Ulvac, Inc.

Narishi Gonohe

Kyuzo Nakamura

Tomoyasu Kondo

Harunori Ushikawa

Satoru Toyoda

Masamichi Harada

Nobuyuki Kato

Eiichi Mizuno

A tantalum nitride film rich in tantalum atoms is formed by simultaneously introducing a raw gas consisting of a coordination compound of elemental tantalum (Ta) having a coordinated ligand of formula: N&#x2550;(R, R') (wherein, R and R&#x2032; each represents an alkyl group having 1 to 6 carbon atoms) and NHgas into a film-forming chamber; reacting the raw gas with the NHgas; forming a reduced compound having Ta&#x2014;NHon a substrate; and introducing a hydrogen atom-containing gas into the chamber to form a tantalum nitride film rich in tantalum atoms. The resulting tantalum nitride film has a low resistance, low contents of C and N atoms, and a high compositional ratio: Ta/N, show sufficiently high adherence to Cu film and can thus be useful as a barrier film. Moreover, tantalum particles are implanted in the resulting film according to the sputtering technique to further enrich the film with tantalum.

Method for forming tantalum nitride film

A technique that enables the formation of a low resistivity barrier film at low temperatures, in which a catalyst is placed inside a vacuum chamber and heated, a raw material gas and a reactive gas (such as H, NHor SiH) are introduced alternately into the vacuum chamber, and a reaction is effected between the raw material gas adsorbed to the surface of an object, and radicals generated by decomposition of the reactive gas on contact with the catalyst, thereby depositing a thin film on the object. Furthermore, a technique for removal of impurities (such as oxides, fluorides, carbides or nitrides), in which the catalyst is placed in a vacuum atmosphere and heated, and a treatment gas having a hydrogen atom in its chemical structure is brought into contact with the catalyst, thereby generating radicals. The surface of an object to be treated is exposed to these radicals.

Method of manufacturing film

A tantalum nitride film-forming method comprises the steps, according to the CVD technique, of introducing a raw gas consisting of a coordination compound constituted by an elemental tantalum (Ta) having a coordinated ligand represented by the general formula: N&#x2550;(R, R') (in the formula, R and R&#x2032; may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms) and a halogen gas into a film-forming chamber to thus form a film of a halogenated compound represented by the following general formula: TaN(Hal)(R, R&#x2032;)(in the formula, Hal represents a halogen atom), reacting the halogenated compound film with a hydrogen atom-containing gas by the introduction thereof into the chamber to thus form a tantalum nitride film rich in tantalum atoms. The resulting tantalum nitride film has a low resistance, low contents of C and N, and a high compositional ratio: Ta/N, can ensure high adherence to the electrical connection-forming film and can thus be useful as a barrier film. Moreover, tantalum particles are implanted in the resulting film according to the sputtering technique to thus further enrich the film with tantalum.

A tantalum nitride film-forming method comprises the steps of introducing a raw gas consisting of a coordination compound constituted by an elemental tantalum (Ta) having a coordinated ligand represented by the general formula: N&#x2550;(R,R') (in the formula, R and R&#x2032; may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms), and a halogen gas into a vacuum chamber; and reacting these components with one another on a substrate to thus form a surface adsorption film comprising a mono-atomic or multi (several)-atomic layer and composed of a compound represented by the following general formula: TaN(Hal)(R, R&#x2032;)(in the formula, Hal represents a halogen atom), then introducing radicals generated from an H atom-containing compound to thus remove Ta&#x2014;N bonds present in the resulting compound through breakage thereof and remove, at the same time, the remaining R(R&#x2032;) groups bonded to the N atoms present in the compound through the cleavage thereof and to thus form a tantalum nitride film rich in tantalum atoms. The resulting tantalum nitride film has a low resistance, low contents of C and N atoms, and a high compositional ratio: Ta/N, can ensure sufficiently high adherence to the distributing wire-forming film and can thus be useful as a barrier film. Moreover, tantalum particles are implanted in the resulting film according to the sputtering technique to thus further enrich the film with tantalum.

A tantalum nitride film-forming method comprises the steps of introducing, into a vacuum chamber, a raw gas consisting of a coordination compound constituted by elemental Ta having a coordinated ligand represented by the general formula: N&#x2550;(R,R') (in the formula, R and R&#x2032; may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms) to thus adsorb the gas on a substrate; then introducing an NHgas and then activated H radicals derived from a reactant gas into a vacuum chamber to thus remove the R(R&#x2032;) groups bonded to the nitrogen atom present in the reaction product through cleavage, and to thus form a tantalum nitride film rich in tantalum atoms. The resulting tantalum nitride film has a low resistance, low contents of C and N atoms, and a high compositional ratio: Ta/N, can ensure sufficiently high adherence to the distributing wire-forming film and can thus be useful as a barrier film. Moreover, tantalum particles are implanted in the resulting film according to the sputtering technique to thus further enrich the film with tantalum.

A substrate provided thereon with an electrical insulating film which carries holes or the like filled with a Cu-containing electrical interconnection film is subjected to a pre-treatment in which the surface of the electrical insulating film and that of the Cu-containing electrical interconnection film are treated at a temperature of not more than 300&#xb0; C. using, in a predetermined state, a gas of a compound containing an atom selected from the group consisting of N, H and Si atoms within the chemical formula thereof, before selectively forming a W-capping film on the electrical interconnection film. After the completion of the pre-treatment, a W-capping film is selectively formed on the electrical interconnection film and then an upper Cu electrical interconnection is further formed.

Selective W-CVD method and method for forming multi-layered Cu electrical interconnection

A method for forming a tungsten nitride film including a first material gas supply step of supplying a first material gas composed of a tungsten compound gas, a reduction step of supplying a reducing gas, a second material gas supply step of supplying a second material gas composed of a tungsten compound gas, and a nitridation step of supplying a nitriding gas. Since a step of depositing tungsten on a substrate, and a step of forming tungsten nitride are performed separately, by varying the flow rate of each gas, the pressure when each gas is supplied, and the supply time, or the number of times each step is performed and the order in which the steps are performed, the quantity of tungsten deposited and the quantity of tungsten nitride formed can be controlled easily.

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Shizuoka-ken, Japan

Narishi Gonohe