Uniformity enhancement of incident dose on concave surface in plasma immersion ion implantation assisted by beam-line ion source

Plasma immersion ion implantation (PIII) is a promising surface treatment technique for the irregular-shaped components. However, it is difficult to achieve uniform implantation along the surface of a concave sample due to the propagation and overlapping effect of plasma sheath. In this paper, a new ion implantation process is presented for improving the dose uniformity, especially for enhancing the lateral dose of the samples with concavities. In PIII enhanced by beam-line ions process, a beam-line ion source with certain energy is introduced from an external source into the concavity to suppress the sheath propagation and consequently to improve the dose uniformity. The time-dependent evolution of the potential, electrical field and the particle movement surrounding the surface of concave sample is studied by a particle-in-cell/Monte Carlo collision (PIC/MCC) simulation during a single bias high voltage (HV) pulse. The simulation results show that the plasma sheath propagation surrounding the concave sample is suppressed effectively by beam-line ions, and can be quasi-steady state during a single HV pulse. The influence of the energy of induced beam-line ions on the incident ion dose and energy distribution is discussed. Compared with the traditional PIII process, the dose uniformity of the sample surface is improved obviously due to the increase of the ions implanted into the lateral surface.     

Reactive plasma immersion ion implantation for surface passivation

Plasma immersion ion implantation (PIII) using halogen or oxygen plasmas has been employed for the surface passivation of advanced alloys with a view to their applications for high-temperature oxidation protection and in medicine. Special devices have been designed to ensure efficient plasma generation and reduce sample contamination arising from the interaction of the aggressive plasmas with the chamber components under bias. The paper addresses two main applications of PIII, namely oxidation protection of gamma-titanium aluminides (γ-TiAl), and modification of the surface properties of shape-memory superelastic nickel-titanium (NiTi) alloys. TiAl intermetallics are of great interest for advanced automobile, aerospace and power generation applications due to their low specific weight and high strength. However, excessive oxidation occurring in these materials at temperatures above 700 °C has hindered their widespread use. Samples of technical γ-TiAl alloys have been treated by both beamline implantation of Cl or F, and PIII of Cl using an Ar/Cl gaseous blend or alternative precursor gases. High-temperature oxidation behavior has been examined under conditions of either isothermal or thermocyclic oxidation at 900 °C. Optimized implantation processing produces marked improvement in the oxidation behavior of the γ-TiAl samples. On the basis of these results, a commercially viable process for enhancing the high-temperature oxidation resistance of γ-TiAl alloys using PIII of halogens is being developed. NiTi alloys are promising materials for use in biomedicine, provided that the release of Ni ions into the body environment can be sufficiently reduced. Oxygen PIII at substrate temperatures below 250 °C results in the formation of a transparent rutile TiO₂ surface layer with a Ni content down to below 1 at.%. This layer in turn serves as a barrier to the corrosion and out-diffusion of Ni ions. Biocompatibility tests show superior in vitro blood compatibility in comparison with untreated NiTi samples.     

High frequency and low voltage plasma immersion ion implantation of nitrogen on industrial pure iron at different Rf power

Traditional plasma ion immersion implantation (PIII) can effectively improve material mechanical property and corrosion resistance. But the modified layer by PIII is too thin for many industrial applications. High frequency and low voltage plasma immersion ion implantation (HLPIII) has advantages of PIII and nitriding. Comparing with traditional ion nitriding, HLPIII can obtain higher implantation energy and create a thick modified surface layer. In the present paper nitriding layers were synthesized on industrial pure iron using high frequency and low voltage plasma immersion ion implantation with different RF power (400 W, 600 W, and 800 W). The microstructure of the nitriding layers was characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The mechanical properties such as microhardness and wear resistance were analyzed using HXD1000 microhardness and CSEM pin-on-disk wear testing machine. The anodic polarization characteristics were measured in a 0.9% NaCl solution at room temperature to examine the corrosion resistance of the nitriding layer. The results reveal that Fe₂N, Fe₃N and Fe₄N coexist in the nitriding layer. The nitriding layer is a corrosion protective coating on industrial pure iron in 0.9% NaCl solution. The hardness, wear resistance and corrosion resistance of the nitrided layers on industrial pure iron increase with RF power.     

AlN nanoclusters formation by plasma ion immersion implantation

We report on simultaneous (Al + N) implantation of Al and N into layers of amorphous thermal silica (SiO₂) in an attempt to bond Al with N and form the binary compound AlN. As an implantation technique, plasma ion immersion implantation (PIII) is used. The energy and ion fluence were varied in order to obtain nanocluster containing films in the thickness range 10-50 nm. The elemental distribution profiles in the substrate were evaluated by means of elastic recoil detection analysis technique (ERDA). The nature of the chemical bonds was determined by X-ray photoelectron spectroscopy (XPS). The simultaneous implantation using rf plasma source for N ions and a cathodic arc to produce the Al ions provides good overlap of the elemental profiles and high retained doses of Al and N are achieved. The binding energies of the Al 2p and N 1s core electrons indicate that formation of near-stoichiometric aluminium nitride is achieved.     

COMPUTATIONAL SCHEME FOR SIMULATING PLASMA DYNAM-ICS DURING PLASMA-IMMERSION ION IMPLANTATION

Plasma--immersionionimplantation(Pill)isapowerfultechniqueforsurfacemodificationofmaterials[1'2].InthePillprocess)theobjectbeingimplantedisimmersedinaplasmaandrepeatedlypulsedtoahigh,negativevoltage(scallto--100kV).AtypicaltargetgeometryisshowninFig.la.Theapplicationofthisbiascreatesasheaththatexpandsintothesurroundingplasma,uncoveringpositiveionsandacceleratingthemtothetargetsurfaCe,wheretheymaybeimplanted.Theseimplantedionsmodifythesurfacewhiletightdimensionaltolerancesaremaintained.Aprin…     

Investigation of nitrogen mass transfer within an industrial plasma nitriding system II: Application of a biased screen

Active screen plasma nitriding (ASPN) was conceived in order to reduce negative effects observed in direct current plasma nitriding arising from the application of bias to the components. The mechanism of nitrogen mass transfer in ASPN is still not fully understood. Here, we compare the microstructure, composition and hardness response of AISI P20 and H13 steels after nitriding. A set of samples was nitrided with sample bias applied directly and another set was nitrided at floating potential under an active screen. Similar nitrogen content and hardness profiles were obtained for the samples treated using a bias and under an active screen separated from the samples by 12 mm. When the sample-screen separation was increased from 12 to 70 mm the hardness response improved. The principle processes occurring during ASPN are proposed based on the experimental results. In ASPN, a flux of energetic nitrogen species is generated by the active screen which, provided that the samples are within the range of the energetic species, bombards the surface of the samples being treated. This flux is critical in establishing a nitrogen potential and a satisfactory response in the components.     

Corrosion behavior and surface characterization of tantalum implanted TiNi alloy

TiNi shape memory alloy has been modified by Ta plasma immersion ion implantation technology to improve corrosion resistance. The results of the polarization tests show that the corrosion resistance of TiNi alloy in Ringer's solution at 310 K has been improved by the Ta ion implantation and the Ta/TiNi sample with a moderate incident dose of 1.5 × 10¹⁷ ions/cm² exhibits the best corrosion resistance ability. The surface characterization and chemical composition of the Ta/TiNi samples were determined by Auger electron spectroscopy (AES), Atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) methods. AFM images reveal that compact aggregates of nano-grains uniformly disperse on the surface of the Ta/TiNi samples. AES and XPS analyses on the Ta/TiNi sample show that the component of the surface layer is mainly composed of TiO₂ and Ta₂O₅, which is benefit to the corrosion resistance ability and biocompatibility.     

Surface characteristics, nano-indentation and corrosion behavior of Nb implanted NiTi alloy

NiTi shape memory alloy has been modified by Nb implantation with different implantation parameters including incident dose and current. The surface morphology and chemical components are determined by atomic force microscopy (AFM), Auger Electron Spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). The results show that Nb implantation leads to the formation of compact Nb₂O₅/TiO₂ thin film about 30 nm in thickness on the surface of the NiTi alloy and decreases the surface concentration of Ni. A larger incident dose or incident current causes a higher surface roughness and a higher Nb content in the implantation layer of NiTi alloy. The nano-indentation measurements indicate the obvious reduction of both nano-hardness and Young's modulus of the Nb implanted NiTi alloy in the implantation layer and even in deeper NiTi matrix. The results of potentiodynamic polarization test show that the corrosion resistance of NiTi alloy in Hanks's solution has been evidently improved by Nb implantation. The NiTi alloy with a moderate implantation parameter of 1.5 × 10¹⁷ ions/cm² and 2 mA exhibits the best corrosion resistance ability.     

Synchronous plasma enhancement in RF-driven plasma source for ion implantation

We report an original method to increase periodically the plasma density in RF-driven plasma source for surface treatment of materials by ion implantation. The method consists of supplementary injection of ions, electrons and metastable atoms into the processing RF plasma using very short high voltage pulsed discharges applied on a separate electrode at the same repetition rate as the negative accelerating pulses applied on the target. Thus plasma density is periodically increased by an order of magnitude so that the synchronized negative pulses applied on the target for ion implantation find a background plasma about 10 times denser. The advantages of this new method were revealed by nitrogen implanted tests on copper and brass samples.     

Nitrogen diffusion in medical CoCrNiW alloys after plasma immersion ion implantation

CoCr alloys are widely used for medical applications, e.g. total hip replacements or coronary stents. Nevertheless, an increase in the surface hardness and a reduction of the wear rate is still desirable to improve the biocompatibility. Plasma immersion ion implantation (PIII) at different temperatures, acceleration voltages and working pressures is used to determine the nitrogen diffusivity in the CoCr alloys SY21med, L605 and HS188. Depending on the temperature, two different treatment regimes can be distinguished, independent of the ion energy. At low temperatures, a diffusion process with an activation energy of 1.0-1.1 eV is present, indicative of interstitial nitrogen diffusion. Beyond 350 °C, a reduced activation energy of 0.5-0.7 eV is observed. Additionally, a strong dependency of the layer thickness on the working pressure in the range 0.3-0.8 Pa was observed for the temperature dependent diffusion regime, which suggests a synergistic interplay of adsorption and implantation during PIII. Below 500 °C, an increase of the diffusion coefficient by three orders of magnitude was observed for PIII, compared with pure plasma nitriding.     

Electrochemical studies of stainless steel implanted with nitrogen and oxygen by plasma immersion ion implantation

Plasma Immersion Ion Implantation (PIII) of stainless steel with nitrogen at temperatures lower than 400 °C has been reported to increase the hardness of the material by several times. However, expectations that the corrosion resistance will remain unaffected after implantation were not found to be so. In the present study the influence of post-oxygen implantation on the corrosion resistance of nitrogen implanted stainless steel is presented. Stainless steel samples were subjected to oxygen, nitrogen and post-oxygen ion implantation at different temperatures. GIXRD and microRaman studies of the implanted samples showed that oxygen implantation leads to the formation of an oxide layer consisting of corundum and spinel structures. The corrosion properties of the implanted samples were studied by potentiodynamic polarization and electrochemical impedance techniques in 3.5% NaCl solution. After nitrogen implantation the corrosion current increased and the corrosion potential shifted to the less noble side to − 0.486 V as compared to − 0.284 V for the substrate. Oxygen implantation at 400 °C shifted the corrosion potential to the nobler side to − 0.2 V with decrease of corrosion current. For post-oxygen ion implantation at temperatures lower than 400 °C, the corrosion current was higher than the substrate and the corrosion potential was also on the less noble side. However, post-oxygen ion implantation at 400 °C after nitrogen ion implantation resulted in improved corrosion resistance as the corrosion potential shifted to nobler side and the corrosion current was lower than that of substrate.     

Improve retained dose and impact energy of inner surface plasma immersion ion implantation using long pulse duration with deflecting electric field

Not restricted by the line-of-sight process, plasma immersion ion implantation (PIII) has shown great potential for inner surface modification, but the impact energy and retained dose turned to be very low. The process was investigated numerically and experimentally in this paper. The results show that a high percentage of low impact energy ions was the key factor that resulted in low impact energy on the inner surface. This was caused by sheath overlapping and appearance of the dead zone during inner surface PIII. Long pulse duration could alleviate this problem and increase ion impact energy on the inner surface, hence the implant depth, which was key factor for the modifying effect of PIII. Also, long pulse duration was helpful in improving the retained dose on the inner surface.     

High density large area hydrogen plasma by hollow cathode plasma array

Hydrogen plasma becomes an alternative to the conventional oxygen plasma in stripping photoresist in the next generation semiconductor processing because the conventional oxygen plasma is known to degrade ultralow dielectric constant films by depleting carbons from the films. An array of hollow cathode plasma is designed to have uniform and high density hydrogen plasma. From many combinations of cavity size and distribution, it is found that cylindrical ceramic cavity with 6 mm inner diameter, 10 mm depth and 30 mm spacing between neighboring cavities shows the widest process window. Nineteen cavities are engraved into the cathode plate of 200 mm diameter. Ceramic cavities are needed to survive against energetic ion bombardment. Dependence of the stripping rate on mixture ratio of N₂/H₂, gas flow rate, chamber pressure and RF power is investigated, and we have found that a stripping rate of more than 260 nm/min with 7% uniformity can be achieved when chamber pressure is 213 Pa, gas flow rate 10000 sccm, N₂/H₂ mixture ratio of 3:7 and RF power 2.5 KW. This high density hydrogen plasma in the order of 10¹¹/cm³can be a very effective method of photoresist stripping in the dual damascene process of copper metal and low-k dielectrics where oxygen plasma cannot be used.     

Surface modification of silica glass by CHF3 plasma treatment and carbon negative-ion implantation for cell pattern adhesion

We have investigated a method for the patterning of cell adhesion on a silica glass by using two-steps of surface modification processes of CHF₃ plasma treatment and negative-ion pattern implantation. For the first step, exposure of CHF₃ plasma to silica glass (SG) was used to obtain hydrophobic surface, leading to eliminate cell-adhesion property. After treatment with RF power of 20 W and exposure time of 120 s, the hydrophobicity was occurred from the increase in contact angle of SG from 43° to 88° and its reason based on XPS analysis was due to formations of C―F, C―F₂, and C―F₃ bonds, so-called fluorocarbonated bonds. Culture of mesenchymal stem cells (MSC) and rat adrenal pheochromocytoma cells (PC12h) showed the degradation of cell adhesion property on the plasma-treated SG surface. For the second step, carbon negative-ion implantation into the hydrophobic fluorocarbonated-SG surface was used to pattern the hydrophilic region, leading to enhance cell adhesion property. The contact angle of C-modified surface decreased to 76° at conditions of 15 keV and 1 × 10¹⁵ ions/cm². XPS showed that the hydrophilicity was due to reduction of C―F_x bonds and formation of C―O and C═O bonds. After 3 days culture of MSC and PC12h on the C-implanted surface of the plasma-treated SG, a fairly good adhesion patterning of both cells was obtained on the ion-implanted regions.     

Exploring the potential of high power impulse magnetron sputtering for growth of diamond-like carbon films

Amorphous carbon films are deposited employing high power impulse magnetron sputtering (HiPIMS) at pulsing frequencies of 250 Hz and 1 kHz. Films are also deposited by direct current magnetron sputtering (dcMS), for reference. In both HiPIMS and dcMS cases, unipolar pulsed negative bias voltages up to 150 V are applied to the substrate to tune the energy of the positively charged ions that bombard the growing film. Plasma analysis reveals that HiPIMS leads to generation of a larger number of ions with larger average energies, as compared to dcMS. At the same time, the plasma composition is not affected, with Ar⁺ ions being the dominant ionized species at all deposition conditions. Analysis of the film properties shows that HiPIMS allows for growth of amorphous carbon films with sp³ bond fraction up to 45% and density up to 2.2 g cm^− 3. The corresponding values achieved by dcMS are 30% and 2.05 g cm^− 3, respectively. The larger fraction of sp³ bonds and mass density found in films grown by HiPIMS are explained in light of the more intense ion irradiation provided by the HiPIMS discharge as compared to the dcMS one.     

Comparison testing of diamond-like a-C:H coatings prepared in plasma cathode-based gas discharge and ta-C coatings deposited by vacuum arc

The method of amorphous carbon coating deposition based on decomposition of acetylene in a non-self-sustained hollow cathode pulsed-DC discharge is investigated. The discharge is maintained by the electron emission of a grid-stabilized plasma cathode based on a DC glow discharge. The method allows the gas pressure in the discharge gap and the non-self-sustained discharge parameters to be varied in a wide range. It makes it possible to optimize the properties of the deposited coating and to perform in situ the preliminary ion cleaning of sample surface and the plasma immersion ion implantation to form an interface and to improve the coating's adhesion. The 0.1-10-μm-thick a-C:H films were deposited on tungsten carbide and stainless steel substrates at a deposition rate of 0.5-8 μm/h. The coatings were investigated using the methods of atomic-force microscopy (AFM), scanning electron microscopy (SEM) and Raman spectroscopy. The arithmetic average surface roughness (9-34 nm), the friction coefficients (0.01-0.3), the density (2.2-2.4 g/cm³), the microhardness (16-75 GPa) and the internal stresses in the films (3-7 GPa) were measured. Comparison was made between the properties of the resulted a-C:H coating with the properties of the ta-C coating obtained by cathodic vacuum arc deposition.     

Relation of the polymeric ion species in plasma to the hardness of a-C:H film made by PSII&D

The amorphous carbon (a-C:H) films formed by plasma source ion implantation and deposition (PSII&D) have expanded the tribological properties. Especially, the hardness can be widely changed by adequately selecting RF power, pulse bias voltage, gas species and gas pressure. Previously, we reported that a-C:H film hardness depended on the electron temperature in C₂H₂ plasma which was ignited with pulsed RF power, and that the hardness was in inverse proportion to the electron temperature in the range of less than 2.5 eV. We have discovered that the film hardness is, in some cases, changing even if the electron temperature is constant. This suggests that there are some new factors to determine the film hardness besides the electron temperature in the plasma. In this study, we employ a quadrupole mass spectrometer to measure the intensity of each polymeric ion in C₂H₂. The film hardness is determined by the synergy of the polymeric ion abundances and ion irradiation.     

Effect of pulse rise time on charging effects in plasma immersion ion implantation with dielectric substrates with planar and cylindrical geometries

Using a one-dimensional self-consistent fluid model, the effect of pulse rise time on charging effects at dielectric surfaces is investigated during plasma immersion ion implantation (PIII) with planar and cylindrical geometries. The numerical results demonstrate that the pulse rise time plays an important role in PIII process with dielectric substrates. It is found that the charge dose accumulated on the dielectric surface is significant as decreasing pulse rise time, and the surface potential decreases at the later stage of the pulse, which results in the lower ion impact energy. On the other hand, the longer pulse rise time would lead to the lower charge dose accumulated on the dielectric surface and higher ion impact energy at the later stage of the pulse, which would elevate the effective implanted dose and introduce the ions to the depth deep enough for surface modification.     

Incident ion fluence gradients on the front and backside of flat samples

Plasma immersion ion implantation (PIII) is ideal for fast and efficient treatment into three-dimensional objects, as shown by experiments and simulations. In this presentation, a direct comparison of implantations into the front and backside of flat sample (disc, square and rectangle) at 5-15 kV pulse voltage with argon ions is performed with the spatial distribution of the incident ion fluence measured by spectroscopic ellipsometry on SiO₂/Si coupons. A strong influence of the supporting rod for the fluence distribution on the backside of the low symmetry samples, i.e. square and rectangle was observed, in contrast to no influence for the disc sample.     

Hybrid elevated-temperature,low/high-voltage plasma immersion ion implantation of AISI304 stainless steel

Elevated-temperature plasma immersion ion implantation (PIII) is an effective non-line-of-sight technique to harden austenitic stainless steel by producing expanded austenitic phases in the near surface region. We report here a hybrid elevated-temperature, low/high voltage approach, which improves the efficiency while retaining the non-line-of-sight advantages of PIII. A low-voltage (4 kV), elevated-temperature (355°C) PIII process is first used to produce the modified layer, but the nitrogen concentration in this layer is typically relatively low and the thickness may not be adequate. This is followed by high-voltage (25 kV) PIII at a lower temperature to increase the nitrogen concentration and to achieve the desirable surface enhancement effects. To assess the efficacy of the technique, the samples are characterized using X-ray diffraction (XRD), nanohardness measurements, and secondary ion mass spectrometry (SIMS) depth profiling. The experimental results show that the nitrogen concentration increases by nearly 75% and the nitrogen penetration depth nearly doubles that of the low-voltage sample. The surface microhardness also improves by 150% and our data suggest that it is due to the formation of expanded austenites.