Air Products and Chemicals, Inc.

John A Norman

David A Roberts

John C Ivankovits

Paul N Dyer

Robert E Stevens

David A Bohling

Beth A Muratore

Yoshihide Senzaki

Thomas Lee Ellison

Guido Peter Pez

Arthur Kenneth Hochberg

Dorai Ramprasad

Stephen M Fine

Daryle H Busch

John Cameron Gordon

In a process for the synthesis of a first metal-ligand complex, M.sup.+n (L.sup.-).sub.n, where n.gtoreq.1, from a metal compound precursor and a ligand precursor, where the metal of the metal compound precursor may during the synthesis change to a valence in excess of n; the improvement, to suppress formation of a second metal-ligand complex of the metal with a valence in excess of n, of adding the elemental form of the metal to the synthesis of the first metal-ligand complex.

Production of metal-ligand complexes

A process for recovering a 1,1,1,5,5,5-hexafluoro-2,4-pentanedione ligand from a metal-ligand complex byproduct such as Cu.sup.+2 (1,1,1,5,5,5-hexafluoro-2,4-pentanedionate.sup.-1).sub.2, comprising: providing a copper-ligand complex byproduct of Cu.sup.+2 (1,1,1,5,5,5-hexafluoro-2,4-pentanedionate.sup.-1).sub.2 in a process stream; cooling and condensing the copper-ligand complex byproduct of Cu.sup.+2 (1,1,1,5,5,5-hexafluoro-2,4-pentanedionate.sup.-1).sub.2 to separate it from the process stream; contacting the copper-ligand complex byproduct of Cu.sup.+2 (1,1,1,5,5,5-hexafluoro-2,4-pentanedionate.sup.-1).sub.2 with a protonation agent, such as: sulfuric acid, hydrochloric acid, hydroiodic acid, hydrobromic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, acid ion exchange resin, hydrogen sulfide, water vapor and mixtures thereof; and recovering 1,1,1,5,5,5-hexafluoro-2,4-pentanedione.

Regeneration of metal CVD precursors

Chemical Vapor Deposition of copper films is enhanced by simultaneously introducing in the reactor vapor of an organometallic copper precursor and copper complex vapor of a volatile ligand or the hydrate of the ligand.

Process for improved quality of CVD copper films

Novel volatile barium complexes are disclosed which are very stable and evaporate cleanly at elevated temperatures. Such complexes are highly suited for use as a barium source in OMCVD processes.

Volatile barium precursor and use of precursor in OMCVD process

An improved method is provided for depositing a thin copper aluminum alloy film on a patterned silicon substrate. A copper base layer conforming to the existing pattern is initially formed on the surface of the substrate, followed by contact with vapors of an aminealane compound, which causes aluminum to be selectively deposited on the copper base layer portion of the substrate. Preferably, copper is applied to a diffusion barrier surface such as tungsten using chemical vapor deposition from a complex of copper (I) perfluoroalkyl-.beta.-diketonate and an olefin or silylolefin. The entire process of developing an alloy film can be carried out without exceeding 200.degree. C.

Process for selectively depositing copper aluminum alloy onto a substrate

Volatile .beta.-diketonate alkaline earth metal complexes useful in chemical vapor deposition (CVD) operations are formed using a cyclic ligand, such as a macrocyclic crown ether, to increase the degree of coordination and shielding around the individual metal ions in the diketonate structure. The resultant monomeric complexes readily volatize to give a chemically stable vapor.

Volatile crown ligand .beta.-diketonate alkaline earth metal complexes

This invention is a residue-free vapor-phase process for etching metallic layers during the manufacturing of integrated circuits. The process comprises contacting a portion of the metallic surface to be etched with an effective amount of an etching agent comprising a .beta.-diketone or .beta.-ketoimine dispersed in an atmosphere capable of oxidizing the metal to be removed at a temperature sufficient to form a volatile metal-ligand complex. The volatile metal-ligand complex is sublimed from the surface thereby etching successive layers of the metal.

Etching agents comprising .beta.-diketone and .beta.-ketoimine ligands

Volatile liquid or low melting solid organometallic copper complexes are provided which are capable of selectively depositing a copper film onto metallic or other electrically conducting portions of a substrate surface under CVD conditions. These organometallic copper complexes are represented by the structural formula: ##STR1## wherein R.sup.1 and R.sup.3 are each independently C.sub.1 -C.sub.8 perfluoroalkyl, R.sup.2 is H, F or C.sub.1 -C.sub.8 perfluoroalkyl, R.sup.4 is C.sub.1 -C.sub.8 alkyl, phenyl, or Si(R.sup.5).sub.3, and each R.sup.5 is independently C.sub.1 -C.sub.8 alkyl or phenyl. A process for depositing copper films using these organometallic copper complexes is also provided.

Volatile precursors for copper CVD

Volatile liquid organometallic copper complexes are provided which are capable of selectively depositing a copper film onto metallic or other electrically conducting portions of a substrate surface under CVD conditions. There organometallic copper complexes are represented by the structural formula: ##STR1## wherein R.sup.1 and R.sup.3 are each independently C.sub.1 -C.sub.8 perfluoroalkyl, R.sup.2 is H, F or C.sub.1 -C.sub.8 perfluoroalkyl, R.sup.4 is H, C .sub.1 -C.sub.8 alkyl, or Si(R.sup.6).sub.3, each R.sup.5 is independently H or C.sub.1 -C.sub.8 alkyl and each R .sup.6 is independently phenyl or C.sub.1 -C.sub.8 alkyl. A process for depositing copper films using these organometalic copper complexes is also provided.

Volatile liquid precursors for the chemical vapor deposition of copper

A process is provided for selectively depositing copper films on metallic or other electrically conducting portions of substrate surfaces by contacting the substrate at a temperature from 110.degree. to 190.degree. C. with a volatile organometallic copper complex, in the gas phase, represented by the structural formula: ##STR1## wherein R.sup.1 and R.sup.3 are each independently C.sub.1 -C.sub.8 perfluoroalkyl, R.sup.2 is H or C.sub.1 -C.sub.8 perfluoroalkyl and L is carbon monoxide, an isonitrile, or an unsaturated hydrocarbon ligand containing at least one non-aromatic unsaturation.

Processes for the chemical vapor deposition of copper and etching of

This invention is a residue-free cleaning process for removing metal-containing contaminants from a surface of a substrate of the type used in manufacturing semi-conductor devices. The process comprises contacting the substrate with an effective amount of a cleaning agent comprising a .beta.-diketone or .beta.-ketoimine dispersed in an atmosphere capable of oxidizing the metal-contaminants at a temperature sufficient to form volatile metal-ligand complexes on the surface of the substrate. The volatile metal-ligand complexes are sublimed from the surface of the substrate leaving essentially no residue.

Cleaning agents comprising beta-diketone and beta-ketoimine ligands and

Volatile liquid organometallic copper complexes are provided which are capable of selectively depositing a copper film onto metallic or other electrically conducting portions of a substrate surface under CVD conditions. These organometallic copper complexes are represented by the structural formula: ##STR1## wherein R.sup.1 and R.sup.3 are each independently C.sub.1 -C.sub.8 perfluoroalkyl, R.sup.2 is H, F or C.sub.1 -C.sub.8 perfluoroalkyl, R.sup.4 is H, C.sub.1 -C.sub.8 alkyl, or Si(R.sup.6).sub.3, each R.sup.5 is independently H or C.sub.1 --C.sub.8 alkyl and each R.sup.6 is independently phenyl or C.sub.1 -C.sub.8 alkyl. A process for depositing copper films using these organometallic copper complexes is also provided.

A residue-free fluxing process wherein the active fluxing agent comprises a .beta.-diketone or .beta.-ketoimine ligand. Such ligands react with surface metal oxides on workpieces to be soldered to form volatile metal-ligand complexes as reaction products which are sublimed from the surface leaving essentially no residue on the workpieces. The fluxing agents can be utilized in gas-phase processes wherein the workpieces are contacted with an effective amount of one or more ligands which are dispersed in a carrier gas or solvent or by incorporating the ligands into an alloy-vehicle mixture for use as conventional creams or pastes. The invention eliminates the need for post-reflow cleaning using solvents since no flux residue remains on the workpieces to be soldered following volitilization of the metal-ligand complex.

Fluxing agents comprising .beta.-diketone and .beta.-ketoimine ligands

A process for the vapor-phase synthesis of non-adduct volatile fluorinated and non-fluorinated metal-ligand complexes comprising contacting a .beta.-diketone or .beta.-ketoimine ligand with an inert carrier gas to vaporize the ligand, reacting the vaporized ligand with a metal species at a temperature sufficient to form the metal-ligand complex and recovering the metal-ligand complex by sublimation. The process is conducted in the absence of solvent thereby providing pure non-adduct metal-ligand complexes. Such complexes are particularly suited for specialty applications requiring use of high purity compounds.

Synthesis of volatile fluorinated and non-fluorinated

A residue-free fluxing process wherein the active fluxing agent comprises a .beta.-diketone or .beta.-ketoimine ligand. Such ligands react with surface metal oxides on workpieces to be soldered to form volatile metal-ligand complexes as reaction products which are sublimed from the surface leaving essentially no residue on the workpieces. The fluxing agents can be utilized in gas-phase processes wherein the workpieces are contacted with an effective amount of one or more ligands which are dispersed in a carrier gas or solvent or by incorporating the ligands into an alloy-vehicle mixture for use as conventional creams or pastes. The invention eliminates the need for post-reflow cleaning using solvents since no flux residue remains on the workpieces to be soldered following volatilization of the metal-ligand complex.

Growing community of inventors

Whitehall, PA, United States of America

John A Norman