Chemical vapor deposition of titanium, zirconium, and hafnium nitride thin films

Journal Article · · Chemistry of Materials; (United States)

DOI:https://doi.org/10.1021/cm00018a034· OSTI ID:7040212

Fix, R; Gordon, R G ^[1]; Hoffman, D M ^[2]

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1. Harvard Univ., Cambridge, MA (United States)
2. Univ. of Houston, TX (United States)

Titanium, zirconium, and hafnium nitride thin films were synthesized from tetrakis(dialkylamido)metal(IV) complexes and ammonia by atmospheric pressure chemical vapor deposition with high growth rates at low substrate temperatures (200-450C). Depositions were successfully carried out on silicon, low-sodium glass, soda lime glass, vitreous carbon, and boron substrates. Stainless steel and polyester were also used as substrates for depositions of titanium nitride below 250C. All of the films showed good adhesion to the substrates and were chemically resistant. The films were characterized by Rutherford backscattering spectrometry, X-ray photoelectron spectroscopy, ellipsometry, and transmission electron microscopy. Reflectance and transmission spectra were also recorded. Hydrogen in the films was estimated by hydrogen forward recoil scattering spectrometry. The titanium nitride coatings were slightly nitrogen-rich TiN (N/M ratio 1.05-1.15). These films displayed metallic properties and were crystalline as deposited. The zirconium and hafnium nitride films were Zr{sub 3}N{sub 4} and nitrogen-rich Hf{sub 3}N{sub 4} (N/M ratios 1.35 {plus minus} 0.05 and 1.7 {plus minus} 0.1, respectively). They were crystalline, yellow-colored, transparent, and insulating. The hydrogen content of the films diminished as the deposition temperature increased. For depositions carried out at 400C the TiN films contained 9 atom % hydrogen and at 300C the Zr{sub 3}N{sub 4} and Hf{sub 3}N{sub 4} films contained 10 and 16 atom % hydrogen, respectively. The hydrogen is proposed to be incorporated in the films as NH and NH{sub 2} groups in the amorphous portion of a mix composed of amorphous material and imbedded nitride crystallites.

• OSTI ID: 7040212
• Journal Information: Chemistry of Materials; (United States), Journal Name: Chemistry of Materials; (United States) Vol. 3:6; ISSN CMATE; ISSN 0897-4756
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
360201* -- Ceramics
Cermets
& Refractories-- Preparation & Fabrication
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
CHEMICAL COATING
CHEMICAL REACTIONS
CHEMICAL VAPOR DEPOSITION
DATA
DEPOSITION
ELASTIC SCATTERING
ELECTRON MICROSCOPY
ELECTRON SPECTROSCOPY
ELLIPSOMETRY
EXPERIMENTAL DATA
FILMS
HAFNIUM COMPOUNDS
HAFNIUM NITRIDES
INFORMATION
MEASURING METHODS
MICROSCOPY
NITRIDES
NITROGEN COMPOUNDS
NUMERICAL DATA
OPTICAL PROPERTIES
PHOTOELECTRON SPECTROSCOPY
PHYSICAL PROPERTIES
PNICTIDES
REFLECTIVITY
REFRACTORY METAL COMPOUNDS
RUTHERFORD SCATTERING
SCATTERING
SPECTROSCOPY
STOICHIOMETRY
SUBSTRATES
SURFACE COATING
SURFACE PROPERTIES
TEMPERATURE EFFECTS
THIN FILMS
TITANIUM COMPOUNDS
TITANIUM NITRIDES
TRANSITION ELEMENT COMPOUNDS
TRANSMISSION
TRANSMISSION ELECTRON MICROSCOPY
X-RAY SPECTROSCOPY
ZIRCONIUM COMPOUNDS
ZIRCONIUM NITRIDES