DON26BZ01-DV002 TITLE: DIRECT TO PHASE II: Domestic Production of Zirconium and Hafnium Metal Organic Precursors

COMPONENT TECHNOLOGY PRIORITY AREA(S): Advanced Materials;Hypersonics

PROJECTED CMMC LEVEL REQUIREMENT: Level 2 (Self)

OBJECTIVE: Develop and demonstrate a pilot-scale manufacturing process for producing high purity tetrakis(dimethylamido)zirconium(IV) (TDMAZ), tetrakis(dimethylamido)hafnium(IV) (TDMAH) and related metal dimethylamide compounds, with a targeted annual production capacity exceeding 6,000 kg of TDMAZ.

DESCRIPTION: The Department of the Navy is seeking a domestic source of critical chemical feedstocks including TDMAZ, TDMAH, and other metal dimethylamide compounds. These chemical feedstocks can be used as metal organic precursors for atomic layer deposition (ALD), chemical vapor deposition (CVD), and chemical vapor infiltration (CVI) of metal oxides, nitrides, and carbonitrides used in microelectronics and ceramic manufacturing [Refs 1-3]. While TDMAZ is a vital ceramic precursor for the electronics and semiconducting industry, this effort will also support the use of TDMAZ for the preparation of metal nitrides and carbonitrides for ceramics and ceramic matrix composites.

This SBIR topic seeks to establish a domestic manufacturing capability for the production of > 6,000 kg/year of TDMAZ. Synthesis of TDMAZ and other metal dimethylamides often involves pyrophoric and air/water sensitive reagents, and the proper storage and handling of these reagents is crucial for the development of a cost-effective and large-scale manufacturing process. Along with the production volumes mentioned above, the metal precursors must have a purity > 99% and a target retail price of < $4,000/kg of TDMAZ, preferably < $2,500/kg. The proposed manufacturing facility must be located in the United States or US territories, and the company owning and operating this manufacturing facility must be wholly US owned and based.

PHASE I: For a Direct to Phase II topic, the Government expects that the small business would have accomplished the following in a Phase I-type effort and developed a concept for a workable prototype or design to address, at a minimum, the basic requirements of the stated objective above. The below actions would be required to satisfy the requirements of Phase I:

Proposing SBCs will have demonstrated expertise in the synthesis of air and water-sensitive compounds and access to facilities that will enable them to produce zirconium and hafnium organic precursors at the kilogram scale.

FEASIBILITY DOCUMENTATION: Offerors interested in participating in Direct to Phase II must include in their response to this topic Phase I feasibility documentation that substantiates the scientific and technical merit and Phase I feasibility described in Phase I above has been met (i.e., the small business must have performed Phase I-type research and development related to the topic NOT solely based on work performed under prior or ongoing federally funded SBIR/STTR work) and describe the potential commercialization applications. The documentation provided must validate that the proposer has completed development of technology as stated in Phase I above.

PHASE II: Identify a chemical process to manufacture TDMAZ and perform a safety analysis on the handling, storage, and waste management of air and water sensitive reagents and intermediates used in production scale synthesis. Facility upgrades to allow for safety compliance during manufacture of metal dimethylamides is allowed. The ability to expand and manufacture other metal dimethylamide compounds, such as TDMAH is encouraged.

Demonstrate a scalable approach for the synthesis of TDMAZ and provide 1 kg of material for analysis and internal verification by Navy researchers. Demonstrate pilot scale production of at least 50 kg TDMAZ/month. It is expected that the optimized approach will be consistent with a target production of > 6,000 kg TDMAZ/year. Conduct a technoeconomic analysis based on production at the > 6,000 kg/year scale. Identification of manufacturing or production issues and business model modifications required to further improve the process (e.g., reduced cost, increased availability, safety) will be documented. At the end of the Phase II Base period, 100 kg of TDMAZ produced using the new pilot scale manufacturing process will be delivered to the Government.

PHASE III DUAL USE APPLICATIONS: Establish a facility to produce > 6,000 kg of TDMAZ/year. Conduct several production runs to demonstrate the ability to supply zirconium and hafnium carbide precursors at < $2,500/kg to the DoW through the Defense Logistics Agency.

Zirconium and hafnium carbide are used in commercial aerospace structures, microelectronics, cutting tool bits, and coatings in nuclear reactors.

REFERENCES:

1. Hausmann, D.M. and Gordon, R.G. "Surface Morphology and Crystallinity Control in the Atomic Layer Deposition (ALD) of Hafnium and Zirconium Oxide Thin Films." J. Cryst. Growth, 241, pp. 251-261, 2003. https://www.sciencedirect.com/science/article/abs/pii/S0022024802021334
2. Fix, R.; Gordon, R.G. and Hoffman, D.M. "Chemical Vapor Deposition of Titanium, Zirconium, and Hafnium Nitride Thin Films." Chem. Mater., 3, pp. 1138-1148, 1991. https://pubs.acs.org/doi/10.1021/cm00018a034
3. Lamm, B.W. and Mitchell, D.J. "Chemical Vapor Deposition of Zirconium Compounds: A Review." Coatings, 13, pp. 266, 2023. https://www.mdpi.com/2079-6412/13/2/266

KEYWORDS: Zirconium Carbide; Hafnium Carbide; Ceramic Precursors; Pilot Manufacturing; Technoeconomic Analysis; High-Temperature Coatings

TPOC:
NAVAIR SBIR/STTR POC
navair-sbir@us.navy.mil