High concentration erbium doping of silicon-rich SiO2 thin films on silicon

In this work, high concentration erbium doping in silicon-rich SiO₂ thin films is demonstrated. Si plus Er dual-implanted thermal SiO₂ thin films on Si substrates have been fabricated by using a new method, the metal vapor vacuum arc ion source implantation with relatively low ion energy, strong flux and very high dose. X-Ray photoelectron spectroscopy measurement shows that very high Er concentrations on the surfaces of the samples, corresponding to 10 at.% or the doping level of 10²¹ atoms cm⁻³, are achieved. This value is much higher than that obtained by using other fabrication methods such as the high-energy ion implantation and molecular beam epitaxy. Reflective high-energy electron diffraction, atomic force microscopy and cross-section high-resolution transmission electron microscopy observations show that the excess Si atoms in SiO₂ matrix accumulate to form Si clusters and then crystallize gradually into Si nanoparticles embedded in SiO₂ films during dual-ion implantation followed by rapid thermal annealing. Er segregation and precipitates are not formed. Photoluminescence at the wavelength of 1.54 μm exhibits very weak temperature dependence due to the introduction of Si nanocrystals into the SiO₂ matrix. The 1.54-μm light emission signals from annealed samples decrease by less than a factor of 2 when the measuring temperature increases from 77 K to room temperature.     

等离子体基离子注入制备TiN膜的成分结构

采用Ti、N等离子体基离子注入和先在基体表面沉积纯钛层然后离子注氮混合两种方法在铝合金基体上制备了TiN膜.利用XPS分析了两种方法制备TiN薄膜的成分深度分布和元素化学价态,并用力学性能显微探针测试对比了TiN膜的纳米硬度.研究表明:两种方法制备的薄膜均由TiN组成,Ti、N等离子体基离子注入薄膜中Ti/N≈1.1,而离子注入混合薄膜中Ti/N≈1.3,Ti、N等离子体基离子注入薄膜表面区域为TiN和TiO2的混合组织,TiN含量多于TiO2,离子注入混合薄膜表面主要是TiO2;Ti、N等离子体基离子注入所制备的薄膜的纳米硬度峰值为12.26 GPa,高于离子注入混合的7.98 GPa.     

Covalent layer-by-layer assembly of redox active molecular multilayers on silicon (100) by photochemical thiol-ene chemistry

The fabrication of thin organic films covalently grafted onto silicon substrates is of significant interest, as they are expected to give access to a broad range of new materials for integration into microelectronic applications. Covalent layer-by-layer (LbL) assembly offers a high degree of freedom when designing such thin films. In this work an approach for the preparation of covalent redox active molecular multilayers on silicon (100) surfaces is presented using a highly branched decaallylferrocene and thiol-ene click chemistry. The multilayers are analyzed by ellipsometry, X-ray photoelectron sprectroscopy, and cyclic voltammetry. The results indicate that the multilayer growth is linear for at least sixteen layers and the density of ferrocenes per layer is in the range of 6 × 10?11 mol cm?2. Moreover, this method for LbL assembly is extended to surfaces which have been locally passivated by microcontact printing. By atomic force microscopy measurements it is possible to show that the covalent LbL deposition proceeds exclusively in the nonpassivated areas.     

Adhesion enhancements and internal stress in MgF2 films deposited with ion beam assistance

We performed adhesion measurements using a dynamically loaded scratch tester to evaluate MgF₂ coatings deposited onto heated and unheated fused silica substrates. Resistance evaporation at 5 Å s^-1 with Ar⁺ ion beam assistance improved the relative adhesive strength of films deposited onto unheated substrates by over an order of magnitude compared with the results for heated substrates without ion beam assistance. Additional experiments were performed to measure internal stress in MgF₂ films on specially masked BK-7 glass substrates using modulated transmission ellipsometry. We found that ion-assisted deposition can reduce internal stress to approximately 450 kgf cm^-2 (tensile) in films 2300 Å thick. The great potential for stress relaxation in MgF₂ films deposited with ion assistance is suggested by these measurements, but additional work with films of higher purity may be required to identify the relative contributions of stress relief, substrate cleaning and chemical bonding to improved adhesion.     

Decrease in work function of boron ion-implanted ZnO thin films

We have fabricated boron ion-implanted ZnO thin films by ion implantation into sputtered ZnO thin films on a glass substrate. An investigation of the effects of ion doses and activation time on the electrical and optical properties of the films has been made. The electrical sheet resistance and resistivity of the implanted films are observed to increase with increasing rapid thermal annealing (RTA) time, while decreasing as the ion dose increases. Without any RTA process, the variation of the carrier density is insensitive to the ion dose. With the RTA process, however, the carrier density of the implanted films increases and approaches that of the un-implanted ZnO film as the ion dose increases. On the other hand, the carrier mobility is shown to decrease with increasing ion doses when no RTA process is applied. With the RTA process, however, there is almost no change in the mobility. We have achieved the optical transmittance as high as 87% within the visible wavelength range up to 800 nm. It is also demonstrated that the work function can be engineered by changing the ion dose during the ion implantation process. We have found that the work function decreases as the ion dose increases.     

MeV离子辐照引起薄膜附着力的增强:阈剂量随界面原子化学结合能的一个经验关系

根据Pauling给出的金属-非金属双原子结合键能的关系,分析文献报导的高能重离子辐照引起金属膜/聚四氟乙烯基底和金属膜/硅基底系统附着力增强的阈剂量数据后发现,阈剂量随界面原子结合能很好地满足指数关系D_(th)=D_0exp(kE_b)。这说明高能离子辐照引起薄膜附着力的增强可能是离子辐照引起界面原子化学结合键能增强的缘故。     

Polyelectrolyte multilayer films containing silver as antibacterial coatings

A facile approach to fabrication of transparent antimicrobial coatings based on polyelectrolyte multilayers (PEMs) is presented. Counterions existing in PEMs were utilized via ion exchange and in situ reduction to incorporate into the films silver ions and nanoparticles, and the antibacterial efficacy of the films against E. coli was assessed by the Kirby-Bauer method. The PEMs containing silver in the ionic form exhibited high activities in short terms, and the antibacterial effects depended on the ionic strength in the polyelectrolyte solutions used for the PEM fabrication. The PEMs loaded with silver nanoparticles showed lower initial bactericidal effects, but remained active after long periods of time, and the antimicrobial performance can be improved by increasing the silver loading through repeating the ion-exchange/reduction cycle for multiple times. The films were transparent in the visible region. Coatings containing multiple antimicrobial agents for possible synergistic effects can be fabricated in a single process using this method.     

Phenomenological understanding of dewetting and embedding of noble metal nanoparticles in thin films induced by ion irradiation

The present experimental work provides the phenomenological approach to understand the dewetting in thin noble metal films with subsequent formation of nanoparticles (NPs) and embedding of NPs induced by ion irradiation. Au/polyethyleneterepthlate (PET) bilayers were irradiated with 150 keV Ar ions at varying fluences and were studied using scanning electron microscopy (SEM) and cross-sectional transmission electron microscopy (X-TEM). Thin Au film begins to dewet from the substrate after irradiation and subsequent irradiation results in spherical nanoparticles on the surface that at a fluence of 5 × 10¹⁶ ions/cm² become embedded into the substrate. In addition to dewetting in thin films, synthesis and embedding of metal NPs by ion irradiation, the present article explores fundamental thermodynamic principles that govern these events systematically under the effect of irradiation. The results are explained on the basis of ion induced sputtering, thermal spike inducing local melting and of thermodynamic driving forces by minimization of the system free energy where contributions of surface and interfacial energies are considered with subsequent ion induced viscous flow in substrate.     

A theory for the formation of tetrahedral amorphous carbon including deposition rate effects

A theoretical model is presented to describe the effect of ion beam bombardment rate on the formation of tetrahedral amorphous carbon (ta-C) films. The critical ion energy, E_c, corresponding to a 50% sp³ content in the films, is found to be dependent on both the effective thermal resistance and the ion beam bombardment rate. In the model, the ‘window’ width in the ion energy scale for the formation of ta-C material increases with decreasing deposition rate and with a reduction in the effective thermal resistance, until limited by lower and upper boundary thresholds. Experimental data are reproduced by the model. The plasmon energy, which correlates with sp³ fraction, is found experimentally of be higher for lower deposition rate and smaller effective thermal resistance. Data points for high sp³ content ta-C films deposited on silicon substrates at room temperature occupy a region in the ion energy-deposition rate (E-r) diagram similar to that predicated from the theory.     

Ellipsometric analysis of ion-implanted polycrystalline silicon films before and after annealing

A study of arsenic ion-implanted polycrystalline silicon films before and after annealing at various temperatures has been performed using spectroscopic ellipsometry in the ultraviolet to the visible spectral region. Using the Bruggeman effective medium approximation, an optical/structural model is presented for all the annealed samples explaining the measurements. Ellipsometric measurements reveal important structural changes as a function of annealing temperature which provide an interesting inside into the annealing kinetics of ion-implanted polycrystalline silicon films. This work also demonstrates the importance of spectroscopic ellipsometry in determining non-destructively the dielectric functions in materials that have undergone complex processing.     

Effect of ion irradiation on internal stress of amorphic carbon films produced by pulsed laser

Amorphic carbon films either 50 or 160 nm thick were deposited on Si(100) and glass substrates at room temperature in a high-vacuum environment using a Q-switched Nd-YAG pulse laser focused on a graphite target. These films were irradiated with Ti⁺ or C⁺ ions having kinetic energies of 35 and 75 keV, and the changes in internal stresses of the films with varying ion influence were investigated by measuring substrate bending using stylus profilometry. The ion energy and the film thickness were chosen such that the ion penetration depth, R_p, corresponded to either the film thickness or one half of the film thickness. The results indicate that there is an optimum ion fluence leading to a stress-free film for a given ion species and energy. Interpretation of the resulting stress behavior from ion irradiation was made based on the relaxation resulting from damage inside the film together with interfacial mixing. The scanning electron microscopy pictures and surface roughness measurements showed a very smooth surface for both as-deposited and ion-irradiated films. The ion-irradiated films had a Vickers hardness greater than 22 GPa, and were adherent to both Si and glass substrates. An investigation of the film characteristics using Raman scattering and electron-energy loss spectra has revealed that high-energy ion irradiation of an intermediate ion fluence can be utilized successfully to deposit an adherent and hard carbon film with controlled internal stress without changing the film structure significantly.     

离子束增强反应磁控溅射低温快速沉积AlN膜

本文采用氮离子束增强反应磁控溅射,在低温下沉积了 AlN 薄膜.用 X 射线衍射和 X 射线光电子谱对薄膜的晶体结构和电子结构进行了分析,结果表明,随着离子源中氮离子束流的增加,薄膜组成由面心立方的 Al 转变为密排立方的 AlN.氮离子在薄膜制备中的引入,有效地降低了沉积温度,提高沉积速率,并实现了薄膜 N/Al 化学计量比的控制.对 AlN 薄膜的紫外-可见光透射谱和红外吸收谱也进行了测定.     

Magnetic force microscopy of nano-size magnetic domain ordering in heavy ion irradiated fullerene films

In the present work, magnetic force microscopy is employed to investigate the magnetic ordering in ion irradiated fullerene films. It is observed that magnetic domain size is approximately 100-200 nm and magnetic signal is stronger at the domain boundaries. Magnetic signal arise in irradiated films is confirmed by magnetic measurements using a superconducting quantum interference device which increases with the ion fluence. The induced magnetism is possibly due to structural defects in the amorphous carbon phase formed by ion irradiation.     

SiO2/TiO2 thin films with variable refractive index prepared by ion beam induced and plasma enhanced chemical vapor deposition

SiO₂/TiO₂ optical thin films with variable compositions have been prepared by ion beam induced and plasma enhanced chemical vapour deposition (IBICVD and PECVD). While the films obtained by IBICVD were very compact, the PECVD ones with a high content of Ti presented a columnar microstructure. The formation of Si–O–Ti bonds and a change in the environment around titanium from four- to six-coordinated has been proved by vibrational and X-ray absorption spectroscopies. The refractive index increased with the titanium content from 1.45 to 2.46 or 2.09 for, respectively, the IBICVD and PECVD films. Meanwhile, the band gap decreased, first sharply and then more smoothly up to the value of pure TiO₂. It is concluded that the optical properties of SiO₂/TiO₂ thin films can be properly tailored by using these two procedures.     

Analysis on Structure and Properties of Diamondlike Carbon Films from Ion Beam Deposition

Diamondlike carbon (DLC) films from a primary ion beam deposition system, were examined using nanoindentation, SEM, AES, XPS, and Raman Spectroscopy. The films have hardness values ranging from 21 to 29 GPa. The results of SEM and AES show that the films are predominantly carbon without any crystalline features, and that nitrogen is incorporated as nitrogen is used as the ion beam source. XPS, and Raman Spectroscopy confirm that the films are amorphous carbon with a combination of sp³ with sp² bonding. It is concluded that DLC films can be directly deposited on steel using a single ion beam to sputter the solid target, and the structure and properties of DLC largely depend on ion beam source.     

Depth profiling of 4-acetamindophenol-doped poly(lactic acid) films using cluster secondary ion mass spectrometry

The feasibility of using cluster secondary ion mass spectrometry for depth profiling of drug delivery systems is explored. The behavior of various biodegradable polymer films under dynamic SF(5)(+) primary ion bombardment was investigated, including several films doped with model drugs. The SF(5)(+) depth profiles obtained from these biodegradable polymer films showed very little degradation in secondary ion signal as a function of increasing primary ion dose, and it was discovered that the characteristic ion signals for the polymers remained constant for ion doses up to approximately 5 x 10(15) ions/cm(2). These results suggest that the polyester structure of the biodegradable polymers studied here allows for a greater ability to depth profile due to ease of main chain scission. Attempts were also made to depth profile through a series of poly(lactic acid) (PLA) films containing varying concentrations of the drug 4-acetamidophenol. The depth profiles obtained from these films show very little decrease in both the 4-acetamidophenol molecular ion and PLA fragment ion signals as a function of increasing SF(5)(+) primary ion dose. Similar results were obtained with theophylline-doped PLA films. These results show that, in some drug delivery devices, it is possible to monitor the distribution of a drug as a function of depth by using cluster primary ion beams.     

Effects of nitrogen ion implantation and implantation energy on surface properties and adhesion strength of TiN films deposited on aluminum by magnetron sputtering

The performance of tribological coatings depends greatly on the adhesion strength between the coatings and substrates. In this work, we investigated the influence of the ion implantation energy of nitrogen on the adhesion and surface properties of TiN deposited on aluminum substrate. Aluminum samples were implanted with 15 keV, 30 keV and 40 keV nitrogen ions before TiN films were deposited using magnetron sputtering in a custom-designed multi-functional ion implanter. The adhesion properties of the implanted TiN films were assessed using nano-scratch tests and were observed to vary with the nitrogen ion implantation energy. Our frictional test results show that an appropriate ion implantation energy and dose can improve the frictional behavior of TiN films deposited on aluminum.     

MASS SELECTED ION BEAM DEPOSITION: A TOOL FOR PARAMETRIC GROWTH STUDIES, PROCESS DEVELOPMENT AND FABRICATION OF DIAMONDLIKE FILMS

Diamondlike films have unique properties that can be tailored between those of diamond and those of graphite to meet industrial applications. The purpose of this review is to emphasize the ability to prepare films with specific properties through control of the deposition parameters. The three basic approaches, plasma deposition, chemical vapor deposition, and ion beam deposition, are presented. Since the first two methods consist of complex chemical-physical systems which limit the possibilities for controlled parametric studies, the focus herein is on the latter technique. This work presents the unique capabilities of mass-selected carbon ion beam deposition in controlling deposition parameters over a wide range, particularly when combined with in-situ analysis of film evolution. The role of different deposition parameters on diamond film growth is discussed. The Houston deposition system that manifests the above features is described. A summary of results of some ongoing experiments is given to demonstrate the system capabilities for both parametric studies of diamondlike film growth and actual production of diamondlike films.     

用PBⅡ方法在硼膜中注入氮形成BN的结构

用电子束蒸发纯硼,在硅片上沉积不同厚度的硼膜,然后用等离子体基离子注入（ＰＢⅡ）技术在硼膜上主入氮以形成氮化硼（ＢＮ）,用ＸＰＳ分析膜的成分深度分布及化学价态;用傅里叶变换红外（ＦＴＩＲ）透射谱分析膜的结构。氮在膜中呈类似高斯分布,随着注入电压增大,膜的Ｎ／Ｂ比增大且影响氮在膜中的分布,在较高的注入电压时,膜基间产生界面混合,对ＸＰＳＢｌｓ谱进行Ｇａｕｓｓ－ｏｒｅｎｔｚ拟合表明,硼在膜中以ＢＮ及游     

Growth of Ti:sapphire single crystal thin films by pulsed laser deposition

This paper documents the growth of single crystal Ti:sapphire thin films, typically 10 μm thick, on undoped sapphire substrates using pulsed laser deposition from a Ti:sapphire single crystal target with a doping level of 0.1 wt.% Ti₂O₃. These thin films are shown to have very high crystal quality using ion beam channelling and X-ray diffraction techniques. The degree of titanium incorporation into the films is investigated using inductively coupled plasma mass spectrometry and particle induced X-ray emission. These techniques show that levels of up to 0.08 wt.% Ti₂O₃ are present in the deposited layers.