Improvements of plasma immersion ion implantation (PIII) and deposition (PIII&D) processing for materials surface modification

Plasma immersion ion implantation (PIII) process is a three dimensional surface modification method that is quite mature and well known to the surface engineering community nowadays, especially to those working in the field of plasma-materials interaction, aiming at both industrial and academic applications. More recently, deposition methods have been added to PIII, the PIII&D, opening possibilities of broader range of applications of these techniques. So, PIII&D is becoming a routine method of surface modification, with the advantage of pushing up the retained dose levels limited by the sputtering due to ion implantation. Therefore, well adherent, thick, three-dimensional films without stress are possible to be achieved, at relatively low cost, using PIII&D. In this paper, we will discuss about a few PIII and PIII&D experiments that have been performed recently to achieve surface improvements in different materials: 1 - high temperature nitrogen PIII in Ti6Al4V alloy in which a deep nitrogen rich treated layer resulted in surface improvements as increase of hardness, corrosion resistance and resistance to wear of the Ti alloy; 2 - nanostructures in ZnO films, obtained by PIII&D of vaporized & ionized Zn source; 3 - combined implantation and deposition of calcium for biomaterial activity of Ti alloy (PIII&D), allowing the growth of hydroxyapatite in a body solution; 4 - magnetron sputtering deposition of Cr that was enhanced by the glow discharge Ar plasma to allow implantation and deposition of Cr on SAE 1070 steel (PIII&D) resulting in surfaces with high resistance to corrosion; and 5 - implantation of nitrogen by ordinary PIII into this Cr film, which improved resistance to corrosion, while keeping the tribological properties as good as for the SAE 1070 steel surface. © 2012 Elsevier B.V.

Optical, mechanical and surface properties of amorphous carbonaceous thin films obtained by plasma enhanced chemical vapor deposition and plasma immersion ion implantation and deposition

Diverse amorphous hydrogenated carbon-based films (a-C:H, a-C:H:F, a-C:H:N, a-C:H:Cl and a-C:H:Si:O) were obtained by radiofrequency plasma enhanced chemical vapor deposition (PECVD) and plasma immersion ion implantation and deposition (PIIID). The same precursors were used in the production of each pair of each type of film, such as a-C:H, using both PECVD and PIIID. Optical properties, namely the refractive index, n, absorption coefficient, α, and optical gap, ETauc, of these films were obtained via transmission spectra in the ultraviolet-visible near-infrared range (wavelengths from 300 to 3300 nm). Film hardness, elastic modulus and stiffness were obtained as a function of depth using nano-indentation. Surface energy values were calculated from liquid drop contact angle data. Film roughness and morphology were assessed using atomic force microscopy (AFM). The PIIID films were usually thinner and possessed higher refractive indices than the PECVD films. Determined refractive indices are consistent with literature values for similar types of films. Values of ETauc were increased in the PIIID films compared to the PECVD films. An exception was the a-C:H:Si:O films, for which that obtained by PIIID was thicker and exhibited a decreased ETauc. The mechanical properties - hardness, elastic modulus and stiffness - of films produced by PECVD and PIIID generally present small differences. An interesting effect is the increase in the hardness of a-C:H:Cl films from 1.0 to 3.0 GPa when ion implantation is employed. Surface energy correlates well with surface roughness. The implanted films are usually smoother than those obtained by PECVD. ©2013 Elsevier B.V. All rights reserved.

Innovative low temperature plasma approach for deposition of alumina films

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Optical properties of boron carbide (B5C) thin films fabricated by plasma-enhanced chemical-vapor deposition

Variable angle of incidence spectroscopic ellipsometry was used to determine the optical constants near the band edge of boron carbide (B5C) thin films deposited on glass and n-type Si(111) via plasma-enhanced chemical-vapor deposition. The index of refraction n, the extinction coefficient k, and the absorption coefficient are reported in the photon energy spectrum between 1.24 and 4 eV. Ellipsometry analysis of B5C films on silicon indicates a graded material, while the optical constants of B5C on glass are homogeneous. Line shape analyses of absorption data for the films on glass indicate an indirect transition at approximately 0.75 eV and a direct transition at about 1.5 eV. ©1996 American Institute of Physics.

Novel metallo-porphyrin based colourimetric amine sensors and their processing via plasma enhanced chemical vapour deposition at atmospheric pressure : synthesis, characterisation and mechanistic studies

Volatile amines are prominent indicators of food freshness, as they are produced during many microbiological food degradation processes. Monitoring and indicating the volatile amine concentration within the food package by intelligent packaging solutions might therefore be a simple yet powerful way to control food safety throughout the distribution chain.rnrnIn this context, this work aims to the formation of colourimetric amine sensing surfaces on different substrates, especially transparent PET packaging foil. The colour change of the deposited layers should ideally be discernible by the human eye to facilitate the determination by the end-user. rnrnDifferent tailored zinc(II) and chromium(III) metalloporphyrins have been used as chromophores for the colourimetric detection of volatile amines. A new concept to increase the porphyrins absorbance change upon exposure to amines is introduced. Moreover, the novel porphyrins’ processability during the deposition process is increased by their enhanced solubility in non-polar solvents.rnrnThe porphyrin chromophores have successfully been incorporated into polysiloxane matrices on different substrates via a dielectric barrier discharge enhanced chemical vapour deposition. This process allows the use of nitrogen as a cheap and abundant plasma gas, produces minor amounts of waste and by-products and can be easily introduced into (existing) roll-to-roll production lines. The formed hybrid sensing layers tightly incorporate the porphyrins and moreover form a porous structure to facilitate the amines diffusion to and interaction with the chromophores.rnrnThe work is completed with the thorough analysis of the porphyrins’ amine sensing performance in solution as well as in the hybrid coatings . To reveal the underlying interaction mechanisms, the experimental results are supported by DFT calculations. The deposited layers could be used for the detection of NEt3 concentrations below 10 ppm in the gas phase. Moreover, the coated foils have been tested in preliminary food storage experiments. rnrnThe mechanistic investigations on the interaction of amines with chromium(III) porphyrins revealed a novel pathway to the formation of chromium(IV) oxido porphyrins. This has been used for electrochemical epoxidation reactions with dioxygen as the formal terminal oxidant.rn

Growth of ultrananocrystalline diamond film by DC Arcjet plasma enhanced chemical vapor deposition

Self-standing diamond films were grown by DC Arcjet plasma enhanced chemical vapor deposition (CVD). The feed gasses were Ar/H 2/CH 4, in which the flow ratio of CH 4 to H 2 (FCH4/FH2) was varied from 5% to 20%. Two distinct morphologies were observed by scanning electron microscope (SEM), i.e. the pineapple-like morphology and the cauliflower-like morphology. It was found that the morphologies of the as-grown films are strongly dependent on the flow ratio of CH 4 to H 2 in the feed gasses. High resolution transmission electron microscope (HRTEM) survey results revealed that there were nanocrystalline grains within the pineapple-like films whilst there were ultrananocrystalline grains within cauliflower-like films. X-ray diffraction (XRD) results suggested that (110) crystalline plane was the dominant surface in the cauliflower-like films whilst (100) crystalline plane was the dominant surface in the pineapple-like films. Raman spectroscopy revealed that nanostructured carbon features could be observed in both types of films. Plasma diagnosis was carried out in order to understand the morphology dependent growth mechanism. It could be concluded that the film morphology was strongly influenced by the density of gas phases. The gradient of C2 radical was found to be different along the growth direction under the different growth conditions. © 2012 Elsevier B.V. All rights reserved.

Carbon nanowalls grown by microwave plasma enhanced chemical vapor deposition during the carbonization of polyacrylonitrile fibers

We used microwave plasma enhanced chemical vapor deposition (MPECVD) to carbonize an electrospun polyacrylonitrile (PAN) precursor to form carbon fibers. Scanning electron microscopy, Raman spectroscopy, and Fourier transform infrared spectroscopy were used to characterize the fibers at different evolution stages. It was found that MPECVD-carbonized PAN fibers do not exhibit any significant change in the fiber diameter, whilst conventionally carbonized PAN fibers show a 33% reduction in the fiber diameter. An additional coating of carbon nanowalls (CNWs) was formed on the surface of the carbonized PAN fibers during the MPECVD process without the assistance of any metallic catalysts. The result presented here may have a potential to develop a novel, economical, and straightforward approach towards the mass production of carbon fibrous materials containing CNWs. © 2013 American Institute of Physics.

Microwave Plasma Assisted ALD Development for the Deposition of Gate Oxides & ALD of High-k Dielectrics

The semiconductor industry's urge towards faster, smaller and cheaper integrated circuits has lead the industry to smaller node devices. The integrated circuits that are now under volume production belong to 22 nm and 14 nm technology nodes. In 2007 the 45 nm technology came with the revolutionary high- /metal gate structure. 22 nm technology utilizes fully depleted tri-gate transistor structure. The 14 nm technology is a continuation of the 22 nm technology. Intel is using second generation tri-gate technology in 14 nm devices. After 14 nm, the semiconductor industry is expected to continue the scaling with 10 nm devices followed by 7 nm. Recently, IBM has announced successful production of 7 nm node test chips. This is the fashion how nanoelectronics industry is proceeding with its scaling trend. For the present node of technologies selective deposition and selective removal of the materials are required. Atomic layer deposition and the atomic layer etching are the respective techniques used for selective deposition and selective removal. Atomic layer deposition still remains as a futuristic manufacturing approach that deposits materials and lms in exact places. In addition to the nano/microelectronics industry, ALD is also widening its application areas and acceptance. The usage of ALD equipments in industry exhibits a diversi cation trend. With this trend, large area, batch processing, particle ALD and plasma enhanced like ALD equipments are becoming prominent in industrial applications. In this work, the development of an atomic layer deposition tool with microwave plasma capability is described, which is a ordable even for lightly funded research labs.

Plasma diagnostics and ITO film deposition by RF-assisted closed-field dual magnetron system

Deposition of indium tin oxide (ITO) among various transparent conductive materials on flexible organic substrates has been intensively investigated among academics and industrials for a whole new array of imaginative optoelectronic products. One critical challenge coming with the organic materials is their poor thermal endurances, considering that the process currently used to produce industry-standard ITO usually involves relatively high substrate temperature in excess of 200°C and post-annealing. A lower processing temperature is thus demanded, among other desires of high deposition rate, large substrate area, good uniformity, and high quality of the deposited materials. For this purpose, we developed an RF-assisted closed-field dual magnetron sputtering system. The “prototype” system consists of a 3-inch unbalanced dual magnetron operated at a closed-field configuration. An RF coil was fabricated and placed between the two magnetron cathodes to initiate a secondary plasma. The concept is to increase the ionization faction with the RF enhancement and utilize the ion energy instead of thermal energy to facilitate the ITO film growth. The closed-field unbalanced magnetrons create a plasma in the intervening region rather than confine it near the target, thus achieving a large-area processing capability. An RF-compensated Langmuir probe was used to characterize and compare the plasmas in mirrored balanced and closed-field unbalanced magnetron configurations. The spatial distributions of the electron density ne and electron temperature Te were measured. The density profiles reflect the shapes of the plasma. Rather than intensively concentrated to the targets/cathodes in the balanced magnetrons, the plasma is more dispersive in the closed-field mode with a twice higher electron density in the substrate region. The RF assistance significantly enhances ne by one or two orders of magnitude higher. The effect of various other parameters, such as pressure, on the plasma was also studied. The ionization fractions of the sputtered atoms were measured using a gridded energy analyzer (GEA) combined with a quartz crystal microbalance (QCM). The presence of the RF plasma effectively increases the ITO ionization fraction to around 80% in both the balanced and closed-field unbalanced configurations. The ionization fraction also varies with pressure, maximizing at 5-10 mTorr. The study of the ionization not only facilitates understanding the plasma behaviors in the RF-assisted magnetron sputtering, but also provides a criterion for optimizing the film deposition process. ITO films were deposited on both glass and plastic (PET) substrates in the 3-inch RF-assisted closed-field magnetrons. The electrical resistivity and optical transmission transparency of the ITO films were measured. Appropriate RF assistance was shown to dramatically reduce the electrical resistivity. An ITO film with a resistivity of 1.2×10-3 Ω-cm and a visible light transmittance of 91% was obtained with a 225 W RF enhancement, while the substrate temperature was monitored as below 110°C. X-ray photoelectron spectroscopy (XPS) was employed to confirm the ITO film stoichiometry. The surface morphology of the ITO films and its effect on the film properties were studied using atomic force microscopy (AFM). The prototype of RF-assisted closed-field magnetron was further extended to a larger rectangular shaped dual magnetron in a flat panel display manufacturing system. Similar improvement of the ITO film conductivities by the auxiliary RF was observed on the large-area PET substrates. Meanwhile, significant deposition rates of 25-42 nm/min were achieved.

Plasma-assisted atomic layer deposition for microelectronics applications

Otto-von-Guericke-Universität Magdeburg, Fakultät für Elektrotechnik und Informationstechnik, Dissertation, 2016

Sticking non-stick: surface and structure control of diamond-like carbon in plasma enhanced chemical vapour deposition

This short review article explores the practical use of diamond-like carbon (DLC) produced by plasma enhanced chemical vapour deposition (PECVD). Using as an example issues relating to the DLC coating of a hand-held surgical device, we draw on previous works using atomic force microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, scanning electron microscopy, tensiometry and electron paramagnetic resonance. Utilising data from these techniques, we examine the surface structure, substrate-film interface and thin film microstructure, such as sp2/sp3 ratio (graphitic/diamond-like bonding ratio) and sp2 clustering. We explore the variations in parameters describing these characteristics, and relate these to the final device properties such as friction, wear resistance, and diffusion barrier integrity. The material and device characteristics are linked to the initial plasma and substrate conditions.

Structure character in small-carbon-cluster deposition on diamond surface

Experimentally, hydrogen-free diamond-like carbon (DLC) films were assembled by means of pulsed laser deposition (PLD), where energetic small-carbon-clusters were deposited on the substrate. In this paper, the chemisorption of energetic C2 and C10 clusters on diamond (001)-( 2×1) surface was investigated by molecular dynamics simulation. The influence of cluster size and the impact energy on the structure character of the deposited clusters is mainly addressed. The impact energy was varied from a few tens eV to 100 eV. The chemisorption of C10 was found to occur only when its incident energy is above a threshold value ( E th). While, the C2 cluster was easily to adsorb on the surface even at much lower incident energy. With increasing the impact energy, the structures of the deposited C2 and C10 are different from the free clusters. Finally, the growth of films synthesized by energetic C2 and C10 clusters were simulated. The statistics indicate the C2 cluster has high probability of adsorption and films assembled of C2 present slightly higher SP3 fraction than that of C10-films, especially at higher impact energy and lower substrate temperature. Our result supports the experimental findings. Moreover, the simulation underlines the deposition mechanism at atomic scale.