A buckminsterfullerene (C60)-based primary ion beam system has been developed for routine application in TOF-SIMS analysis of organic materials. The ion beam system is described, and its performance is characterized. Nanoamp beam currents of C60+ are obtainable in continuous current mode. C602+ can be obtained in pulsed mode. At 10 keV, the beam can be focused to less than 3 μm with 0.1 nA currents. TOF-SIMS studies of a series of molecular solids and a number of polymer systems in monolayer and thick film forms are reported. Very significant enhancement of secondary ion yields, particularly at higher mass, were observed using 10-keV C60+ for all samples other than PTFE, as compared to those observed from 10 keV Ga+ primary ions. Three materials (PS2000, Irganox 1010, PET) were studied in detail to investigate primary ion-induced disappearance (damage) cross sections to determine the increase in secondary ion formation efficiency. The C60 disappearance cross sections observed from monolayer film PS2000 an...

A C60 Primary Ion Beam System for Time of Flight Secondary Ion Mass Spectrometry: Its Development and Secondary Ion Yield Characteristics

The move to implement metal oxide based gate dielectrics in a metal-oxide-semiconductor field effect transistor is considered one of the most dramatic advances in materials science since the invention of silicon based transistors. Metal oxides are superior to SiO 2 in terms of their higher dielectric constants that enable the required continuous down-scaling of the electrical thickness of the dielectric layer while providing a physically thicker layer to suppress the quantum mechanical tunneling through the dielectric layer. Over the last decade, hafnium based materials have emerged as the designated dielectrics for future generation of nano-electronics with a gate length less than 45 nm, though there exists no consensus on the exact composition of these materials, as evolving device architectures dictate different considerations when optimizing a gate dielectric material. In addition, the implementation of a non-silicon based gate dielectric means a paradigm shift from diffusion based thermal processes to atomic layer deposition processes. In this report, we review how HfO 2 emerges from all likely candidates to become the new gold standard in the microelectronics industry, its different phases, reported electrical properties, and materials processing techniques. Then we use specific examples to discuss the evolution in designing hafnium based materials, from binary to complex oxides and to non-oxide forms as gate dielectric, metal gates and diffusion barriers. To address the impact of these hafnium based materials, their interfaces with silicon as well as a variety of semiconductors are discussed. Finally, the integration issues are highlighted, including carrier scattering, interface state passivation, phonon engineering, and nano-scale patterning, which are essential to realize future generations of devices using hafnium-based high- k materials.

Development of hafnium based high-k materials—A review

Cluster secondary ion mass spectrometry (cluster SIMS) has played a critical role in the characterization of polymeric materials over the last decade, allowing for the ability to obtain spatially resolved surface and in-depth molecular information from many polymer systems. With the advent of new molecular sources such as , , , and , there are considerable increases in secondary ion signal as compared to more conventional atomic beams (Ar+, Cs+, or Ga+). In addition, compositional depth profiling in organic and polymeric systems is now feasible, without the rapid signal decay that is typically observed under atomic bombardment. The premise behind the success of cluster SIMS is that compared to atomic beams, polyatomic beams tend to cause surface-localized damage with rapid sputter removal rates, resulting in a system at equilibrium, where the damage created is rapidly removed before it can accumulate. Though this may be partly true, there are actually much more complex chemistries occurring under polyatomic bombardment of organic and polymeric materials, which need to be considered and discussed to better understand and define the important parameters for successful depth profiling. The following presents a review of the current literature on polymer analysis using cluster beams. This review will focus on the surface and in-depth characterization of polymer samples with cluster sources, but will also discuss the characterization of other relevant organic materials, and basic polymer radiation chemistry. © 2009 Wiley Periodicals, Inc., Mass Spec Rev 29:247–293, 2010

Cluster secondary ion mass spectrometry of polymers and related materials.

Cluster-surface interaction: From soft landing to implantation

The mechanism of enhanced desorption initiated by 15-keV C60 cluster ion bombardment of a Ag single crystal surface is examined using molecular dynamics computer simulations. The size of the model microcrystallite of 165 000 atoms and the sophistication of the interaction potential function yields data that should be directly comparable with experiment. The C60 model was chosen since this source is now being used in secondary ion mass spectrometry experiments in many laboratories. The results show that a crater is formed on the Ag surface that is ∼10 nm in diameter, a result very similar to that found for Au3 bombardment of Au. The yield of Ag atoms is ∼16 times larger than for corresponding atomic bombardment with 15-keV Ga atoms, and the yield of Ag3 is enhanced by a factor of 35. The essential mechanistic reasons for these differences is that the C60 kinetic energy is deposited closer to the surface, with the deeply penetrating energy propagation occurring via a nondestructive pressure wave. The number...

Enhancement of Sputtering Yields Due to C60 versus Ga Bombardment of Ag{111} As Explored by Molecular Dynamics Simulations

A cesium sputter ion source has been used to generate novel cluster and monoatomic primary ion beams for secondary ion mass spectrometry (SIMS). The source produces a variety of primary ion beam species with sufficient flux to be usable for both organic surface analysis and semiconductor depth profiling. The primary focus of this work is on the generation and use of carbon and carbon-containing cluster primary ion beams for SIMS. Stability of the sputter ion source is a few percent over 20 min, has useful lifetimes of weeks to months, and produces total primary ion beam currents for C2− ions, measured at the sample, of >1 μA at an extraction voltage of 10 kV. Larger cluster ions (Cx−x=4–10 and CsCx−x=2–8) are produced with tens of nA of beam current. Due to the divergence of the source, focused beam operation gives current densities under optimal conditions of 0.4–0.5 mA/cm2. Cluster bombardment studies of organic films using carbon clusters Cx−x=1–10 indicate that large enhancements (up to a factor of 80...

Negative cesium sputter ion source for generating cluster primary ion beams for secondary ion mass spectrometry analysis

Silicon wafers were preamorphized with 70 keV Si+ at a dose of 1×1015 atoms/cm2, generating a deep amorphous layer of 1800 A. Implants of 500 eV 11B+, with and without 6 keV F+, followed at doses of 1×1015 atoms/cm2 and 2×1015 atoms/cm2, respectively. After annealing at 550 °C, secondary ion mass spectroscopy determined that the diffusivity of boron in amorphous silicon is significantly enhanced in the presence of fluorine. Ellipsometry and cross-sectional transmission electron microscopy indicate the enhanced diffusion only occurs in the amorphous layer. Fluorine increases the boron diffusivity by approximately five orders of magnitude at 550 °C. It is proposed that the ability of fluorine to reduce the dangling bond concentration in amorphous silicon may reduce the formation energy for mobile boron, enhancing its diffusivity.

Fluorine-enhanced boron diffusion in amorphous silicon

A magnetic sector secondary ion mass spectrometry (SIMS) instrument has been fitted with a modified hot filament duoplasmatron ion source for generation of SF5+ primary ion beams for SIMS depth profiling applications. The SF5+ primary ion beam has been evaluated by depth profiling of several low energy boron ion implants, boron delta-doped structures and a Ni/Cr metal multilayer depth profiling standard reference material. Using 3.0 keV impact SF5+ bombardment at a 52° impact angle with oxygen flooding gives a trailing edge decay length (1/e) for the boron implants and delta-doped layers of 1.3 nm. Under the same conditions, O2+ bombardment gives a trailing edge decay length (1/e) of 2.3 nm. The use of the SF5+ beam without oxygen flooding gives a substantial increase in decay length that is related to the formation of ripples as determined by atomic force microscopy. In the case of the Ni/Cr reference material, a significant reduction in sputter-induced topography is observed with SF5+ bombardment.

Use of an SF5+ polyatomic primary ion beam for ultrashallow depth profiling on an ion microscope secondary ion mass spectroscopy instrument

Thermal response of MOCVD hafnium silicate

Sputter rate variations and surface roughening occurring during the initial stages of secondary ion mass spectrometry ultrashallow depth profiling of Si with Cs+ are examined for a range of primary ion incident energies (0.25–5.0 keV) and incident angles (40–80°). Sputter rate variations were derived over the 4.15–36.4 nm range through the analysis of a Boron delta layered structure. A reduction in the sputter rate with sputtering time was noted, with the variation increasing with decreasing primary ion energy and increasing incident angle. From this data set, a relation expressing these sputter rate variations as a function of the primary ion energy and incident angle was derived which, in turn, allows for depth and intensity scale corrections to be carried out. Surface roughening culminating in ripple formation was also observed using atomic force microscopy. These were observed under conditions resulting in excessive sputter rate variations.

Joe Bennett

Papers

Negative cesium sputter ion source for generating cluster primary ion beams for secondary ion mass spectrometry analysis

Fluorine-enhanced boron diffusion in amorphous silicon

Use of an SF5+ polyatomic primary ion beam for ultrashallow depth profiling on an ion microscope secondary ion mass spectroscopy instrument

Thermal response of MOCVD hafnium silicate

A systematic study of the surface roughening and sputter rate variations occurring during SIMS ultrashallow depth profile analysis of Si with Cs