Electron-Enhanced Atomic Layer Deposition of Titanium Nitride Films Using an Ammonia Reactive Background Gas

Electron-enhanced atomic layer deposition (EE-ALD) of titanium nitride (TiN) films was achieved using sequential exposures of tetrakis(dimethylamido)titanium (TDMAT) and low energy electrons in the presence of a continuous NH3 reactive background gas (RBG). Performing EE-ALD concurrently with a RBG is a new ALD film growth technique. The TiN EE-ALD was performed utilizing a hollow cathode plasma electron source (HC-PES). The HC-PES can deliver a high electron flux into background gases at pressures up to several mTorr. The TiN EE-ALD was conducted at temperatures of 30-70 degrees C using an electron acceleration voltage of 100 V and a NH3 pressure of similar to 1 mTorr. The incident electron flux promotes electron stimulated desorption (ESD) and facilitates rapid nucleation and low temperature film growth. The TiN EE-ALD film growth was achieved on a variety of substrates including a native oxide on silicon, a SiO2 thermal oxide, and in situ silicon nitride films grown using electron-enhanced chemical vapor deposition (EE-CVD). Growth rates of 0.75 to 1.8 angstrom per cycle were measured using in situ four-wavelength ellipsometry for different TDMAT precursor exposures. Ex situ X-ray photoelectron spectroscopy (XPS) studies indicated that the TiN films were high purity and slightly nitrogen-rich. The in situ ellipsometry also measured low resistivities of similar to 120 mu Omega cm for the TiN films with thicknesses of >= 60 angstrom. These low resistivities were confirmed by ex situ four-point probe measurements and ex situ spectroscopic ellipsometry. X-ray diffraction investigations determined that the TiN EE-ALD films were crystalline. X-ray reflectivity studies also indicated that the thin TiN films had densities similar to bulk films. The high quality of the TiN EE-ALD films is attributed to the NH3 RBG. Interaction between the low energy electrons and the NH3 RBG is believed to form center dot NH2 and center dot H radical species that react with the surface during EE-ALD and improve film purity. The reactive center dot NH2 and center dot H species likely lead to nitridation and carbon removal from the films. RBGs greatly expand the possibilities for tuning film composition and properties during EE-ALD. In addition, TiN EE-ALD was accomplished on insulating substrates such as an SiO2 thermal oxide. The TiN EE-ALD is believed to be possible on insulating substrates because the secondary electron yield for electron energies of similar to 100 eV is greater than unity.