Apparatus and method for plasma enhanced monolayer processing

Abstract

An apparatus and method for plasma enhanced monolayer (PEM) processing, wherein excited species from a non-condensable gas plasma are delivered to a substrate surface during the reaction of a chemical precursor with a previously chemisorbed monolayer on the substrate surface; the excited species lower the activation energy of the monolayer formation reaction and also modulate the film properties. In preferred embodiments a process reactor has linear injectors arranged diametrically above a substrate and reactive gases are sequentially injected onto the substrate surface while it is being rotated. The reactor can be operated in pulse precursor and pulsed plasma, constant precursor and constant plasma modes, or a combination thereof.

Description

[0001] This application is a continuation-in-part of U.S. application Ser. No. 10 / 019,244 filed on May 20, 2002 which is based on the International Application No. PCT / US 00 / 17202 filed on Jun. 23, 2000 with priority date of Jun. 24, 1999.

[0002] 1. Field of the Invention

[0003] The present invention relates to manufacturing of semiconductor devices, particularly to an apparatus and method for delivery of reactive chemical precursors to the surface of a substrate which is to be treated or coated, e.g., with a synchronized pulsed plasma processing apparatus for processing of thin films on substrates, e.g., in semiconductor device fabrication or in a similar field.

[0004] 2. Description of the Related Art

[0005] Manufacturing of advanced integrated circuits (ICs) in the microelectronic industry is accomplished through numerous and repetitive steps of deposition, patterning, and etching of thin films on the surface of silicon wafers. An extremely complex, monolithic and three-dimensional s...

Examples

example-- 2

EXAMPLE--2

[0078] Deposition of Metal Oxides: A variety of oxides of metals can be deposited by employing metal halides along with the plasma of hydrogen and oxygen mixture (alternatively water and hydrogen plasma) injected in combination with hydrogen, helium or argon as a non-condensable gas. Reaction of hydroxyl and associated reactive species in the plasma with metal halide monolayer generates metal oxides. The metal halide can be selected with a general formula MX.sub.n where, M: Al, Si, In, Sn, Pb, Ba, Sr, Ni, Ti, Ta, Zr, Nb, Hf, Mo, W, Fe, Co, Ni, Co, and Cu and other transition metals. Whereas, X=F, Cl, Br or 1.

example-- 3

EXAMPLE--3

[0079] Deposition of Metal Nitrides: A variety of oxides of corresponding metals can be deposited by employing metal halides through the first injector with hydrogen as a non-condensable gas and ammonia as the second chemical precursor. Alternately, NH.sub.x species can be conveniently generated by pulsing N.sub.2 in hydrogen plasma. The overall reaction can be described as:

[0080] MX.sub.n+Surface.fwdarw.MX.sub.n (adsorbed)

[0081] MX.sub.n (adsorbed)+NHx+H.fwdarw.MNx+n HX

[0082] Examples of M are, but not limited to, Al, Ti, Ta, Zr, Nb, Hf, Mo, W, Co, Ni, Cu and X is selected from F, Cl, Br or 1.

example-- 4

EXAMPLE--4

[0083] Deposition of Metal Carbides: Metal carbides are deposited by employing hydrogen as a non-condensable gas with methyl halide (CH.sub.3X, X=F, Cl, Br and 1) as a carbon precursor and metal halides as the metal precursor in hydrogen plasma. Some examples of metal halides are: SiCl.sub.4, TiCl.sub.4, WF.sub.6, MoF.sub.6, TaCl.sub.5, ZrCl.sub.5 etc. The mechanism of deposition of carbides can be described as:

[0084] MX.sub.n+surface.fwdarw.MX.sub.n (adsorbed)

[0085] MX.sub.n (adsorbed)+CH3X+H.fwdarw.MC.sub.y+n HX

[0001] This application is a continuation-in-part of U.S. application Ser. No. 10 / 019,244 filed on May 20, 2002 which is based on the International Application No. PCT / US 00 / 17202 filed on Jun. 23, 2000 with priority date of Jun. 24, 1999.

[0002] 1. Field of the Invention

[0003] The present invention relates to manufacturing of semiconductor devices, particularly to an apparatus and method for delivery of reactive chemical precursors to the surface of a substrate which is to be treated or coated, e.g., with a synchronized pulsed plasma processing apparatus for processing of thin films on substrates, e.g., in semiconductor device fabrication or in a similar field.

[0004] 2. Description of the Related Art

[0005] Manufacturing of advanced integrated circuits (ICs) in the microelectronic industry is accomplished through numerous and repetitive steps of deposition, patterning, and etching of thin films on the surface of silicon wafers. An extremely complex, monolithic and three-dimensional s...

Examples

example-- 2

EXAMPLE--2

[0078] Deposition of Metal Oxides: A variety of oxides of metals can be deposited by employing metal halides along with the plasma of hydrogen and oxygen mixture (alternatively water and hydrogen plasma) injected in combination with hydrogen, helium or argon as a non-condensable gas. Reaction of hydroxyl and associated reactive species in the plasma with metal halide monolayer generates metal oxides. The metal halide can be selected with a general formula MX.sub.n where, M: Al, Si, In, Sn, Pb, Ba, Sr, Ni, Ti, Ta, Zr, Nb, Hf, Mo, W, Fe, Co, Ni, Co, and Cu and other transition metals. Whereas, X=F, Cl, Br or 1.

example-- 3

EXAMPLE--3

[0079] Deposition of Metal Nitrides: A variety of oxides of corresponding metals can be deposited by employing metal halides through the first injector with hydrogen as a non-condensable gas and ammonia as the second chemical precursor. Alternately, NH.sub.x species can be conveniently generated by pulsing N.sub.2 in hydrogen plasma. The overall reaction can be described as:

[0080] MX.sub.n+Surface.fwdarw.MX.sub.n (adsorbed)

[0081] MX.sub.n (adsorbed)+NHx+H.fwdarw.MNx+n HX

[0082] Examples of M are, but not limited to, Al, Ti, Ta, Zr, Nb, Hf, Mo, W, Co, Ni, Cu and X is selected from F, Cl, Br or 1.

example-- 4

EXAMPLE--4

[0083] Deposition of Metal Carbides: Metal carbides are deposited by employing hydrogen as a non-condensable gas with methyl halide (CH.sub.3X, X=F, Cl, Br and 1) as a carbon precursor and metal halides as the metal precursor in hydrogen plasma. Some examples of metal halides are: SiCl.sub.4, TiCl.sub.4, WF.sub.6, MoF.sub.6, TaCl.sub.5, ZrCl.sub.5 etc. The mechanism of deposition of carbides can be described as:

[0084] MX.sub.n+surface.fwdarw.MX.sub.n (adsorbed)

[0085] MX.sub.n (adsorbed)+CH3X+H.fwdarw.MC.sub.y+n HX

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