WO2000063461A1 - Nouveaux precurseurs organo-cuivreux destines au depot chimique en phase vapeur d'un film de cuivre - Google Patents

Nouveaux precurseurs organo-cuivreux destines au depot chimique en phase vapeur d'un film de cuivre Download PDF

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Publication number
WO2000063461A1
WO2000063461A1 PCT/KR1999/000743 KR9900743W WO0063461A1 WO 2000063461 A1 WO2000063461 A1 WO 2000063461A1 KR 9900743 W KR9900743 W KR 9900743W WO 0063461 A1 WO0063461 A1 WO 0063461A1
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WO
WIPO (PCT)
Prior art keywords
copper film
organocuprous
precursors
hfac
compound
Prior art date
Application number
PCT/KR1999/000743
Other languages
English (en)
Inventor
Shi Woo Rhee
Sang Ho Han
Sang Woo Kang
Original Assignee
Postech Foundation
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 Postech Foundation filed Critical Postech Foundation
Priority to EP99959960A priority Critical patent/EP1102872A4/fr
Priority to JP2000612535A priority patent/JP2002542397A/ja
Publication of WO2000063461A1 publication Critical patent/WO2000063461A1/fr

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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 System
    • 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) .

Abstract

L'invention concerne un composé organo-cuivreux correspondant à la formule (I). On peut utiliser de manière pratique ce composé dans un procédé de dépôt chimique en phase vapeur, dans la production à grande échelle d'un film de cuivre dépourvu de contaminants et possédant une bonne stabilité thermique. Dans la formule (I), R1, R2 et R3 représentent chacun indépendamment un groupe alcoxy C1-8, aryle ou aryloxy, R4 et R5 représentent chacun indépendamment hydrogène, fluor, un groupe CnF2n+1 ou CnH2n+1, n étant un nombre entier compris entre 1 et 6, R6 représente hydrogène, fluor ou un groupe alkyle C1-4, et m vaut 1 ou 2 ; lorsque m vaut 1, C=C représente C‰C, et lorsque m vaut 2, C=C représente C=C.
PCT/KR1999/000743 1999-04-15 1999-12-07 Nouveaux precurseurs organo-cuivreux destines au depot chimique en phase vapeur d'un film de cuivre WO2000063461A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP99959960A EP1102872A4 (fr) 1999-04-15 1999-12-07 Nouveaux precurseurs organo-cuivreux destines au depot chimique en phase vapeur d'un film de cuivre
JP2000612535A JP2002542397A (ja) 1999-04-15 1999-12-07 銅薄膜の化学蒸着のための有機銅（ｉ）前駆体

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1999/13236 1999-04-15
KR1019990013236A KR100298125B1 (ko) 1999-04-15 1999-04-15 구리의 화학 증착에 유용한 유기 구리 전구체

Publications (1)

Publication Number Publication Date
WO2000063461A1 true WO2000063461A1 (fr) 2000-10-26

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PCT/KR1999/000743 WO2000063461A1 (fr) 1999-04-15 1999-12-07 Nouveaux precurseurs organo-cuivreux destines au depot chimique en phase vapeur d'un film de cuivre

Country Status (7)

Country Link
EP (1) EP1102872A4 (fr)
JP (1) JP2002542397A (fr)
KR (1) KR100298125B1 (fr)
CN (1) CN1194117C (fr)
RU (1) RU2181725C2 (fr)
TW (1) TW524881B (fr)
WO (1) WO2000063461A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6337276B1 (en) * 1999-12-22 2002-01-08 Hyundai Electronics Industries Co., Ltd. Methods of forming a copper wiring in a semiconductor device using chemical vapor deposition
US6492268B1 (en) * 1999-12-22 2002-12-10 Hyundai Electronics Industries Co., Ltd. Method of forming a copper wiring in a semiconductor device
WO2004000850A1 (fr) * 2002-06-24 2003-12-31 Merck Patent Gmbh Complexes oxalate de dicuivre(i) utilises en tant que substances precurseurs pour deposer du cuivre metallique
WO2004096816A1 (fr) * 2003-04-29 2004-11-11 Basf Aktiengesellschaft Complexes d'oxalate de dicuivre(i) comme precurseurs pour le depot de cuivre metallique
KR100944144B1 (ko) * 1997-10-03 2010-02-24 메리알 돼지 서코바이러스, 백신 및 진단시약
DE102009023952A1 (de) 2009-06-04 2010-12-09 DüRR DENTAL AG Verfahren und Vorrichtung zur Bestimmung von Zahnfarben

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100347838B1 (ko) * 2000-03-07 2002-08-07 학교법인 포항공과대학교 액상 유기구리 전구체의 열적 안정성 향상방법
US20090098290A1 (en) * 2004-09-27 2009-04-16 Mikio Watanabe Process for formation of copper-containing films
KR101719526B1 (ko) 2010-11-17 2017-04-04 주식회사 유피케미칼 다이아자다이엔계 금속 화합물, 이의 제조 방법 및 이를 이용한 박막 형성 방법

Citations (5)

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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
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
JPH0853468A (ja) * 1994-08-10 1996-02-27 Mitsubishi Materials Corp 蒸気圧の高い有機金属化学蒸着による銅薄膜形成用有機銅化合物
EP0533070B1 (fr) * 1991-09-20 1996-12-18 Air Products And Chemicals, Inc. Précurseurs volatiles pour la déposition chimique en phase vapeur de cuivre
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

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US6090963A (en) * 1998-11-10 2000-07-18 Sharp Laboratories Of America, Inc. Alkene ligand precursor and synthesis method

Patent Citations (6)

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Publication number Priority date Publication date Assignee Title
US5144049A (en) * 1991-02-04 1992-09-01 Air Products And Chemicals, Inc. Volatile liquid precursors for the chemical vapor deposition of copper
EP0533070B1 (fr) * 1991-09-20 1996-12-18 Air Products And Chemicals, Inc. Précurseurs volatiles pour la déposition chimique en phase vapeur de cuivre
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
JPH0853468A (ja) * 1994-08-10 1996-02-27 Mitsubishi Materials Corp 蒸気圧の高い有機金属化学蒸着による銅薄膜形成用有機銅化合物
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
JPH10140352A (ja) * 1996-11-08 1998-05-26 Sharp Corp 銅前駆体混合物、およびそれを用いるｃｖｄ銅の形成方法、並びに被着性銅導体インターフェース

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100944144B1 (ko) * 1997-10-03 2010-02-24 메리알 돼지 서코바이러스, 백신 및 진단시약
US6337276B1 (en) * 1999-12-22 2002-01-08 Hyundai Electronics Industries Co., Ltd. Methods of forming a copper wiring in a semiconductor device using chemical vapor deposition
US6492268B1 (en) * 1999-12-22 2002-12-10 Hyundai Electronics Industries Co., Ltd. Method of forming a copper wiring in a semiconductor device
DE10064042B4 (de) * 1999-12-22 2009-10-01 Hyundai Electronics Industries Co., Ltd., Ichon Verfahren zur Herstellung einer Kupferverdrahtung in einem Halbleiterbauelement
WO2004000850A1 (fr) * 2002-06-24 2003-12-31 Merck Patent Gmbh Complexes oxalate de dicuivre(i) utilises en tant que substances precurseurs pour deposer du cuivre metallique
US7169947B2 (en) 2002-06-24 2007-01-30 Basf Aktiengesellischaft Dicopper(I) oxalate complexes for use as precursor substances in metallic copper deposition
KR100941529B1 (ko) * 2002-06-24 2010-02-10 바스프 에스이 금속 구리 침착에서 전구체 물질로 사용하기 위한이구리(ｉ)옥살레이트 착체
WO2004096816A1 (fr) * 2003-04-29 2004-11-11 Basf Aktiengesellschaft Complexes d'oxalate de dicuivre(i) comme precurseurs pour le depot de cuivre metallique
US7393555B2 (en) 2003-04-29 2008-07-01 Basf Aktiengesellschaft Dicopper(I) oxalate complexes as precursor for metallic copper deposition
DE102009023952A1 (de) 2009-06-04 2010-12-09 DüRR DENTAL AG Verfahren und Vorrichtung zur Bestimmung von Zahnfarben

Also Published As

Publication number Publication date
EP1102872A1 (fr) 2001-05-30
CN1290309A (zh) 2001-04-04
JP2002542397A (ja) 2002-12-10
RU2181725C2 (ru) 2002-04-27
EP1102872A4 (fr) 2008-04-30
KR19990046683A (ko) 1999-07-05
KR100298125B1 (ko) 2001-09-13
CN1194117C (zh) 2005-03-23
TW524881B (en) 2003-03-21

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