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Reflectance-Correcting Pyrometry in Thin Film Deposition Applications

Breiland, William G.

A detailed study of an emissivity-correcting pyrometer instrument for measuring wafer surface temperatures during thin film growth is presented. The basic physics is reviewed and preliminary data showing a temperature over-compensation artifact is shown. The rest of the report presents an exhaustive analysis of the potential sources for the temperature over-compensation effect. This analysis yields an in situ calibration method that can be used to remove temperature over-compensation artifacts that arise from any first-order systematic error in either the reflectance or thermal emission measurement. With corrections applied, artifact-free surface temperatures can be measured with a precision of a few {sup o}C over a wide range of wafer emissivities.

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Nature of the parasitic chemistry during AlGaInN OMVPE

Proposed for publication in Journal of Crystal Growth.

Creighton, J.R.; Creighton, J.R.; Wang, George T.; Breiland, William G.; Coltrin, Michael E.

Using in situ laser light scattering, we have observed gas-phase nanoparticles formed during AlN, GaN and InN OMVPE. The response of the scattering intensity to a wide range of conditions indicates that the AlN parasitic chemistry is considerably different from the corresponding GaN and InN chemistry. A simple CVD particle-growth mechanism is introduced that can qualitatively explain the observed particle size and yields a strong residence time dependence. We also used FTIR to directly examine the reactivity of the metalorganic precursors with NH{sub 3} in the 25-300 C range. For trimethylaluminum/NH{sub 3} mixtures a facile CH{sub 4} elimination reaction is observed, which also produces gas-phase aminodimethylalane, i.e. Al(CH{sub 3}){sub 2}NH{sub 2}. For trimethylgallium and trimethylindium the dominant reaction is reversible adduct formation. All of the results indicate that the AlN particle-nucleation mechanism is predominately of a concerted nature, while the GaN and InN particle-nucleation mechanisms involve homogeneous pyrolysis and radical chemistry.

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Mechanisms of Atmospheric Copper Sulfidation and Evaluation of Parallel Experimentation Techniques

Barbour, J.C.; Breiland, William G.; Moffat, Harry K.; Sullivan, J.P.; Campin, Michael J.; Wright, Alan F.; Missert, Nancy A.; Braithwaite, J.W.; Zavadil, Kevin R.; Sorensen, Neil R.; Lucero, Samuel J.

A physics-based understanding of material aging mechanisms helps to increase reliability when predicting the lifetime of mechanical and electrical components. This report examines in detail the mechanisms of atmospheric copper sulfidation and evaluates new methods of parallel experimentation for high-throughput corrosion analysis. Often our knowledge of aging mechanisms is limited because coupled chemical reactions and physical processes are involved that depend on complex interactions with the environment and component functionality. Atmospheric corrosion is one of the most complex aging phenomena and it has profound consequences for the nation's economy and safety. Therefore, copper sulfidation was used as a test-case to examine the utility of parallel experimentation. Through the use of parallel and conventional experimentation, we measured: (1) the sulfidation rate as a function of humidity, light, temperature and O{sub 2} concentration; (2) the primary moving species in solid state transport; (3) the diffusivity of Cu vacancies through Cu{sub 2}S; (4) the sulfidation activation energies as a function of relative humidity (RH); (5) the sulfidation induction times at low humidities; and (6) the effect of light on the sulfidation rate. Also, the importance of various sulfidation mechanisms was determined as a function of RH and sulfide thickness. Different models for sulfidation-reactor geometries and the sulfidation reaction process are presented.

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Room temperature continuous wave InGaAsN quantum well vertical cavity lasers emitting at 1.3 um

Electronic Letters

Choquette, K.D.; Geib, K.M.; Klem, John F.; Fischer, Arthur J.; Spahn, Olga B.; Allerman, A.A.; Fritz, I.J.; Kurtz, S.R.; Breiland, William G.; Sieg, Robert M.

Selectively oxidized vertical cavity lasers emitting at 1294 nm using InGaAsN quantum wells are reported for the first time which operate continuous wave at and above room temperature. The lasers employ two n-type Al{sub 0.94}Ga{sub 0.06}As/GaAs distributed Bragg reflectors each with a selectively oxidized current aperture adjacent to the optical cavity, and the top output mirror contains a tunnel junction to inject holes into the active region. Continuous wave single mode lasing is observed up to 55 C. These lasers exhibit the longest wavelength reported to date for vertical cavity surface emitting lasers grown on GaAs substrates.

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Agile dry etching of compound semiconductors for science-based manufacturing using in-situ process control

Ashby, Carol I.; Vawter, Gregory A.; Zubrzycki, Walter J.; Breiland, William G.; Bruskas, Larry A.; Woodworth, Joseph R.; Hebner, Gregory A.

In-situ optical diagnostics and ion beam diagnostics for plasma-etch and reactive-ion-beam etch (RIBE) tools have been developed and implemented on etch tools in the Compound Semiconductor Research Laboratory (CSRL). The optical diagnostics provide real-time end-point detection during plasma etching of complex thin-film layered structures that require precision etching to stop on a particular layer in the structure. The Monoetch real-time display and analysis program developed with this LDRD displays raw and filtered reflectance signals that enable an etch system operator to stop an etch at the desired depth within the desired layer. The ion beam diagnostics developed with this LDRD will permit routine analysis of critical ion-beam profile characteristics that determine etch uniformity and reproducibility on the RIBE tool.

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In-Situ Monitoring of GaSb, GaInAsSb, and AlGaAsSb*

Journal of Crystal Growth

Breiland, William G.

The suitability of the wavelength range provided by silicon photodiode detector arrays for monitoring the spectral reflectance during epitaxial growth of GaSb, AlGaAsSb, and GaInAsSb, which have cutoff wavelengths at 25 degree C of 1.7, 1.2, and 2.3 um, respectively, is demonstrated. These alloys were grown lattice matched to GaSb in a vertical rotating-disk reactor, which was modified to accommodate near normal reflectance without affecting epilayer uniformity, By using a virtual interface model, the growth rate and complex refractive index at the growth temperature are extracted for these alloys over the 600 to 1000 nm spectral range. Excellent agreement is obtained between the extracted growth rate and that determined by ex-situ measurement.

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In situ reflectance and virtual interface analysis for compound semiconductor process control

Breiland, William G.

The authors review the use of in-situ normal incidence reflectance, combined with a virtual interface model, to monitor and control the growth of complex compound semiconductor devices. The technique is being used routinely on both commercial and research metal-organic chemical vapor deposition (MOCVD) reactors and in molecular beam epitaxy (MBE) to measure growth rates and high temperature optical constants of compound semiconductor alloys. The virtual interface approach allows one to extract the calibration information in an automated way without having to estimate the thickness or optical constants of the alloy, and without having to model underlying thin film layers. The method has been used in a variety of data analysis applications collectively referred to as ADVISOR (Analysis of Deposition using Virtual Interfaces and Spectroscopic Optical Reflectance). This very simple and robust monitor and ADVISOR method provides one with the equivalent of a real-time reflection high energy electron reflectance (RHEED) tool for both MBE and MOCVD applications.

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In-situ optical photoreflectance during MOCVD

Breiland, William G.

This report summarizes the development of in situ optical photoreflectance as a tool for measuring impurity concentrations in compound semiconductors. The authors have successfully explored the use of photoreflectance as an in situ tool for measuring n-type doping levels in metal-organic chemical vapor deposition (MOCVD) grown GaAs materials. The technique measures phase and frequency shifts in Franz-Keldysh oscillations measured on uniformly doped thin films. Doping concentrations from 5 {times} 10{sup 16} to 1 {times} 10{sup 18} can be measured at temperatures below 130 C. A method has been developed to include photoreflectance as the last step in the pre-growth in situ calibration procedure for MOCVD thin film structures. This combined capability now enables one to rapidly and accurately determine growth rates, chemical composition, and doping levels necessary to generate a recipe to fabricate complex optoelectronic compound semiconductor devices.

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12 Results
12 Results