Metal nitride deposition by ALD with reduction pulse

A method of depositing a material on a substrate in a reaction space, the substrate comprising a surface susceptible to halide attack, the method comprising providing alternated pulses of reactants in a plurality of deposition cycles, each cycle comprising in order:

• supplying a first reactant to chemisorb no more than about one monolayer of a halide-terminated species over the surface;
• removing excess first reactant and reaction by-product from the reaction space;
• supplying a nitrogen-bearing second reactant;
• removing excess second reactant and reaction by-product from the reaction space;
• and
• supplying a third reactant that getters halides from the substrate surface prior to repeating the cycle.

A method of forming a WNxCy thin film on a substrate within a reaction space by an atomic layer deposition (ALD) type process, wherein the ALD type process comprises providing alternating pulses of reactants in a plurality of deposition cycles, each cycle comprising supplying:

• WF6;
• NH3;
• and
• triethyl boron (TEB), wherein excess reactant and/or reactant byproducts are removed from the reaction space prior to supplying the next reactant and wherein TEB is never the next reactant supplied after WF6.

A method of forming a metal nitride carbide thin film on a substrate in a reaction space by an atomic layer deposition (ALD) type process, the ALD type process comprising:

• supplying a first metal-containing reactant to chemisorb no more than about one monolayer over the surface;
• removing excess first reactant and reaction by-product from the reaction space;
• supplying a nitrogen-containing second reactant;
• removing excess second reactant and reaction by-product from the reaction space;
• supplying triethyl boron (TEB);
• and
• removing excess TEB and reaction by-product from the reaction space, wherein the TEB is never the next reactant provided after the metal-containing first reactant.