The present invention relates generally to depositing elemental thin films. In particular, the invention concerns a method of growing elemental metal thin films by Atomic Layer Deposition (ALD) using a boron compound as a reducing agent. In a preferred embodiment the method comprises introducing vapor phase pulses of at least one metal source compound and at least one boron source compound into a reaction space that contains a substrate on which the metal thin film is to be deposited. Preferably the boron compound is capable of reducing the adsorbed portion of the metal source compound into its elemental electrical state.

Production of elemental films using a boron-containing reducing agent

The present invention relates generally to a method of depositing transition metal carbide thin films. In particular, the invention concerns a method of depositing transition metal carbide thin films by atomic layer deposition (ALD), in which a transition metal source compound and a carbon source compound are alternately provided to the substrate. A variety of metal and carbon source gases are disclosed. The methods are applicable to forming metal carbide thin films in semiconductor fabrication, and particularly to forming thin, conductive diffusion barriers within integrated circuits.

Deposition of transition metal carbides

Methods of forming metal carbide thin films are provided. According to preferred embodiments, metal carbide thin films are formed in an atomic layer deposition (ALD) process by alternately and sequentially contacting a substrate in a reaction space with spatially and temporally separated vapor phase pulses of a metal source chemical, a reducing agent and a carbon source chemical. The reducing agent is preferably selected from the group consisting of excited species of hydrogen and silicon-containing compounds.

Vapor deposition of metal carbide films

Methods for performing periodic plasma annealing during atomic layer deposition are provided along with structures produced by such methods. The methods include contacting a substrate with a vapor-phase pulse of a metal source chemical and one or more plasma-excited reducing species for a period of time. Periodically, the substrate is contacted with a vapor phase pulse of one or more plasma-excited reducing species for a longer period of time. The steps are repeated until a metal thin film of a desired thickness is formed over the substrate.

Periodic plasma annealing in an ALD-type process

The present methods provide tools for growing conformal metal thin films, including metal nitride, metal carbide and metal nitride carbide thin films. In particular, methods are provided for growing such films from aggressive chemicals. The amount of corrosive chemical compounds, such as hydrogen halides, is reduced during the deposition of transition metal, transition metal carbide, transition metal nitride and transition metal nitride carbide thin films on various surfaces, such as metals and oxides. Getter compounds protect surfaces sensitive to hydrogen halides and ammonium halides, such as aluminum, copper, silicon oxide and the layers being deposited, against corrosion. Nanolaminate structures incorporating metallic thin films, and methods for forming the same, are also disclosed.

Metal nitride deposition by ALD with reduction pulse

Layers of Ga1-xBxN with compositions from x = 0 to x = 0.07 were grown by organometallic vapor phase epitaxy on sapphire substrates using trimethylgallium, triethylboron (TEB) and NH3 as precursors. Growth was done in the temperature range from 450 to 1000°C. The presence of boron was detected by the shift in the (0002) peak position in x-ray diffraction, by x-ray photoelectron spectroscopy, secondary ion mass spectrometry measurements, and by the changes in the band gap as measured by optical transmission. It was found that for the studied range of compositions the band gap varied from 3.4 eV for x = 0 to 3.63 eVfor x = 0.05. At certain TEB concentrations in the gas phase, the growth rate decreased abruptly, most likely because of a growth poisoning by the onset of growth of a very slow growing B-rich phase. The threshold TEB concentration for this growth poisoning decreased with increasing growth temperature; and at 1000°C, less than 1% of B could be incorporated as a result. GaBN alloys with about 7% substitutional boron were also produced by implantation of 5 × 1016 cm−2 B ions at 60 keV into GaN, as evidenced by the shift of the band edge emission in cathodoluminescence spectra from 3.4 eV for GaN to 3.85 eV for GaBN.

A. Y. Polyakov

Papers

Growth of GaBN ternary solutions by organometallic vapor phase epitaxy