C. W. White

Nanocomposite Materials Formed by Ion Implantation

Ion implantation has become a versatile and powerful technique for synthesizing nanometer-scale clusters and crystals embedded in the near-surface region of a variety of hosts in order to create nanocomposite materials with often unique optical, magnetic, and other properties. Here we review some of the principal features of this nanophase materials synthesis technique as well as the materials properties that are exhibited by nanocomposites created by using ion beams. Outstanding difficulties and future research directions are also discussed.

Ion implantation and annealing of crystalline oxides

The technique of ion implantation is being investigated as a general method for altering the near-surface properties of insulating materials. The primary motivation behind these investigations is to develop ion implantation as a practical means of controlling and improving the near-surface mechanical, optical, or electronic properties of insulators. Changes in these properties depend on the microstructures and compositions developed in the material during the ion implantation process and subsequent thermal treatments. In many cases, structures and compositions can be produced by implantation and thermal annealing that cannot be achieved by conventional techniques. In this work, the response of a wide range of crystalline oxides to ion implantation and subsequent thermal processing will be reviewed. The materials treated here include Al 2 O 3 , LiNbO 3 , CaTiO 3 , SrTiO 3 , ZnO, and MgO, as well as the non-oxide materials Si 3 N 4 and SiC. The response of these insulators to ion implantation varies widely and depends on the specific material, the implantation species and dose, and the implantation temperature. Ion implantation produces displacement and other damage in the near-surface region, and in many cases, the surfaces of originally crystalline insulators are turned amorphous. Thermal annealing can often be used to restore crystallinity to the damaged near-surface region, and additionally, metastable solid solutions can be produced. For a number of oxide materials, the annealing behavior has been studied in detail using both Rutherford backscattering-ion channeling techniques and transmission electron microscopy. These studies show that, in some materials, the annealing behavior is quite simple and takes place by solid-phase epitaxial crystallization where the amorphous-to-crystalline transformation occurs at an interface that moves toward the free surface during the annealing process. In such materials, the regrowth kinetics have been measured, and the associated activation energies for crystallization have been determined. The formation of metastable solid solutions during crystallization of the amorphous phase will also be discussed.

Growth of Ge, Si, and SiGe nanocrystals in SiO2 matrices

Nanocrystals of group‐IV semiconductor materials (Si, Ge, and SiGe) have been fabricated in SiO2 by ion implantation and subsequent thermal annealing. The microstructure of these nanocrystals has been studied by transmission electron microscopy. Critical influences of the annealing temperatures and implantation doses on the nanocrystal size distributions are demonstrated with the Ge‐implanted systems. Significant roughening of the nanocrystals occurs when the annealing temperature is raised above the melting temperature of the implanted semiconductor material.

Laser Method for Synthesis and Processing of Continuous Diamond Films on Nondiamond Substrates

A laser method based upon carbon ion implantation and pulsed laser melting of copper has been used to produce continuous diamond thin film. Carbon ions were implanted with ion energies in the range of 60 to 120 keV, and doses of 1.0 x 1018 to 2.0 x 1018 ions cm–2. The ion-implanted specimens were treated with nanosecond excimer laser pulses with the following parameters: energy density, 3.0 to 5.0 J cm–2; wavelength, 0.308 �m; pulse width, 45 nanoseconds. The specimens were characterized with scanning electron microscopy (SEM), x-ray diffraction, Rutherford backscattering/ion channeling, Auger, and Raman spectroscopy. The macroscopic Raman spectra contained a strong peak at 1332 cm–1 with full width at half maximum of 5 cm–1, which is very close to the quality of the spectra obtained from single-crystal diamond. The selected area electron diffraction patterns and imaging confirmed the films to be defect-free single crystal over large areas of up to several square micrometers with no grain boundaries. Low voltage SEM imaging of surface features indicated the film to be continuous with presence of growth steps.

Nanocomposites formed by ion implantation: Recent developments and future opportunities

Abstract Ion implantation is a versatile and powerful technique for forming many types of nanocrystalline precipitates embedded in the near-surface region of a wide variety of crystalline and amorphous host materials. The unique optical, electronic and magnetic properties of these nanocomposites has stimulated considerable recent research interest. In this review, we discuss recent developments in the field as well as some of the problems that currently hinder the potential applications of nanocomposites formed by ion implantation.

Optical properties of gold nanocluster composites formed by deep ion implantation in silica

Planar layers of Au clusters with diameters between 5 and 30 nm were synthesized by implanting 2.75‐MeV Au+ ions in fused silica. The metal‐glass composite layer was 0.85 μm below the surface and had a width of 0.5 μm. Thermal annealing enhanced the optical absorption of the annealed samples near 2.4 eV. The third‐order nonlinear optical response time is ≤35 ps; the magnitude of the effective nonlinear susceptibility is 200 times that of similar clusters embedded in ruby‐gold melt glass.

Nonlinear optical properties of metal-quantum-dot composites synthesized by ion implantation

Abstract Over a decade ago, it was demonstrated that composites comprising metal clusters embedded in dielectric hosts could be synthesized by ion implantation. The optical properties of these metal-cluster composites are dominated by two phenomena which alter the susceptibilities from those of bulk metals: One is a classical field enhancement effect, dielectric confinement, which leads to the characteristic surface plasmon resonance of the metal clusters seen in absorption spectra. The other effect is quantum confinement of the conduction-band electrons which enhances the nonlinear susceptibility of the metal clusters for diameters smaller than about 10 nm and makes them behave as quantum dots with electronic properties which approximate those of independent electrons confined in a spherical potential well. This paper reviews our studies of the nonlinear optical behavior of quantum-dot composites synthesized by ion implantation. We also consider the potential of these quantum-dot composites as materials for nonlinear waveguide devices.

Formation of epitaxial layers of Ge on Si substrates by Ge implantation and oxidation

Thin epitaxial layers of Ge‐Si alloys have been formed on Si(100) substrates by steam oxidation of Ge‐implanted samples. During the oxidation, the Ge is totally piled up ahead of the SiO2/Si interface. This segregation of Ge leads to the formation of a distinct, Ge‐rich layer which is epitaxial with the underlying Si. The thickness of the Ge layer is dependent on the implantation dose. This layer and its two bounding interfaces with the oxide and Si are characterized as a function of the implantation dose and energy, using Rutherford backscattering and high‐resolution transmission electron microscopy.

Single‐crystal diamond plate liftoff achieved by ion implantation and subsequent annealing

We describe a new method for removing thin, large area sheets of diamond from bulk or homoepitaxial diamond crystals. This method consists of an ion implantation step, followed by a selective etching procedure. High energy (4–5 MeV) implantation of carbon or oxygen ions creates a well‐defined layer of damaged diamond that is buried at a controlled depth below the surface. For C implantations, this layer is graphitized by annealing in vacuum, and then etched in either an acid solution, or by heating at 550–600 °C in oxygen. This process successfully lifts off the diamond plate above the graphite layer. For O implantations of a suitable dose (3×1017 cm−2 or greater), the liftoff is achieved by annealing in vacuum or flowing oxygen. In this case, the O required for etching of the graphitic layer is also supplied internally by the implantation. This liftoff method, combined with well‐established homoepitaxial growth processes, has considerable potential for the fabrication of large area single crystalline dia...

Effects of hydrogen in the annealing environment on photoluminescence from Si nanoparticles in SiO2

The role of hydrogen in enhancing the photoluminescence (PL) yield observed from Si nanocrystals embedded in SiO{sub 2} has been studied. SiO{sub 2} thermal oxides and bulk fused silica samples have been implanted with Si and subsequently annealed in various ambients including hydrogen or deuterium forming gases (Ar+4%H{sub 2} or Ar+4%D{sub 2}) or pure Ar. Results are presented for annealing at temperatures between 200 and 1100 C. Depth and concentration profiles of H and D at various stages of processing have been measured using elastic recoil detection. Hydrogen or deuterium is observed in the bulk after annealing in forming gas but not after high temperature (1100 C) anneals in Ar. The presence of hydrogen dramatically increases the broad PL band centered in the near-infrared after annealing at 1100 C but has almost no effect on the PL spectral distribution. Hydrogen is found to selectively trap in the region where Si nanocrystals are formed, consistent with a model of H passivating surface states at the Si/SiO{sub 2} interface that leads to enhanced PL. The thermal stability of the trapped H and the PL yield observed after a high temperature anneal have been studied. The hydrogen concentration and PL yield are unchanged for subsequent anneals up to 400 C. However, above 400 C the PL decreases and a more complicated H chemistry is evident. Similar concentrations of H or D are trapped after annealing in H{sub 2} or D{sub 2} forming gas; however, no differences in the PL yield or spectral distribution are observed, indicating that the electronic transitions resulting in luminescence are not dependent on the mass of the hydrogen species.