surface roughness, but a decrease in the non-uniformity. Correlation study revealed that the surface roughness was strongly related to the ion energy and the ion energy flux. The neural network model predicts the high ion energy as the most influential diagnostic parameter.     

Characterisation of kilo electron volt neutron fluence standard with the 45Sc(p,n)45Ti reaction at NMIJ

We are developing a national standard of a monoenergetic kilo electron volt neutron field with the (45)Sc(p,n)(45)Ti resonance reaction. A wide resonance yields 27.4 keV neutrons at 0 degrees with respect to the proton beam. The proton energy was precisely determined in the measurement of the relative neutron yield as a function of the proton energy from the threshold energy to 2.942 MeV. Absolute measurement of the monoenergetic neutron fluence was performed using a (3)He proportional counter. Relative measurement was also carried out using a Bonner sphere calibrated at our 144 keV standard neutron field. Calibration factors were obtained between the count of a neutron monitor and the neutron fluence. A silicon-surface barrier detector with a (6)LiF foil converter was also being developed for the neutron fluence measurement. Successful results were obtained in the tests in the 144 keV standard neutron field.     

Resonance in the efficiency of the conduction-state formation in ion-bombarded crystalline quartz

A resonance in the ion conductivity as function of the bombarding-ion mass number was observed in ion-irradiated crystalline quartz. The resonance is observed at the optimum ratio of the energy losses for the nuclear and electron stopping of the impinging ions interacting with crystalline quartz in the range of ion mass numbers from 35 to 45 amu.     

Laser ablative shaping of plastic optical components for phase control

A new scheme for phase control of optical components with laser ablation has been developed. One can ablate the surface shape of optical plastic material coated on a glass plate by using 193-nm laser light to control the transmission wave front. The surface shape is monitored in situ and corrected to attain the desired aberration level. The irradiation fluence is approximately 40 mJ/cm(2), and the ablation depth/pulse is approximately 0.01 mum/pulse for UV-cured resin. A wave-front aberration of 3.0 lambda is reduced to 0.17 lambda for flat surface shaping. For spherical surface generation, an aberration of 2.5 lambda is reduced to 0.2 lambda. The increase in surface roughness is kept within acceptable levels.     

Interface roughness in Mo/Si multilayers

In this work we present a study of surface roughness development at the molybdenum-on-silicon and silicon-on-molybdenum interfaces in Mo/Si multilayers as employed in Extreme UV lithography. Thin Mo/Si multilayers, with layer thicknesses of 3–5 nm, were deposited using electron beam evaporation. The effect of ion treatment on the surface roughness was studied by X-ray reflectometry and transmission electron microscopy. Without ion treatment we observed build up of correlated roughness. The roughness development is shown here to depend strongly on the thickness of the crystalline Mo layer. Independent of the Mo ratio in a period, we show that a minimal amount of ion treatment is required to smoothen the multilayer roughness, which is also confirmed by EUV reflectivity measurements. At high ion energies the layers become smoother due to a larger ion penetration depth. The higher penetration depth is also shown to initiate additional interdiffusion and structural changes at buried interfaces.