WO2009143452A1 - Films diélectriques à constante diélectrique élevée et procédés de production au moyen de précurseurs à base de cérium - Google Patents

Films diélectriques à constante diélectrique élevée et procédés de production au moyen de précurseurs à base de cérium Download PDF

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WO2009143452A1
WO2009143452A1 PCT/US2009/045024 US2009045024W WO2009143452A1 WO 2009143452 A1 WO2009143452 A1 WO 2009143452A1 US 2009045024 W US2009045024 W US 2009045024W WO 2009143452 A1 WO2009143452 A1 WO 2009143452A1
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cerium
zirconium
hafnium
group
oxide
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Paul Raymond Chalker
Peter Nicholas Heys
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Sigma Aldrich Co LLC
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Sigma Aldrich Co LLC
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/66—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the type of materials
    • H10P14/668—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the type of materials the materials being characterised by the deposition precursor materials
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/63—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the formation processes
    • H10P14/6326—Deposition processes
    • H10P14/6328—Deposition from the gas or vapour phase
    • H10P14/6334—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/63—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the formation processes
    • H10P14/6326—Deposition processes
    • H10P14/6328—Deposition from the gas or vapour phase
    • H10P14/6334—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H10P14/6339—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/69—Inorganic materials
    • H10P14/692—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses
    • H10P14/6938—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides
    • H10P14/6939—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides characterised by the metal
    • H10P14/69392—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides characterised by the metal the material containing hafnium, e.g. HfO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/69—Inorganic materials
    • H10P14/692—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses
    • H10P14/6938—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides
    • H10P14/6939—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides characterised by the metal
    • H10P14/69394—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides characterised by the metal the material containing titanium, e.g. TiO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/69—Inorganic materials
    • H10P14/692—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses
    • H10P14/6938—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides
    • H10P14/6939—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides characterised by the metal
    • H10P14/69395—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides characterised by the metal the material containing zirconium, e.g. ZrO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/69—Inorganic materials
    • H10P14/692—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses
    • H10P14/6938—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides
    • H10P14/6939—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides characterised by the metal
    • H10P14/69397—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides characterised by the metal the material containing two or more metal elements

Definitions

  • the present invention relates to methods of forming high- ⁇ dielectric thin metallic films, improving such films, and a lattice capable of forming such films.
  • Various organometallic precursors are used to form high- ⁇ dielectric thin metal films for use in the semiconductor industry.
  • Various deposition processes are used to form the metal films, such as chemical vapor deposition ("CVD”) or atomic layer deposition (“ALD”), also known as atomic layer epitaxy.
  • CVD chemical vapor deposition
  • ALD atomic layer deposition
  • CVD is a chemical process whereby precursors are deposited on a substrate to form a solid thin film.
  • the precursors are passed over a substrate (wafer) within a low pressure or ambient pressure reaction chamber.
  • the precursors react and/or decompose on the substrate surface creating a thin film of deposited material.
  • Volatile by-products are removed by gas flow through the reaction chamber.
  • the deposited film thickness can be difficult to control because it depends on coordination of many parameters such as temperature, pressure, gas flow volumes and uniformity, chemical depletion effects and time.
  • ALD is a chemical process which separates the precursors during the reaction.
  • the first precursor is passed over the substrate producing a monolayer on the substrate. Any excess unreacted precursor is pumped out of the reaction chamber.
  • a second precursor is then passed over the substrate and reacts with the first precursor, forming a second monolayer of film over the first-formed film on the substrate surface. This cycle is repeated to create a film of desired thickness.
  • ALD film growth is self-limited and based on surface reactions, creating uniform depositions that can be controlled at the nanometer- thickness scale.
  • Zirconia, hafnia and TiO 2 have been used to create dielectric films, generally to replace silicon dioxide gates for use in the semiconductor industry. Replacing silicon dioxide with a high- ⁇ dielectric material allows increased gate capacitance without concomitant leakage effects.
  • the method comprises delivering at least one metal-source precursor and at least one cerium precursor to a substrate, wherein the at least one cerium precursor corresponds in structure to Formula I:
  • L is a cyclopentadienyl ring optionally substituted with one or more substituents selected from the group consisting of alkyl, alkoxy and NRiR 2 ; or L is alkoxy;
  • Ri and R 2 are independently hydrogen or alkyl; and x is 3 or 4.
  • the method comprises using at least one cerium precursor to form a high- ⁇ dielectric film for use in the semiconductor device, wherein the at least one cerium precursor corresponds in structure to Formula I.
  • the method comprises adding at least one cerium precursor to the high- ⁇ dielectric material wherein the at least one cerium precursor corresponds in structure to Formula I.
  • a high- ⁇ dielectric film-forming lattice wherein the lattice is comprised of hafnium oxide, titanium oxide or mixtures thereof and the lattice contains cerium atoms.
  • high- ⁇ dielectric refers to a material, such as a metal-containing film, with a higher dielectric constant (K) when compared to silicon dioxide (which has a dielectric constant of about 3.7).
  • a high- ⁇ dielectric film is used in semiconductor manufacturing processes to replace the silicon dioxide gate dielectric.
  • a high- ⁇ dielectric film may be referred to as having a "high- ⁇ gate property" when the dielectric film is used as a gate material and has at least a higher dielectric constant than silicon dioxide.
  • the term "relative permittivity" is synonymous with dielectric constant (K).
  • the term "vapor deposition process" is used to refer to any type of vapor deposition technique such as CVD or ALD.
  • CVD may take the form of liquid injection CVD.
  • ALD may be either photo-assisted ALD or liquid injection ALD.
  • precursor refers to an organometallic molecule, complex and/or compound which is deposited or delivered to a substrate to form a thin film by a vapor deposition process such as CVD or ALD.
  • alkyl refers to a saturated hydrocarbon chain of 1 to 10 carbon atoms in length, such as, but not limited to, methyl, ethyl, propyl and butyl.
  • the alkyl group may be straight-chain or branched-chain.
  • propyl encompasses both w-propyl and /so-propyl; butyl encompasses w-butyl, sec-butyl, zso-butyl and tert-butyl.
  • alkoxy refers to a substituent, i.e., -O-alkyl.
  • substituent include methoxy (-0-CH 3 ), ethoxy, etc.
  • the alkyl portion may be straight-chain or branched- chain.
  • propoxy encompasses both w-propoxy and iso- propoxy; butoxy encompasses w-butoxy, zso-butoxy, sec-butoxy, and tert-butoxy.
  • cyclopentadienyl or "Cp” (C 5 H 5 ) refers to a 5- membered carbon ring which is bound to a transition metal. As used herein, all five carbon atoms of the Cp ligand are bound to the metal center in ⁇ 5 -coordination by ⁇ bonding.
  • a method to form a high- ⁇ dielectric film by a vapor deposition process comprises delivering at least one metal- source precursor and at least one cerium precursor to a substrate, wherein the at least one cerium precursor corresponds in structure to Formula I:
  • L is a cyclopentadienyl ring optionally substituted with one or more substituents selected from the group consisting of alkyl, alkoxy and NRiR 2 ; or L is alkoxy; Ri and R 2 are independently hydrogen or alkyl; and x is 3 or 4.
  • L is a cyclopentadienyl ring optionally substituted with one or more substituents such as alkyl, alkoxy and NRiR 2 .
  • the cyclopentadienyl ring is substituted with one or more substituents such as alkyl, alkoxy and NRiR 2 .
  • L is a cyclopentadienyl ring and x is 3, therefore in this embodiment there are three cyclopentadienyl rings attached to cerium.
  • L is alkoxy group such as methoxy, ethoxy, propoxy, butoxy or pentoxy.
  • L is alkoxy and x is 4, therefore in this embodiment there are four alkoxy groups attached to cerium.
  • At least one cerium precursor examples include, without limitation:
  • any metal-source precursor suitable for forming a film may be used according to the invention.
  • the at least one metal-source precursor is compatible with the at least one cerium precursor.
  • the at least one metal-source precursor may be compatible with the at least one cerium precursor for purposes of depositing a metal oxide film with the composition Ce x Mi_ x O y where M is either Hf, Zr or Ti; x has a value between about zero and about 0.5; and y has a value less than about 2.
  • Examples of the at least one metal-source precursor include, without limitation: a metal amide, such as Hafnium dimethylamide, Zirconium dimethylamide, Titanium dimethylamide, Hafnium ethylmethylamide, Zirconium ethylmethylamide, Titanium ethylmethylamide, Hafnium diethylamide, Zirconium diethylamide and Titanium diethylamide; a metal alkoxide, such as Hafnium t-butoxide, Zirconium t-butoxide, Titanium t-butoxide, Hafnium i-propoxide, Zirconium i-propoxide, Titanium i-propoxide, Hafnium bis t-butoxy bis 2-methyl-2-methoxy propoxide, Zirconium bis t-butoxy bis 2-methyl-2-methoxy propoxide, Titanium bis t-butoxy bis 2-methyl-2-methoxy propoxide, Zirconium bis t-butoxy bis
  • the high- ⁇ dielectric film formed by a method of the invention may comprise:
  • At least one cerium precursor is used in a vapor deposition process with at least one hafnium precursor to create a cerium-doped hafnium oxide film.
  • at least one cerium precursor is used in a vapor deposition process with at least one zirconium precursor to create a cerium-doped zirconium oxide film.
  • At least one cerium precursor is used in a vapor deposition process with at least one titanium precursor to create a cerium-doped titanium oxide film.
  • a cerium precursor is used in a vapor deposition process with at least one hafnium precursor, zirconium precursor and/or titanium precursor to create a cerium doped "mixed" metal oxide film.
  • a "mixed" metal oxide film refers to a metal oxide film comprising cerium and one or more of the following: hafnium oxide, zirconium oxide and titanium oxide.
  • the method of the invention creates either hafnium oxide, zirconium oxide, titanium oxide or a mixed metal oxide dielectric film that contains from about 0.5 to about 35 atomic metal % cerium.
  • the metal oxide or mixed metal oxide film contains from about 5 to about 20 atomic metal % cerium.
  • the metal oxide or mixed metal oxide film contains from about 8 to about 12 atomic metal % cerium.
  • the at least one metal source precursor and/or the at least one cerium precursor may be dissolved in an appropriate hydrocarbon or amine solvent.
  • Appropriate hydrocarbon solvents include, but are not limited to aliphatic hydrocarbons, such as hexane, heptane and nonane; aromatic hydrocarbons, such as toluene and xylene; aliphatic and cyclic ethers, such as diglyme, triglyme and tetraglyme.
  • appropriate amine solvents include, without limitation, octylamine and N 5 N- dimethyldodecylamine.
  • a precursor may be dissolved in toluene to yield a 0.05 to IM solution.
  • the at least one cerium precursor is dissolved in an organic solvent, such as toluene, heptane, octane, nonane or tetrahydrofuran (THF).
  • an organic solvent such as toluene, heptane, octane, nonane or tetrahydrofuran (THF).
  • THF tetrahydrofuran
  • the cerium-doped films of the invention can be formed by chemical vapor deposition.
  • the chemical vapor deposition is liquid injection chemical vapor deposition.
  • the cerium-doped films of the invention can be formed by atomic layer deposition.
  • the atomic layer deposition is photo-assisted atomic layer deposition.
  • the atomic layer deposition is liquid injection atomic layer deposition.
  • each precursor is deposited and/or delivered onto a substrate in pulses alternating with pulses of an oxygen source.
  • Any suitable oxygen source may be used, for example, H 2 O, O 2 or ozone.
  • each precursor is deposited onto a substrate in pulses with a continuous supply of the oxygen source such as H 2 O, O 2 or ozone.
  • the oxygen source such as H 2 O, O 2 or ozone.
  • the cerium-doped high- ⁇ dielectric film has a relative permittivity of about 20 to about 100, particularly from about 40 to about
  • the high- ⁇ dielectric film is capable of maintaining a relative permittivity of about 20 to about 100 at frequencies of about IKHz to about IGHz.
  • a variety of substrates can be used in the methods of the present invention.
  • the precursors according to Formula I may be deposited on substrates such as, but not limited to, silicon, silicon oxide, silicon nitride, tantalum, tantalum nitride, or copper.
  • a method is provided to improve the high- ⁇ gate property of a semiconductor device.
  • the method comprises using at least one cerium precursor to form a high- ⁇ dielectric film for use in the semiconductor device, wherein the at least one cerium precursor corresponds in structure to Formula I above.
  • Including at least one cerium precursor according to Formula I in a metal oxide film improves the high- ⁇ gate property by either increasing the dielectric constant, allowing longer maintenance of a high dielectric constant or both, when compared to the particular metal oxide film without the at least one cerium precursor. This improves the high- ⁇ gate property of the semiconductor device by increasing gate capacitance and improving permittivity for faster transistors and smaller devices.
  • the dielectric constant can be increased about 20 to about 50 units by using at least one cerium precursor according to Formula I; or a high dielectric constant can be maintained at about IKHz to about IGHz, when compared to not using at least one cerium precursor according to Formula I.
  • a method is provided to stabilize a high- ⁇ dielectric material.
  • the method comprises adding at least one cerium precursor to the high- ⁇ dielectric material wherein the at least one cerium precursor corresponds in structure to Formula (I) above.
  • stabilize refers generally to altering the high- K dielectric material such that the high- ⁇ dielectric material is able to maintain a high dielectric constant at frequencies of about IKHz to about IGHz.
  • the cerium-doped high- ⁇ dielectric film has a relative permittivity of about 20 to about 100, particularly from about 40 to about 70. Further, the high- ⁇ dielectric film is capable of maintaining a relative permittivity of about 20 to about 100 at frequencies of about IKHz to about IGHz.
  • the high- ⁇ dielectric material may be any material wherein stabilization is needed to improve or maintain a high dielectric constant.
  • the high- ⁇ dielectric material may be provided by a film composed of one or more of hafnium oxide, zirconium oxide, titanium oxide or a "mixed" metal oxide, for example, a hafnium, zirconium and/or titanium oxide mixture. Additionally, if three metals are present, then a "ternary" mixed metal oxide film can be stabilized.
  • hafnium, zirconium, or titanium with a +3-oxidation-state rare earth element causes or permits 'dielectric relaxation' in the film-forming materials or film thereby formed.
  • High frequencies cause the dielectric constant (or relative permittivity) of the material to decrease, which is known as dielectric relaxation. It is hypothesized that dielectric relaxation occurs because substitution of hafnium, zirconium or titanium with the +3 element in the lattice causes an oxygen vacancy in order to maintain balanced charge.
  • a hafnium oxide, zirconium oxide, titanium oxide or mixed oxide film can be created using a precursor as disclosed herein such that cerium (IV) is incorporated into the lattice.
  • the high- ⁇ dielectric material is stabilized by stabilizing the metastable phase of the metal used.
  • pure zirconium oxide and hafnium oxide exhibit a stable monoclinic crystalline phase with dielectric constant typically in the range of about 18 to about 22.
  • the metastable phases such as tetragonal and cubic crystal structures of these materials, have high permittivities.
  • some of the Group IV metal may be replaced with one or more cerium precursors of Formula I which can adopt a +4 charge and may obviate the formation of charged oxygen ion vacancies.
  • cerium precursor(s) to stabilize different phases also has implications for radiation hardness, as the resistance to radiation can be increased which is very useful for space applications where resistance to degradation by various forms of radiation is key to device lifetimes and efficiencies. Therefore, these stabilized high- ⁇ dielectric materials are useful in semiconductor devices and are useful for computer memory and logic applications, such as dynamic random access memory (DRAM) and complementary metal oxide semi-conductor (CMOS) circuitry.
  • DRAM dynamic random access memory
  • CMOS complementary metal oxide semi-conductor
  • a high- ⁇ dielectric film-forming lattice is provided.
  • the lattice which is an array of points repeating periodically in three dimensions, is comprised of hafnium oxide, titanium oxide, or mixtures thereof; and the lattice contains cerium atoms. The atoms are arranged upon the points of the lattice. The points form unit cells that fill the space of the lattice.
  • the cerium may also have an effect on the polarizability of the unit cell, i.e. the relative tendency of a charge distribution, like the electron cloud of an atom or molecule, to be distorted from its normal shape by an external electric field, which may be caused by the presence of a nearby ion or dipole.
  • this polarizability is enhanced which may impact the dielectric constant value beneficially by increasing or maintaining the dielectric constant longer.
  • Polarizability of the unit cell coupled with stabilization of the highest dielectric constant phase of each metal oxide may ensure that the maximum dielectric constant value can be obtained from the particular material system in use.
  • cerium atoms for the lattice are provided from at least one cerium precursor corresponding in structure to Formula I.
  • the cerium may be substitutional on the Group IV atomic sites or located interstitially, as interstitial inclusions.
  • the lattice is capable of forming a high- ⁇ dielectric film by a vapor deposition process, such as CVD or ALD.
  • the film formed by the lattice has a thickness from about 0.2 nm to about 500 nm; and contains from about 0.5 to about 35 atomic metal % cerium.
  • the metal oxide or mixed metal oxide film contains from about 5 to about 20 atomic metal % cerium. In a further particular embodiment, the metal oxide or mixed metal oxide film contains from about 8 to about 12 atomic metal % cerium.
  • the film formed by the lattice has a relative permittivity of about 20 to about 100, particularly from about 40 to about 70. Further, the film formed is capable of maintaining a relative permittivity of about 20 to about 100 at frequencies of about IKHz to about IGHz.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
  • Formation Of Insulating Films (AREA)

Abstract

L'invention concerne des procédés pour former et stabiliser des films à constante diélectrique élevée par des processus de dépôt en phase vapeur faisant intervenir des précurseurs de source métalliques et des précurseurs à base de cérium selon la formule (I) : Ce(L)x, dans laquelle L représente un anneau cyclopentadiényle éventuellement substitué par un ou plusieurs substituants indépendamment sélectionnés à partir du groupe comprenant alkyle, alcoxy et NR1R2; ou L représente alcoxy; R1 et R2 représentent indépendamment hydrogène ou alkyle; et x vaut 3 ou 4. L'invention concerne également des procédés pour améliorer la propriété de grille à constante diélectrique élevée de dispositifs à semi-conducteurs au moyen de précurseurs à base de cérium selon la formule (I). L'invention concerne en outre des réseaux de formation de films diélectriques à constante diélectrique élevée qui comprennent des précurseurs à base de cérium selon la formule (I).
PCT/US2009/045024 2008-05-23 2009-05-22 Films diélectriques à constante diélectrique élevée et procédés de production au moyen de précurseurs à base de cérium Ceased WO2009143452A1 (fr)

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US61/055,620 2008-05-23

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8476467B2 (en) 2007-07-24 2013-07-02 Sigma-Aldrich Co. Llc Organometallic precursors for use in chemical phase deposition processes
US8481121B2 (en) 2007-07-24 2013-07-09 Sigma-Aldrich Co., Llc Methods of forming thin metal-containing films by chemical phase deposition
US8568530B2 (en) 2005-11-16 2013-10-29 Sigma-Aldrich Co. Llc Use of cyclopentadienyl type hafnium and zirconium precursors in atomic layer deposition
US8613975B2 (en) 2008-05-23 2013-12-24 Sigma-Aldrich Co. Llc Methods of producing high-K dielectric films using cerium-based precursors
USRE45124E1 (en) 2007-09-14 2014-09-09 Sigma-Aldrich Co. Llc Methods of atomic layer deposition using titanium-based precursors
US8927748B2 (en) 2011-08-12 2015-01-06 Sigma-Aldrich Co. Llc Alkyl-substituted allyl carbonyl metal complexes and use thereof for preparing dielectric thin films
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US8613975B2 (en) 2008-05-23 2013-12-24 Sigma-Aldrich Co. Llc Methods of producing high-K dielectric films using cerium-based precursors
US9028917B2 (en) 2009-08-07 2015-05-12 Sigma-Aldrich Co. Llc High molecular weight alkyl-allyl cobalttricarbonyl complexes and use thereof for preparing dielectric thin films
US9802220B2 (en) 2010-08-27 2017-10-31 Merck Patent Gmbh Molybdenum (IV) amide precursors and use thereof in atomic layer deposition
US8927748B2 (en) 2011-08-12 2015-01-06 Sigma-Aldrich Co. Llc Alkyl-substituted allyl carbonyl metal complexes and use thereof for preparing dielectric thin films
US9175023B2 (en) 2012-01-26 2015-11-03 Sigma-Aldrich Co. Llc Molybdenum allyl complexes and use thereof in thin film deposition
US11976352B2 (en) 2018-02-12 2024-05-07 Merck Patent Gmbh Methods of vapor deposition of ruthenium using an oxygen-free co-reactant
CN111834230A (zh) * 2020-06-22 2020-10-27 华南师范大学 一种铈掺杂的氧化锆薄膜的制备方法及其在制备晶体管中的应用
CN111834230B (zh) * 2020-06-22 2023-01-13 华南师范大学 一种铈掺杂的氧化锆薄膜的制备方法及其在制备晶体管中的应用

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