EP1102872A1 - Novel organocuprous precursors for chemical vapor deposition of a copper film - Google Patents
Novel organocuprous precursors for chemical vapor deposition of a copper filmInfo
- Publication number
- EP1102872A1 EP1102872A1 EP99959960A EP99959960A EP1102872A1 EP 1102872 A1 EP1102872 A1 EP 1102872A1 EP 99959960 A EP99959960 A EP 99959960A EP 99959960 A EP99959960 A EP 99959960A EP 1102872 A1 EP1102872 A1 EP 1102872A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- copper film
- organocuprous
- precursors
- hfac
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000010949 copper Substances 0.000 title claims abstract description 42
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 21
- 239000002243 precursor Substances 0.000 title description 28
- 238000005229 chemical vapour deposition Methods 0.000 title description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011737 fluorine Chemical group 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims description 16
- 238000000151 deposition Methods 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 230000008016 vaporization Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract 1
- 239000010408 film Substances 0.000 description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 229960004132 diethyl ether Drugs 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- PKXHXOTZMFCXSH-UHFFFAOYSA-N 3,3-dimethylbut-1-ene Chemical compound CC(C)(C)C=C PKXHXOTZMFCXSH-UHFFFAOYSA-N 0.000 description 3
- PPWNCLVNXGCGAF-UHFFFAOYSA-N 3,3-dimethylbut-1-yne Chemical compound CC(C)(C)C#C PPWNCLVNXGCGAF-UHFFFAOYSA-N 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 2
- AASUFOVSZUIILF-UHFFFAOYSA-N diphenylmethanone;sodium Chemical compound [Na].C=1C=CC=CC=1C(=O)C1=CC=CC=C1 AASUFOVSZUIILF-UHFFFAOYSA-N 0.000 description 2
- -1 e.g. Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- 239000012691 Cu precursor Substances 0.000 description 1
- 229910004166 TaN Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- GCSJLQSCSDMKTP-UHFFFAOYSA-N ethenyl(trimethyl)silane Chemical compound C[Si](C)(C)C=C GCSJLQSCSDMKTP-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- HYWCXWRMUZYRPH-UHFFFAOYSA-N trimethyl(prop-2-enyl)silane Chemical compound C[Si](C)(C)CC=C HYWCXWRMUZYRPH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/08—Copper compounds
Definitions
- the present invention relates to novel organocuprous precursors which are useful in the chemical vapor deposition of a copper film having high purity; and to a process for the preparation of a copper film using same.
- a metallic interconnect is typically formed by a chemical vapor deposition (CVD) method using a metallorganic precursor compound, and Cu films have previously been prepared using various organic copper (II) precursors such as Cu(II) (hfac) 2 , wherein hfac stands for hexafluoroacetyl- acetonate.
- II organic copper
- a CVD process using such Cu(II) precursors requires a high deposition temperature and the resulting Cu film is often contaminated by various impurities .
- Organic copper (I) precursor compounds usable in a low- temperature, selective CVD process have been recently described.
- organocuprous precursors such as (hfac) Cu(I) (VTMS) (VTMS : vinyltrimethylsilane) and (hfac) Cu (I) (ATMS) (ATMS : allyltrimethylsilane) in a low- temperature CVD process to selectively deposit a Cu film on a conductive substrate surface
- VTMS VTMS : vinyltrimethylsilane
- ATMS ATMS
- U.S. Patent No. 5,098,516 teaches the use of Cu(I)- olefin precursors such as (hfac) Cu (I) ⁇ COD (COD: cyclooctadiene) and (hfac) Cu (I) • NBD (NBD: norbonadiene) in a low temperature CVD process.
- Cu(I) -olefin precursors are solids, and they must be sublimed at a temperature below their thermal decomposition temperatures, e.g., about 105 °C for (hfac) Cu (I) • COD .
- 5,098,516 is hampered by the difficulty in handling solid precursors in a mass production system. Moreover, the CVD of a copper film using, e.g., (hfac) Cu (I) • COD requires a relatively high substrate temperature of above 150 °C and the resulting copper film is often of poor quality.
- an organic copper (I) precursor which can be advantageously used in a low-temperature CVD process for the mass production of a contaminant -free copper film.
- R. , R 2 and R 3 are each independently a C,_ 8 alkyl, C,,_ 8 alkoxy, aryl or aryloxy group,
- R, and R 5 are each independently hydrogen, fluorine, a C n F 2n+1 or C H 2 +1 group, n being an integer in the range of 1 to 6,
- a process for depositing a copper film on a substrate which comprises vaporizing the compound of formula (I) and bringing the resulting vapor into contact with the substrate.
- Fig. 1 depicts the thermal decomposition characteristics of the inventive organocuprous precursor ( (hfac) Cu(DMB) ) , as analyzed by TGA (thermal gravimetric analyzer) and DSC (differential scanning calorimeter) _
- Fig. 2 exhibits the thermal decomposition characteristics of (hfac) Cu (VTMS) , as analyzed by TGA and
- FIG. 3 shows the vapor pressure changes of the inventive organocuprous precursor ( (hfac) Cu (DMB) ) and
- Fig. 4 illustrates the copper film deposition rate as function of the substrate temperature in a CVD process using the inventive organocuprous precursor ( (hfac) Cu (DMB) ) , (hfac) C (VTMS) and (hfac) Cu (ATMS) ; and
- Fig. 5 presents the change in the specific resistance of the copper film derived from the inventive precursor ( (hfac) Cu (DMB) ) with the substrate temperature.
- R 1 , R 2 and R 3 are each independently methyl, ethyl, methoxy or ethoxy group
- R 4 and R 5 are each dependently a C n F 2n+1 or C n H 2n+1 group wherein n is 1 or 4
- R 6 is hydrogen
- More preferred compounds of formula (I) according to the present invention are those represented by formula (I -a) and (I-b) :
- R and R 5 are each dependently a C n F 2n+1 or C n H 2n+1 group (n is an integer of 1 to 4), ' preferably trifluoromethyl group .
- the compound of formula (I -a) may be prepared by reacting 1, 1, 1, 5, 5, 5-hexafluoro-2,4-pentanedione (Hhfac) , 3,3- dimethyl-1-butene (DMB) and cuprous oxide (Cu 2 0) in the presence of an organic solvent, e.g., diethylether or dichloromethane, at a temperature ranging from 0 to 20 °C under an ambient pressure for 2 to 3 hours.
- the reactants may be preferably employed in an Hhfac : DMB : Cu 2 0 molar ratio of about 2 : 2 : 1.
- the compound of formula (I-b) wherein R 4 and R 5 are each a trifluoromethyl group may be prepared by using 3 , 3-dimethyl -1-butyne (i .e . , tert-butylacetylene) (TBA) in place of 3 , 3 -dimethyl -1-butene (DMB) , in the process for the synthesis of the compound of formula (I-a) .
- TSA 3-dimethyl -1-butyne
- DMB 3 -dimethyl -1-butene
- the compound of formula (I) according to the present invention has good thermostability and high volatility, and in a CVD process for the formation of a copper film on a specified surface of a substrate, it may be conveniently vaporized in a bubbler or evaporator at a temperature ranging from about 15 to 100 °C in a gas delivering system or a liquid delivery system.
- the CVD process for the formation of a copper thin film using the inventive organocuprous precursor may be carried out in a conventional manner, e.g., by vaporizing the inventive precursor and conveying the resulting vapor with a carrier gas such as argon to a substrate, e.g., platinum, silica, TiN, TaN, WN, etc., which is preferably heated to a temperature ranging from 100 to 300 °C, more preferably from 150 to 250 °C, under a reduced pressure, e.g., 0.1 to 10 torr .
- a carrier gas such as argon
- the thickness of the copper film may be conveniently controlled by adjusting the deposition time.
- the copper film obtained according to the present invention is useful as a metallized or seed layer of a semiconductor device.
- the resulting reddish suspension was stirred for 1 hour and cooled to 0 °C, and slowly added thereto with a canula was a solution of 1.46 g (7.0 mmol) of 1 , 1 , 1 , 5 , 5 , 5-hexafluoro- 2, 4-pentanedione (Hhfac) in diethyl ether.
- the resulting mixture was stirred at room temperature for 2 hours and, at this time, the color of the mixture turned yellow.
- the resulting solution was filtered through a bed of CELLITETM and the solvent was removed therefrom under a reduced pressure to obtain 1.75 g of the titled compound as a yellow solid (yield 73 %) .
- Figs. 1 and 2 respectively.
- the thermal decomposition temperature of the inventive organocuprous precursor is higher than that of the prior art precursor, and thus, the inventive precursor has good thermal stability.
- the changes in the vapor pressure of the titled compound and (hfac) Cu (VTMS) were determined at various temperatures.
- the result in Fig. 3 demonstrates that the inventive precursor has a higher vapor pressure than the prior art compound.
- Example 3 Deposition of a copper film on a substrate
- Copper films were deposited on a TiN or Si0 2 -coated substrate by a CVD process, using the inventive precursor synthesized in Example 1, as well as (hfac) Cu (VTMS) and
- the change in the specific resistance of the film deposited using the inventive precursor depends on the substrate temperature, as shown in Fig. 5. It can be seen from Fig. 5 that the specific resistance of the film deposited at a substrate temperature of 150 °C to 250 °C approximately reaches that of bulk copper (about 1.67 ⁇ cm) .
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Vapour Deposition (AREA)
- Electrodes Of Semiconductors (AREA)
- Chemically Coating (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
An organocuprous compound of formula (I) of the present invention can be conveniently used in a low-temperature CVD process for the mass production of a contaminant-free copper film having good thermal stability, wherein: R1, R2 and R3 are each independently a C1-8 alkoxy, aryl or aryloxy group, R4 and R5 are each independently hydrogen, fluorine, a CnF2n+1 or CnH2n+1 group, n being an integer in the range of 1 to 6, R6 is hydrogen, fluorine or C1-4 alkyl group, and m is 1 or 2, when m is 1, C=C represents C‰C, and when m is 2, C=C represents C=C.
Description
NOVEL ORGANOCUPROUS PRECURSORS FOR CHEMICAL VAPOR
DEPOSITION OF A COPPER FILM
FIELD OF THE INVENTION
The present invention relates to novel organocuprous precursors which are useful in the chemical vapor deposition of a copper film having high purity; and to a process for the preparation of a copper film using same.
BACKGROUND OF THE INVENTION
Hitherto, many metals such as tungsten and aluminum have been widely used as interconnecting materials in many electronic devices such as semiconductors. However, an aluminum interconnect (specific resistance: about 2.7 μΩ- cm) tends to be hampered by the problem of electromigration, while tungsten has the problem of high resistivity (specific resistance: about 5.4 μΩ- cm) . Therefore, attempts have been recently made to use copper which is highly conductive (specific resistance: about 1.67 μΩ- cm) and electromigration resistant, as an interconnecting material in advanced devices such as ultra-large semiconductor integrated circuits . A metallic interconnect is typically formed by a chemical vapor deposition (CVD) method using a metallorganic precursor compound, and Cu films have previously been
prepared using various organic copper (II) precursors such as Cu(II) (hfac)2, wherein hfac stands for hexafluoroacetyl- acetonate. However, a CVD process using such Cu(II) precursors requires a high deposition temperature and the resulting Cu film is often contaminated by various impurities .
Organic copper (I) precursor compounds usable in a low- temperature, selective CVD process have been recently described. For example, the use of organocuprous precursors such as (hfac) Cu(I) (VTMS) (VTMS : vinyltrimethylsilane) and (hfac) Cu (I) (ATMS) (ATMS : allyltrimethylsilane) in a low- temperature CVD process to selectively deposit a Cu film on a conductive substrate surface has been disclosed by Norman et al . in U.S. Patent No. 5,085,731 and Electrochemical and Solid-State Letters, 1(1) 32-33 (1998), respectively. However, the above CVD process has a low productivity due to the low vapor pressure and the low thermal stability of the organic copper precursors .
U.S. Patent No. 5,098,516 teaches the use of Cu(I)- olefin precursors such as (hfac) Cu (I) ■ COD (COD: cyclooctadiene) and (hfac) Cu (I) • NBD (NBD: norbonadiene) in a low temperature CVD process. The above Cu(I) -olefin precursors are solids, and they must be sublimed at a temperature below their thermal decomposition temperatures, e.g., about 105 °C for (hfac) Cu (I) • COD . Thus, the CVD process disclosed in U.S. Patent No. 5,098,516 is hampered by the difficulty in handling solid precursors in a mass
production system. Moreover, the CVD of a copper film using, e.g., (hfac) Cu (I) • COD requires a relatively high substrate temperature of above 150 °C and the resulting copper film is often of poor quality.
SUMMARY OF THE INVENTION
Accordingly, it is a primary object of the present invention to provide an organic copper (I) precursor which can be advantageously used in a low-temperature CVD process for the mass production of a contaminant -free copper film.
In accordance with one aspect of the present invention, there is provided an organocuprous compound of formula (I)
wherein: R. , R2 and R3 are each independently a C,_8 alkyl, C,,_8 alkoxy, aryl or aryloxy group,
R, and R5 are each independently hydrogen, fluorine, a CnF2n+1 or C H2 +1 group, n being an integer in the range of 1 to 6, R6 is hydrogen, fluorine or a C,_4 alkyl group, and is 1 or 2, when m is 1, C=C represents C≡C, and when m is 2, C="C represents C=C.
In accordance with another aspect of the present
invention, there is provided a process for depositing a copper film on a substrate, which comprises vaporizing the compound of formula (I) and bringing the resulting vapor into contact with the substrate.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and other objects and features of the present invention will become apparent from ' the following description of the invention taken in conjunction with the accompanying drawings, in which:
Fig. 1 depicts the thermal decomposition characteristics of the inventive organocuprous precursor ( (hfac) Cu(DMB) ) , as analyzed by TGA (thermal gravimetric analyzer) and DSC (differential scanning calorimeter) _
Fig. 2 exhibits the thermal decomposition characteristics of (hfac) Cu (VTMS) , as analyzed by TGA and
DSC; Fig. 3 shows the vapor pressure changes of the inventive organocuprous precursor ( (hfac) Cu (DMB) ) and
(hfac) Cu (VTMS) determined with temperature;
Fig. 4 illustrates the copper film deposition rate as function of the substrate temperature in a CVD process using the inventive organocuprous precursor ( (hfac) Cu (DMB) ) , (hfac) C (VTMS) and (hfac) Cu (ATMS) ; and
Fig. 5 presents the change in the specific resistance
of the copper film derived from the inventive precursor ( (hfac) Cu (DMB) ) with the substrate temperature.
DETAILED DESCRIPTION OF THE INVENTION
Among the compounds according to the present invention, preferred are those of formula (I) wherein R1 , R2 and R3 are each independently methyl, ethyl, methoxy or ethoxy group, R4 and R5 are each dependently a CnF2n+1 or CnH2n+1 group wherein n is 1 or 4, and R6 is hydrogen.
More preferred compounds of formula (I) according to the present invention are those represented by formula (I -a) and (I-b) :
wherein R and R5 are each dependently a CnF2n+1 or CnH2n+1 group (n is an integer of 1 to 4),' preferably trifluoromethyl group .
When R4 and R5 are each a trifluoromethyl group, the
compound of formula (I -a) may be prepared by reacting 1, 1, 1, 5, 5, 5-hexafluoro-2,4-pentanedione (Hhfac) , 3,3- dimethyl-1-butene (DMB) and cuprous oxide (Cu20) in the presence of an organic solvent, e.g., diethylether or dichloromethane, at a temperature ranging from 0 to 20 °C under an ambient pressure for 2 to 3 hours. The reactants may be preferably employed in an Hhfac : DMB : Cu20 molar ratio of about 2 : 2 : 1.
Further, the compound of formula (I-b) wherein R4 and R5 are each a trifluoromethyl group may be prepared by using 3 , 3-dimethyl -1-butyne (i .e . , tert-butylacetylene) (TBA) in place of 3 , 3 -dimethyl -1-butene (DMB) , in the process for the synthesis of the compound of formula (I-a) .
The compound of formula (I) according to the present invention has good thermostability and high volatility, and in a CVD process for the formation of a copper film on a specified surface of a substrate, it may be conveniently vaporized in a bubbler or evaporator at a temperature ranging from about 15 to 100 °C in a gas delivering system or a liquid delivery system.
The CVD process for the formation of a copper thin film using the inventive organocuprous precursor may be carried out in a conventional manner, e.g., by vaporizing the inventive precursor and conveying the resulting vapor with a carrier gas such as argon to a substrate, e.g., platinum, silica, TiN, TaN, WN, etc., which is preferably heated to a temperature ranging from 100 to 300 °C, more preferably from
150 to 250 °C, under a reduced pressure, e.g., 0.1 to 10 torr .
The thickness of the copper film may be conveniently controlled by adjusting the deposition time. The copper film obtained according to the present invention is useful as a metallized or seed layer of a semiconductor device.
The following Examples are intended to further illustrate the present invention without limiting its scope.
Example 1: Synthesis of (hfac) Cu (I) (DMB)
0.5 g (3.5 mmol) of Cu20 and 0.84 g (7.0 mmol) of MgS04 were charged to a Schlenk flask and thereto was added 30 ml of diethylether which had been previously distilled from sodium benzophenone under an argon atmosphere, and then slowly added 0.59 g (7.0 mmol) of 3 , 3 -dimethyl -1-butene . The resulting reddish suspension was stirred for 1 hour and cooled to 0 °C, and slowly added thereto with a canula was a solution of 1.46 g (7.0 mmol) of 1 , 1 , 1 , 5 , 5 , 5-hexafluoro- 2 , 4-pentanedione (Hhfac) in diethyl ether. The resulting mixture was stirred at room temperature for 2 hours and, at this time, the color of the mixture turned dark green. The resulting solution was filtered through a bed of CELLITE™ and the solvent was removed therefrom under a reduced pressure to obtain 1.74 g of the titled compound as a dark green liquid (yield 70 %) . 1H-NMR (CDC13, ppm) δ 6.12 (s, 1H) , 5.38 (m, 1H) , 4.30 (dd, 2H) ,
1.15(s, 9H)
13C-NMR (CDC13, ppm) δ 177.83 (q, CF-.COCH) , 119.73, 115.8 (q, CF3) , 89.97 (COCHCO) , 75.69, 35.16, 29.99 19F-NMR (TFA, ppm) δ -0.14 (s, 6F)
Example 2 : Synthesis of (hfac)Cu(I) (TBA)
0.5 g (3.5 mmol) of Cu20 and 0.84 g (7.0 mmol) of MgS04 were charged to a Schlenk flask and thereto was added 30 ml of diethylether which had been previously distilled from sodium benzophenone under an argon atmosphere, and then slowly added 0.58 g (7.0 mmol) of 3 , 3 -dimethyl -1-butyne . The resulting reddish suspension was stirred for 1 hour and cooled to 0 °C, and slowly added thereto with a canula was a solution of 1.46 g (7.0 mmol) of 1 , 1 , 1 , 5 , 5 , 5-hexafluoro- 2, 4-pentanedione (Hhfac) in diethyl ether. The resulting mixture was stirred at room temperature for 2 hours and, at this time, the color of the mixture turned yellow. The resulting solution was filtered through a bed of CELLITE™ and the solvent was removed therefrom under a reduced pressure to obtain 1.75 g of the titled compound as a yellow solid (yield 73 %) .
1H-NMR (CDC13, ppm) δ 6.09(s, 1H) , 4.25(s, 1H) , 1.38(s, 9H) 3C-NMR (C6D6, ppm) δ 178.57 (q, CF3COCH) , 116.52 (q, CF3) , 105.25, 90.36 (COCHCO) , 70.83, 31.73, 30.63 M.P. : 98 - 99 °C
In order to compare the thermal decomposition
characteristics of the compound synthesized in Example 1 and
(hfac) Cu (VTMS) as a prior art precursor, each compound was analyzed with TGA (thermal gravimetric analyzer) and DSC
(differential scanning calorimeter) , and the results are presented in Figs. 1 and 2, respectively. As can be seen in Fig. 1 and Fig. 2, the thermal decomposition temperature of the inventive organocuprous precursor is higher than that of the prior art precursor, and thus, the inventive precursor has good thermal stability. The changes in the vapor pressure of the titled compound and (hfac) Cu (VTMS) were determined at various temperatures. The result in Fig. 3 demonstrates that the inventive precursor has a higher vapor pressure than the prior art compound.
Example 3 : Deposition of a copper film on a substrate
Copper films were deposited on a TiN or Si02-coated substrate by a CVD process, using the inventive precursor synthesized in Example 1, as well as (hfac) Cu (VTMS) and
(hfac) Cu (ATMS) as prior art precursors. Specifically, each compound was fed to a bubbler maintained at 45 °C, and the vapor thereof was conveyed in an argon flow at a rate of 50 seem to the surface of the substrate positioned in a CVD chamber under a pressure of 0.3 mmHg . The copper film deposition rates depending on the substrate temperature are shown in Fig. 4. The results in Fig. 4 demonstrate that the
inventive precursor forms a copper film at a rate which is about 5-6 times higher than those of the prior art precursors .
On the other hand, the change in the specific resistance of the film deposited using the inventive precursor depends on the substrate temperature, as shown in Fig. 5. It can be seen from Fig. 5 that the specific resistance of the film deposited at a substrate temperature of 150 °C to 250 °C approximately reaches that of bulk copper (about 1.67 μΩ cm) .
While the invention has been described with respect to the above specific embodiments, it should be recognized that various modifications and changes may be made to the invention by those skilled in the art which also fall within the scope of the invention as defined by the appended claims .
Claims
1. An organocuprous compound of formula (I)
wherein: R1 , R2 and R3 are each independently a C,_8 alkyl, C,_8 alkoxy, aryl or aryloxy group,
R4 and R5 are each independently hydrogen, fluorine, a CnF2n+1 or CnH2n+1 group, n being an integer in the range of 1 to 6,
R6 is hydrogen, fluorine or a C,_4 alkyl group, and m is 1 or 2 , when m is 1, C-≤C represents C≡C, and when m is
2, Cs»C represents C=C.
2. The compound of claim 1, which is selected from the compounds of the following formulas.
3. A process for depositing a copper film on a substrate, which comprises vaporizing the compound recited in claim 1 and bringing the resulting vapor into contact with the substrate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR9913236 | 1999-04-15 | ||
| KR1019990013236A KR100298125B1 (en) | 1999-04-15 | 1999-04-15 | Organocuprous precursors for chemical deposition of copper |
| PCT/KR1999/000743 WO2000063461A1 (en) | 1999-04-15 | 1999-12-07 | Novel organocuprous precursors for chemical vapor deposition of a copper film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1102872A1 true EP1102872A1 (en) | 2001-05-30 |
| EP1102872A4 EP1102872A4 (en) | 2008-04-30 |
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| EP99959960A Withdrawn EP1102872A4 (en) | 1999-04-15 | 1999-12-07 | Novel organocuprous precursors for chemical vapor deposition of a copper film |
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| Country | Link |
|---|---|
| EP (1) | EP1102872A4 (en) |
| JP (1) | JP2002542397A (en) |
| KR (1) | KR100298125B1 (en) |
| CN (1) | CN1194117C (en) |
| RU (1) | RU2181725C2 (en) |
| TW (1) | TW524881B (en) |
| WO (1) | WO2000063461A1 (en) |
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| UA78180C2 (en) * | 1997-10-03 | 2007-03-15 | Меріаль | Porcine circovirus, vaccines and diagnostic reagents |
| KR100338112B1 (en) * | 1999-12-22 | 2002-05-24 | 박종섭 | Method of forming a copper wiring in a semiconductor device |
| KR100358045B1 (en) * | 1999-12-22 | 2002-10-25 | 주식회사 하이닉스반도체 | Method of forming a copper wiring in a semiconductor device |
| KR100347838B1 (en) * | 2000-03-07 | 2002-08-07 | 학교법인 포항공과대학교 | Process for improving the thermal stability of liquid organocuprous precursors |
| DE10228050A1 (en) * | 2002-06-24 | 2004-01-15 | Merck Patent Gmbh | Dikupfer (I) oxolate complexes as precursor substances for metallic copper deposition |
| DE10319454A1 (en) | 2003-04-29 | 2004-11-18 | Merck Patent Gmbh | Dikupfer (I) oxalate complexes as a precursor for metallic copper deposition |
| CN100537837C (en) * | 2004-09-27 | 2009-09-09 | 株式会社爱发科 | Copper-containing film formation method |
| DE102009023952A1 (en) | 2009-06-04 | 2010-12-09 | DüRR DENTAL AG | Method for determining tooth color of e.g. dental prosthesis, involves providing difference between color values of images and tooth color pattern as measurement for correlating colors of tooth region and tooth color pattern |
| JP5779823B2 (en) * | 2010-11-17 | 2015-09-16 | ユーピー ケミカル カンパニー リミテッド | Diazadiene-based metal compound, method for producing the same, and method for forming a thin film using the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1001047A2 (en) * | 1998-11-10 | 2000-05-17 | Sharp Kabushiki Kaisha | Alkene ligand precursor and synthesis method |
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| US5144049A (en) * | 1991-02-04 | 1992-09-01 | Air Products And Chemicals, Inc. | Volatile liquid precursors for the chemical vapor deposition of copper |
| US5187300A (en) * | 1991-02-04 | 1993-02-16 | Air Products And Chemicals, Inc. | Volatile precursors for copper CVD |
| US5358743A (en) * | 1992-11-24 | 1994-10-25 | University Of New Mexico | Selective and blanket chemical vapor deposition of Cu from (β-diketonate)Cu(L)n by silica surface modification |
| JP3282392B2 (en) * | 1994-08-10 | 2002-05-13 | 三菱マテリアル株式会社 | Organocopper compounds for copper thin film formation by metalorganic chemical vapor deposition with high vapor pressure |
| US5744192A (en) * | 1996-11-08 | 1998-04-28 | Sharp Microelectronics Technology, Inc. | Method of using water vapor to increase the conductivity of cooper desposited with cu(hfac)TMVS |
-
1999
- 1999-04-15 KR KR1019990013236A patent/KR100298125B1/en not_active IP Right Cessation
- 1999-12-07 RU RU2000118774/04A patent/RU2181725C2/en not_active IP Right Cessation
- 1999-12-07 EP EP99959960A patent/EP1102872A4/en not_active Withdrawn
- 1999-12-07 CN CNB998026484A patent/CN1194117C/en not_active Expired - Fee Related
- 1999-12-07 JP JP2000612535A patent/JP2002542397A/en active Pending
- 1999-12-07 WO PCT/KR1999/000743 patent/WO2000063461A1/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1001047A2 (en) * | 1998-11-10 | 2000-05-17 | Sharp Kabushiki Kaisha | Alkene ligand precursor and synthesis method |
Non-Patent Citations (4)
| Title |
|---|
| DATABASE CA [Online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; RHEWE, SHI-WOO ET AL: "Property of hfac (hexafluoroacetylacetonate)Cu(I)DMB (3,3-dimethyl-1- butene) as a liquid precursor for chemical vapor deposition of copper films" XP002473287 retrieved from STN Database accession no. 132:159098 & HAN'GUK CHAELYO HAKHOECHI , 9(11), 1148-1152 CODEN: HCHAEU; ISSN: 1225-0562, 1999, * |
| DOPPELT P ET AL: "Alkyne complexes of copper(I) (1,1,1,5,5,5-hexafluoro-2,4-pentanedion ato): syntheses and characterization of (eta<2>-bis(trimethylsilyl) acetylene) copper(I) (hfac), (mu-eta<2>-bis(trimethylsilyl) acetylene) bis(copper(I) (hfac)) and a series of (eta<2>-alkyne) Cu(hfac) complexes" JOURNAL OF ORGANOMETALLIC CHEMISTRY, ELSEVIER-SEQUOIA S.A. LAUSANNE, CH, vol. 517, no. 1, 28 June 1996 (1996-06-28), pages 53-62, XP004035961 ISSN: 0022-328X * |
| KANG S-W ET AL: "(hfac)Cu(I)(MP) (hfac=hexafluoroacetylacetonate, MP=4-methyl-1-pentene) and (hfac)Cu(I)(DMB) (DMB=3,3-dimethyl-1-bute ne) for the chemical vapor deposition of copper film" THIN SOLID FILMS, ELSEVIER-SEQUOIA S.A. LAUSANNE, CH, vol. 350, no. 1-2, 15 August 1999 (1999-08-15), pages 10-13, XP004180583 ISSN: 0040-6090 * |
| See also references of WO0063461A1 * |
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| KR100298125B1 (en) | 2001-09-13 |
| JP2002542397A (en) | 2002-12-10 |
| RU2181725C2 (en) | 2002-04-27 |
| CN1194117C (en) | 2005-03-23 |
| EP1102872A4 (en) | 2008-04-30 |
| WO2000063461A1 (en) | 2000-10-26 |
| CN1290309A (en) | 2001-04-04 |
| KR19990046683A (en) | 1999-07-05 |
| TW524881B (en) | 2003-03-21 |
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