Patent US4948623A successfully refreshed from Google Patents.
US4948623A
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Method of chemical vapor deposition of copper, silver, and gold using a cyclopentadienyl/metal complex
Assignee: International Business Machines Corp
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Filing: 1989-09-29
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Granted: 1990-08-14
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Expires: 2009-09-29
Abstract
Abstract Improved processes are described for the deposition of Cu and group IB metals such as Ag and Au. These processes include thermal CVD, photothermal depositions and photochemical deposition. The gaseous precursor which leads to successful deposition of high quality films at low temperatures includes a cyclopentadienyl ring, a two electron donor ligand, and the group IB metal in a +1 oxidation state. In addition, derivatives of the cyclopentadienyl ring can be used where the substituents on the ring include those selected from alkyl groups, halide groups, and psuedohalide groups. In addition, the two electron donor ligand can be selected from the group consisting of trivalent phosphines, amines and arsines. A representative precursor for the deposition of Cu is triethylphosphine cyclopentadienyl copper (I).
Inventors
- 👤 David B. Beach
- 👤 Joseph M. Jasinski
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-24 06:13
CPC Classifications
H; H10; H10P; H10P14/00; H10P14/40; H10P14/412; C; C23; C23C; C23C16/00; C23C16/06; C23C16/18
Claims Analysis
Total Claims: 48
Claim 1
Independent Claim
59 words
A method for depositing a group IB metal, said method including the step of decomposing onto a substrate a vapor of a precursor comprising a cyclopentadienyl ring, a 2 electron donor ligand selected from the group consisting of trivalent phosphines, amines, and arsines, and said group IB metal which is present in said precursor in a +1 oxidation state.
Claim 2
Independent Claim
59 words
A method for depositing a group IB metal, said method including the step of decomposing onto a substrate a vapor of a precursor comprising a cyclopentadienyl ring, a 2 electron donor ligand selected from the group consisting of trivalent phosphines, amines, and arsines, and said group IB metal which is present in said precursor in a +1 oxidation state.
Claim 3
Dependent Claim
19 words
The method of claim 1, where said metal is selected from the group consisting of Cu, Ag, and Au.
Claim 4
Dependent Claim
26 words
The method of claim 1, where said cyclopentadienyl ring includes substituents thereon, said substituents selected from the group consisting of alkyl, halide, and psuedo halide groups.
Claim 5
Dependent Claim
21 words
The method of claim 1, where said substrate is at a temperature sufficiently high to decompose said vapor of the precursor.
Claim 6
Dependent Claim
17 words
The method of claim 4, where the temperature of said substrate is less than about 400° C.
Claim 7
Dependent Claim
19 words
The method of claim 4, where the temperature of said substrate is between about 120° C. and 300° C.
Claim 8
Dependent Claim
25 words
The method of claim 1, where said substrate is selected from the group consisting of glossy insulators such as oxides, polymers, metals, ceramics and semiconductors.
Claim 9
Dependent Claim
20 words
The method of claim 1, where said method deposits said group IB metal conformally on a substrate having recesses therein.
Claim 10
Dependent Claim
21 words
The method of claim 1, where said step of decomposing said vapor occurs at a temperature less than about 500° C.
Claim 11
Dependent Claim
14 words
The method of claim 1, where said substrate is heated by a radiation beam.
Claim 12
Dependent Claim
14 words
The method of claim 10, where said radiation beam is produced by a laser.
Claim 13
Independent Claim
106 words
A method for depositing a metal selected from the group consisting of Cu, Ag, and Au, including the steps of: heating a substrate onto which deposition of said metal is to occur, said substrate being located in a deposition chamber, producing a vapor of a precursor containing said metal in said chamber in the vicinity of said substrate, said precursor including a cyclopentadienyl ring, a 2 electron donor ligand attached thereto, said ligand being selected from the group consisting of trivalent phosphines, amines, and arsines, and said metal to be deposited in a +1 oxidation state, decomposing said vapor to deposit said metal on said substrate.
Claim 14
Independent Claim
106 words
A method for depositing a metal selected from the group consisting of Cu, Ag, and Au, including the steps of: heating a substrate onto which deposition of said metal is to occur, said substrate being located in a deposition chamber, producing a vapor of a precursor containing said metal in said chamber in the vicinity of said substrate, said precursor including a cyclopentadienyl ring, a 2 electron donor ligand attached thereto, said ligand being selected from the group consisting of trivalent phosphines, amines, and arsines, and said metal to be deposited in a +1 oxidation state, decomposing said vapor to deposit said metal on said substrate.
Claim 15
Dependent Claim
15 words
The method of claim 12, where said deposited metal includes less than about 15% carbon.
Claim 16
Dependent Claim
14 words
The method of claim 12, where said method is a chemical vapor deposition method.
Claim 17
Dependent Claim
27 words
The method of claim 12, where the temperature of said substrate is sufficiently high that said vapor will decompose at said substrate to deposit said metal thereon.
Claim 18
Dependent Claim
37 words
The method of claim 12, where a vapor precursor containing aluminum is also present in said chamber, said vapor containing aluminum being decomposed to deposit aluminum on said substrate simultaneously with the deposition of said metal thereon.
Claim 19
Dependent Claim
33 words
The method of claim 12, including the further steps of decomposing a vapor containing Al to deposit an Al film, and annealing the resulting Al-Cu composite to produce a Cu doped Al layer.
Claim 20
Dependent Claim
27 words
The method of claim 12, where said cyclopentadienyl ring includes at least one substituent thereon selected from the group consisting of alkyl, halide, and psuedo halide groups.
Claim 21
Dependent Claim
17 words
The method of claim 12, where said substrate is heated by a beam of radiation incident thereon.
Claim 22
Dependent Claim
15 words
The method of claim 19, where said beam of radiation is produced by a laser.
Claim 23
Dependent Claim
18 words
The method of claim 12, where said substrate has recesses thereon, said metal being deposited in said recesses.
Claim 24
Dependent Claim
14 words
The method of claim 21, where said recesses are located in a polymer layer.
Claim 25
Dependent Claim
17 words
The method of claim 12, where said substrate is heated to a temperature less than 500° C.
Claim 26
Dependent Claim
29 words
The method of claim 12, where said metal is copper and said substrate has copper lines thereon onto which said method deposits copper for repair of said copper lines.
Claim 27
Dependent Claim
105 words
A thermal CVD method for depositing copper onto a substrate, comprising the steps of: placing said substrate in a chamber into which a vapor of a Cu precursor is produced, heating said substrate, producing a vapor of said precursor in said chamber, said vapor transporting to said substrate to be decomposed thereat, said Cu precursor being a cyclopentadienyl ring of copper and including a 2 electron donor ligand, said ligand being selected from the group consisting of trivalent phosphines, amines, and arsines, said copper being present in said precursor in a +1 oxidation state, and decomposing said vapor to deposit copper therefrom onto said substrate.
Claim 28
Dependent Claim
105 words
A thermal CVD method for depositing copper onto a substrate, comprising the steps of: placing said substrate in a chamber into which a vapor of a Cu precursor is produced, heating said substrate, producing a vapor of said precursor in said chamber, said vapor transporting to said substrate to be decomposed thereat, said Cu precursor being a cyclopentadienyl ring of copper and including a 2 electron donor ligand, said ligand being selected from the group consisting of trivalent phosphines, amines, and arsines, said copper being present in said precursor in a +1 oxidation state, and decomposing said vapor to deposit copper therefrom onto said substrate.
Claim 29
Dependent Claim
20 words
A method of claim 25, where the temperature to which said substrate is heated is sufficient to decompose said vapor.
Claim 30
Dependent Claim
14 words
The method of claim 26, where said substrate is heated by a laser beam.
Claim 31
Dependent Claim
26 words
The method of claim 25, where said cyclopentadienyl ring of Cu has substituents thereon selected from the group consisting of alkyl, halide, and psuedo halide groups.
Claim 32
Dependent Claim
20 words
The method of claim 25, where the temperature of said substrate during deposition thereon is less than about 500° C.
Claim 33
Dependent Claim
16 words
The method of claim 25, where said chamber is essentially a cold wall, heated substrate apparatus.
Claim 34
Dependent Claim
18 words
The method of claim 25, where said chamber is heated to promote the transport of said vapor therein.
Claim 35
Independent Claim
104 words
A method for chemical vapor deposition of Cu, including the following steps: placing a substrate in a reaction chamber, evacuating said chamber to remove contaminants therefrom, producing a vapor of a Cu precursor in said chamber, said precursor being a cyclopentadienyl ring of copper having attached thereto a 2 electron donor ligand, said ligand being selected from the group consisting of trivalent phosphines, amines, and arsines, said copper being present in said precursor in a +1 oxidation state, heating said substrate, transporting said vapor to said substrate, the temperature of said substrate being sufficient to decompose said vapor to deposit copper on said substrate.
Claim 36
Independent Claim
104 words
A method for chemical vapor deposition of Cu, including the following steps: placing a substrate in a reaction chamber, evacuating said chamber to remove contaminants therefrom, producing a vapor of a Cu precursor in said chamber, said precursor being a cyclopentadienyl ring of copper having attached thereto a 2 electron donor ligand, said ligand being selected from the group consisting of trivalent phosphines, amines, and arsines, said copper being present in said precursor in a +1 oxidation state, heating said substrate, transporting said vapor to said substrate, the temperature of said substrate being sufficient to decompose said vapor to deposit copper on said substrate.
Claim 37
Dependent Claim
13 words
The method of claim 32, where said precursor is a cyclopentadienyl-trialkyl phosphine complex.
Claim 38
Dependent Claim
15 words
The method of claim 32, where said substrate is heated by radiation from a laser.
Claim 39
Dependent Claim
18 words
The method of claim 32, where said substrate is heated to a temperature less than about 400° C.
Claim 40
Independent Claim
121 words
A method for chemical vapor deposition of a Cu-doped Al film, including the following steps: placing a substrate in a reaction chamber, evacuating said chamber to remove contaminants therefrom, producing a first vapor of a Cu precursor in said chamber, said precursor being a cyclopentadienyl ring of copper having attached thereto a 2 electron donor ligand selected from the group consisting of trivalent phosphines, amines, and arsines, said copper being present in said precursor in a +1 oxidation state, producing a second vapor of an Al precursor in said chamber, heating said substrate, transporting said first and second vapors to said substrate, and decomposing said vapors to deposit Cu and Al on said substrate, thereby producing said Cu doped Al film.
Claim 41
Independent Claim
121 words
A method for chemical vapor deposition of a Cu-doped Al film, including the following steps: placing a substrate in a reaction chamber, evacuating said chamber to remove contaminants therefrom, producing a first vapor of a Cu precursor in said chamber, said precursor being a cyclopentadienyl ring of copper having attached thereto a 2 electron donor ligand selected from the group consisting of trivalent phosphines, amines, and arsines, said copper being present in said precursor in a +1 oxidation state, producing a second vapor of an Al precursor in said chamber, heating said substrate, transporting said first and second vapors to said substrate, and decomposing said vapors to deposit Cu and Al on said substrate, thereby producing said Cu doped Al film.
Claim 42
Dependent Claim
14 words
The method of claim 36, where said Cu precursor is a cyclopentadienyl-trialkyl phosphine complex.
Claim 43
Dependent Claim
15 words
The method of claim 36, where said substrate is heated by radiation from a laser.
Claim 44
Independent Claim
137 words
A method for chemical vapor deposition of a Cu doped Al layer including the following steps: placing a substrate in a reaction chamber, evacuating said chamber to remove contaminants therefrom, producing a first vapor of a Cu precursor in said chamber, said precursor being a cyclopentadienyl ring of copper having attached thereto a 2 electron donor ligand selected from the group consisting of trivalent phosphines, amines, and arsines, said copper being present in said precursor in a +1 oxidation state, heating said substrate, transporting said first vapor to said substrate, decomposing said first vapor to deposit copper on said substrate, producing a second vapor of an Al precursor in said chamber, transporting said second vapor to said substrate to deposit Al thereon, producing an Al-Cu composite, and annealing said Al-Cu composite to produce a Cu-doped Al layer.
Claim 45
Independent Claim
137 words
A method for chemical vapor deposition of a Cu doped Al layer including the following steps: placing a substrate in a reaction chamber, evacuating said chamber to remove contaminants therefrom, producing a first vapor of a Cu precursor in said chamber, said precursor being a cyclopentadienyl ring of copper having attached thereto a 2 electron donor ligand selected from the group consisting of trivalent phosphines, amines, and arsines, said copper being present in said precursor in a +1 oxidation state, heating said substrate, transporting said first vapor to said substrate, decomposing said first vapor to deposit copper on said substrate, producing a second vapor of an Al precursor in said chamber, transporting said second vapor to said substrate to deposit Al thereon, producing an Al-Cu composite, and annealing said Al-Cu composite to produce a Cu-doped Al layer.
Claim 46
Dependent Claim
14 words
The method of claim 39, where said precursor is a cyclopentadienyl-trialkyl phosphine copper complex.
Claim 47
Independent Claim
74 words
A method for depositing a group IB metal into a via in a substrate including the step of decomposing into said via a vapor of a precursor comprising a cyclopentadienyl ring, a 2 electron donor ligand selected from the group consisting of trivalent phosphines, amines, and arsines, and said group IB metal which is present in said precursor in a +1 oxidation state, said deposited metal forming an electrically continuous conductor in said via.
Claim 48
Independent Claim
74 words
A method for depositing a group IB metal into a via in a substrate including the step of decomposing into said via a vapor of a precursor comprising a cyclopentadienyl ring, a 2 electron donor ligand selected from the group consisting of trivalent phosphines, amines, and arsines, and said group IB metal which is present in said precursor in a +1 oxidation state, said deposited metal forming an electrically continuous conductor in said via.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1993-08-13 | 1994-02-12 | 1994-08-14 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1997-08-13 | 1998-02-12 | 1998-08-14 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2001-08-13 | 2002-02-12 | 2002-08-14 | $7700.00 | Window Closed / Lapsed |