WO2002086189A1 - Nouveaux precurseurs du cuivre a substitution cycloalcene pour depot chimique en phase vapeur de couches minces de cuivre - Google Patents

Nouveaux precurseurs du cuivre a substitution cycloalcene pour depot chimique en phase vapeur de couches minces de cuivre Download PDF

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Publication number
WO2002086189A1
WO2002086189A1 PCT/JP2001/003257 JP0103257W WO02086189A1 WO 2002086189 A1 WO2002086189 A1 WO 2002086189A1 JP 0103257 W JP0103257 W JP 0103257W WO 02086189 A1 WO02086189 A1 WO 02086189A1
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WO
WIPO (PCT)
Prior art keywords
copper
cyclohexene
methyl
hfac
vapor deposition
Prior art date
Application number
PCT/JP2001/003257
Other languages
English (en)
Inventor
Wei-Wei Zhuang
Tue Nguyen
Lawrence J. Charneski
David R. Evans
Sheng Teng Hsu
Original Assignee
Sharp Kabushiki Kaisha
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sharp Kabushiki Kaisha filed Critical Sharp Kabushiki Kaisha
Priority to PCT/JP2001/003257 priority Critical patent/WO2002086189A1/fr
Priority to JP2002583699A priority patent/JP3998138B2/ja
Priority to KR1020037013540A priority patent/KR100600468B1/ko
Priority to EP01919965A priority patent/EP1387898A4/fr
Publication of WO2002086189A1 publication Critical patent/WO2002086189A1/fr

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/77—Preparation of chelates of aldehydes or ketones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/92—Ketonic chelates
    • 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

Definitions

  • This invention relates to the synthesis of volatile liquid copper precursors and their applications in chemical vapor deposition of copper metal thin films.
  • copper metal thin film material is considered to be ideal for use as metal interconnections in integrated circuits.
  • Chemical vapor deposition (CVD) of copper requires the use of a stable yet volatile precursor.
  • the cost of the copper precursor is an issue.
  • the copper precursor must have good adhesion to metal nitride coated substrates, low resistivity, ⁇ 1,8 ⁇ -cm, excellent conformity to surface structures, and good electromigration resistance.
  • CVD processes generally performed at elevated temperatures, the copper precursor must have a vapor pressure high enough to achieve a reasonable deposition rate, and must also be stable at deposition temperatures, without any decomposition in the CVD liquid delivery line or during vaporizer.
  • Copper metal thin films may be prepared via chemical vapor deposition using a variety of copper precursors.
  • D. B. Beach et ⁇ Z Low-Temperature Chemical Vapor Deposition of High Purity Copper from an Organometallic Source, Chem. Mater. (2) 216 (1990) obtained pure copper films via CVD by using At about the same time,
  • Copper® fluorinated p-di etonate complexes were synthesize* by Gerald Doyle, as described in U.S. Patent No. 4,385,005, granted May 24, 1983, for Process for separating unsaturated hydrocarbons using copper or silver complexes with fluorinated diketonates, and U.S. Patent No.4,425,281, granted Jan 10, 1984, for Copper or silver complexes with fluorinated diketones and unsaturated ligands, in which he presented the synthesis method and its application in the separation of unsaturated organic hydrocarbons.
  • 1,5-dimethyl l,5 «cyclooctadiene copper(I)hexafluoroacetylacetonate mixed with 1,6-dimethyl 1,5-cyclooctadiene copper(I)hexafluoroacetylacetonate ((DMCOD)Cu(hfac)) and hexyne copper(I)hexafluoroacetylacetonate ((HYN)Cu(hfac)) were evaluated in detail.
  • the copper thin films deposited using (DMCOD)Cu(hfac) have very good adhesion to metal or metal nitride substrates, but a high resistivity, ⁇ .e., '-2,5 ⁇ 'c , and a low deposition rate, whereas by using (HyN)Cu(hfac), the copper film has poor adhesion to a TiN substrate, and high resistivity, i.e. ⁇ ⁇ 2.1 ⁇ -cm.
  • This liquid copper precursor has been used for the preparation of copper metal thin films via CVD for some time, but still has some drawbacks: stability, the poor adhesion of the copper film, and the cost o£the trimethylvinylsilane stabilizer are significant impediments to the widespread use of this technique.
  • An object of the invention is to provide a series of new high volatile liquid copper precursors for chemical vapor deposition of copper metal thin films.
  • Another object of the invention is to provide such precursors in an economical and stable form.
  • Fig. 1 depiots the structure of (n-R ' m-cyclohexene)Cu(I)(hfac).
  • Fig. 2. depicts the structure of (n-R-m-cyclo ⁇ entene)Cu(I)(hfac).
  • Fig. 3 depicts the structure of (l»methyl-l-cyclohexene) Cu(I)(hfac).
  • the invention involves the chemical vapor deposition (CVD) synthesis of a series of volatile copper precursors, to form copper metal thin films, and the synthesis of the precursors.
  • the copper films deposited using these new liquid copper precursors exhibit excellent electrical properties, and good adhesion to metal and metal nitride substrates, such as W, Ti, TiN, Ta, TaN, Al, Pt, and the like.
  • a precursor must: a. have a high volatile liquid phase and a high deposition rate of copper to form a copper thin film; b. be stable at room temperature to provide easy storage and handling; and c. have reasonable synthesis cost for commercialization.
  • Copper films prepared via CVD using this new copper precursor must; a. have good adhesion to metal and metal nitride substrates, such as TiN, WN, TaN, etc.; b, have low resistivity, ⁇ 1.9 ⁇ -cm; c. have high electromigration resistance; and d. have excellent conformity to extreme surface morphology.
  • the invention described herein includes the preparation of a new, highly volatile liquid thin metal copper precursor, known as (l-methyl-l-cyclohe ⁇ ene)-copper(I) hexa luoroacetylacetonate, or (lMlCH)Cu(I)(hfac).
  • the price for 1-methyM-cyclohexene is' approximately US$120,00 for lOOg, which is much lower than that of trimethylvinylsilane, used in the prior art, whic generally costs about US$180.00 for lOOg.
  • Experimental use of this precursor in CVD tests have proven that this new, highly volatile liquid copper thin metal precursor has the desired properties and meets all of the requirements listed above.
  • the copper films deposited using these new liquid copper precursors have exhibited excellent electrical properties, and good adhesion to metal and metal nitride substrates, such as , Ti, TiN, Ta, TaN, Al, Pt, and the like.
  • metal and metal nitride substrates such as , Ti, TiN, Ta, TaN, Al, Pt, and the like.
  • organometaHic copper complexes are represented by the structural formula (n-R-m-cyclohexene)Cu(0(hfac), shown in Fig, 1, or (n-R-m-cyelopentene) Cu(I)(hfac), shown in Fig.
  • R is alkyl, such as methyl and ethyl
  • R is CHs, whereby (l-methyl « l-cyclohexene)Ou(I)(hfac) compound is formed, as shown in Fig. 3.
  • L is unsaturated organic hydrocarbon l gand.
  • the green filtrate is stripped under vacuum for two hours and then heated to 35°C, under vacuum, for another half-hour of stripping. This produces a green liquid organometallic copper compound containing a small number of little green crystals, which is then filtered through a fine filter (I ⁇ m) to yield 145.7g of product, having a yield of 82.64%, based on hfac.
  • the theoretical yield based on ,H(hfac) is 176.8g.
  • 1-methyl-l-cyclohexene (6,437 g) was introduced into the product (138.621, total of 145.058 gram), in which the product contained 4.44% free 1-methyl-l-oyclohexene.
  • the NMR structural analysis was carried out on a QE 800 MHz
  • the results of copper metal thin film deposition via CVD using (lMlCH)Cu(hfac) liquid precursor were very good.
  • the copper thin films have shown good adhesion to metal and metal nitride substrates, low resistivity, - 1.8 ⁇ « cm, and very good reproducibility.
  • the precursor is very volatile, and an extremely high deposition rate, approximately 500 ⁇ per minute using 0.1 ml/ in liquid injection rate at 50°C of very low vaporizer temperature, has been achieved,

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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)

Abstract

La présente invention concerne un procédé de formation d'un précurseur volatil du cuivre pour dépôt chimique en phase vapeur de couches minces de cuivre. Ce procédé implique la formation d'un liquide volatile représenté par la formule (n-R-m-cyclohexène)Cu(I)(hfac) ou (n-R-m-cyclopentène)Cu(I)(hfac), n et m valant 1 à 6, et R étant alkyle, tel que méthyle et éthyle.
PCT/JP2001/003257 2001-04-16 2001-04-16 Nouveaux precurseurs du cuivre a substitution cycloalcene pour depot chimique en phase vapeur de couches minces de cuivre WO2002086189A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
PCT/JP2001/003257 WO2002086189A1 (fr) 2001-04-16 2001-04-16 Nouveaux precurseurs du cuivre a substitution cycloalcene pour depot chimique en phase vapeur de couches minces de cuivre
JP2002583699A JP3998138B2 (ja) 2001-04-16 2001-04-16 銅金属薄膜の化学蒸着のための置換型シクロアルケン新規銅前駆物質
KR1020037013540A KR100600468B1 (ko) 2001-04-16 2001-04-16 시클로알켄 구리 전구체의 제조방법
EP01919965A EP1387898A4 (fr) 2001-04-16 2001-04-16 Nouveaux precurseurs du cuivre a substitution cycloalcene pour depot chimique en phase vapeur de couches minces de cuivre

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2001/003257 WO2002086189A1 (fr) 2001-04-16 2001-04-16 Nouveaux precurseurs du cuivre a substitution cycloalcene pour depot chimique en phase vapeur de couches minces de cuivre

Publications (1)

Publication Number Publication Date
WO2002086189A1 true WO2002086189A1 (fr) 2002-10-31

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PCT/JP2001/003257 WO2002086189A1 (fr) 2001-04-16 2001-04-16 Nouveaux precurseurs du cuivre a substitution cycloalcene pour depot chimique en phase vapeur de couches minces de cuivre

Country Status (4)

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EP (1) EP1387898A4 (fr)
JP (1) JP3998138B2 (fr)
KR (1) KR100600468B1 (fr)
WO (1) WO2002086189A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5098516A (en) * 1990-12-31 1992-03-24 Air Products And Chemicals, Inc. Processes for the chemical vapor deposition of copper and etching of copper
JPH11200048A (ja) * 1998-01-21 1999-07-27 Tori Chemical Kenkyusho:Kk 銅合金膜形成材料及び銅合金膜形成方法
JP2001140075A (ja) * 1999-11-18 2001-05-22 Ube Ind Ltd 銅薄膜形成用有機銅錯体

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4385005A (en) * 1981-07-13 1983-05-24 Exxon Research And Engineering Co. Process for separating unsaturated hydrocarbons using copper or silver complexes with fluorinated diketonates
US4425281A (en) * 1981-07-13 1984-01-10 Exxon Research And Engineering Co. Copper or silver complexes with fluorinated diketones and unsaturated ligands
US6090963A (en) * 1998-11-10 2000-07-18 Sharp Laboratories Of America, Inc. Alkene ligand precursor and synthesis method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5098516A (en) * 1990-12-31 1992-03-24 Air Products And Chemicals, Inc. Processes for the chemical vapor deposition of copper and etching of copper
JPH11200048A (ja) * 1998-01-21 1999-07-27 Tori Chemical Kenkyusho:Kk 銅合金膜形成材料及び銅合金膜形成方法
JP2001140075A (ja) * 1999-11-18 2001-05-22 Ube Ind Ltd 銅薄膜形成用有機銅錯体

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
BAUM THOMAS H. ET AL.: "Ligand-stabilized copper(I) hexafluoroacetylacetonate complexes: NMR spectroscopy and the nature of the copper-alkene bond", JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 425, no. 1-2, 1992, pages 189 - 200, XP002943432 *
DOYLE G. ET AL.: "Alkene and carbon monoxide derivatives of copper(I) and silver(I) beta-diketonates", ORGANOMETALLICS, vol. 4, no. 5, 1985, pages 830 - 835, XP002943431 *
See also references of EP1387898A4 *

Also Published As

Publication number Publication date
JP3998138B2 (ja) 2007-10-24
EP1387898A4 (fr) 2008-08-13
JP2004526867A (ja) 2004-09-02
KR20030092077A (ko) 2003-12-03
EP1387898A1 (fr) 2004-02-11
KR100600468B1 (ko) 2006-07-13

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