The microstructure evolution during preparation of thin Si(111) samples for surface sensitive imaging has been studied using ultra-high vacuum (UHV) transmission electron microscopy (TEM). The effects of ion beam sputtering and electron annealing have been investigated. A unique and routine sample preparation method for surface sensitive TEM imaging that combines TEM sample preparations with surface science sample preparation was developed. The microstructure evolution during the sample preparation process was studied in detail.

A highly sensitive x-ray fluorescence (XRF) technique has been developed for the determination of low metal concentrations in the etch resistant layer of surface-imaged photoresists. The samples may be analyzed quickly and the method is applicable to a wide variety of surfaceimaging processes. For each metal of interest the XRF spectrometer is easily calibrated using polymer films containing known concentrations of a metal-containing reagent. Examples of the application of this technique to the analysis of Ti, Si and Zr-containing films are described.

It has been recognized since the 1960's that bombardment of a growing thin film by energetic particles strongly influences film properties. Particle bombardment has generally been accomplished by accelerating ions into the growing film. However, it has also been recognized since the 1960's that energetic particles reflected from the target influence the characteristics of films grown by physical sputtering and many experiments have been interpreted on this basis. A systematic study of the energy reflected from the surface by normally incident, singly charged noble-gas ions on five substrates of different masses has recently been published. This data along with sputter yields from the literature allow estimates to be made which were previously unavailable. The energy reflected from the target is carried away by electrons, sputtered particles and reflected ions (neutrals). The purpose of this paper is to provide basic information which will allow thin film scientists to estimate the influence of various experimental parameters on the amount of energy arriving at the growing film. The energy reflected from the target per sputtered atom will be given as a function of ion mass, target mass, and ion energy. TRIM.SP Monte Carlo calculations will be used to estimate the ratio of the energy carried away by sputtered atoms to that carried away by reflected ions. Calculations will also be used to estimate the average energy of the sputtered atoms as a function of ion mass, substrate mass and ion energy. It will be shown how this information can be used to guide the adjustment of experimental parameters in sputtering environments so as to control film characteristics.

We have performed computer simulations of epitaxial growth and low-energy ion bombardment for comparison with reflection high-energy electron diffraction (RHEED) mesurements. The simulations are based on a hybrid Monte Carlo/rate equation approach which includes the processes of defect creation (adatom and surface vacancy), surface diffusion, and attachment and detachment from steps and islands. In this work, we focus on simulating the experimental observations of ion-induced RHEED oscillations and cancellation of RHEED oscillations during simultaneous ion bombardment and growth. For the interaction of the low-energy ion with the surface, we consider two mechanisms: preferential sputtering (where the sputtering cross section depends on the atomic coordination) and mobile vacancies. Our results indicate that the primary interaction of the ion beam with the surface is probably through the creation of mobile vacancies, and that the degree of preferential sputtering is not large.

Three important effects of low energy direct Ion Beam Deposition (IBD) are the athermal incorporation of material into a substrate, the enhancement of atomic mobility in the subsurface, and the modification of growth kinetics it creates. All lead to a significant lowering of the temperature necessary to induce epitaxial growth and chemical reactions. The fundamental understanding and new applications of low temperature kinetics induced by low energy ions in thin film growth and surface processing of semiconductors are reviewed. It is shown that the mechanism of IBD growth can be understood and computed quantitatively using a simple model including ion induced defect generation and sputtering, elastic recombination, thermal diffusion, chemical reactivity, and desorption The energy, temperature and dose dependence of growth rate, epitaxy, and chemical reaction during IBD is found to be controlled by the net recombination rate of interstitials at the surface in the case of epitaxy and unreacted films, and by the balance between ion beam decomposition and phase formation induced by ion beam generated defects in the case of compound thin films. Recent systematic experiments on the formation of oxides and nitrides on Si, Ge/Si(100), heteroepitaxial SixGe1−x/Si(100) and GaAs(100) illustrate applications of this mechanism using IBD in the form of Ion Beam Nitridation (IBN), Ion Beam Oxidation (IBO) and Combined Ion and Molecular beam Deposition (CIMD). It is shown that these techniques enable (1) the formation of conventional phases in conditions never used before, (2) the control and creation of properties via new degrees of freedom such as ion energy and lowered substrate temperatures, and (3) the formation of new metastable heterostructures that cannot be grown by pure thermal means.

In rf silane plasmas, growing process and behavior of dust particles and presence of negative ions are studied by square-wave-amplitude-modulating an rf discharge voltage. By combining the rf modulation method with Mie scattering methods, particle behavior together with temporal evolutions of particle size and density is revealed. While the rf modulation is effective for the suppression of particle growth, small particles are found to exist still in the discharge space for a larger duty cycle. Further, particles seem to be suspended around an rf electrode by counter balance between an electrostatic force due to time-averaged sheath electric field and a force increasing with particle size. The development of particle growth also affects the rf discharge itself, resulting in inhomogeneity of film properties. Negative ion detection is carried out as a first step for studying whether they cause the particle formation. It is found that negative ions are formed in rf silane discharges even for a low concentration of 0.5%SiH4 and their formation is due to attachment to dissociated radicals rather than dissociative attachment of SiH4.

CVD deposited diamond-like carbon (DLC) films have been studied for possible use as a secondary standard for Low Earth Orbit materials degradation. Samples of various thicknesses have been exposed to a simulated Low Earth Orbit atomic oxygen (AO) environment using a plasma asher. Mass loss measurements indicate that DLC degrades at a rate of 0.7 mg/hr which is two to three times the rate of currently used Kapton samples which degrade at a rate of.3 mg/hr. Thickness measurements show that DLC thins at a rate of 77 Angstroms/min. Since DLC is not as susceptible to environmental factors such as moisture absorption, it could potentially provide more accurate measurements of AO fluence on short space flights. Adhesion of DLC films to both fused silica and crystalline silicon substrates has been studied under thermal cycling conditions. Film adhesion to fused silica can be enhanced by sputtering a thin layer of silicon dioxide onto the substrate prior to deposition. In addition to the above, the index of refraction and extinction coefficient of various thicknesses of DLC films has been characterized by Variable Angle Spectroscopic Ellipsometry.

The incorporation of hydrogen into silicon nitride films grown downstream from an electron cyclotron resonance (ECR) plasma decreased rapidly with increasing substrate temperature (100-600°C). Fourier transform infra-red (FTIR) spectroscopy showed that the hydrogen in the as-grown material was primarily bonded to nitrogen. However, an applied bias of -200 V caused an increase in the number of Si-H bonds relative to N-H bonds, as a result of increased ion-beam damage. In addition, ion irradiation of an asgrown film with 175 keV Ar+ at room temperature showed that H transferred from N-H bonds to Si-H bonds without a loss of H. Elastic recoil detection (ERD) and FTIR of thermally annealed films showed that the stability of H incorporated during deposition increased with deposition temperature, and that the N-H bond was more stable than the Si-H bond above 700°C. Deuterium plasma treatments, at 600°C, of annealed films caused isotopic substitution with a conservation of bonds. Therefore, hydrogen loss from annealed films is apparently accompanied by a reduction in dangling bonds.

Silicon was oxidized at low temperature with an oxygen plasma generated by an electron cyclotron resonance (ECR) source. The ECR source utilized a multicusp magnetic field formed by permanent magnets. Microwave power at 2.45 GHz was applied to the source and rf power at 13.56 MHz was applied to the sample stage. Si oxidation was studied as a function of source distance, pressure, microwave power, and rf power. The oxide thickness increases with microwave and rf power but decreases with source distance. The oxidation rate increases with pressure up to 12 mTorr, then decreases at higher pressure. The relative emission intensities in the plasma monitored using optical emission spectroscopy showed similar dependence on the source distance and microwave power. Oxidation temperature was estimated to be <100°C. Using ellipsometry and X-ray photoelectron spectroscopy, the oxidized films were found to be close to that of thermal oxide with refractive index at 1.45 and oxygen to silicon ratio of 2. From the current-voltage and capacitance-voltage measurements, the breakdown fields of these oxide films were 6.3 MV/cm and the fixed charge densities were 7×1010 cm−2.

Ion beam modification of polyimide (PI) by low energy and surface analysis were performed using XPS. The surface chemistry was monitored as a function of ion dose. The results indicate that even low energy ion beam (LEIB) induces a drastic change in chemical compositions on the PI surface, and the modification begins to occur at the onset of beam treatment, contrary to previous observations. Damage level is severely restricted to surface region. It is also proven that LEIB modification is a direct way to control interface chemistry.

The paper presents the results of AES, SIMS, RBS and electron microscopy investigation of compound metal oxide films. The films were deposited by sputtering compound targets with oxygen ion beam, extracted from hollow cold cathode ion source.

Ultra-high molecular weight polyethylene (UHMW-PE) has a highly chain-extended and crystalline structure which is functionally inert and requires surface-modification before it can successfully operate as a reinforcement in polymer-matrix composites. Although plasma treatments are adequate for this purpose, recent work has shown that irradiation with low-energy inert gas ions can produce increases in interfacial shear strength (ISS), in epoxy matrices, which exceed those of commercial plasma treatments, and cause little degradation in tensile properties. Low energy ions are readily produced in high-current beams using gridded sources having moderate cost, and processing times may be a short as a few seconds. In this paper, we present results of recent experiments using argon ions accelerated to energies between 100 eV and 1 keV to irradiate 20-30 µm diameter UHMW-PE fibers to doses between 1×1016 and 1×1017 cm−2, and compare our findings with previous work at higher accelerating potentials. At the optimum dose (which increases with decreasing energy), greater than 9-fold improvements in ISS level, measured in epoxy-resin droplet pulloff tests, were found for ion irradiation at 0.25 keV. Scanning electron microscopy of fiber surfaces, of ion irradiated as well as commercial oxygen plasmatreated materials, revealed small crack-like pits in both cases, with the pits smaller and more uniformly distributed on the ion-irradiated fibers. Surface chemistry studies using X-ray photoelectron spectroscopy (XPS) and attenuated total reflectance Fourier-transform infrared spectroscopy (ATR-FTIR) indicate that irradiation resulted in high surface concentrations of polar functional groups, and extensive surface oxidation. This was accompanied by a substantial increase in the polar component of surface energy, which resulted in improved fiber wetting by the resin.

Thin films of SiO2 were deposited on Si substrates by remote PECVD following an in-situ cleaning/surface passivation with atomic-H. Si-N bonds were found in the immediate vicinity of the SiO2/Si interface when nitrous oxide, N2O, was used as O-atom source gas in the remote PECVD process. Si-N bonds, as well as Si-surface roughening produced by H-atom etching, contribute to the formation of high densities of midgap trapping states, Dit ∼1011 cm−2eV−1, at the SiO2/Si interface. Eliminating the H-atom processing step, and exposing the Si surface to plasma-generated O-atoms prior to the SiO2 deposition: i) eliminated Si-N bonding at the Si/SiO2 interface; ii) reduced midgap Dit to ∼1−3×1010 cm−2eV−1; iii) eliminated surface roughening; and iv) improved process latitude and reproducibility.

Silicon epitaxial growth on silicon wafers were investigated by using plasma enhanced chemical vapor deposition from SiH4/He/H2. The epitaxial layers were growm at temperatures of 350°C or lower. The base pressure of the chamber was greater than 2 × 10−5 Torr. Prior to epitaxial growth, the wafer was in-situ cleaned by H2 baking for 30 min. The epi/substrate interface and epitaxial layers were observed by cross-sectional transmission electron microscopy (XTEM). Finally, the influence of the ex-situ and in-situ cleaning processes on the qualities of the interface and epitaxial layers was discussed in detail.

Remote Plasma-enhanced Chemical Vapor Deposition (RPCVD) has been used to grow GexSi1−x/Si heteroepitaxial thin films at low temperatures (∼450°C). In situ RHEED has been used to confirm that smooth, single crystal heteroepitaxial films can be grown by RPCVD. Plan-view and cross-sectional TEM have been employed to study the microstructure of the heteroepitaxial films. Lattice imaging high resolution TEM (HRTEM) has shown perfect epitaxial lattice alignment at the heterojunction interfaces. GexSi1−x/Si films which exceed their CLT's appreciably show dense Moiré fringes under plan-view TEM. The spacings between the fringes have been used to estimate the relaxed lattice constants. In addition to the inhomogeneous strain observed in XTEM, Selected Area electron Diffraction (SAD) analysis of the interfaces displays two split patterns. The spacings between the diffraction spots have been used to calculate the lattice constants in the epitaxial films in different crystal directions, which agree very well with the prediction by Vegard's law as well as the estimate from planview TEM analysis. HRTEM analysis also reveals the crystallographic nature of the interfacial misfit dislocations in the relaxed films.

We consider the feasibility of using an excimer laser to planarize copper deposited over polyimide. Even though the polyimide is thermally sensitive, a 2.8 µn thick copper film, deposited over polyimide, was planarized with 248 nm, 25 ns, laser fluences from 1.7 to 2.6 J/cm2. Although planar surfaces were readily produced, a variety of defects were observed in the underlying structures. The defects observed include stress induced fractures of the interconnect structure, polyimide surface roughening, and changes in the electrical characteristics of the polyimide. We also describe cross sectional TEM images of cavities formed in interlayer contacts during laser planarization that support recent descriptions of the surface tension driven flow.

We report here the use of a low pressure Hg lamp to grow oxide layers on Si in N 2O and O2. Layer thicknesses up to 100Å, whose IR absorption characteristics are similar to those exhibited by thermal oxides, have been produced. Preliminary modelling of the process is described.

A silicon carbide-like layer was produced in the near-surface region of teflon by irradiating with an ArF excimer laser in a SiH4 and B(CH3)3 mixed gas atmosphere. The pure photochemical reaction was employed in the modification process, and the defluorination of the surface was performed with boron atoms which were photodissociated from B(CH3)3. The CH3 radicals, also photodissociated, induced the dehydrogenation of SiH4 gas; which followed the production of SiHx radicals. The SiHx radicals and CH3 radicals which could not have induced the dehydrogenation of SiH4 were substituted for fluorine atoms of the surface. As a result, the surface was photomodified into silicon carbide. Chemical composition of the photomodified surface was inspected by the XPS and the ATR-FT-IR spectra measurement, and the bonding of the Si-CH3 radicals which traded off the reduction of the fluorine atoms was comfirmed. The Si/C composition ratio of the photomodified surface was 0.7.

A thin film of aluminum, detected by x-ray photoelectron spectroscopy, is left at the surface of aluminum nitride (AIN) substrates exposed to a high intensity excimer laser beam of UV radiation. Due to the presence of this film, there is a decrease in the surface resistivity of the substrate with increasing number of laser pulses. In addition, line profilometry shows a decrease of the surface roughness with the number of pulses.

The thermal decomposition of AIN is assumed to take place in two stages. In the first, liquid aluminum is produced together with the evolution of gaseous nitrogen, and in the second, aluminum evaporates. Using a computer model to simulate the laser heating cycle, it is shown that the thickness of the aluminum film saturates at a given laser energy density. The saturation thickness is a strong function of the substrate absorption and reflectivity and, therefore, of the laser light frequency. The influence of the substrate roughness on the electrical resistivity of the aluminum film is discussed.

The application of this process to direct laser writing in high density hybrid circuits is illustrated. During hole drilling by excimer laser, a thin aluminum film is continuously produced at the hole walls. This process can also be employed for substrate planarization.

This work describes phosphorus (P) and boron (B) doping of polysilicon filns deposited on quartz. Doping is achieved by means of a pulsed ArF excimer laser to melt a controlled thickness of amorphous or polycristalline silicon film coated with a spinon silicate glass (SOG) film containing the dopant (P or B). We have investigated the influence of doping parameters such as laser fluence, number of shots and dopant film thickness on the sheet resistance and the incorporation rate. From these results, we have shown that high doped, shallow junctions presenting sheet resistance lower than 5 kΩ/∠ can be obtained. Poly-Si TFT's with good electrical characteristics were successfully fabricated using this doping technique.