WO2006021850A2 - Solution de precurseur de cvd destinee a produire un film mince contenant un metal de la serie des lanthanides, et procede de production d'un film mince faisant appel a ladite solution - Google Patents

Solution de precurseur de cvd destinee a produire un film mince contenant un metal de la serie des lanthanides, et procede de production d'un film mince faisant appel a ladite solution Download PDF

Info

Publication number
WO2006021850A2
WO2006021850A2 PCT/IB2005/002397 IB2005002397W WO2006021850A2 WO 2006021850 A2 WO2006021850 A2 WO 2006021850A2 IB 2005002397 W IB2005002397 W IB 2005002397W WO 2006021850 A2 WO2006021850 A2 WO 2006021850A2
Authority
WO
WIPO (PCT)
Prior art keywords
ligand
thin film
metal
lanthanide series
cvd precursor
Prior art date
Application number
PCT/IB2005/002397
Other languages
English (en)
Other versions
WO2006021850A3 (fr
Inventor
Yuzo Tasaki
Shuji Yoshizawa
Original Assignee
Toshima Mfg. Co. Ltd.
Saes Getters S.P.A.
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 Toshima Mfg. Co. Ltd., Saes Getters S.P.A. filed Critical Toshima Mfg. Co. Ltd.
Publication of WO2006021850A2 publication Critical patent/WO2006021850A2/fr
Publication of WO2006021850A3 publication Critical patent/WO2006021850A3/fr

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
    • C23C16/22—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 inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/405—Oxides of refractory metals or yttrium
    • 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
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
    • 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
    • C23C16/22—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 inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides

Definitions

  • the present invention relates to a CVD precursor used for production of a thin film by Chemical Vapor Deposition (CVD) method, which comprises a lanthanide series metal, and to a thin film obtained by using the same.
  • CVD Chemical Vapor Deposition
  • the present invention relates to a CVD precursor used for production of a thin film, which allows obtaining a thin film comprising a lanthanide series metal, by using a small amount of a precursor and solvent in the solution vaporization CVD method with low production cost.
  • a precursor vapor is supplied by a bubbling method consisting of using a precursor which is liquid at room temperature such as trimethylgallium (a precursor for GaAs thin films) ; and tetraethoxysilane (a precursor for SiO 2 thin films) , of bubbling a carrier gas through liquid precursors, of evaporating the precursor into a reactant vapor,' and of guiding the reactant vapor entrained in the carrier gas into a reactor.
  • a precursor which is liquid at room temperature such as trimethylgallium (a precursor for GaAs thin films) ; and tetraethoxysilane (a precursor for SiO 2 thin films)
  • the precursor when the precursor is a solid, widely employed are the sublimation method in which a reactant vapor of a precursor is generated by sublimation.
  • a solid precursor is dissolved in an organic solvent such as tetrahydrofuran, butyl acetate and toluene at a specific concentration and the obtained solution is injected into a vaporizer controlling the flow rate, thus all of the injected solution is vaporized to obtain a constant amount of vaporization.
  • the specific metal complexes illustratively represented by metal complexes of ⁇ -diketones such as dipivaloylmethane (DPM) are widely used by virtue that (1) in general, they have excellent thermal stability such that they hardly decompose and react up to a temperature to some extent even in the presence of oxygen, and that
  • some superconductors "or ferroelectrics of a metal- oxide such as YBa 2 Cu 3 Oy , Bi 2 Sr 2 Ca 2 Cu 3 O y and SrBi 2 Ta 2 O 9 , contain an alkaline-earth metal (such as Ca, Sr, Ba) as an essential component, while alkaline-earth metal complexes containing a ⁇ -diketone have the volatility, thermal stability and stability against oxygen necessary for the CVD method.
  • the solution vaporization method is mainly employed in these days.
  • BLT bismuth lanthanum titanate
  • BNT bismuth neodymium titanate
  • FeRAM ferroelectrics memory
  • LNO lanthanum nickelate
  • ⁇ -diketonato metal complexes such as dipivaloylmethanato (DPM) complex, 2, 2, 6, 6-tetramethyl-3, 5-octanedionato (TMOD) complex, and diisobutyrylmethanato (DIBM) complex.
  • a lanthanide series metal is barely introduced into the produced film, even if each precursor were supplied in the same ratios as the desired metal composition of the film.
  • the first method increases the ratio of the metal complex (in the case of a BLT film: lanthanum compound) whose metal is hardly introduced into the produced film based on the precursor solution.
  • the second method changes the precursor of the metal complex whose metal is hardly introduced in the produced film, therefore changing it into another complex, which is more easily decomposed.
  • the amount of a lanthanide series metal substantially introduced into the film is 1/3 or less of the ratio of the desired composition of the film, even if the ratio of the lanthanum complex in the precursor solution is 10 times of the desired composition of the film.
  • lanthanum in the obtained film is 1/10 or less of the ratio of the desired composition of the film same as the case when La(DPM) 3 is used.
  • JP No. (Tokkai) 2001-355070 describes yttrium and zirconium precursors .
  • JP No. (Tokkai) 5-98444 describes rare earth complexes.
  • JP No. (Tokuhyo) 7-500318 describes rare earth or alkaline earth / 3-diketonates.
  • JP No. (Tokkai) 7-188271 describes compounds comprising the linear amine adduct of a metal complex. Therefore, the inventions described in these references are made on the purpose to prevent that these different precursor complexes react each other such as a ligand exchange resulting in the formation of precipitation in the solution, or in the solid precipitation in gas phase bringing into a generation of a conduit clogging, to prevent a polymerization of a precursor complex resulting in increase of the vapor pressure or the stability, or to • suppress a reaction of the moisture and the like in the solution with the other substances preventing the time varying deterioration of precursor solution. Accordingly, these known CVD precursor complexes have a neutral ligand aiming at the stability of the metal complex.
  • ⁇ -diketonato lanthanide complex is a stable precursor, which hardly varies with time even without an addition of a neutral ligand, while the addition of a neutral ligand to the ⁇ -diketonato lanthanide complex makes vapor pressure down.
  • the complex has never been used positively as a CVD precursor in order to increase conversion efficiency into a film.
  • the purpose of the present invention is to obtain a lanthanide series multi-metal oxide thin film containing plural components, wherein the desired composition of the film is achieved constantly.
  • the inventors have made intensive and extensive studies on the above problems and found that by the coordination of a lanthanide series metal atom of ⁇ -diketonato lanthanide complex with some specific neutral ligands in order to cover the metal atom, the reactivity of the metal atom with a precursor other than the lanthanide series metal precursor complex is decreased and the conversion efficiency of the lanthanide series metal into a film is significantly increased.
  • the present invention relates to the inventions described in claims.
  • a complex of formula (I) Ln( ⁇ -dik) 3 -L -" (I) wherein "Ln” represents a lanthanide series metal atom, “ ⁇ - dik” represents a ⁇ -diketone ligand, “L” represents a neutral ligand being at least one chosen among 1,10- phenanthroline, 2,2' -bipyridyl and their derivatives, is used for preparing a thin film CVD precursor solution, in order to produce a thin film comprising a lanthanide series metal and a metal other than the lanthanide series.
  • the conversion efficiency into the lanthanide series metal film significant increased in a range of from 3 to 100 folds or more than the prior art.
  • the amount of the lanthanide series metal precursor to be used is decreased substantially. Also, the decrease of the total amount of the used solvent achieved an increased conversion efficiency of a metal other than lanthanide complex into a film. The reason is considered as that the decrease of the total amount of a solvent, which wastes energy necessary for film formation reaction, brings the increase of the amount of energy to be used for film formation reaction. Hence, the present invention allows high quality thin film containing a lanthanide series metal, wherein the desired composition of the film is achieved constantly.
  • the complex of formula (I) ( ⁇ -diketonato lanthanide complex with a neutral ligand adduct) of the present invention, is obtained by forming a metal complex of three
  • the above lanthanide series metal is a lanthanum series element shown in the Periodic table of the element selected from lanthanum of element number 57 to lutetium of element number 71, preferably lanthanum (La), cerium (Ce), praseodymium (Pr) , neodymium (Nd) , samarium (Sm) , europium (Eu) , gadolinium (Gd) and ytterbium (Yb) .
  • La lanthanum
  • Ce cerium
  • Pr praseodymium
  • Nd neodymium
  • Sm samarium
  • Eu europium
  • Gd gadolinium
  • Yb ytterbium
  • Preferably included are DPM, DIBM, IBPM and TMOD.
  • a single lanthanide oxide film is produced by using a ⁇ -diketonato lanthanide complex, there is not a great difference in the conversion efficiency of the ⁇ - diketonato lanthanide complex into a film compared to a precursor complex comprising a metal other than the lanthanide series. From the above, it is considered that when a multi-metal oxide thin film is produced by using a ⁇ - diketonato lanthanide complex, the lanthanide complex is changed into a form (such as multi-core complex, or reaction intermediate) which is hardly introduced into the film by reacting with a precursor complex including another metal, a solvent and the like.
  • a form such as multi-core complex, or reaction intermediate
  • the neutral ligand of the present invention never leaves in vaporization of the complex of formula (I) ( ⁇ -diketonato lanthanide complex with a neutral ligand adduct) .
  • thermogravimetry differential thermal analysis TG-DTA
  • a neutral ligand does not leave in the vaporization means that ⁇ TG curve obtained by the thermogravimetric analysis (TG) of the complex of formula (I) has a single vaporization point peak without an inflection point which shows the other vaporization point peak on the shoulder of the peak.
  • the presence of another vaporization point peak means that the neutral ligand left prior to the vaporization.
  • Figure 1 shows a thermogravimetric analysis (TG) curve of Nd(TMOD) 3 'phen in Example 1.
  • Figure 2 shows a TG analysis curve of La (TMOD) 3 •phen in Example 2.
  • Figure 3 shows a TG analysis curve of Nd(IBPM) 3 -phen.
  • Figure 4 shows a TG analysis curve of Nd(TMOD) 3 in Comparative Example 1.
  • Figure 5 shows a TG analysis curve of Nd(TMOD) 3 * tetraglyme in Comparative Example 2.
  • Figure 6 shows a TG analysis curve of La(TMOD) 3 in Comparative Example 3.
  • Figure 7 shows an embodiment of a solution vaporization CVD apparatus .
  • Figure 1 shows TG-DTA data (In Ar flow, atmospheric pressure) of the complex of formula (I), tris (2, 2, 6, 6- tetramethyl-3 , 5-octanedionato) neodymiu ⁇ r1, 10-phenanthroline adduct .
  • a hairline shows a TG curve
  • a bold line shows a ⁇ TG curve.
  • Figure 1 shows a TG curve uniformly decreasing until the end of the vaporization, and one single peak is appeared in a ⁇ TG curve.
  • TG-DTA data In Ar flow, atmospheric pressure
  • Nd(TMOD) 3 • tetraglyme neodymium -tetraglyme adduct
  • the vaporization temperature varies depending on the types of the other precursor or vaporization apparatus to be used.
  • a neutral ligand which shows ⁇ TG curve having the main peak without another peak and never leaves at a selected vaporization temperature can be used in the present invention, even if the TG curve decreases uniformly.
  • the neutral ligand of the present invention includes, 1, 10-phenanthroline (phen) , 2,2' -bipyridyl (bpy) and their derivatives and the like.
  • the organometallic complex containing a metal other than the lanthanide series used in the present invention includes a complex in which a compound coordinates with a metal, an organometallic complex in which an organic compound bonds to a metal and the like.
  • the metal contained in the above organometallic complex is a metal commonly used in the solution CVD method, which includes for example, Bismuth (Bi) , Strontium (Sr) , Barium (Ba) , Yttrium (Y) , Zirconium (Zr) , Manganese (Mn) , Iron (Fe) , Cobalt (Co) , Copper (Cu) , Titanium (Ti) , Lead (Pb) , Zinc (Zn) , Calcium (Ca) , Tantalum (Ta) , Niobium (Nb) , Lithium (Li) , Potassium (K) , Rubidium (Rb) , Ruthenium (Ru) , Hafnium (
  • compounds which coordinate with or bond to a metal in the above organometallic complex include compounds commonly used in the solution CVD method for example, a compound selected from a group consisting of dipivaloylmethane ligand (DPM) , pentafluoropropanoylpivaloylmethane ligand, diisobutyrylmethane ligand (DIBM) , isobutyrylpivaloylmethane ligand (IBPM), acetylacetone ligand, hexafluoroacetylacetone ligand, 2 , 2, 6, 6-tetramethyl-3, 5-octanedione ligand (TMOD), 6-ethyl-2 , 2-dimethyl-3 , 5-octanedione ligand (EDMOD) , 2,4- octanedione ligand, 6-ethyl-2,2-dimethyl-3, 5-decanedione
  • DPM dip
  • the above diols include 1, 3-propanediol, 2-methyl-2, 4- pentane diol and the like.
  • the above dialkylamido complexes includes diethylamido, dimethylamido, ethylmethylamido and the like.
  • the above alkoxides include iso-propoxide (Oi-
  • Pr ethoxide, methoxide, t-amyioxide (Ot-Am) , t-butoxide (Ot- Bu), sec-butoxide (Os-Bu) , l-methoxy-2-methyl-2-propoxide, 2- ethoxyethoxide and the like, preferably dipivaloylmethane ligand, pentafluoropropanoylpivaloylmethane ligand, diisobutyrylmethane ligand, isobutyrylpivaloylmethane ligand, acetylacetone ligand, hexafluoroacetylacetone ligand, 2, 2, 6, 6-tetramethyl-3, 5-octanedione ligand, alkoxide, cyclopentadiene ligand and their derivatives.
  • dipivaloylmethane ligand pentafluoropropanoylpivaloylmethane
  • the above compound can be used independently or in combination.
  • the organometallic complex in the present invention can be for example, alkoxide compound a part of which is substituted with ⁇ -diketone such as Ti(Oi-Pr) 2 (DPM) 2 .
  • the non-limiting examples of the complex of formula (I) whose neutral ligand never leaves in the vaporization stage ( ⁇ -diketonato lanthanide complex with a neutral ligand adduct) include, La (TMOD) 3 -phen, Nd(TMOD) 3 -phen, Nd(IBPM) 3 - phen, La(DPM) 3 -phen, La (DPM) 3 -bpy, La (DIBM) 3 -phen, La(DIBM) 3 - bpy, La (IBPM) 3 -phen, La (IBPM) 3 -bpy, La (DIBM) 3 -phen, La(DIBM) 3 • bpy, Ce (DPM) 3 -phen, Ce (DPM) 3 -bpy, Ce (DIBM) 3 -phen, Ce(DIBM) 3 - bpy, Ce (IBPM) 3 -phen, Ce (IBPM) 3 -phen, Ce
  • the concentration of the complex of formula (I) and organometallic complex contained in the CVD precursor for producing thin film of the present invention does not have any specific limitation as long as the solution can be supplied constantly.
  • the concentration is usually selected depending on the flow rate of a precursor, film production rate in the film producing stage and the like, while the saturated concentration, about 5 to 70% at room temperature (25°C) , is commonly preferable.
  • the concentration of the solution is not able to determine precisely since solubilities are different according to a precursor. However, the concentration is usually 0.02 to 1 mol/ liter, preferably 0.05 to 0.8 mol/ liter.
  • the concentration is less than the above range, problems tend to arise such as the deterioration with time of the precursor solution, decrease of the film production rate, deterioration of the formed thin film surface, and inclusion of carbon into the produced thin film.
  • the precipitation of a precursor tends to occur along with the vaporization of the solvent resulting in the clogging in the vaporizer.
  • the solvent of the present invention selected is that does not react with the complex of formula (I) .
  • THF acetic acid n-butyl ester (butyl acetate), benzene, toluene, hexane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane, 1, 2-epoxycyclohexane, methanol, ethanol, isopropylalcohol, diethyleneglycol dimethylether (diglyme) , acetone, methyl ethyl ketone, 1,2- dimethoxyethane and the like can be mentioned.
  • the concentration of the solution is selected depending on the film production rate in the film producing stage, the structure of the vaporizer, vaporization manner and the like, as long as the clogging in the vaporizer and the deterioration with time hardly occurs.
  • the organometallic complexes may require the presence of a stabilizing agent, whose main purpose is to prevent the organometallic complex degradation with time and the formation of a solid precipitation in the solution.
  • a nucleophilic agent can be used.
  • the stabilizing agent includes; ethyleneglycolethers such as glyme, diglyme, triglyme, and tetraglyme; crownethers such as 18-crown-6, dicyclohexyl-18-crown-6, 24-crown-8, dicyclohexyl-24-crown- 8, dibenzo-24-crown-8; polyamines such as ethylenediamine, N,N' -tetramethylethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 1,1,4,7,7- pentamethyldiethylenetriamine, and 1,1,4,7,10,10- hexamethyltriethylenetetramine; cyclic polyamines; ⁇ -keto esters such as methyl acetoacetate, ethyl acetoa
  • the thin film obtained by using a CVD precursor used for production of a thin film of the present invention is a thin film comprising one selected from the group of bismuth lanthanum titanate, bismuth neodymium titanate, lead lanthanum titanate zirconate, lanthanum titanate, lanthanum nickelate, samarium nickelate, gadolinium zirconate, lanthanum strontium cobaltate, praseodymium calcium manganate, cerium manganate, neodymium barium copper oxide, dysprosium barium copper oxide, ytterbium barium copper oxide, cerium barium yttrium oxide and the like.
  • the above film is very useful in many fields such as superconductor, dielectric, electroconductor, especially, dielectric for capacitance, piezoelectric resonator, infrared monitor and the like.
  • the precursor solution is generally mixed and vaporized according to the any one of the following method (D to (4) .
  • a precursor solution containing two or more organometallic complexes at a specific ratio (herein-below it may be referred as "cocktail") is supplied into a single vaporizer directly (one bottle-type) .
  • the composition of the supplied vapor can be changed easily, while method (4) is excellent in low investment cost of the apparatus, low operation cost and easy operability in operation.
  • the CVD precursor used for production of a thin film may composed of two or more precursor solutions, or may be a single solution (cocktail) containing two or more organometallic complexes.
  • the CVD precursor of the present invention can be applied to any one of the above methods (1) to (4) .
  • Another possible method for growing thin films employing the precursor of the present invention is by means of its sublimation, starting from the precursor in the solid form.
  • thin film producing methods known to the skilled in the art can be used, for example, thermal CVD method, plasma CVD method, photo CVD method and the like.
  • thermal CVD a precursor is vaporized to a vapor (vaporization stage) , the precursor vapor is introduced onto a substrate, then the precursor is decomposed on the substrate to form a thin film on the substrate (film production stage) .
  • the vaporization stage it is preferable that the vaporization rate of the precursor is increased, and the vaporization is conducted under reduced pressure not more than 13330Pa, more preferably not more than 8000Pa and at a temperature less than the decomposition temperature of the precursor in order to prevent the decomposition of the precursor.
  • the substrate is preliminary heated to the decomposition temperature of the precursor or more, more preferably 350 °C or more, further more preferably 450 0 C or more.
  • An annealing treatment can be carried out on the obtained thin film if required.
  • Any apparatus can be used for the production of the thin film of the present invention. For example, mentioned are an apparatus used in the MOCVD (metal-organic chemical vapor deposition) method illustrated in Figure 7 and the like.
  • a complex of formula (I) is dissolved in an organic solvent at a concentration of 0.05 to 1 mol/1, for example.
  • prepared is a CVD precursor solution of a metal other than the lanthanide series necessary for producing the desired film.
  • the composition ratio of each CVD precursors is not necessarily the same as the desired composition of the film and the optimum ratio is selected depending on the film production conditions, apparatus structure and the like.
  • a solution vaporization CVD apparatus illustrated in Figure 7 can be used for a multi-bottle A-type manner in order to produce a lanthanide series metal-containing thin film in one embodiment of the invention.
  • a precursor solution containing a complex of formula (I) is filled in a precursor container, which is connected to a solution vaporization CVD apparatus, while a precursor solution containing an organometallic complex containing a metal other than the lanthanide series is filled in the other precursor container which is connected to the solution vaporization CVD apparatus.
  • the temperature of the vaporizer is set at in a range of for example 150 to 300 0 C, the precursor solution is supplied at a flow rate of for example 0.1 to 1 ml/min to a vaporizer. The whole amount of the supplied precursor solution is vaporized.
  • the vapor is entrained in Ar carrier gas to a reactor charging an inert gas such as Ar as a carrier gas.
  • oxygen can be used for example.
  • the pressure in the reactor is maintained at 0.1 to 50 torr, the substrate located in the reactor is heated in the range of 400 to 850 0 C to form the lanthanide series metal-containing thin film on the substrate.
  • Example 1 (Preparation of a precursor solution) 2.75 g of Nd(TMOD) 3 'phen were dissolved in toluene to obtain 100 ml of a solution having a concentration of 0.03 mol/1.
  • DPM Ti(Oi-Pr) 2
  • the evaporated vapor in the vaporizer was entrained in Ar carrier gas with a flow rate of 200 ml/min to a reactor (pressure; 10.7 hPa, temperature; 250 0 C) while a pressure in the vaporizer was maintained at 47 hPa .
  • the film production was conducted on a Pt/TiO 2 /Si substrate (temperature; 550 0 C) in the reactor with a reaction gas of oxygen (flow rate 100 ml/min) for 10 minutes.
  • the Nd molar ratio in the composition of the obtained film was significantly lower than that of the desired composition of a bismuth neodymium titanate film.
  • the evaporated vapor in the vaporizer was entrained in Ar carrier gas with a flow rate of 200 ml/min to a reactor (pressure; 10.7 hPa, temperature; 250 °C)while a pressure in the vaporizer was maintained at 47 hPa.
  • the film production was conducted on a silicone single crystal substrate (temperature; 600 0 C) in the reactor with a reaction gas of oxygen (flow rate 100 ml/min) for 10 minutes.
  • a composition analysis of the obtained film results La: 41.9 ⁇ g/cm 2 and Ni: 17.6 ⁇ g/cm 2 .
  • the molar ratio was almost the same as the molar ratio of 1:1 of the desired lanthanum nickelate composition.
  • the specific resistance of the obtained thin film was 8x10 " 4 ⁇ cm at the substrate.
  • the CVD precursor used for production of a thin film of the present invention allows the conversion efficiency of the lanthanide series metal into a film to be significantly increased, by using in a small amount of a precursor and solvent to produce a high quality lanthanide series metal-containing thin film constantly.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic 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)
  • Pyridine Compounds (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention a pour objectif de produire un film mince à base de multiples oxydes de métaux de la série des lanthanides, qui contient de multiples composants, la composition désirée du film étant obtenue de manière constante. La présente invention se rapporte à un précurseur de CVD utilisé pour produire un film mince contenant un ou plusieurs métaux de la série des lanthanides et un ou plusieurs métaux ne faisant pas partie de la série des lanthanides. Ledit précurseur est obtenu par la dissolution d'un composé représenté par la formule Ln (β-dik)3 L, dans laquelle Ln représente l'atome métallique de la série des lanthanides, β-dik est de préférence sélectionné parmi un ligand dipivaloylméthane (DPM), un ligand diisobutyrylméthane (DIBM), un ligand isobutyriylpivaloylméthane (IBPM), un ligand 2,2,6,6-tétraméthyle-3,5-octanedione (TMOD), un ligand acétylacétone, un ligand 6-éthyl-2,2-diméthyl-3,5-octanedione, un ligand 5-méthyl-2,4-hexanedione et un ligand 5,5-diméthyl-2,4-hexanedione, L représente un ligand neutre sélectionné de préférence parmi 1,10-phénanthroline, 2,2'-bipyridyle et leurs dérivés. Le précurseur selon l'invention renferme également, dans un solvant, un complexe organométallique contenant un métal ne faisant pas partie de la série des lanthanides. Une courbe TG obtenue par l'analyse thermogravimétrique (TG) du composé représenté par la formule (I) présente une seule crête d'un point de pulvérisation.
PCT/IB2005/002397 2004-08-24 2005-08-10 Solution de precurseur de cvd destinee a produire un film mince contenant un metal de la serie des lanthanides, et procede de production d'un film mince faisant appel a ladite solution WO2006021850A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2004-244014 2004-08-24
JP2004244014A JP4738775B2 (ja) 2004-08-24 2004-08-24 ランタニド系金属含有薄膜製造に用いるｃｖｄ用原料溶液及びこれを用いた薄膜の製造方法

Publications (2)

Publication Number Publication Date
WO2006021850A2 true WO2006021850A2 (fr) 2006-03-02
WO2006021850A3 WO2006021850A3 (fr) 2006-10-26

Family

ID=35967905

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2005/002397 WO2006021850A2 (fr) 2004-08-24 2005-08-10 Solution de precurseur de cvd destinee a produire un film mince contenant un metal de la serie des lanthanides, et procede de production d'un film mince faisant appel a ladite solution

Country Status (2)

Country Link
JP (1) JP4738775B2 (fr)
WO (1) WO2006021850A2 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100034719A1 (en) * 2008-08-06 2010-02-11 Christian Dussarrat Novel lanthanide beta-diketonate precursors for lanthanide thin film deposition
EP2017368A3 (fr) * 2007-07-13 2011-01-19 Rohm and Haas Electronic Materials LLC Compositions de précurseur et procédés
KR20140041477A (ko) 2011-08-02 2014-04-04 가부시키가이샤 아데카 알콕시드 화합물 및 박막 형성용 원료
WO2015066558A1 (fr) * 2013-11-01 2015-05-07 President And Fellows Of Harvard College Transitions de phase entrainées par dopant dans des oxydes métalliques corrélés
US11162171B2 (en) 2019-03-13 2021-11-02 Metox Technologies, Inc. Solid precursor feed system for thin film depositions

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007308789A (ja) * 2006-04-19 2007-11-29 Tokyo Electron Ltd 成膜装置及び成膜方法
CN101802255A (zh) * 2007-09-21 2010-08-11 东京毅力科创株式会社 成膜装置和成膜方法
JP6359246B2 (ja) * 2013-06-11 2018-07-18 宇部興産株式会社 プラセオジム化合物およびその製造方法
KR102168174B1 (ko) 2014-03-19 2020-10-20 삼성전자주식회사 니켈 화합물 및 이를 이용한 박막 형성 방법

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996040690A1 (fr) * 1995-06-07 1996-12-19 Advanced Technology Materials, Inc. Reactifs a base de complexes metalliques pour depot en phase gazeuse par procede chimique
US5837321A (en) * 1993-11-24 1998-11-17 The Associated Octel Company Limited Volatile organic lanthanide compounds and methods for the preparation of lanthanide-containing layered materials form these compounds
WO1999000530A1 (fr) * 1997-06-26 1999-01-07 Advanced Technology Materials, Inc. Procede de depot chimique en phase vapeur basse temperature servant a former de minces films de ceramique contenant du bismuth utiles dans des dispositifs a memoires ferroelectriques
WO1999027030A1 (fr) * 1997-11-20 1999-06-03 Advanced Technology Materials, Inc. Compositions de solvant alcane/polyamine pour procede de depot chimique en phase vapeur avec apport de liquide

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08975B2 (ja) * 1991-10-17 1996-01-10 東ソー・アクゾ株式会社 酸化物薄膜形成用金属アセチルアセトナト錯体
JP2003321475A (ja) * 2002-04-26 2003-11-11 Kojundo Chem Lab Co Ltd トリス（ジイソブチリルメタナート）ランタンとその製法およびそれを用いた化学気相成長法によるｐｌｚｔ薄膜の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5837321A (en) * 1993-11-24 1998-11-17 The Associated Octel Company Limited Volatile organic lanthanide compounds and methods for the preparation of lanthanide-containing layered materials form these compounds
WO1996040690A1 (fr) * 1995-06-07 1996-12-19 Advanced Technology Materials, Inc. Reactifs a base de complexes metalliques pour depot en phase gazeuse par procede chimique
WO1999000530A1 (fr) * 1997-06-26 1999-01-07 Advanced Technology Materials, Inc. Procede de depot chimique en phase vapeur basse temperature servant a former de minces films de ceramique contenant du bismuth utiles dans des dispositifs a memoires ferroelectriques
WO1999027030A1 (fr) * 1997-11-20 1999-06-03 Advanced Technology Materials, Inc. Compositions de solvant alcane/polyamine pour procede de depot chimique en phase vapeur avec apport de liquide

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
BARBILLAT J ET AL: "Near-infrared Fourier transform room-temperature photoluminescence of erbium complexes" REVIEW OF SCIENTIFIC INSTRUMENTS, AMERICAN INSTITUTE OF PHYSICS, US, vol. 74, no. 11, November 2003 (2003-11), pages 4954-4957, XP012060685 ISSN: 0034-6748 *
MORAIS C R S ET AL: "Kinetic study of the thermal decomposition of Eu<3+> with beta-diketone ligands and 1,10-phenanthroline or 2,2-dipyridine" JOURNAL OF ALLOYS AND COMPOUNDS, ELSEVIER SEQUOIA, LAUSANNE, CH, vol. 344, no. 1-2, 7 October 2002 (2002-10-07), pages 101-104, XP004387044 ISSN: 0925-8388 *
ZHONG X L ET AL: "Electrical properties of Nd-substituted Bi4Ti3O12 thin films fabricated by chemical solution deposition" JOURNAL OF CRYSTAL GROWTH, ELSEVIER, AMSTERDAM, NL, vol. 277, no. 1-4, 15 April 2005 (2005-04-15), pages 233-237, XP004831639 ISSN: 0022-0248 *
ZOAN T A ET AL: "Synthesis, structure and properties of volatile lanthanide pivalates" JOURNAL OF ALLOYS AND COMPOUNDS, ELSEVIER SEQUOIA, LAUSANNE, CH, vol. 225, 15 July 1995 (1995-07-15), pages 396-399, XP004072043 ISSN: 0925-8388 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2017368A3 (fr) * 2007-07-13 2011-01-19 Rohm and Haas Electronic Materials LLC Compositions de précurseur et procédés
US8142847B2 (en) 2007-07-13 2012-03-27 Rohm And Haas Electronic Materials Llc Precursor compositions and methods
US20100034719A1 (en) * 2008-08-06 2010-02-11 Christian Dussarrat Novel lanthanide beta-diketonate precursors for lanthanide thin film deposition
KR20140041477A (ko) 2011-08-02 2014-04-04 가부시키가이샤 아데카 알콕시드 화합물 및 박막 형성용 원료
US10118940B2 (en) 2011-08-02 2018-11-06 Adeka Corporation Alkoxide compound and raw material for forming thin film
DE112012003201B4 (de) 2011-08-02 2022-06-15 Adeka Corp. Alkoxidverbindung und Rohmaterial zum Bilden eines dünnen Films
WO2015066558A1 (fr) * 2013-11-01 2015-05-07 President And Fellows Of Harvard College Transitions de phase entrainées par dopant dans des oxydes métalliques corrélés
US11162171B2 (en) 2019-03-13 2021-11-02 Metox Technologies, Inc. Solid precursor feed system for thin film depositions
US11584988B2 (en) 2019-03-13 2023-02-21 Metox Technologies, Inc. Solid precursor feed system for thin film depositions

Also Published As

Publication number Publication date
JP4738775B2 (ja) 2011-08-03
WO2006021850A3 (fr) 2006-10-26
JP2006063352A (ja) 2006-03-09

Similar Documents

Publication Publication Date Title
EP1698614B1 (fr) Compose metallique, materiau permettant de former un film mince, et procede de preparation d&#39;un film mince
US7335783B2 (en) Thin film-forming material and method for producing thin film
WO2006021850A2 (fr) Solution de precurseur de cvd destinee a produire un film mince contenant un metal de la serie des lanthanides, et procede de production d&#39;un film mince faisant appel a ladite solution
EP0873343B1 (fr) Reactifs a base de complexes metalliques pour depot en phase gazeuse par procede chimique
US20090035464A1 (en) Alkoxide compound, material for thin film formation, and process for thin film formation
US20140127913A1 (en) Titanium-containing precursors for vapor deposition
WO2006043418A1 (fr) Compose alcoxyde, materiau de formation de film mince et procede de formation de film mince
US20010007034A1 (en) Tetrahydrofuran-adducted Group II beta-diketonate complexes as source reagents for chemical vapor deposition
US20060088660A1 (en) Methods of depositing lead containing oxides films
KR102600214B1 (ko) 금속 알콕사이드 화합물, 박막 형성용 원료 및 박막의 제조 방법
WO2018088078A1 (fr) Composé, matière première de formation de couche mince, matière première de formation de couche mince pour procédé de dépôt de couche atomique, et procédé de production de couche mince
JP4823069B2 (ja) 金属化合物、薄膜形成用原料及び薄膜の製造方法
KR20220116524A (ko) V족 원소 함유 막 형성 조성물 및 v족 원소 함유 막의 기상 증착
EP3643700A1 (fr) Composé alcoxyde métallique, matière première de formation de couche mince, et procédé de production de couche mince
US20030124251A1 (en) Process of forming thin film and precursor for chemical vapor deposition
US20230002423A1 (en) Novel tin compound, thin-film forming raw material containing said compound, thin film formed from said thin-film forming raw material, method of producing said thin film using said compound as precursor, and method of producing said thin film
US11807652B2 (en) Tungsten compound, raw material for thin film formation and method for producing thin film
JP4107923B2 (ja) イットリウム含有複合酸化物薄膜の製造方法
WO2004076712A1 (fr) Solution precurseur de bismuth s&#39;utilisant dans un procede de depot chimique en phase vapeur, procede de fabrication d&#39;un bismuth renfermant un film mince de ladite solution
WO2006045885A1 (fr) Procede permettant de deposer des films contenant du plomb
EP3951006A1 (fr) Matière première permettant la formation d&#39;un film mince, procédé de production d&#39;un film mince et composé de scandium
US20240060177A1 (en) Indium compound, thin-film forming raw material, thin film, and method of producing same
JP2004360058A (ja) Ｃｖｄ用原料溶液及びこれを用いた薄膜の製造方法
JP2004360059A (ja) Ｃｖｄ用原料溶液及びその気化方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS KE KG KM KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU LV MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase in:

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 05786354

Country of ref document: EP

Kind code of ref document: A2