Design and Operation of an Optically-Accessible Modular Reactor for Diagnostics of Thermal Thin Film Deposition Processes.

The design and operation of a simple, optically-accessible modular reactor for probing thermal thin film deposition processes, such as atomic layer deposition processes (ALD) and chemical vapor deposition (CVD), is described. This reactor has a nominal footprint of 225 cm(2) and a mass of approximately 6.6 kg, making it small enough to conveniently function as a modular component of an optical train. The design is simple, making fabrication straightforward and relatively inexpensive. Reactor operation is characterized using two infrared absorption measurements to determine exhaust times for tetrakis(dimethylamino)titanium and water, proto-typical ALD precursors, in a pressure and flow regime commonly used for ALD.

In situ gas phase measurements during metal alkylamide atomic layer deposition.

Metal alkylamide compounds, such as tetrakis(ethylmethylamido) hafnium (TEMAH), represent a technologically important class of metalorganic precursors for the deposition of metal oxides and metal nitrides via atomic layer deposition (ALD) or chemical vapor deposition. The development of in situ diagnostics for processes involving these compounds could be beneficial in, e.g., developing deposition recipes and validating equipment-scale simulations. This report describes the performance of the combination of two techniques for the simultaneous, rapid measurement of the three major gas phase species during hafnium oxide thermal ALD using TEMAH and water: TEMAH, water, and methylethyl amine (MEA), the only major reaction by-product. For measurement of TEMAH and MEA, direct absorption methods based on a broadband infrared source with different mid-IR bandpass filters and utilizing amplitude modulation and synchronous detection were developed. For the measurement of water, wavelength modulation spectroscopy utilizing a near-IR distributed feedback diode laser was used. Despite the relatively simple reactor geometry employed here (a flow tube), differences were easily observed in the time-dependent species distributions in 300 mL/min of a helium carrier gas and in 1000 mL/min of a nitrogen carrier gas. The degree of TEMAH entrainment was lower in 300 mL/min of helium compared to that in 1000 mL/min of nitrogen. The capability to obtain detailed time-dependent species concentrations during ALD could potentially allow for the selection of carrier gas composition and flow rates that would minimize parasitic wall reactions. However, when nitrogen was employed at the higher flow rates, various flow effects were observed that, if detrimental to a deposition process, would effectively limit the upper range of useful flow rates.