Organometallic compounds and their use as precursors for forming films and powders of metal or metal derivatives
First Claim
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1. A method comprising:
- providing a substrate; and
depositing metal or a metal containing material on the surface of said substrate;
said depositing including contacting said substrate surface with an organometallic compound of the formula (R1)mM(PR23)x, where M is a metal selected from a Group VIIb, VIII, IX or X metal wherein (a) when M is manganese, technetium, or rhenium, m is 1;
x is 5 and m+x is 6;
(b) when M is iron, ruthenium or osmium, m is 0, 1, 2, 3 or 4;
x is 2, 3, 4 or 5 and m+x is 4, 5, 6 or 7;
(c) when M is cobalt, rhodium or iridium, m is 1, 2, 3 or 4 and x is 2, 3 or 4 and m+x is 4, 5, 6, 7 or 8; and
(d) when M is nickel, palladium or platinum, m is 0 or 2, x is 2, 3 or 4 and m+x is 2, 3, 4, 5 or 6;
each R1 is independently selected from the group consisting of hydrogen, deuterium, N2, H2, D2 and a group of the formula —
CR32—
CR32—
R4;
each R2 is independently selected from the group consisting of lower alkyl, aryl, arylalkyl, alkoxy, aryloxy, arylalkoxy, alkylsilyl, arylsilyl, arylalkylsilyl, alkoxysilyl, aryloxysilyl, arylalkoxysilyl, alkylsiloxy, arylsiloxy, arylalkylsiloxy, alkoxysiloxy, aryloxysiloxy, arylalkoxysiloxy, alkylsilylalkyl, arylsilylalkyl, arylalkysilylalkyl, alkoxysilylalkyl, aryloxysilylalkyl, arylalkoxysilylalkyl, alkylsiloxyalkyl, arylsiloxyalkyl, arylalkylsiloxyalkyl, alkoxysiloxyalkyl, aryloxysiloxyalkyl, arylalkoxysiloxyalkyl, alkylsilylalkoxy, arylsilylalkoxy, arylalkylsilylalkoxy, alkoxysilylalkoxy, aryloxysilylalkoxy arylalkyloxysilylalkoxy, alkylsiloxyalkoxy, arylsiloxyalkoxy, arylalkylsiloxyalkoxy, alkoxysiloxyalkoxy, aryloxysiloxyalkoxy, and arylalkoxysiloxyalkoxy;
each R3 is independently selected from the group consisting of hydrogen, deuterium, C1-C6 alkyl, C1-C6 cycloalkyl, phenyl, benzyl, (C1-C2 alkyl or alkoxy)3-silyl, and (C1-C2 alkyl or alkoxy)3-siloxy and wherein at least two groups R3 are selected from the group consisting of hydrogen and deuterium;
when R4 is hydrogen or deuterium; and
wherein when M is cobalt and one group R1 is selected to be N2, then m is 2 and the second group R1 is hydrogen or deuterium.
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Abstract
Disclosed are organometallic compounds derived from Groups VIIb, VIII, IX, and X metals useful as precursors for the formation of metal containing powders and for the chemical deposition of the metals on substrates, particularly for the chemical vapor deposition of metal films suitable for the manufacture of electronic devices. Methods for their use are also disclosed. The preferred organometallic compounds of the present invention are of the formula (R1)mM(PR23)x, where M is a metal selected from the group consisting of manganese, technetium, rhenium, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium iridium and platinum wherein m is 0, 1, 2, 3 or 4; x is 2, 3, 4 or 5 and m+x are 2, 3, 4, 5, 6, 7 or 8, m and x selected according to each metals appropriate valence; each R1is independently selected from the group consisting of hydrogen, deuterium, N2, H2, D2 and a variety of substituted alkyl groups; each R2 is independently selected from the group consisting of lower alkyl, aryl, arylalkyl, and alkyl-Z, aryl-Z and arylalkyl-Z where Z is selected from the group consisting of oxy, silyl, siloxy, oxysilyl, siloxy, oxysiloxy, silyalkyl, oxysilylalkyl, siloxyalkyl, oxysiloxyalkyl, silylalkoxy, silylalkoxy, siloxyalkoxy and oxysiloxyalkoxy; and wherein when M is cobalt and one group R1 is selected to be N2, then m is 2 and the second group R1 is hydrogen or deuterium.
29 Citations
57 Claims
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1. A method comprising:
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providing a substrate; and
depositing metal or a metal containing material on the surface of said substrate;
said depositing including contacting said substrate surface with an organometallic compound of the formula (R1)mM(PR23)x, where M is a metal selected from a Group VIIb, VIII, IX or X metal wherein (a) when M is manganese, technetium, or rhenium, m is 1;
x is 5 and m+x is 6;
(b) when M is iron, ruthenium or osmium, m is 0, 1, 2, 3 or 4;
x is 2, 3, 4 or 5 and m+x is 4, 5, 6 or 7;
(c) when M is cobalt, rhodium or iridium, m is 1, 2, 3 or 4 and x is 2, 3 or 4 and m+x is 4, 5, 6, 7 or 8; and
(d) when M is nickel, palladium or platinum, m is 0 or 2, x is 2, 3 or 4 and m+x is 2, 3, 4, 5 or 6;
each R1 is independently selected from the group consisting of hydrogen, deuterium, N2, H2, D2 and a group of the formula —
CR32—
CR32—
R4;
each R2 is independently selected from the group consisting of lower alkyl, aryl, arylalkyl, alkoxy, aryloxy, arylalkoxy, alkylsilyl, arylsilyl, arylalkylsilyl, alkoxysilyl, aryloxysilyl, arylalkoxysilyl, alkylsiloxy, arylsiloxy, arylalkylsiloxy, alkoxysiloxy, aryloxysiloxy, arylalkoxysiloxy, alkylsilylalkyl, arylsilylalkyl, arylalkysilylalkyl, alkoxysilylalkyl, aryloxysilylalkyl, arylalkoxysilylalkyl, alkylsiloxyalkyl, arylsiloxyalkyl, arylalkylsiloxyalkyl, alkoxysiloxyalkyl, aryloxysiloxyalkyl, arylalkoxysiloxyalkyl, alkylsilylalkoxy, arylsilylalkoxy, arylalkylsilylalkoxy, alkoxysilylalkoxy, aryloxysilylalkoxy arylalkyloxysilylalkoxy, alkylsiloxyalkoxy, arylsiloxyalkoxy, arylalkylsiloxyalkoxy, alkoxysiloxyalkoxy, aryloxysiloxyalkoxy, and arylalkoxysiloxyalkoxy;
each R3 is independently selected from the group consisting of hydrogen, deuterium, C1-C6 alkyl, C1-C6 cycloalkyl, phenyl, benzyl, (C1-C2 alkyl or alkoxy)3-silyl, and (C1-C2 alkyl or alkoxy)3-siloxy and wherein at least two groups R3 are selected from the group consisting of hydrogen and deuterium;
when R4 is hydrogen or deuterium; and
wherein when M is cobalt and one group R1 is selected to be N2, then m is 2 and the second group R1 is hydrogen or deuterium.- View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35)
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36. A method of chemical deposition of metal on a substrate surface comprising:
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contacting the substrate surface with an organometallic precursor compound of the formula (R1)mM(PR23)x, where M is a metal selected from the group consisting of manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, and platinum wherein (a) when M is manganese, technetium or rhenium, m is 1, x is 5 and m+x is 6;
(b) when M is iron, ruthenium or osmium, m is 0, 1, 2, 3 or 4;
x is 2, 3, 4 or 5 and m+x is 4, 5, 6, or 7;
(c) when M is cobalt, rhodium or iridium, m is 1, 2, 3 or 4 and x is 2, 3 or 4 and m+x is 4, 5, 6, 7 or 8; and
(d) when M is nickel, palladium or platinum, m is 0 or 2, x is 2, 3 or 4 and m+x is 2, 3, 4, 5 or 6;
each R1 is independently selected from the group consisting of hydrogen, deuterium, N2, H2, D2 and a group of the formula —
CR32—
CR32—
R4;
each R2 is independently selected from the group consisting of lower alkyl, aryl, arylalkyl, alkoxy, aryloxy, arylalkoxy, alkylsilyl, arylsilyl, arylalkylsilyl, alkoxysilyl, aryloxysilyl, arylalkoxysilyl, alkylsiloxy, arylsiloxy, arylalkylsiloxy, alkoxysiloxy, aryloxysiloxy, arylalkoxysiloxy, alkylsilylalkyl, arylsilylalkyl, arylalkysilylalkyl, alkoxysilylalkyl, aryloxysilylalkyl, arylalkoxysilylalkyl, alkylsiloxyalkyl, arylsiloxyalkyl, arylalkylsiloxyalkyl, alkoxysiloxyalkyl, aryloxysiloxyalkyl, arylalkoxysiloxyalkyl, alkylsilylalkoxy, arylsilylalkoxy, arylalkylsilylalkoxy, alkoxysilylalkoxy, aryloxysilylalkoxy arylalkyloxysilylalkoxy, alkylsiloxyalkoxy, arylsiloxyalkoxy, arylalkylsiloxyalkoxy, alkoxysiloxyalkoxy, aryloxysiloxyalkoxy, and arylalkoxysiloxyalkoxy;
each R3 is independently selected from the group consisting of hydrogen, deuterium, C1-C6 alkyl, C1-C6 cycloalkyl, phenyl, benzyl, (C1-C2 alkyl or alkoxy)3-silyl, and (C1-C2 alkyl or alkoxy)3-siloxy and wherein at least two groups R3 are selected from the group consisting of hydrogen and deuterium;
R4 is hydrogen or deuterium; and
wherein when M is cobalt, rhodium or iridium and one group R1 is selected to be N2, then m is 2 and the second group R1 is hydrogen or deuterium; and
heating an area of the substrate surface desired to be coated to a temperature at or above the thermal decomposition temperature of the organometallic precursor compound. - View Dependent Claims (37, 38, 39, 40, 41, 42, 43)
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44. A film including a metal, obtainable by chemical vapor deposition of an organometallic compound of the formula (R1)mM(PR23)x, where M is a metal selected from the group consisting of manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, and platinum wherein (a) when M is manganese, technetium, or rhenium, m is 1, x is 5 and m+x is 6;
- (b) when M is iron, ruthenium or osmium, m is 0, 1, 2, 3 or 4;
x is 2, 3, 4 or 5 and m+x is 4, 5, 6 or 7;
(c) when M is cobalt, rhodium or iridium, m is 1, 2, 3 or 4 and x is 2, 3 or 4 and m+x is 4, 5, 6, 7 or 8; and
(d) when M is nickel, palladium or platinum, m is 0 or 2, x is 2, 3, or 4 and m+x is 2, 3, 4, 5 or 6;
each R1 is independently selected from the group consisting of hydrogen, deuterium, N2, H2, D2 and a group of the formula —
CR32—
CR32—
R4;
each R2 is independently selected from the group consisting of lower alkyl, aryl, arylalkyl, alkoxy, aryloxy, arylalkoxy, alkylsilyl, arylsilyl, arylalkylsilyl, alkoxysilyl, aryloxysilyl, arylalkoxysilyl, alkylsiloxy, arylsiloxy, arylalkylsiloxy, alkoxysiloxy, aryloxysiloxy, arylalkoxysiloxy, alkylsilylalkyl, arylsilylalkyl, arylalkysilylalkyl, alkoxysilylalkyl, aryloxysilylalkyl, arylalkoxysilylalkyl, alkylsiloxyalkyl, arylsiloxyalkyl, arylalkylsiloxyalkyl, alkoxysiloxyalkyl, aryloxysiloxyalkyl, arylalkoxysiloxyalkyl, alkylsilylalkoxy, arylsilylalkoxy, arylalkylsilylalkoxy, alkoxysilylalkoxy, aryloxysilylalkoxy arylalkyloxysilylalkoxy, alkylsiloxyalkoxy, arylsiloxyalkoxy, arylalkylsiloxyalkoxy, alkoxysiloxyalkoxy, aryloxysiloxyalkoxy, and arylalkoxysiloxyalkoxy;
each R3 is independently selected from the group consisting of hydrogen, deuterium, C1-C6 alkyl, C1-C6cycloalkyl, phenyl, benzyl, (C1-C2 alkyl or alkoxy)3-silyl, and (C1-C2 alkyl or alkoxy)3-siloxy and wherein at least two groups R3 are selected from the group consisting of hydrogen and deuterium;
R4 is hydrogen or deuterium; and
wherein when M is cobalt and one group R1 is selected to be N2, then m is 2 and the second group R1 is hydrogen or deuterium. - View Dependent Claims (45)
- (b) when M is iron, ruthenium or osmium, m is 0, 1, 2, 3 or 4;
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47. A method comprising:
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providing an integrated circuit device work piece; and
depositing a metal or a metal containing material on the work piece;
said depositing including contacting said work piece or a portion thereof with an organometallic compound of the formula (R1)mM(PR23)x, where M is a metal selected from the group consisting of manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, and platinum wherein (a) when M is manganese, technetium, or rhenium, m is 1, x is 5 and m+x is 6;
(b) when M is iron, ruthenium or osmium, m is 0, 1, 2, 3 or 4;
x is 2, 3, 4 or 5 and m+x is 4, 5, 6 or 7;
(c) when M is cobalt, rhodium or iridium, m is 1, 2, 3 or 4 and x is 2, 3 or 4 and m+x is 4, 5, 6, 7 or 8; and
(d) when M is nickel, palladium or platinum, m is 0 or 2, x is 2, 3, or 4 and m+x is 2, 3, 4, 5 or 6;
each R1 is independently selected from the group consisting of hydrogen, deuterium, N2, H2, D2 and a group of the formula —
CR32—
CR32—
R4;
each R2 is independently selected from the group consisting of lower alkyl, aryl, arylalkyl, alkoxy, aryloxy, arylalkoxy, alkylsilyl, arylsilyl, arylalkylsilyl, alkoxysilyl, aryloxysilyl, arylalkoxysilyl, alkylsiloxy, arylsiloxy, arylalkylsiloxy, alkoxysiloxy, aryloxysiloxy, arylalkoxysiloxy, alkylsilylalkyl, arylsilylalkyl, arylalkysilylalkyl, alkoxysilylalkyl, aryloxysilylalkyl, arylalkoxysilylalkyl, alkylsiloxyalkyl, arylsiloxyalkyl, arylalkylsiloxyalkyl, alkoxysiloxyalkyl, aryloxysiloxyalkyl, arylalkoxysiloxyalkyl, alkylsilylalkoxy, arylsilylalkoxy, arylalkylsilylalkoxy, alkoxysilylalkoxy, aryloxysilylalkoxy arylalkyloxysilylalkoxy, alkylsiloxyalkoxy, arylsiloxyalkoxy, arylalkylsiloxyalkoxy, alkoxysiloxyalkoxy, aryloxysiloxyalkoxy, and arylalkoxysiloxyalkoxy;
each R3 is independently selected from the group consisting of hydrogen, deuterium, C1-C6 alkyl, C1-C6cycloalkyl, phenyl, benzyl, (C1-C2 alkyl or alkoxy)3-silyl, and (C1-C2 alkyl or alkoxy)3-siloxy and wherein at least two groups R3 are selected from the group consisting of hydrogen and deuterium;
R4 is hydrogen or deuterium; and
wherein when M is cobalt and one group R1is selected to be N2, then m is 2 and the second group R1 is hydrogen or deuterium.- View Dependent Claims (46, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57)
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Specification
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Current AssigneeBoard of Trustees of The University of Illinois
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Original AssigneeBoard of Trustees of The University of Illinois
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InventorsChoi, Hyungsoo
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Primary Examiner(s)Dang, Phuc T.
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Application NumberUS10/290,719Publication NumberTime in Patent Office592 DaysField of Search438/613, 438/650, 438/656, 438/681, 556/110, 556/113, 556/114, 556/136US Class Current438/613CPC Class CodesC07F 15/065 without a metal-carbon linkageC23C 16/18 from metallo-organic compoundsC23C 16/42 SilicidesH01L 29/665 using self aligned silicida...
