Brian P. Gorman

Rapid repair of plasma ash damage in low-k dielectrics using supercritical CO2

Plasma damage to methylsilsequioxane (MSQ) based low-k dielectrics degrades the material’s resistance to subsequent wet etch processes. In addition, the loss of methyl species during plasma exposure increases their susceptibility to water absorption leading to increased dielectric permittivities. In this article, we introduce a process in which silylating agents dissolved in supercritical CO2 are used to functionalize ash-damaged surfaces. This silylation process greatly decreases the time necessary to induce hydrophobicity (less than 1 min as determined by a change in contact angle from 18° to 90°). The process also reduces the concentration of reactive silylation agents needed for full hydrophobicity to less than 1 vol %. Further, this process is also shown to reduce material loss during subsequent wet etch processes. Film thickness measured by scanning electron microscopy before and after treatment illustrates a difference of approximately 0.1 μm after etching in a dilute HF solution for 30 s.

Atom Probe Analysis of III–V and Si-Based Semiconductor Photovoltaic Structures

The applicability of atom probe to the characterization of photovoltaic devices is presented with special emphasis on high efficiency III-V and low cost ITO/a-Si:H heterojunction cells. Laser pulsed atom probe is shown to enable subnanometer chemical and structural depth profiling of interfaces in III-V heterojunction cells. Hydrogen, oxygen, and phosphorus chemical profiling in 5-nm-thick a-Si heterojunction cells is also illustrated, along with compositional analysis of the ITO/a-Si interface. Detection limits of atom probe tomography useful to semiconductor devices are also discussed. Gaining information about interfacial abruptness, roughness, and dopant profiles will allow for the determination of semiconductor conductivity, junction depletion widths, and ultimately photocurrent collection efficiencies and fill factors.

Atom probe tomography evaporation behavior of C-axis GaN nanowires: Crystallographic, stoichiometric, and detection efficiency aspects

The field evaporation behavior of c-axis GaN nanowires was explored in two different laser-pulsed atom probe tomography (APT) instruments. Transmission electron microscopy imaging before and after atom probe tomography analysis was used to assist in reconstructing the data and assess the observed evaporation behavior. It was found that the ionic species exhibited preferential locations for evaporation related to the underlying crystal structure of the GaN and that the species which evaporated from these locations was dependent on the pulsed laser energy. Additionally, the overall stoichiometry measured by APT was significantly correlated with the energy of the laser pulses. At the lowest laser energies, the apparent composition was nitrogen-rich, while higher laser energies resulted in measurements of predominantly gallium compositions. The percent of ions detected (detection efficiency) for these specimens was found to be considerably below that shown for other materials, even for laser energies which pr...

Exploring the limits of N-type ultra-shallow junction formation.

Low resistivity, near-surface doping in silicon represents a formidable challenge for both the microelectronics industry and future quantum electronic devices. Here we employ an ultra-high vacuum strategy to create highly abrupt doping profiles in silicon, which we characterize in situ using a four point probe scanning tunnelling microscope. Using a small molecule gaseous dopant source (PH3) which densely packs on a reconstructed silicon surface, followed by encapsulation in epitaxial silicon, we form highly conductive dopant sheets with subnanometer control of the depth profiles. This approach allows us to test the limits of ultra-shallow junction formation, with room temperature resistivities of 780 Ω/□ at an encapsulation depth of 4.3 nm, increasing to 23 kΩ/□ at an encapsulation depth of only 0.5 nm. We show that this depth-dependent resistivity can be accounted for by a combination of dopant segregation and surface scattering.

High strength, low dielectric constant fluorinated silica xerogel films

The mechanical, electrical, and microstructural properties of low-k fluorinated silica xerogels produced using a one step spin-on process are reported. Derived from a fluorinated silane monomer, these films are easily processed and exhibit very low dielectric constants (2.1 as processed and 2.3 after heat treating at 450 °C in air). Structural determination by Fourier transform infrared spectrophotometry indicates a fluorinated silica structure with shortened Si–O bonds; however, some of the fluorine is lost during annealing. Nanoindentation studies show high elastic moduli (12 GPa) and hardness (1 GPa). Microstructural analyses by transmission and scanning electron microscopy indicate an unusual morphology with highly linked features and pore sizes in the 20–30 nm range. We believe the low dielectric constants and robust mechanical properties are due to the unusual microstructure of these films.

Investigation of Polymerization and Cyclization of Dimethyldiethoxysilane by 29Si NMR and FTIR

Dimethyldiethoxysilane (DMDES) appears to be a very promising modifier to introduce functional groups to a silicate network. The polymerization and cyclization of DMDES under acid-catalyzed conditions (DMDES : Ethanol : water : HCl = 1:4:4:3.68 × 10−4 in molar ratio) were investigated by high resolution liquid 29Si nuclear magnetic resonance (NMR) and Fourier transform infrared spectrometry (FTIR). Time-dependent NMR and FTIR data illustrate that monomers of (CH3)2Si(OC2H5)2, (CH3)2Si(OC2H5)(OH), and (CH3)2Si(OH)2 reach meta-equilibrium in less than 4 minutes. 3-membered rings ((CH3)2SiO)3 appear about half an hour later and 4-membered rings ((CH3)2SiO)4 an hour later, which continue to be formed over 24 hours. The relative concentrations of monomers, linear structures and cyclic structures suggest a modified model for the kinetics of cyclization, where 4-membered rings are formed by dimer-dimer interactions, as opposed to monomer-trimer interactions previously proposed.

Field-directed sputter sharpening for tailored probe materials and atomic-scale lithography

Fabrication of ultrasharp probes is of interest for many applications, including scanning probe microscopy and electron-stimulated patterning of surfaces. These techniques require reproducible ultrasharp metallic tips, yet the efficient and reproducible fabrication of these consumable items has remained an elusive goal. Here we describe a novel biased-probe field-directed sputter sharpening technique applicable to conductive materials, which produces nanometer and sub-nanometer sharp W, Pt-Ir and W-HfB(2) tips able to perform atomic-scale lithography on Si. Compared with traditional probes fabricated by etching or conventional sputter erosion, field-directed sputter sharpened probes have smaller radii and produce lithographic patterns 18-26% sharper with atomic-scale lithographic fidelity.

Techniques for Consecutive TEM and Atom Probe Tomography Analysis of Nanowires

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Temperature dependence of the band gap of GaAsSb epilayers

We have optically characterized a series of GaAs1−xSbx epilayers (0.19<x<0.71) grown by molecular bean epitaxy on semi-insulating GaAs substrates, with surface orientations of (001), (001) 8° toward (111)B, (001) 8° toward (111)A, and (115)B. For each of these samples, we have investigated the absorption as a function of temperature (4 K<T<300 K) using Fourier transform infrared spectroscopy techniques. The band gap at each temperature was determined from the photon energy dependence of the absorption coefficient and compared with theoretical predictions. From our results we have obtained the Varshni coefficients, α=(4.2±0.1)×10−4 eV/K and β=(189±9) K, which describe well not only the temperature dependence of the band gap for the entire alloy range of our samples, but also for the past experimental work of others. These values differ significantly from what we believe are the only other reported values by K. G. Merkel et al. [K. G. Merkel et al., Appl. Phys. Lett. 65, 2442 (1994)].

Atomic Layer Deposition of Tungsten Disulphide Solid Lubricant Nanocomposite Coatings on Rolling Element Bearings

Atomic layer deposition (ALD) has the potential to provide highly conformal coatings with precise control of thickness. This article describes the application of ALD nanocomposite containing ZnF2 in WS2 matrix solid lubricant coatings on fully assembled rolling element bearings. The torque behavior of the coated bearings was studied during oscillatory contacts and after exposure to vibration. The coatings exhibited a hexagonal layered structure with predominant preferentially orientated (002) basal planes. These basal planes when sheared imparted very low running torque values of ∼ 0.5 mN· m in dry nitrogen. The outer race, inner race, and ball surfaces showed WS2 transfer film protection on the native coating necessary to achieve low torque in dry nitrogen. Structural (re)ordering of the basal and prismatic planes with multiple random and branched orientations was observed through the thickness of the transfer films. There was no evidence of uniformly aligned c-axis perpendicular-orientated basal planes on the transfer film surface. The unique advantages of ALD to apply solid lubricant coatings on rolling elements of fully assembled miniature bearings are compared with conventional solid lubrication techniques.