A low-temperature (>450 °C) thermal chemical vapor deposition (CVD) process was developed for the growth of TaNx from the reaction of tantalum pentabromide, ammonia, and hydrogen. Studies of process reaction kinetics yielded two sequential rate-controlling steps, with an activation energy of 0.45 eV for the kinetically limited reaction regime. Additionally, a systematic design of experiments approach examined the effects of key process parameters, namely, substrate temperature, source temperature, and hydrogen and ammonia flows, on film properties. A wide CVD process window was established for nitrogen-rich amorphous TaNx with contamination below 1 at.%. Film conformality was higher than 95% in nominally 0.30 μm, 4.5: 1 aspect ratio, trench structures.

Low-temperature chemical vapor deposition of tantalum nitride from tantalum pentabromide for integrated circuitry copper metallization applications

Effect of tantalum addition on microstructure and optical properties of TiN thin films

Titanium and titanium nitride layers can be produced by chemical vapor deposition (CVD) processes conducted at temperatures below 475° C. The layers may serve as diffusion and adhesion barriers for ultra-large scale integration (ULSI) microelectronic applications. The processes use a titanium halide precursor, such as titanium tetraiodide, and hydrogen or hydrogen in combination with nitrogen, argon, or ammonia to either produce pure titanium metal films, titanium films which alloy with the underlying silicon, or titanium nitride films. The deposition of titanium metal from titanium halide and hydrogen or the deposition of titanium nitride from titanium halide with nitrogen and hydrogen is achieved with the assistance of a low energy plasma. The process allows smooth and reversible transition between deposition of films of either titanium metal or titanium nitride by introduction or elimination of nitrogen or ammonia.

Methods for chemical vapor deposition and preparation of conformal titanium-based films

Development of TiSiN CVD process using TiCl4/SiH4/NH3 chemistry for ULSI anti-oxidation barrier applications

Solid‐phase reactions at the interface between Al‐Si‐Cu and reactively sputtered TiN thin films have been investigated by cross‐sectional transmission electron microscopy, Auger electron spectroscopy, and x‐ray diffraction. In the case in which the internal stress in the TiN thin film is extremely compressive at 209 MPa, a very thin amorphous Al‐Ti‐Si ternary compound layer (a‐Al‐Ti‐Si) containing microcrystallites, about 4 nm thick, is found to form at the Al‐Si‐Cu/TiN interface by annealing at the temperature of 450 °C for 30 min. On the other hand, in the case of a minimally compressive stress of 21 MPa, it is in a marked contrast to form a polycrystalline TiAl3 layer (c‐TiAl3) on the amorphous intermediate layer ununiformly. Behavior of the internal stress in the latter TiN film as a function of heating and cooling temperature shows nonlinear characteristics, indicating that a rearrangement of the TiN film actively occurs even at low temperatures below 300 °C. Monte Carlo simulations of internal micro...

Effect of internal stresses and microstructure of sputtered TiN films on solid-phase reactions with Al-Si-Cu alloy films

We have studied the properties of reactively sputtered TiN films used as diffusion barriers for Al‐Cu metallization in submicron bipolar transistors. Emitter‐base diodes with shallow junctions were fabricated to monitor the integrity of the barrier via junction leakage measurements. Scanning and transmission electron microscopy were used to study the morphology and step coverage of these films, and also for barrier failure analysis. The effectiveness of the barrier depends on both the nominal thickness of the TiN layer and on the device dimensions. For thin TiN layers (∼47 nm), high junction leakage was observed on narrow emitters (0.5 μm) but not on wide emitters (5 μm). These observations highlight the reliability and yield concerns associated with the use of sputtered TiN films for deep submicron technologies. In some cases, low‐temperature (500 °C) epitaxial alignment of the emitter polysilicon was observed, associated with Al penetration of the barrier. This indicates that the Al provides an enhancement of the tendency towards epitaxial alignment of the polysilicon grains. For thicker TiN layers (∼83 nm), low leakage was observed on both narrow and wide emitters, and no unusual epitaxial alignment was observed.

Diffusion barrier properties of TiN films for submicron silicon bipolar technologies

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Diffusion barrier properties of TiN films for submicron silicon bipolar technologies