EP1102872A1 - 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

Info

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Withdrawn
Application number
EP99959960A
Other languages
German (de)
English (en)
Other versions
EP1102872A4 (fr
Inventor
Shi Woo Kyosu Apt. 9-1301 RHEE
Sang Ho Hyojagreen Apt. HAN
Sang Woo Kang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Pohang University of Science and Technology Foundation POSTECH
Original Assignee
Pohang University of Science and Technology Foundation POSTECH
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 Pohang University of Science and Technology Foundation POSTECH filed Critical Pohang University of Science and Technology Foundation POSTECH
Publication of EP1102872A1 publication Critical patent/EP1102872A1/fr
Publication of EP1102872A4 publication Critical patent/EP1102872A4/fr
Withdrawn legal-status Critical Current

Links

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) .

Landscapes

  • 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

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.
EP99959960A 1999-04-15 1999-12-07 Nouveaux precurseurs organo-cuivreux destines au depot chimique en phase vapeur d'un film de cuivre Withdrawn EP1102872A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
KR9913236 1999-04-15
KR1019990013236A KR100298125B1 (ko) 1999-04-15 1999-04-15 구리의 화학 증착에 유용한 유기 구리 전구체
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

Publications (2)

Publication Number Publication Date
EP1102872A1 true EP1102872A1 (fr) 2001-05-30
EP1102872A4 EP1102872A4 (fr) 2008-04-30

Family

ID=19580072

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99959960A Withdrawn EP1102872A4 (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)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
UA78180C2 (uk) * 1997-10-03 2007-03-15 Меріаль Кільцевий вірус свині типу ii, вакцини та діагностичні реагенти
KR100358045B1 (ko) * 1999-12-22 2002-10-25 주식회사 하이닉스반도체 반도체 소자의 구리 금속 배선 형성 방법
KR100338112B1 (ko) * 1999-12-22 2002-05-24 박종섭 반도체 소자의 구리 금속 배선 형성 방법
KR100347838B1 (ko) * 2000-03-07 2002-08-07 학교법인 포항공과대학교 액상 유기구리 전구체의 열적 안정성 향상방법
DE10228050A1 (de) 2002-06-24 2004-01-15 Merck Patent Gmbh Dikupfer(I)oxolat-Komplexe als Precursor-Substanzen zur metallischen Kupferabscheidung
DE10319454A1 (de) 2003-04-29 2004-11-18 Merck Patent Gmbh Dikupfer(I)oxalat-Komplexe als Precursor zur metallischen Kupferabscheidung
WO2006035784A1 (fr) * 2004-09-27 2006-04-06 Ulvac, Inc. Procédé de formation de film contenant du cuivre
DE102009023952A1 (de) 2009-06-04 2010-12-09 DüRR DENTAL AG Verfahren und Vorrichtung zur Bestimmung von Zahnfarben
JP5779823B2 (ja) * 2010-11-17 2015-09-16 ユーピー ケミカル カンパニー リミテッド ジアザジエン系金属化合物、これの製造方法及びこれを利用した薄膜形成方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1001047A2 (fr) * 1998-11-10 2000-05-17 Sharp Kabushiki Kaisha Précurseur de ligand à base d'alcène et procédé de synthèse

Family Cites Families (5)

* Cited by examiner, † Cited by third party
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
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 (ja) * 1994-08-10 2002-05-13 三菱マテリアル株式会社 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

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1001047A2 (fr) * 1998-11-10 2000-05-17 Sharp Kabushiki Kaisha Précurseur de ligand à base d'alcène et procédé de synthèse

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
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 *

Also Published As

Publication number Publication date
JP2002542397A (ja) 2002-12-10
CN1194117C (zh) 2005-03-23
WO2000063461A1 (fr) 2000-10-26
EP1102872A4 (fr) 2008-04-30
RU2181725C2 (ru) 2002-04-27
KR19990046683A (ko) 1999-07-05
KR100298125B1 (ko) 2001-09-13
TW524881B (en) 2003-03-21
CN1290309A (zh) 2001-04-04

Similar Documents

Publication Publication Date Title
US5187300A (en) Volatile precursors for copper CVD
US7329768B2 (en) Chemical vapor deposition precursors for deposition of tantalum-based materials
US4992305A (en) Chemical vapor deposition of transistion metals
US7064224B1 (en) Organometallic complexes and their use as precursors to deposit metal films
US20070160761A1 (en) Tungsten and molybdenum compounds and thier use for chemical vapour deposition (CVD)
US7442407B2 (en) Tantalum and niobium compounds and their use for chemical vapour deposition (CVD)
JP2006241137A (ja) 揮発性金属β−ケトイミナート錯体
US7396949B2 (en) Class of volatile compounds for the deposition of thin films of metals and metal compounds
EP3538533A1 (fr) Complexes métalliques contenant des ligands de cyclopentadiényle
US10723749B2 (en) Metal complexes containing allyl ligands
EP1102872A1 (fr) Nouveaux precurseurs organo-cuivreux destines au depot chimique en phase vapeur d&#39;un film de cuivre
US6982341B1 (en) Volatile copper aminoalkoxide complex and deposition of copper thin film using same
US6090964A (en) Organocuprous precursors for chemical vapor deposition of a copper film
EP1121474A2 (fr) Precurseur du type organocuivre pour le depot chimique en phase vapeur
JP2876980B2 (ja) 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
JPH0853468A (ja) 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
JP2757762B2 (ja) 蒸気圧の高い有機金属化学蒸着による銀薄膜形成用有機銀化合物
JPH0853470A (ja) 蒸気圧の高い有機金属化学蒸着による銀薄膜形成用有機銀化合物
JPH07188256A (ja) 蒸気圧の高い有機金属化学蒸着による銀薄膜形成用有機銀化合物
KR100600468B1 (ko) 시클로알켄 구리 전구체의 제조방법
WO2018086730A1 (fr) Complexes métalliques contenant des ligands de cyclopentadiényle
JPH07133285A (ja) 蒸気圧の高い有機金属化学蒸着による銀薄膜形成用有機銀化合物
KR20160062675A (ko) 신규 니켈-비스베타케토이미네이트 전구체 및 이를 이용한 니켈 함유 필름 증착방법
KR20000025984A (ko) 구리의 화학 증착에 유용한 액상 전구체
JPH0770162A (ja) 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

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20000706

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

A4 Supplementary search report drawn up and despatched

Effective date: 20080402

17Q First examination report despatched

Effective date: 20090116

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20090528