用掩蔽注入法研究钛注入H13钢的耐磨性

采用由金属蒸汽真空弧离子源引出的强束流钛、碳离子对H13钢进行表面改性研究.钛和碳离子注入剂量分别为3×1017和1×1017cm-2,引出电压分别为48和30kV，平均束流密度分别为47和20μA·cm-2.为了保持相同的摩擦磨损实验条件，注 入过程中采用掩蔽注入技术.摩擦磨损实验结果表明，钛离子注入H13钢提高了其耐磨性，并大幅度降低其摩擦系数.利用卢瑟福背散射谱测量了离子注入表面的成分，并采用逐层递推 法得出了钛在H13钢中的浓度深度分布，借助掠面x射线衍射考察了注入表面的相结构. 关键词： 钛离子注入 金属蒸汽真空弧 卢瑟福背散射 掠面x射线衍射     

Structural characterization of titanium oxide layers prepared by plasma based ion implantation with oxygen on Ti6Al4V alloy

Ti6Al4V alloy was implanted with oxygen by using plasma based ion implantation (PBII) at pulsed voltage ranging from −10 to −50 kV with a frequency of 100 Hz. In order to maintain a lower implantation temperature, an oil cooling working table was employed. The structure of the modified layers was characterized by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The results show that the thickness of the titanium oxide layer increases significantly with the increase of implanted voltage. The structure of the modified layer changes along depth. It is found that the surface layer consists of TiO₂, and the subsurface layer is a mixing structure of TiO_2, Ti₂O₃ and TiO. There is crystalline rutile phase existing in the modified layer of sample implanted at high implanted voltage. In addition, in the outmost modified surface, aluminum present as oxidized state, and vanadium could not be detected.     

MicroRaman study of the effect of oxide layer on nitriding of Ti-6Al-4V

Ti-6Al-4V samples were subjected to nitrogen ion implantation and low pressure RF plasma nitriding in a PIII equipment after chemical etching in Kroll's reagent. The samples were characterized by optical microscopy, AFM, microRaman, XRD and micro hardness measurements. From microRaman, oxides of titanium were found in the inter-granular β region whereas the oxide on the α region was extremely thin. The oxide on the β region was found to be amorphous and from intensity dependent Raman spectra, it was found to have a layered structure. The top layer was rutile and the inner layer anastase. Presence of Ti₂O₃ was also found. After PIII treatment at 600 °C, microRaman showed the presence of nitride in both the regions and the oxide was absent in the β regions. Also, from intensity dependent Raman spectra, it was found that in-take of nitrogen by β regions was higher. The oxide layer remained unaffected after plasma nitriding. Nitride presence in the α was established by microRaman. Even though Raman spectra from β regions were nearly the same as that of oxide, presence of nitrogen was indicated by the spectra. XRD studies of implanted and nitrided samples showed the prsence of TiN and Ti₂N in implanted sample and presence of Ti₂N in the nitrided sample. The β regions were found to have higher microhardness values after PIII and nitriding treatments. This is attributed to the deeper diffusion of nitrogen in these regions.     

Microstructure and thermal stability of Fe,Ti, and Ag implanted yttria-stabilized zirconia

Yttria-stabilized zirconia (YSZ) was implanted with 15 keV Fe or Ti ions up to a dose of 8×10¹⁶ at cm^–2. The resulting dopant concentrations exceeded the concentrations corresponding to the equilibrium solid solubility of Fe₂O₃ or TiO₂ in YSZ. During oxidation in air at 400° C, the Fe and Ti concentration in the outermost surface layer increased even further until a surface layer was formed of mainly Fe₂O₃ and TiO₂, as shown by XPS and ISS measurements. From the time dependence of the Fe and Ti depth profiles during anneal treatments, diffusion coefficients were calculated. From those values it was estimated that the maximum temperature at which the Fe- and Ti-implanted layers can be operated without changes in the dopant concentration profiles was 700 and 800° C, respectively. The high-dose implanted layer was completely amorphous even after annealing up to 1100° C, as shown by scanning transmission electron microscopy. Preliminary measurements on 50 keV Ag implanted YSZ indicate that in this case the amorphous layer recrystallizes into fine grained cubic YSZ at a temperature of about 1000° C. The average grain diameter was estimated at 20 nm, whereas the original grain size of YSZ before implantation was 400 nm. This result implies that the grain size in the surface of a ceramic material can be decreased by ion beam amorphisation and subsequent recrystallisation at elevated temperatures.     

Modification of thin oxide films on Be,Si, Al,Ti, Zr,and W under bombardment by He<Superscript>+</Superscript> and Ar<Superscript>+</Superscript> ion beams with a broad energy spectrum

Data on the distribution of Be, Al, Ti, Fe, Cu, Zr, Mo, and W atoms implanted in oxide film on metal substrates by ion mixing under the action of He⁺ and Ar⁺ ion beams with a broad energy spectrum, with average energy of 10 keV, and with radiation doses up to 1 × 10²¹ ion/cm² are presented. It is shown that layers with different concentration gradients of implanted atoms form in a thin oxide layer due to simultaneous implantation, but their concentration decreases dramatically to the background value at the oxide-metal interface. Analysis of experimental data suggests that the migration of implanted atoms takes place by means of the diffusion mechanism and is determined by the parameters of physicochemical interaction of implanted atoms with substrate atoms.     

氮氟复合注入对注氧隔离SOI材料埋氧层内固定正电荷密度的影响

为了抑制埋层注氮导致的埋层内正电荷密度的上升, 本文采用氮氟复合注入方式, 向先行注氮的埋层进行了注氮之后的氟离子注入, 并经适当的退火, 对埋层进行改性. 利用高频电容-电压 (C-V) 表征技术, 对复合注入后的埋层进行了正电荷密度的表征. 结果表明, 在大多数情况下, 氮氟复合注入能够有效地降低注氮埋层内的正电荷密度, 且其降低的程度与注氮后的退火时间密切相关. 分析认为, 注氟导致注氮埋层内的正电荷密度降低的原因是在埋层中引入了与氟相关的电子陷阱. 另外, 实验还观察到, 在个别情况下, 氮氟复合注入引起了埋层内正电荷密度的进一步上升. 结合测量结果, 讨论分析了该现象产生的原因. 关键词： 绝缘体上硅(SOI) 材料 注氮 注氟 埋氧层正电荷密度     

高剂量注氮对注氧隔离硅材料埋氧层中正电荷密度的影响

为研究注氮改性对注氧隔离硅材料中埋氧层性质的影响,向其埋氧层内注入了10¹⁶ cm^-2的高剂量氮.实验结果表明,与未注氮的埋氧层相比,所有注氮的埋氧层中的正电荷密度显著增加.实验还发现,注氮后的退火可使埋氧层内的正电荷密度进一步上升.但与注氮导致的埋氧层内正电荷密度的显著上升相比,退火时间对注氮的埋氧层内正电荷密度的影响不大.电容-电压测量结果显示,在埋氧层内部,注氮后未退火的样品与在1100 ℃的氮气气氛下退火2.5 h的样品相比,二者具有近似相同的等效正电荷 关键词： 注氧隔离 埋氧 注氮 正电荷密度     

Boron implantations in silicon: A comparison of charge carrier and boron concentration profiles

The concentration profiles of boron implanted in silicon were measured using secondary ion mass spectrometry. The accompanying charge carrier profiles were determined by Hall-effect sheet-resistivity measurements combined with layer removal by anodic oxidation and etching. From a mutual comparison of these profiles an electrically inactive boron fraction was found to exist in the region of maximum boron concentration. This fraction can be correlated with boron precipitates. In high dose implantations the precipitates still exist after annealing at 1000°C. In the tail of the profile a small electrically inactive boron fraction was observed. This fraction was correlated with fast diffusing non-substitutional boron. Near the surface a charge carrier peak was found that can be correlated with the damage caused by implantation. The interpretation of the observed electrical effects was facilitated by investigations on boron concentration profiles of layers implanted with different doses and annealed in accordance with different time-temperature schedules.     

High-intensity ion implantation - a technique to form finely dispersed intermetallic compounds in surface layers of metals

The results of experimental investigations of microstructure and phase composition of surface ion-alloyed layers of nickel, titanium, and iron formed under the conditions of high-intensity aluminum-ion implantation are presented. It is established that aluminum-ion implantation under high-intensity modes makes it possible to form finely-dispersed intermetallic phases of Me₃Al (Me = Ni, Ti, Fe) and MeAl (Ni, Ti), as well as solid solutions of a composition variable with respect to depth in the surface layers measuring up to 2000 nm. It is shown that the average grain-size of intermetallic phases formed in ion-alloyed layers is 20–80 nm. Regions of localization of the phases thus formed over the implanted layer depth are determined.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 9, pp. 44–52, September 2004.     

The lateral extension of radiation damage in ion-implanted semiconductors

Implantation into a confined surface area produces considerable radiation damage even outside the implanted area. The distance between the damage boundary and the implantation boundary can be determined by simultaneously recording the sample current and the characteristic x-ray signal in a scanning electron microscope. This method was applied to investigate the lateral extent of radiation damage in Si, GaAs, and GaP. Annealing studies were performed with Si. It was found that the lateral excess of damage over the implanted area can be more than 1 m even if the projected range is less than 0.1 m. In Si, this marginal damage, except for oxidation induced stacking faults, can be annealed under the same conditions as necessary for the annealing of the implanted zone itself. Experimental support is given to the prediction of Campisano and Barbarino [1] that within the implanted region the recrystallization rate of the amorphous layer reaches a maximum within a range of concentration near the maximal solid solubility.     

Improved biological performance of low modulus Ti-24Nb-4Zr-7.9Sn implants due to surface modification by anodic oxidation

Dental implants are usually made from commercially pure titanium or titanium alloys. The purpose of this study was to evaluate the influence of surface treatment to low modulus Ti-24Nb-4Zr-7.9Sn (TNZS) on cell and bone responses. The TNZS alloy samples were modified using anodic oxidation (AD). Surface oxide properties were characterized by using various surface analytic techniques, involving scanning electron microscopy (SEM) equipped with energy dispersive spectrometer (EDS), X-ray diffractometry (XRD) and surface profilometer. During the AD treatment, porous titanium oxide layer was formed and Ca ions were incorporated into the oxide layer. The viability and morphology of osteoblasts on Ca-incorporated TNZS were studied. The bone responses of Ca-incorporated TNZS were evaluated by pull-out tests and morphological analysis after implantation in rabbit tibiae. The non-treated Ti and TNZS samples were used as the control. Significant increases in cell viability and pull-out forces (p < 0.05) were observed for Ca-incorporated TNZS implants compared with those for the control groups. Porous structures supplied positive guidance cues for osteoblasts to attach. The enhanced cell and bone responses to Ca-incorporated TNZS implants could be explained by the surface chemistry and microtopography.     

Ablation plasma ion implantation using a dc power supply

Experiments are reported in which ablation plasma ion implantation (APII) has been demonstrated using a dc power supply. The ability to use a dc power supply for APII has been accomplished by using a perpendicular orientation between the target and the substrate. This perpendicular orientation significantly reduces the arcing between the target and the substrate, in contrast to previous experiments using a parallel target–substrate orientation. With this new technique a KrF laser may be fired during the dc high voltage, accelerating full-energy ions. Initial experiments using dc APII have shown that Ti is deposited and implanted onto the Si substrate, with the highest concentration of Ti located beneath the surface of the film. The deposition/implantation of Ti ions onto Si was verified by X-ray photoelectron spectroscopy. PACS 52.38.Mf     

Novel approaches for low cost fabrication of SOI

Two trials for low cost manufacture of silicon-on-insulator (SOI) wafers were implemented. Low dose separation by implantation of oxygen (SIMOX) procedure has been conducted on a beam-line ion implanter with mass analyzer. The energy dependence of the formed SOI structure was studied at varied implant dosages. The integrity of the buried oxide (BOX) layer was examined by transmission electron microscopy (TEM) and the threading dislocation in the top silicon layer was evaluated by Secco technique. The results indicated that not only the implanted oxygen dose but also the oxygen ion energy plays an important role in the formation of SOI structure with good crystallinity of top silicon, sharp Si/SiO₂ interfaces and highly integrated BOX layer free of silicon inclusion. For separation by plasma implantation of oxygen (SPIMOX) approach, water plasma, rather than oxygen plasma, was employed to avoid oxygen spread in the implant depth profile. The SPIMOX process using water plasma was carried out on a beam-line ion implanter without mass selector to simulate the plasma implantation procedure. Cross-sectional TEM study revealed that uniform BOX layer was formed under single crystal silicon superficial layer with the present approach. The interfaces between silicon superficial layer, BOX layer and bulk silicon were smooth and sharp. An implant dose window has been identified for fabricating the desirable SOI structure.     

Marker experiments to determine diffusing species and diffusion path in medical Nitinol alloys

The out-diffusion of toxic Ni ions from NiTi (Nitinol), often used for biomedical applications, can be strongly reduced using oxygen plasma immersion ion implantation (PIII). Non-radioactive isotope markers, ⁶⁰Ni and ⁴⁶Ti, were implanted at 180 keV into NiTi prior to the oxygen implantation with fluences between 0.4 × 10¹⁶ and 4 × 10¹⁶ at./cm². Implanting oxygen ions by PIII in the temperature range of 400-550 °C leads to a surface oxide layer consisting of pure TiO₂. The results prove that Ni cations are the mobile species, while Ti is immobile during the oxygen insertion.     

Interaction of high-power laser pulses with glasses containing implanted metallic nanoparticles

Sodium calcium silicate glasses with Ag⁺ implanted ions are studied. The ion implantation conditions are as follows: the energy is 60 keV, the dose is 7×10¹⁶ cm⁻², and the ion current density is 10 μA/cm². Ion implantation provides the formation of a composite layer that incorporates silver nanoparticles in the surface region of glass. The size distribution of nanoparticles over the depth in the composite layer is strongly nonuniform. The effect of a high-power pulsed excimer laser on the composite layer is investigated. It is found that, under laser irradiation, the size of silver nanoparticles in the implanted layer decreases but the size distribution of nanoparticles over the depth remains nonuniform, even though it becomes slightly narrower compared to that observed prior to irradiation. The experimental results are interpreted in terms of the effects of the melting of glass and metallic particles on a nanosecond scale. __________ Translated from Fizika Tverdogo Tela, Vol. 43, No. 11, 2001, pp. 2100–2106. Original Russian Text Copyright ? 2001 by Stepanov, Popok, Hole, Bukharaev.     

Correlation between implantation defects and dopants in Fe-implanted SiC

SiC single crystals were implanted with Fe ions and the effects of implantation temperature, Fe concentration, and subsequent swift heavy ion irradiation on both dopant and damage depth distributions were evaluated by using RBS and channelling techniques. It is found that an increase of the implantation temperature above the threshold temperature for amorphization can lead to the formation of a broad layer (∼50 nm) containing a large concentration of implanted Fe atoms (∼2 at.%) but almost free of implantation defects. This particular configuration is likely due to dynamic annealing during implantation combined with defect annihilation at the surface. It is only observed when the implanted species concentration does not exceed a critical value (which lies between 2 and 5 at.% in the present system). Post-implantation swift heavy ion irradiation leads to a further decrease of the damage level, while the Fe distribution is not affected. The Fe substitutional fraction has been evaluated in the different tested conditions. A maximum value of ∼50% is found when implantation is performed at the temperature above that required to prevent amorphization (470 K in the present system). Swift-heavy ion irradiation seems to induce Fe atoms relocation at substitutional positions.     

Structure and micro-mechanical properties of helium-implanted layer on Ti by plasma-based ion implantation

The present paper concentrates on structure and micro-mechanical properties of the helium-implanted layer on titanium treated by plasma-based ion implantation with a pulsed voltage of −30 kV and doses of 3, 6, 9 and 12 × 10¹⁷ ions/cm², respectively. X-ray photoelectron spectroscopy and transmission electron microscopy are employed to characterize the structure of the implanted layer. The hardnesses at different depths of the layer were measured by nano-indentation. We found that helium ion implantation into titanium leads to the formation of bubbles with a diameter from a few to more than 10 nm and the bubble size increases with the increase of dose. The primary existing form of Ti is amorphous in the implanted layer. Helium implantation also enhances the ingress of O, C and N and stimulates the formations of TiO₂, Ti₂O₃, TiO, TiC and TiN in the near surface layer. And the amount of the ingressed oxygen is obviously higher than those of nitrogen and carbon due to its higher activity. At the near surface layer, the hardnesses of all implanted samples increases remarkably comparing with untreated one and the maximum hardness has an increase by a factor of up to 3.7. For the samples implanted with higher doses of 6, 9 and 12 × 10¹⁷ He/cm², the local displacement bursts are clearly found in the load-displacement curves. For the samples implanted with a lower dose of 3 × 10¹⁷ He/cm², there is no obvious displacement burst found. Furthermore, the burst width increases with the increase of the dose.     

Zinc-ion implanted and deposited titanium surfaces reduce adhesion of Streptococccus mutans

While titanium (Ti) is a commonly used dental implant material with advantageous biocompatible and mechanical properties, native Ti surfaces do not have the ability to prevent bacterial colonization. The objective of this study was to evaluate the chemical composition and bacterial adhesive properties of zinc (Zn) ion implanted and deposited Ti surfaces (Zn-PIIID-Ti) as potential dental implant materials. Surfaces of pure Ti (cp-Ti) were modified with increasing concentrations of Zn using plasma immersion ion implantation and deposition (PIIID), and elemental surface compositions were characterized by X-ray photoelectron spectrometry (XPS). To evaluate bacterial responses, Streptococcus mutans were seeded onto the modifiedTi surfaces for 48 h and subsequently observed by scanning electron microscopy. Relative numbers of bacteria on each surface were assessed by collecting the adhered bacteria, reculturing and counting colony forming units after 48 h on bacterial grade plates. Ti, oxygen and carbon elements were detected on all surfaces by XPS. Increased Zn signals were detected on Zn-PIIID-Ti surfaces, correlating with an increase of Zn-deposition time. Substantial numbers of S. mutans adhered to cp-Ti samples, whereas bacterial adhesion on Zn-PIIID-Ti surfaces signficantly decreased as the Zn concentration increased (p < 0.01). In conclusion, PIIID can successfully introduce Zn onto a Ti surface, forming a modified surface layer bearing Zn ions that consequently deter adhesion of S. mutans, a common bacterium in the oral environment.     

Influence of ion implantation on titanium surfaces for medical applications

The implantation of ions into the near surface layer is a new approach to improve the osseointegration of metallic biomaterials like titanium. Meanwhile it is well known that surface topography and surface physico-chemistry as well as visco-elastic properties influence the cell response after implantation of implants into the human body. To optimize the cell response of titanium, ion implantation techniques have been used to integrate calcium and phosphorus, both elements present in the inorganic bone phase. In this context, the concentration profile of the detected elements and their chemical state have been investigated using X-ray photoelectron spectroscopy and Auger electron spectroscopy depth profiling. Ion implantation leads to strong changes of the chemical composition of the near surface region, which are expected to modify the biofunctionality as observed in previous experiments on the cell response. The co-implantation of calcium and phosphorus samples, which showed best results in the performed tests (biological and physical), leads to a strong modification of the chemical surface composition.     

A model of oxygen adsorption at liquid copper surfaces

A model of O-adsorption at liquid metal surfaces has been constructed, using liquid Cu as an example. The modeling approach used is similar to the regular solution scheme previously used successfully for modeling the adsorption/segregation behavior of metal alloys, in that the internal energy of the system is evaluated by nearest neighbor bond energies. In the model, the adsorption of oxygen in the near-surface region is allowed to occur at both surface and sub-surface sites. The model predicts a variety of possible adsorption characteristics, including the possibility of first order adsorption transitions which involve the formation of a 2-dimensional surface oxide, and different sequences for the occupancy of surface and sub-surface adsorption sites. In particular, by fitting the model to the experimental dependence of Cu surface energy on O-partial pressure, it is possible to conclude that O-adsorption in that case most likely occurs by the occupancy of sub-surface sites.