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WO2003014134A1 - Precurseurs pour depot chimique en phase vapeur a partir de precurseur organometalliques - Google Patents

Precurseurs pour depot chimique en phase vapeur a partir de precurseur organometalliques Download PDF

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Publication number
WO2003014134A1
WO2003014134A1 PCT/GB2002/003657 GB0203657W WO03014134A1 WO 2003014134 A1 WO2003014134 A1 WO 2003014134A1 GB 0203657 W GB0203657 W GB 0203657W WO 03014134 A1 WO03014134 A1 WO 03014134A1
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WO
WIPO (PCT)
Prior art keywords
dbm
ligand
deposition
precursor
oet
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.)
Ceased
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PCT/GB2002/003657
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English (en)
Inventor
Copeland Jones Anthony
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.)
Inorgtech Ltd
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Inorgtech Ltd
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Filing date
Publication date
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Publication of WO2003014134A1 publication Critical patent/WO2003014134A1/fr
Anticipated expiration legal-status Critical
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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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/005—Compounds of elements of Group 5 of the Periodic Table without metal-carbon linkages
    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages

Definitions

  • This invention concerns precursors for metalorganic chemical vapour deposition (MOCVD).
  • MOCVD metalorganic chemical vapour deposition
  • This invention is particularly, but not exclusively, concerned with precursors for growth of lead scandium tantalate
  • PST is a very sensitive pyroelectric material, which has several potential applications in uncooled thermal imaging, including military night vision, fire detection, medical diagnosis and automotive vision enhancement.
  • MOCVD offers the most flexible approach having the potential for large area growth, excellent film uniformity and compositional control, high film densities and deposition rates
  • MOCVD processes are compatible with existing silicon chemical vapour deposition processes.
  • liquid injection MOCVD has been used to deposit PST using a single solution of Pb(thd) 2 , Sc(thd) 3 and Ta(OEt) 5 dissolved in tetrahydrofuran.
  • thd is 2,2,6,6- tetramethylheptane-3,5-dionate.
  • co-precursors should, as far as possible, be compatible with similar physical properties (e.g. solubility, vapour pressure etc.) and should not undergo deleterious reactions with each other in solution. They should also evaporate at similar temperatures and deposit oxide films at similar substrate temperatures.
  • Pb(thd) 2 , Sc(thd) 3 and Ta(OEt) 5 allowed PST growth at low temperatures, these precursors are not compatible. For instance, problems were encountered due to the low volatility of the Sc precursor relative to the Pb and Ta precursors. Due to the low volatility of Sc(thd) 3 , a relatively high evaporator temperature, typically of 250
  • a more thermally stable precursor is, therefore, required in order to improve the MOCVD process for the deposition of Sc 2 O 3 and Pb(Sco. 5 Tao .5 )0 3 .
  • a tantalum oxide source which is more thermally stable than Ta(OEt) 5 would also be beneficial for the MOCVD of other complex oxides containing tantalum, such as strontium bismuth tantalate, SrBi 2 Ta 2 Og (SBT) and strontium bismuth tantalate niobate, SrBi 2 (Ta x Nbi -x ) 2 Og (SBTN), where it is desirable to use a tantalum precursor which deposits oxide in a similar temperature regime to the commonly used Sr and Bi precursors, Sr(thd) 2 and
  • a more thermally stable Ta oxide precursor may also be desirable for the coating of glass substrates by CVD, such as on a float glass production line in which substrate temperatures in the order of 600°C are generally employed. It has been surprisingly found that the dibenzoylmethanate group (1 ,3- diphenyl-1 ,3-propanedionate) can be used as a ligand to produce a tantalum oxide and other metal oxide precursors for deposition of metal oxides by chemical vapour deposition techniques.
  • the present invention provides metal
  • the present invention provides a method
  • the present invention further provides a method of depositing metal
  • Preferred precursors according to the invention have the following general formula:
  • M is a metal selected from Ta, Pb, Ti, Ni, Cu, La, Nb, In and Zr,
  • L is a ligand
  • x is 0 or the valency of the metal minus y
  • D is a ⁇ -
  • R 1 -C(O)CH(O)C-R 2 wherein R 1 is an aryl group and R 2 is an aryl group or an alkyl group and y is 1 to 4.
  • the preferred ligand L is an alkoxy group having from 1 to 4 carbon atoms. Methoxy, ethoxy and isopropoxy groups are preferred ligands L.
  • the preferred ligand D is a dibenzoylmethanate group (dbm).
  • a preferred alternative might be benzoylacetonate (1-phenyl-1 ,3- butanedionate).
  • Important precursors according to the invention include the following: Ta(OEt) 4 (dbm) Ti(OP ⁇ j ) 2 (dbm) 2
  • L' is a unidentate or multidentate donor ligand Ni(dbm) 2 Me 2 ln(dbm) Cu"(dbm) 2 Nb(OEt) 4 dbm
  • L is selected from alkene (e.g. trimethylvinyl silane, trimethoxy vinylsilane, triethoxyvinylsilane), alkyne , trialkyl phosphine (e.g. PEt 3 , PMe 3 etc) and trialkyl phosphite, eg. P(OEt) 3 ,
  • precursors for chemical vapour deposition techniques that have dbm as a ligand have increased thermal stability relative to precursors containing other ⁇ -diketonate ligands, such as
  • thd and acetylacetonate (acac), which can lead to improved performance in certain liquid injection MOCVD applications, which may require the use of relatively high evaporator or substrate temperatures.
  • the aryl group or groups of the ligand D may be substituted and it is envisaged that different substituents may alter the thermal stability and/or volatility of the resultant precursor possibly due to the electron attracting or donating property of the substituents.
  • a suitable precursor could be produced having, for example, dbm or a suitably substituted dbm as a ligand.
  • electron donating groups such as NH 2
  • PR 3 NR 3
  • R alkyl
  • electron withdrawing groups such as NO 2 , CN, halide and SO 3 H.
  • One or two substituents may be provided on an aryl group.
  • Precursors according to the invention may be used in depositing single or mixed oxide layers or metal films. Examples of uses of precursors of the invention include the following:
  • Pb(dbm) 2 and its adducts with donor ligands, such as crown ethers, may be used with scandium and tantalum precursors for deposition of Pb(Sco .5 ,Tao .5 )0 3 and with zirconium and titanium precursors for deposition of Pb(Zr,Ti)O 3 .
  • La(dbm) 3 (L) may be used with a manganese precursor for deposition of LaMnO 3 and with a nickel precursor for deposition of LaNiO 3 .
  • Ni(dbm) 2 may be used as a precursor for deposition of LaNiO 3 .
  • Ti(OP ⁇ J ) 2 (dbm) 2 may be used in the deposition of TiO 2 , (Ba.Sr) TiO 3 (BST) and Pb (Zr, Ti)O 3 (PZT).
  • Cu"(dbm) 2 and Cu'(dbm)(L) may be used as precursors for depositing copper oxide or copper films by chemical vapour deposition.
  • Me 2 ln(dbm) may be used as a precursor for depositing indium oxide layers alone or with tin.
  • Ta(OEt) (dbm) has potential applications as a precursor for Pb(Sco .5 ,Tao .5 )0 3 and for chemical vapour deposition of SrBi 2 Ta 2 O g and
  • Nb(OEt) (dbm) has potential applications for the MOCVD of
  • Zr(dbm) has applications in ZrO 2 CVD at high substrate temperatures.
  • Figure 1 shows an envisaged structure for Ta(OEt) 4 (dbm);
  • Figure 2 shows an envisaged structure for Nb(OEt) (dbm);
  • Figure 3 shows an envisaged structure for lead bis-(dbm);
  • Figure 4 is a graph showing the variation of the growth rate of tantalum oxide with substrate temperature for Ta(OEt) (dbm) on silicon substrate;
  • Figure 5 is a graph showing the variation of tantalum oxide growth rate with evaporator temperature for Ta(OEt) (dbm) on silicon substrate;
  • Figure 6 is a graph showing the variation of niobiumoxide growth rate with substrate temperature for Nb(OEt) (dbm); and Figure 7 is a graph showing variation of niobium oxide growth rate with evaporator temperature for Nb(OEt) (dbm).
  • Nb(OEt) 4 (dbm) was prepared using identical methodology to
  • FIG. 1 of the drawings shows the envisaged structure for Nb(OEt) 4 (dbm).
  • the first being always a silicon one towards the front of the susceptor and the second a sapphire one towards the rear of the susceptor. In all cases the deposition on the sapphire was thicker.
  • the results are a thickness obtained for the injection of a fixed volume of precursor. Two silicon substrates were used. The thickness data listed below in Table 7 is taken from the substrate placed towards the front of the susceptor.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

L'invention concerne des composés métalliques qui comprennent un groupe β-dicétonate contenant un groupe aryle ou un dérivé substitué de ce dernier en tant qu'au moins un ligand desdits composés. L'invention concerne également l'utilisation desdits composés métalliques dans des techniques de dépôt chimique en phase vapeur.
PCT/GB2002/003657 2001-08-07 2002-08-07 Precurseurs pour depot chimique en phase vapeur a partir de precurseur organometalliques Ceased WO2003014134A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0119224.4 2001-08-07
GBGB0119224.4A GB0119224D0 (en) 2001-08-07 2001-08-07 Precursors for metalorganic chemical vapour deposition

Publications (1)

Publication Number Publication Date
WO2003014134A1 true WO2003014134A1 (fr) 2003-02-20

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PCT/GB2002/003657 Ceased WO2003014134A1 (fr) 2001-08-07 2002-08-07 Precurseurs pour depot chimique en phase vapeur a partir de precurseur organometalliques

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GB (1) GB0119224D0 (fr)
WO (1) WO2003014134A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007058571A1 (de) * 2007-12-05 2009-06-10 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Substrat mit einer Kupfer enthaltenden Beschichtung und Verfahren zu deren Herstellung mittels Atomic Layer Deposition
US7601278B2 (en) * 2003-07-04 2009-10-13 Nxp B.V. Precursor solution, method of preparation thereof and use thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3153000A (en) * 1960-09-28 1964-10-13 Hughes Aircraft Co Ordered organo-silicon-chelated titanium oxide copolymers and methods of making same
WO1984003042A1 (fr) * 1983-02-09 1984-08-16 Byk Gulden Lomberg Chem Fab Procede pour la fabrication de preparations therapeutiques antineoplastiques
US6099903A (en) * 1999-05-19 2000-08-08 Research Foundation Of State University Of New York MOCVD processes using precursors based on organometalloid ligands
WO2000069863A1 (fr) * 1999-05-19 2000-11-23 Research Foundation Of State University Of New York Precurseurs de depot chimique metal-oxyde en phase vapeur a base de ligands organometalloidiques

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3153000A (en) * 1960-09-28 1964-10-13 Hughes Aircraft Co Ordered organo-silicon-chelated titanium oxide copolymers and methods of making same
WO1984003042A1 (fr) * 1983-02-09 1984-08-16 Byk Gulden Lomberg Chem Fab Procede pour la fabrication de preparations therapeutiques antineoplastiques
US6099903A (en) * 1999-05-19 2000-08-08 Research Foundation Of State University Of New York MOCVD processes using precursors based on organometalloid ligands
WO2000069863A1 (fr) * 1999-05-19 2000-11-23 Research Foundation Of State University Of New York Precurseurs de depot chimique metal-oxyde en phase vapeur a base de ligands organometalloidiques

Non-Patent Citations (9)

* Cited by examiner, † Cited by third party
Title
ANAL. CHIM. ACTA (1963), 28, 227-35 *
BULLETIN OF THE KOREAN CHEMICAL SOCIETY (1996), 17(11), 1023-1031 *
CHEMICAL VAPOR DEPOSITION (2002), 8(3), 110-116 PUBLISHED IN: ADV. MATER. (WEINHEIM, GER.), 14(9), 2002 *
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; LIM, JONG TAE ET AL: "Study on the development of CVD precursors. II. Synthesis and properties of new lanthanum.beta.-diketonates", XP002219908, retrieved from STN Database accession no. 126:69303 *
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; STARY, J. ET AL: "Systematic study of the solvent extraction of metal.beta.-diketonates", XP002219906, retrieved from STN Database accession no. 58:76615 *
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; TROYANOV, S. I. ET AL: "Packing in crystal structures of metal.beta.-diketonates used in MOCVD and its correlation to volatility", XP002219907, retrieved from STN Database accession no. 128:264125 *
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; WILLIAMS, PAUL A. ET AL: "The unusual thermal stabilization of MOCVD precursors by the dibenzoyl methanate group: liquid injection MOCVD of tantalum oxide and niobium oxide using M(OEt)4(dbm) precursors", XP002219909, retrieved from STN Database accession no. 137:145913 CA *
KAPOOR, R. N. ET AL: "Organic compounds of niobium and tantalum. Reactions of niobium and tantalum pentaethoxides with dibenzoylmethane", BULL. CHEM. SOC. JPN. (1967), 40(6), 1384-6, 1967, XP002219905 *
PROCEEDINGS - ELECTROCHEMICAL SOCIETY (1997), 97-25(CHEMICAL VAPOR DEPOSITION), 886-892 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7601278B2 (en) * 2003-07-04 2009-10-13 Nxp B.V. Precursor solution, method of preparation thereof and use thereof
DE102007058571A1 (de) * 2007-12-05 2009-06-10 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Substrat mit einer Kupfer enthaltenden Beschichtung und Verfahren zu deren Herstellung mittels Atomic Layer Deposition
DE102007058571B4 (de) * 2007-12-05 2012-02-16 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Substrat mit einer Kupfer enthaltenden Beschichtung und Verfahren zu deren Herstellung mittels Atomic Layer Deposition und Verwendung des Verfahrens
US8507038B2 (en) 2007-12-05 2013-08-13 Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. Substrate having a coating comprising copper and method for the production thereof by means of atomic layer deposition

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GB0119224D0 (en) 2001-09-26

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